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Chinese Chemical Letters
Chinese Chemical Letters
主管 : 中国科学技术协会
刊期 : 月刊主编 : 钱旭红
语种 : 英文主办 : 中国化学会、中国医学科学院药物研究所
ISSN : 1001-8417 CN : 11-2710/O6本刊创办于1990年7月，是由中国化学会主办，中国医学科学院药物研究所承办的核心期刊。本刊由著名化学家梁晓天院士任主编，其内容涵盖化学研究的各个领域，及时报道我国化学界各个研究领域的最新进展及世界上一些化学研究的热点问题。本刊自1993年起为SCI、CA、日本科技文献速报等收录，2000年美国化学文摘引用中国期刊频次中位列第四。展开 > - 影响因子: 8.9
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Synthesis of a new ratiometric emission Ca2+ indicator for in vivo bioimaging
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Synthesis of a water-soluble macromolecular light stabilizer containing hindered amine structures
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Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
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Superiority of poly(L-lactic acid) microspheres as dermal fillers
2026, 37(2): 110588
doi: 10.1016/j.cclet.2024.110588
摘要:
Exploring new material systems and enhancing the birefringence of compounds is a highly valuable endeavor. In this study, we introduce a novel method to enhance the birefringence of inorganic compounds by inducing structural alignment through linear groups and fluoride ions. We report on two new compounds: HgGa2(SeO3)4 and Hg2Ga(SeO3)2F. HgGa2(SeO3)4 crystallizes in a non-centrosymmetric (NCS) space group, exhibiting a second harmonic generation (SHG) efficiency of approximately 60% that of commercial KH2PO4 (KDP), with a birefringence of 0.032@546 nm. Hg2Ga(SeO3)2F, on the other hand, crystallizes in a centrosymmetric space (CS) group and represents the first reported HgⅠ-based selenite birefringent material. Due to the influence of the linear group Hg2O2, its birefringence is significantly enhanced to 0.111@546 nm, which is 3.5 times that of HgGa2(SeO3)4. Moreover, both compounds demonstrate high stability and a broad optical transparency window. These findings indicate that Hg2Ga(SeO3)2F is a promising candidate for birefringent material in the mid-infrared (MIR) range. Our research provides an innovative strategy for improving the birefringence of compounds.
Exploring new material systems and enhancing the birefringence of compounds is a highly valuable endeavor. In this study, we introduce a novel method to enhance the birefringence of inorganic compounds by inducing structural alignment through linear groups and fluoride ions. We report on two new compounds: HgGa2(SeO3)4 and Hg2Ga(SeO3)2F. HgGa2(SeO3)4 crystallizes in a non-centrosymmetric (NCS) space group, exhibiting a second harmonic generation (SHG) efficiency of approximately 60% that of commercial KH2PO4 (KDP), with a birefringence of 0.032@546 nm. Hg2Ga(SeO3)2F, on the other hand, crystallizes in a centrosymmetric space (CS) group and represents the first reported HgⅠ-based selenite birefringent material. Due to the influence of the linear group Hg2O2, its birefringence is significantly enhanced to 0.111@546 nm, which is 3.5 times that of HgGa2(SeO3)4. Moreover, both compounds demonstrate high stability and a broad optical transparency window. These findings indicate that Hg2Ga(SeO3)2F is a promising candidate for birefringent material in the mid-infrared (MIR) range. Our research provides an innovative strategy for improving the birefringence of compounds.
2026, 37(2): 110590
doi: 10.1016/j.cclet.2024.110590
摘要:
In comparison with their 2D and 3D counterparts, 1D covalent organic frameworks (COFs) have rarely been investigated due to the synthetic challenge arising from the strict necessary matching in the molecular symmetry between corresponding building blocks and linking units in addition to the unmanageable packing of 1D organic chains once formed. Herein, two novel imide-linked 1D COFs with phthalocyanine building blocks, namely NiPc-CZDM-COF and NiPc-CZDL-COF, were fabricated from the hydrothermal synthesis reaction of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato nickel(Ⅱ) (NiPc(COOH)8) with 9H-carbazole-3,6-diamine (CZDM) and 4,4′-(9H-carbazole-3,6-diyl)dianiline (CZDL), respectively. Two COFs have high crystallinity on the basis of powder X-ray diffraction analysis and high-resolution transmission electron microscopy. Due to their high ratio of exposed active centers on the edge sites of porous ribbons, both NiPc-CZDM-COF and NiPc-CZDL-COF electrodes display high utilization efficiency of NiPc electroactive sites of 8.0% and 7.5% according to the electrochemical measurement, resulting in their excellent capacity toward electrocatalytic nitrate reduction with the nitrate-to-NH3 Faradaic efficiency of nearly 100%. In particular, NiPc-CZDM-COF electrode exhibits superior electrocatalytic performance with high NH3 partial current density of −246 mA/cm2, ammonia yield rate of 19.5 mg cm−2 h−1, and turnover frequency of 5.8 s−1 at −1.2 V in an H-type cell associated with its higher conductivity. This work reveals the good potential of 1D porous crystalline materials in electrocatalysis.
In comparison with their 2D and 3D counterparts, 1D covalent organic frameworks (COFs) have rarely been investigated due to the synthetic challenge arising from the strict necessary matching in the molecular symmetry between corresponding building blocks and linking units in addition to the unmanageable packing of 1D organic chains once formed. Herein, two novel imide-linked 1D COFs with phthalocyanine building blocks, namely NiPc-CZDM-COF and NiPc-CZDL-COF, were fabricated from the hydrothermal synthesis reaction of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato nickel(Ⅱ) (NiPc(COOH)8) with 9H-carbazole-3,6-diamine (CZDM) and 4,4′-(9H-carbazole-3,6-diyl)dianiline (CZDL), respectively. Two COFs have high crystallinity on the basis of powder X-ray diffraction analysis and high-resolution transmission electron microscopy. Due to their high ratio of exposed active centers on the edge sites of porous ribbons, both NiPc-CZDM-COF and NiPc-CZDL-COF electrodes display high utilization efficiency of NiPc electroactive sites of 8.0% and 7.5% according to the electrochemical measurement, resulting in their excellent capacity toward electrocatalytic nitrate reduction with the nitrate-to-NH3 Faradaic efficiency of nearly 100%. In particular, NiPc-CZDM-COF electrode exhibits superior electrocatalytic performance with high NH3 partial current density of −246 mA/cm2, ammonia yield rate of 19.5 mg cm−2 h−1, and turnover frequency of 5.8 s−1 at −1.2 V in an H-type cell associated with its higher conductivity. This work reveals the good potential of 1D porous crystalline materials in electrocatalysis.
2026, 37(2): 110591
doi: 10.1016/j.cclet.2024.110591
摘要:
Commercial carbonate electrolytes suffer from ion transport difficulty in bulk electrolytes and interphase at low temperatures, bringing challenges to the application of lithium-ion batteries (LIBs) at low temperatures. Herein, the ester solvent of methyl propionate (MP) with low melting point and low viscosity was used to tackle ion transport difficulty in electrolytes. Fluorinated ester was further added to accelerate interfacial transport through intermolecular interactions. The influence of fluorinated esters with different fluorination degrees on the solvation structure of electrolytes and the performance of batteries was further studied. As a result, methyl pentafluoropropionate (M5F) with five fluorine atoms was selected for its optimal interactions with both Li+ and MP solvent in the primary solvation structure, contributing to desired solvation structure for fast interfacial transport. The LiFePO4 (LFP)||graphite cell with LiFSI-MP-M5F electrolyte exhibited a high cyclability of 85.8% after 120 cycles and retained 81.2% of room-temperature capacity when charged and discharged at −30 ℃. 1 Ah LFP||graphite pouch cell with high cathode loading (20 mg/cm2) in LiFSI-MP-M5F electrolyte exhibited 0.85 Ah capacity when charged and discharged at −20 ℃. This work provides a guidance for electrolyte design by synergistic fluorinated and non-fluorinated solvents for LIBs at low-temperature application.
Commercial carbonate electrolytes suffer from ion transport difficulty in bulk electrolytes and interphase at low temperatures, bringing challenges to the application of lithium-ion batteries (LIBs) at low temperatures. Herein, the ester solvent of methyl propionate (MP) with low melting point and low viscosity was used to tackle ion transport difficulty in electrolytes. Fluorinated ester was further added to accelerate interfacial transport through intermolecular interactions. The influence of fluorinated esters with different fluorination degrees on the solvation structure of electrolytes and the performance of batteries was further studied. As a result, methyl pentafluoropropionate (M5F) with five fluorine atoms was selected for its optimal interactions with both Li+ and MP solvent in the primary solvation structure, contributing to desired solvation structure for fast interfacial transport. The LiFePO4 (LFP)||graphite cell with LiFSI-MP-M5F electrolyte exhibited a high cyclability of 85.8% after 120 cycles and retained 81.2% of room-temperature capacity when charged and discharged at −30 ℃. 1 Ah LFP||graphite pouch cell with high cathode loading (20 mg/cm2) in LiFSI-MP-M5F electrolyte exhibited 0.85 Ah capacity when charged and discharged at −20 ℃. This work provides a guidance for electrolyte design by synergistic fluorinated and non-fluorinated solvents for LIBs at low-temperature application.
2026, 37(2): 110592
doi: 10.1016/j.cclet.2024.110592
摘要:
There are limitations to using hard carbon (HC) in K+ storage due to its insufficient high-current reversible capacity and plateau potential, which result from the lack of effective active sites and low intercalation capabilities. The construction of HC cathodes with more available functional groups and ordered carbon nanocrystal structures is essential for improving K+ storage efficiency. Herein, a new perspective is proposed for synthesizing hard carbon nanosheets (HCNS) with abundant hydroxyl groups (O-H)/carboxylic groups (O-C = O) and rational carbon nanocrystals by interfacial assembly and carbonization. Systematic in ex-situ observations, dynamic analysis and theory calculations elucidate that the superior electrochemical capability of HCNS is ascribed to the synergistic effect of abundant available functional groups and ordered graphitic microcrystalline. Consequently, the HCNS exhibits outstanding K+ storage capabilities in terms of superb energy density (146.2 Wh/kg), high power density (1,7800 Wh/kg), and ultralong lifespan (102.9% capacity retention after 10,000 cycles). It was also found that the HC structure correlates with the discharge/charge plateau, confirming the 'adsorption-insertion' charge storage mechanism. Furthermore, the proposed work provides a theoretical basis for making high-performance HC anodes by understanding the effect of their microstructure on K+ storage.
There are limitations to using hard carbon (HC) in K+ storage due to its insufficient high-current reversible capacity and plateau potential, which result from the lack of effective active sites and low intercalation capabilities. The construction of HC cathodes with more available functional groups and ordered carbon nanocrystal structures is essential for improving K+ storage efficiency. Herein, a new perspective is proposed for synthesizing hard carbon nanosheets (HCNS) with abundant hydroxyl groups (O-H)/carboxylic groups (O-C = O) and rational carbon nanocrystals by interfacial assembly and carbonization. Systematic in ex-situ observations, dynamic analysis and theory calculations elucidate that the superior electrochemical capability of HCNS is ascribed to the synergistic effect of abundant available functional groups and ordered graphitic microcrystalline. Consequently, the HCNS exhibits outstanding K+ storage capabilities in terms of superb energy density (146.2 Wh/kg), high power density (1,7800 Wh/kg), and ultralong lifespan (102.9% capacity retention after 10,000 cycles). It was also found that the HC structure correlates with the discharge/charge plateau, confirming the 'adsorption-insertion' charge storage mechanism. Furthermore, the proposed work provides a theoretical basis for making high-performance HC anodes by understanding the effect of their microstructure on K+ storage.
2026, 37(2): 110605
doi: 10.1016/j.cclet.2024.110605
摘要:
The intrinsic insulation and drastic volume change of the red phosphorus during the 3-electron alloying process greatly limits its widespread applications in sodium-ion batteries. Here, we report a monomicelle-directed assembly approach for controllable synthesis of monodispersed mesoporous polypyrrole (PPy) nanospheres, which allows for the shape-preserving conversion into N-doped carbon with regular mesoscopic pore and high surface area, thus affording a high dispersion of red phosphorus during melt impregnation process due to the available diffusion apertures and strong molecular chemical anchoring. Moreover, the theoretical calculations further revealed that positively polarized pyridine N atoms in N-doped mesoporous carbon nanospheres can empower comprehensive regulation of red phosphorus adsorption by strong chemical binding. Benefitting from the above advantages, the resultant red phosphorus host for sodium-ion batteries delivered an outstanding reversible capacity of 856 mAh/g with a capacity fading rate of only 0.025% per cycle during 1000 cycles at 1.0 A/g. This work provides an effective approach based on monomicelle-directed assembly engineering of carbon-based phosphorus hosts for advanced energy conversion and storage systems.
The intrinsic insulation and drastic volume change of the red phosphorus during the 3-electron alloying process greatly limits its widespread applications in sodium-ion batteries. Here, we report a monomicelle-directed assembly approach for controllable synthesis of monodispersed mesoporous polypyrrole (PPy) nanospheres, which allows for the shape-preserving conversion into N-doped carbon with regular mesoscopic pore and high surface area, thus affording a high dispersion of red phosphorus during melt impregnation process due to the available diffusion apertures and strong molecular chemical anchoring. Moreover, the theoretical calculations further revealed that positively polarized pyridine N atoms in N-doped mesoporous carbon nanospheres can empower comprehensive regulation of red phosphorus adsorption by strong chemical binding. Benefitting from the above advantages, the resultant red phosphorus host for sodium-ion batteries delivered an outstanding reversible capacity of 856 mAh/g with a capacity fading rate of only 0.025% per cycle during 1000 cycles at 1.0 A/g. This work provides an effective approach based on monomicelle-directed assembly engineering of carbon-based phosphorus hosts for advanced energy conversion and storage systems.
2026, 37(2): 110622
doi: 10.1016/j.cclet.2024.110622
摘要:
The high voltage of Li||LiCoO2 battery can increase the energy density. However, the cycling performance associated with cathode structural stability remains challenging. To address this question, we proposed an electrolyte strategy for improving the performance of 4.6 V Li||LiCoO2 battery by using trimethylsilyl isocyanate (TMIS) as electrolyte additive. The trimethylsilyl group of TMIS can trap HF while the isocyanate group brings polyamide components to the CEI and the SEI. By the synergistic action, the Co3+ dissolution problem of the LiCoO2 cathode was effectively curbed. Furthermore, TMIS regulates the construction of anion-dominated LiF-rich SEI by influencing the solvation structure of Li+. As expected, the 4.6 V Li||LiCoO2 battery with TMIS retains 77.9% initial capacity after 200 cycles at 0.5 C.
The high voltage of Li||LiCoO2 battery can increase the energy density. However, the cycling performance associated with cathode structural stability remains challenging. To address this question, we proposed an electrolyte strategy for improving the performance of 4.6 V Li||LiCoO2 battery by using trimethylsilyl isocyanate (TMIS) as electrolyte additive. The trimethylsilyl group of TMIS can trap HF while the isocyanate group brings polyamide components to the CEI and the SEI. By the synergistic action, the Co3+ dissolution problem of the LiCoO2 cathode was effectively curbed. Furthermore, TMIS regulates the construction of anion-dominated LiF-rich SEI by influencing the solvation structure of Li+. As expected, the 4.6 V Li||LiCoO2 battery with TMIS retains 77.9% initial capacity after 200 cycles at 0.5 C.
2026, 37(2): 110828
doi: 10.1016/j.cclet.2025.110828
摘要:
The insufficient performance of Pt and Pd benchmark catalysts remains a significant obstacle to the practical application of direct liquid fuel cells. In this study, we report a synthesis of amorphous PdSe/crystalline Pt nanoparticles (AC-PdPtSe NPs) by chemical leaching of PdPtSe NPs. AC-PdPtSe NPs display significantly enhanced activity and stability for the electrooxidation of ethylene glycol and glycerol, far surpassing that of amorphous-dominant PdPtSe NPs, commercial Pd/C, and Pt/C catalysts. Notably, the integration of crystalline and amorphous domains leverages the advantages of high electrical conductivity and a wealth of active sites, which can substantially accelerate reaction kinetics. Furthermore, detailed investigations reveal that the boundary between the Pt crystalline and PdSe amorphous phases induces a 3% surface tensile strain. The formation of amorphous-crystalline heterointerfaces optimizes the d-band states, thereby strengthening the adsorption and activation of ethylene glycol and glycerol. This study highlights the advance in phase engineering toward the development of highly active noble-metal nanostructures.
The insufficient performance of Pt and Pd benchmark catalysts remains a significant obstacle to the practical application of direct liquid fuel cells. In this study, we report a synthesis of amorphous PdSe/crystalline Pt nanoparticles (AC-PdPtSe NPs) by chemical leaching of PdPtSe NPs. AC-PdPtSe NPs display significantly enhanced activity and stability for the electrooxidation of ethylene glycol and glycerol, far surpassing that of amorphous-dominant PdPtSe NPs, commercial Pd/C, and Pt/C catalysts. Notably, the integration of crystalline and amorphous domains leverages the advantages of high electrical conductivity and a wealth of active sites, which can substantially accelerate reaction kinetics. Furthermore, detailed investigations reveal that the boundary between the Pt crystalline and PdSe amorphous phases induces a 3% surface tensile strain. The formation of amorphous-crystalline heterointerfaces optimizes the d-band states, thereby strengthening the adsorption and activation of ethylene glycol and glycerol. This study highlights the advance in phase engineering toward the development of highly active noble-metal nanostructures.
2026, 37(2): 110830
doi: 10.1016/j.cclet.2025.110830
摘要:
Designing a highly active and stable bifunctional catalyst is essential for achieving superior overall water splitting (OWS). In this study, a three-dimensional (3D) core-shell structure Co3S4/CuS@NiFe LDH nanocoral spheres electrocatalyst was constructed on nickel foam (NF) via an interfacial engineering strategy. This 3D core-shell heterostructure maximizes the exposure of active sites, optimizes the charge transport pathway and accelerates gas release rates. The protective shell strategy of NiFe LDH provides favorable stability, which contributes to inhibiting the electrochemical corrosion of the electrocatalyst and mitigating the toxic effects of Cl− and other microorganisms during the seawater splitting process. Moreover, the introduction of NiFe LDH induces a change in the OER mechanism from an adsorption evolution mechanism (AEM) to a lattice oxygen mechanism (LOM), which improves the intrinsic activity of the catalyst. Consequently, Co3S4/CuS@NiFe LDH demonstrates exceptional performance in the oxygen evolution reaction (OER) (η100 = 251 mV) and in the hydrogen evolution reaction (HER) (η100 = 254 mV), alongside remarkable stability over 100 h. For OWS, it exhibits a voltage of 1.46 V at 10 mA/cm2 and maintain stability for 100 h. Impressively, Co3S4/CuS@NiFe LDH still possesses outstanding activity and stability in natural alkaline seawater. This work proposes interfacial engineering to construct bifunctional catalysts with core-shell heterostructures, providing instructive guidelines for the design of highly efficient electrocatalysts toward seawater electrolysis.
Designing a highly active and stable bifunctional catalyst is essential for achieving superior overall water splitting (OWS). In this study, a three-dimensional (3D) core-shell structure Co3S4/CuS@NiFe LDH nanocoral spheres electrocatalyst was constructed on nickel foam (NF) via an interfacial engineering strategy. This 3D core-shell heterostructure maximizes the exposure of active sites, optimizes the charge transport pathway and accelerates gas release rates. The protective shell strategy of NiFe LDH provides favorable stability, which contributes to inhibiting the electrochemical corrosion of the electrocatalyst and mitigating the toxic effects of Cl− and other microorganisms during the seawater splitting process. Moreover, the introduction of NiFe LDH induces a change in the OER mechanism from an adsorption evolution mechanism (AEM) to a lattice oxygen mechanism (LOM), which improves the intrinsic activity of the catalyst. Consequently, Co3S4/CuS@NiFe LDH demonstrates exceptional performance in the oxygen evolution reaction (OER) (η100 = 251 mV) and in the hydrogen evolution reaction (HER) (η100 = 254 mV), alongside remarkable stability over 100 h. For OWS, it exhibits a voltage of 1.46 V at 10 mA/cm2 and maintain stability for 100 h. Impressively, Co3S4/CuS@NiFe LDH still possesses outstanding activity and stability in natural alkaline seawater. This work proposes interfacial engineering to construct bifunctional catalysts with core-shell heterostructures, providing instructive guidelines for the design of highly efficient electrocatalysts toward seawater electrolysis.
2026, 37(2): 110951
doi: 10.1016/j.cclet.2025.110951
摘要:
New-skeleton terpenoids have prompted considerable interest owing to their chemical and biological significance. A chemical study on the bark of Croton laui led to the isolation and identification of a new norsesterterpenoid, crolatinoid A (1), and two new neoclerodane diterpenoids, crolatinoids B and C (2 and 3). Structurally, compound 1 exhibits an unprecedented 12,17-cyclo20-nor phenyllabdane skeleton. Compound 2 features a novel 19(5→4)-abeo-3,5-cycloneoclerodane skeleton, which is hypothetically derived from precursor 3 through an oxa-di-π-methane rearrangement process. Furthermore, compound 1 demonstrated a significant capacity to reverse multidrug resistance in paclitaxel-resistant HCT-15 cells with a reversal fold value of 16. All three compounds displayed adipogenesis inhibition in 3T3-L1 adipocytes.
New-skeleton terpenoids have prompted considerable interest owing to their chemical and biological significance. A chemical study on the bark of Croton laui led to the isolation and identification of a new norsesterterpenoid, crolatinoid A (1), and two new neoclerodane diterpenoids, crolatinoids B and C (2 and 3). Structurally, compound 1 exhibits an unprecedented 12,17-cyclo20-nor phenyllabdane skeleton. Compound 2 features a novel 19(5→4)-abeo-3,5-cycloneoclerodane skeleton, which is hypothetically derived from precursor 3 through an oxa-di-π-methane rearrangement process. Furthermore, compound 1 demonstrated a significant capacity to reverse multidrug resistance in paclitaxel-resistant HCT-15 cells with a reversal fold value of 16. All three compounds displayed adipogenesis inhibition in 3T3-L1 adipocytes.
2026, 37(2): 110961
doi: 10.1016/j.cclet.2025.110961
摘要:
Triple-negative breast cancer (TNBC) presents significant diagnostic and therapeutic challenges due to the lack of targeted treatments, rapid progression, high recurrence and metastasis rates, and overall poorer prognosis. Herein, the targeted theranostic platform of cysteine-modified gold nanodots-sulfhydrated luteinizing hormone releasing hormone (CGN-SLR) nanosystem was designed for target recognition and precise dual-mode imaging-guided photothermal therapy (PTT) against TNBC. On the one hand, the CGN-SLR nanosystem can serve as an ideal targeting fluorescent probe and computed tomography (CT) enhancer to facilitate the accurate diagnosis and surgical guidance of TNBC. On the other hand, the CGN-SLR nanosystem with great targeting and PTT ability can significantly inhibit the growth of TNBC, without causing harm to normal tissues and healthy organs. It provides an effective strategy for the diagnosis and treatment of TNBC through the rational design of multifunctional nanoplatform with target recognition, multiple imaging guidance/monitoring, and high-efficiency PTT.
Triple-negative breast cancer (TNBC) presents significant diagnostic and therapeutic challenges due to the lack of targeted treatments, rapid progression, high recurrence and metastasis rates, and overall poorer prognosis. Herein, the targeted theranostic platform of cysteine-modified gold nanodots-sulfhydrated luteinizing hormone releasing hormone (CGN-SLR) nanosystem was designed for target recognition and precise dual-mode imaging-guided photothermal therapy (PTT) against TNBC. On the one hand, the CGN-SLR nanosystem can serve as an ideal targeting fluorescent probe and computed tomography (CT) enhancer to facilitate the accurate diagnosis and surgical guidance of TNBC. On the other hand, the CGN-SLR nanosystem with great targeting and PTT ability can significantly inhibit the growth of TNBC, without causing harm to normal tissues and healthy organs. It provides an effective strategy for the diagnosis and treatment of TNBC through the rational design of multifunctional nanoplatform with target recognition, multiple imaging guidance/monitoring, and high-efficiency PTT.
2026, 37(2): 110965
doi: 10.1016/j.cclet.2025.110965
摘要:
Triterpenoids are valuable medicinal scaffolds, characterized by excellent pharmacological properties and the presence of hydroxyl and carboxyl groups that allow for further structural modifications. Expanding the scope of oxidative modifications on these molecules is crucial for increasing their synthetic structural diversity and unlocking new potential pharmacological activities. However, the progress has been limited by the scarcity of suitable tailoring enzymes. Here, we reported a break-through in achieving targeted and remote dual-site oxidation of licorice triterpenoids using a single P450 mutant. This approach successfully enabled the selective synthesis of the rare triterpenoid, liquiritic acid and 24-OH-liquiritic acid. Our findings demonstrate that microenvironmental accessibility engineering of triterpenoid substrates within the P450 enzyme is essential for continuous and regioselective oxidation. This study not only sheds light on the mechanistic aspects of P450 catalysis but also expands the enzymatic toolkit for selective oxidative modifications in triterpenoid biosynthesis.
Triterpenoids are valuable medicinal scaffolds, characterized by excellent pharmacological properties and the presence of hydroxyl and carboxyl groups that allow for further structural modifications. Expanding the scope of oxidative modifications on these molecules is crucial for increasing their synthetic structural diversity and unlocking new potential pharmacological activities. However, the progress has been limited by the scarcity of suitable tailoring enzymes. Here, we reported a break-through in achieving targeted and remote dual-site oxidation of licorice triterpenoids using a single P450 mutant. This approach successfully enabled the selective synthesis of the rare triterpenoid, liquiritic acid and 24-OH-liquiritic acid. Our findings demonstrate that microenvironmental accessibility engineering of triterpenoid substrates within the P450 enzyme is essential for continuous and regioselective oxidation. This study not only sheds light on the mechanistic aspects of P450 catalysis but also expands the enzymatic toolkit for selective oxidative modifications in triterpenoid biosynthesis.
2026, 37(2): 110977
doi: 10.1016/j.cclet.2025.110977
摘要:
The level of glutathione (GSH) is significantly associated with numerous pathological processes, thus, real-time detection of the GSH level is of significance for early diagnosis of GSH-related diseases. Herein, we developed in vivo second near-infrared (NIR-Ⅱ) window fluorescence (FL) and ratiometric photoacoustic (RPA) dual-modality imaging of GSH using a GSH-activatable probe (LET-14). LET-14 was synthesized based on a rhodamine hybrid xanthene skeleton with a FL shielding 2,4-dinitrobenzene sulfonyl group that can be specifically cleaved by GSH, thus resulting in a markedly bathochromic-shift absorption, a 6.5-fold increase in NIR-Ⅱ FL intensity (FL920) and a 13-fold increase in RPA signal (PA880/PA705) in vitro. Intriguingly, LET-14 exhibits good selectivity and sensitivity for NIR-Ⅱ FL and RPA dual-modality imaging of GSH in 4T1 tumor-bearing mouse model. Our findings develop an in vivo detection tool of GSH, which has great potential in the field of cancer diagnosis.
The level of glutathione (GSH) is significantly associated with numerous pathological processes, thus, real-time detection of the GSH level is of significance for early diagnosis of GSH-related diseases. Herein, we developed in vivo second near-infrared (NIR-Ⅱ) window fluorescence (FL) and ratiometric photoacoustic (RPA) dual-modality imaging of GSH using a GSH-activatable probe (LET-14). LET-14 was synthesized based on a rhodamine hybrid xanthene skeleton with a FL shielding 2,4-dinitrobenzene sulfonyl group that can be specifically cleaved by GSH, thus resulting in a markedly bathochromic-shift absorption, a 6.5-fold increase in NIR-Ⅱ FL intensity (FL920) and a 13-fold increase in RPA signal (PA880/PA705) in vitro. Intriguingly, LET-14 exhibits good selectivity and sensitivity for NIR-Ⅱ FL and RPA dual-modality imaging of GSH in 4T1 tumor-bearing mouse model. Our findings develop an in vivo detection tool of GSH, which has great potential in the field of cancer diagnosis.
2026, 37(2): 110992
doi: 10.1016/j.cclet.2025.110992
摘要:
The von Hippel-Lindau tumor suppressor (VHL) has been extensively used to develop degraders targeting numerous proteins of interest. However, studies on the rational design of VHL-proteolysis-targeting chimeras (PROTACs) remain scarce. This study aimed to develop strategies to investigate VHL-recruiting PROTACs connecting with varying attachment sites on VHL ligands, which could be utilized for KRASG12C degraders development and expanded to additional targets. We developed a molecular dynamics (MD)-based strategy to explore the stability of ternary complexes induced by KRASG12C PROTACs with four distinct attachment sites of VH032. We found a potent degrader namely YN14-H, linked to hydroxyl group on VH032 benzene ring, exhibited the most superior ability of inducing ternary complexes, reflected by the lowest dissociation constant (Kd) for ternary complex induction and the highest AlphaScreen (AS)-based interaction. YN14-H inhibited cell growth with low nanomolar half maximal inhibitory concentration (IC50) and half maximal degradation concentration (DC50) values as well as >98% of maximum degradation (Dmax) in NCI-H358 and MIA PaCa-2 cells harboring KRASG12C-mutation. Mechanistically, YN14-H significantly induced apoptosis and inhibited the migratory capacity. Notably, YN14-H demonstrated favorable pharmacokinetic properties and excellent antitumor activity in vivo. Furthermore, bromodomain-containing protein 7 (BRD7) and Bruton tyrosine kinase (BTK) degraders attached to distinct sites on VH032 further verified the rationality and universality of our MD-based strategies. Our findings demonstrated that YN14-H could serve as a promising candidate for the treatment of tumors with KRASG12C-mutation and present a strategy for the rational design of VHL-recruiting PROTACs that target additional proteins at distinct attachment sites.
The von Hippel-Lindau tumor suppressor (VHL) has been extensively used to develop degraders targeting numerous proteins of interest. However, studies on the rational design of VHL-proteolysis-targeting chimeras (PROTACs) remain scarce. This study aimed to develop strategies to investigate VHL-recruiting PROTACs connecting with varying attachment sites on VHL ligands, which could be utilized for KRASG12C degraders development and expanded to additional targets. We developed a molecular dynamics (MD)-based strategy to explore the stability of ternary complexes induced by KRASG12C PROTACs with four distinct attachment sites of VH032. We found a potent degrader namely YN14-H, linked to hydroxyl group on VH032 benzene ring, exhibited the most superior ability of inducing ternary complexes, reflected by the lowest dissociation constant (Kd) for ternary complex induction and the highest AlphaScreen (AS)-based interaction. YN14-H inhibited cell growth with low nanomolar half maximal inhibitory concentration (IC50) and half maximal degradation concentration (DC50) values as well as >98% of maximum degradation (Dmax) in NCI-H358 and MIA PaCa-2 cells harboring KRASG12C-mutation. Mechanistically, YN14-H significantly induced apoptosis and inhibited the migratory capacity. Notably, YN14-H demonstrated favorable pharmacokinetic properties and excellent antitumor activity in vivo. Furthermore, bromodomain-containing protein 7 (BRD7) and Bruton tyrosine kinase (BTK) degraders attached to distinct sites on VH032 further verified the rationality and universality of our MD-based strategies. Our findings demonstrated that YN14-H could serve as a promising candidate for the treatment of tumors with KRASG12C-mutation and present a strategy for the rational design of VHL-recruiting PROTACs that target additional proteins at distinct attachment sites.
2026, 37(2): 111014
doi: 10.1016/j.cclet.2025.111014
摘要:
The protein corona formation has been reported to influence the liposomes’ behavioral performance in vivo. Accordingly, the effect of physiologically relevant inorganic ion pairs (sodium chloride, sodium sulfate, magnesium chloride, and magnesium sulfate) was investigated. Bovine serum albumin (BSA) was selected as the model protein. Parameters including particle size and zeta potential were assessed, while various spectroscopic techniques were utilized to elucidate the changes in BSA during its interaction with liposomes. The particle size and light intensity distribution changes indicated that the introduction of inorganic pairs, especially the metal cations, could significantly influence both the adsorption of BSA and the aggregation of particles. Furthermore, spectral characterization elucidated that BSA exhibited more extended peptide chains with enhanced exposure to hydrophobic acid amino residues upon adding ion pairs. Electrostatic adsorption and chelation insertion were proposed as metal ion binding modes and the corresponding BSA corona formation. In the electrostatic adsorption mode, sodium ions can enhance the electrostatic interactions, facilitating the “connection” between BSA and liposomes. Magnesium ions can induce stronger hydrophobic interactions through chelation, effectively “drag” BSA segments into the lipid bilayer. This work highlighted important physiological factors for protein-liposome interaction and provided rational model constructions to lay the foundation for further relevant studies.
The protein corona formation has been reported to influence the liposomes’ behavioral performance in vivo. Accordingly, the effect of physiologically relevant inorganic ion pairs (sodium chloride, sodium sulfate, magnesium chloride, and magnesium sulfate) was investigated. Bovine serum albumin (BSA) was selected as the model protein. Parameters including particle size and zeta potential were assessed, while various spectroscopic techniques were utilized to elucidate the changes in BSA during its interaction with liposomes. The particle size and light intensity distribution changes indicated that the introduction of inorganic pairs, especially the metal cations, could significantly influence both the adsorption of BSA and the aggregation of particles. Furthermore, spectral characterization elucidated that BSA exhibited more extended peptide chains with enhanced exposure to hydrophobic acid amino residues upon adding ion pairs. Electrostatic adsorption and chelation insertion were proposed as metal ion binding modes and the corresponding BSA corona formation. In the electrostatic adsorption mode, sodium ions can enhance the electrostatic interactions, facilitating the “connection” between BSA and liposomes. Magnesium ions can induce stronger hydrophobic interactions through chelation, effectively “drag” BSA segments into the lipid bilayer. This work highlighted important physiological factors for protein-liposome interaction and provided rational model constructions to lay the foundation for further relevant studies.
2026, 37(2): 111017
doi: 10.1016/j.cclet.2025.111017
摘要:
Hemorrhagic shock (HS) is a leading cause of death worldwide, particularly within the first 24 h post-injury. Current treatments are limited, especially in low-resource settings. Therapeutic hypothermia (TH) offers potential benefits by reducing metabolic demands and protecting organs, but its application in HS is challenged by cooling difficulties and side effects. This study introduces a novel nasal gel formulation of N6-cyclohexyladenosine (CHA), an adenosine A1 receptor agonist, designed to enhance brain delivery while minimizing peripheral side effects. In a mouse model of HS, administration of CHA nasal gel significantly improved survival rates, reduced metabolic rates, and protected major organs without worsening coagulopathy. Metabolomics analysis revealed a shift towards fatty acid oxidation and increased antioxidant capacity. These findings demonstrate that CHA nasal gel effectively induces TH, offering a safe and innovative treatment strategy for HS, particularly in resource-limited environments.
Hemorrhagic shock (HS) is a leading cause of death worldwide, particularly within the first 24 h post-injury. Current treatments are limited, especially in low-resource settings. Therapeutic hypothermia (TH) offers potential benefits by reducing metabolic demands and protecting organs, but its application in HS is challenged by cooling difficulties and side effects. This study introduces a novel nasal gel formulation of N6-cyclohexyladenosine (CHA), an adenosine A1 receptor agonist, designed to enhance brain delivery while minimizing peripheral side effects. In a mouse model of HS, administration of CHA nasal gel significantly improved survival rates, reduced metabolic rates, and protected major organs without worsening coagulopathy. Metabolomics analysis revealed a shift towards fatty acid oxidation and increased antioxidant capacity. These findings demonstrate that CHA nasal gel effectively induces TH, offering a safe and innovative treatment strategy for HS, particularly in resource-limited environments.
2026, 37(2): 111020
doi: 10.1016/j.cclet.2025.111020
摘要:
Thermoplastic polyurethane (TPU) consists of a hard segment and a soft segment, where the former affords mechanical strength and thermal stability, while the latter provides a possibility of good ionic conductivity by promoting dissociation of ions from the lithium salt. Thus, TPU attracts a wide interest recently as a promising polymer electrolyte for solid-state lithium batteries. However, the relatively low ionic conductivity of TPU still restricts its actual applications due to the aggregation of polymer chains, which greatly reduces the dissociation of lithium salts. Herein, a strategy to address this challenge was adopted by in situ polymerization poly(ethylene glycol diacrylate) (PEGDA) in fully dispersed TPU. Hence a stretchable solid-state electrolyte (denoted as TELL and the contrast sample was denoted as TLL) with high ionic conductivity of 7.18 × 10−4 S/cm was obtained at room temperature. The Li+ transference number is 0.85 in Li|TELL|Li cell and can stably undergo charge-discharge cycles for 1400 h at a current density of 0.1 mA/cm2, while the contrast sample is short-circuited after 634 h of cycling. The LiFePO4|TELL|Li cell achieves a capacity retention of 78.93% after 200 cycles at 2 C. The LiFePO4|TLL|Li cell only gains the capacity retention of 51.9% after 50 cycles at the same current density. So, the method adopted here may provide a new approach to realize a flexible solid-state electrolyte with high ion-conductivity.
Thermoplastic polyurethane (TPU) consists of a hard segment and a soft segment, where the former affords mechanical strength and thermal stability, while the latter provides a possibility of good ionic conductivity by promoting dissociation of ions from the lithium salt. Thus, TPU attracts a wide interest recently as a promising polymer electrolyte for solid-state lithium batteries. However, the relatively low ionic conductivity of TPU still restricts its actual applications due to the aggregation of polymer chains, which greatly reduces the dissociation of lithium salts. Herein, a strategy to address this challenge was adopted by in situ polymerization poly(ethylene glycol diacrylate) (PEGDA) in fully dispersed TPU. Hence a stretchable solid-state electrolyte (denoted as TELL and the contrast sample was denoted as TLL) with high ionic conductivity of 7.18 × 10−4 S/cm was obtained at room temperature. The Li+ transference number is 0.85 in Li|TELL|Li cell and can stably undergo charge-discharge cycles for 1400 h at a current density of 0.1 mA/cm2, while the contrast sample is short-circuited after 634 h of cycling. The LiFePO4|TELL|Li cell achieves a capacity retention of 78.93% after 200 cycles at 2 C. The LiFePO4|TLL|Li cell only gains the capacity retention of 51.9% after 50 cycles at the same current density. So, the method adopted here may provide a new approach to realize a flexible solid-state electrolyte with high ion-conductivity.
2026, 37(2): 111031
doi: 10.1016/j.cclet.2025.111031
摘要:
In situ tumor vaccines, which leverage the antigenic profile of individual tumors, have demonstrated significant potential in tumor immunotherapy. However, their efficacy is often limited by the immunosuppressive tumor microenvironment (TME) and insufficient tumor targeting. To address these challenges, we engineered in situ nanovaccines through the self-assembly of the photosensitizer indocyanine green, immune adjuvant aluminum (Al3+), and hydrophilic drug zoledronic acid (ZOL). Intravenous injection of these nanovaccines led to efficient tumor accumulation, enhancing drug bioavailability and enabling the release of tumor-associated antigens via photothermal therapy. Additionally, the built-in ZOL induces polarization of tumor-associated macrophages, reversing the immunosuppressive TME. The potent antitumor immune response triggered by these nanovaccines effectively suppresses tumor growth. This study, which integrates a straightforward assembly method, substantial drug loading capacity, and promising therapeutic outcomes, introduces a novel and effective paradigm for carrier-free in situ nanovaccines in cancer treatment.
In situ tumor vaccines, which leverage the antigenic profile of individual tumors, have demonstrated significant potential in tumor immunotherapy. However, their efficacy is often limited by the immunosuppressive tumor microenvironment (TME) and insufficient tumor targeting. To address these challenges, we engineered in situ nanovaccines through the self-assembly of the photosensitizer indocyanine green, immune adjuvant aluminum (Al3+), and hydrophilic drug zoledronic acid (ZOL). Intravenous injection of these nanovaccines led to efficient tumor accumulation, enhancing drug bioavailability and enabling the release of tumor-associated antigens via photothermal therapy. Additionally, the built-in ZOL induces polarization of tumor-associated macrophages, reversing the immunosuppressive TME. The potent antitumor immune response triggered by these nanovaccines effectively suppresses tumor growth. This study, which integrates a straightforward assembly method, substantial drug loading capacity, and promising therapeutic outcomes, introduces a novel and effective paradigm for carrier-free in situ nanovaccines in cancer treatment.
2026, 37(2): 111048
doi: 10.1016/j.cclet.2025.111048
摘要:
Hyperactivation of DNA repairing pathway is highly associated with the chemosensitivity and chemoresistance of cancer cells. In this manuscript, guided by cascaded one strain many compounds-global natural products social molecular networking (OSMAC-GNPS) strategy, a pair of epimeric environmental-induced metabolites were isolated from Aspergillus sp. EGF 15-0-3. Structurally, sterpiperazines A (1) and B (2) represent the first steroid-based indole alkaloids with unprecedented backbones. Biologically, compound 1 could be identified as a novel tyrosyl-DNA phosphodiesterase 1 (Tdp1) inhibitor with a unique mechanism distinct from the reported modulators, and was able to significantly enhance the sensitivity of NCI-H460 cells to the clinic chemotherapeutic drug through inhibiting the DNA repairment and enhanced the DNA damage of cancer cells.
Hyperactivation of DNA repairing pathway is highly associated with the chemosensitivity and chemoresistance of cancer cells. In this manuscript, guided by cascaded one strain many compounds-global natural products social molecular networking (OSMAC-GNPS) strategy, a pair of epimeric environmental-induced metabolites were isolated from Aspergillus sp. EGF 15-0-3. Structurally, sterpiperazines A (1) and B (2) represent the first steroid-based indole alkaloids with unprecedented backbones. Biologically, compound 1 could be identified as a novel tyrosyl-DNA phosphodiesterase 1 (Tdp1) inhibitor with a unique mechanism distinct from the reported modulators, and was able to significantly enhance the sensitivity of NCI-H460 cells to the clinic chemotherapeutic drug through inhibiting the DNA repairment and enhanced the DNA damage of cancer cells.
2026, 37(2): 111055
doi: 10.1016/j.cclet.2025.111055
摘要:
Novel antibacterial strategies such as antibacterial photodynamic therapy (aPDT) and photothermal therapy (PTT) have gained significant attention, however, relying on a single-treatment approach still faces challenges of insufficient therapeutic efficiency and the potential for drug resistance. In this study, a multimodal synergistic antibacterial nanoplatform by coupling a carbon monoxide (CO) donor (4-(3-hydroxy-4-oxo-4H-chromen-2-yl)benzoic acid (4-BA)) with carbon dots (CDs) is developed, referred to as CDs-CO, which integrates multiple antibacterial modes of aPDT, PTT, and gas therapy. This nanoplatform is designed for highly efficient antibacterial action with a low risk of inducing drug resistance. CDs are engineered to possess tailored functions, including deep-red light-triggered heat and singlet oxygen (1O2) production. After modification with 4-BA and exposure to 660 nm laser irradiation, CDs-CO exhibits favorable photothermal conversion efficiency (η = 52.7%), robust 1O2 generation, and 1O2-activated CO release. Antibacterial experiments demonstrated the excellent sterilization effects of CDs-CO against both Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), underscoring the enhanced antibacterial efficiency of this multimodal nanoplatform. This study offers a rational approach for designing multimodal synergistic antibacterial platforms, highlighting their potential for effectively treating bacterial infections.
Novel antibacterial strategies such as antibacterial photodynamic therapy (aPDT) and photothermal therapy (PTT) have gained significant attention, however, relying on a single-treatment approach still faces challenges of insufficient therapeutic efficiency and the potential for drug resistance. In this study, a multimodal synergistic antibacterial nanoplatform by coupling a carbon monoxide (CO) donor (4-(3-hydroxy-4-oxo-4H-chromen-2-yl)benzoic acid (4-BA)) with carbon dots (CDs) is developed, referred to as CDs-CO, which integrates multiple antibacterial modes of aPDT, PTT, and gas therapy. This nanoplatform is designed for highly efficient antibacterial action with a low risk of inducing drug resistance. CDs are engineered to possess tailored functions, including deep-red light-triggered heat and singlet oxygen (1O2) production. After modification with 4-BA and exposure to 660 nm laser irradiation, CDs-CO exhibits favorable photothermal conversion efficiency (η = 52.7%), robust 1O2 generation, and 1O2-activated CO release. Antibacterial experiments demonstrated the excellent sterilization effects of CDs-CO against both Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), underscoring the enhanced antibacterial efficiency of this multimodal nanoplatform. This study offers a rational approach for designing multimodal synergistic antibacterial platforms, highlighting their potential for effectively treating bacterial infections.
Mechanical force-induced switchable multiple-color and white-light circularly polarized luminescence
2026, 37(2): 111060
doi: 10.1016/j.cclet.2025.111060
摘要:
Achieving rational control over polarization states and color of circularly polarized luminescence (CPL) through simple modulation poses a challenging yet highly practical problem. To address this issue, we developed a mechano-responsive chiral supramolecular system based on a cyclohexanediamide-derived gelator CCPy. This molecule exhibited a strong blue fluorescence accompanied by a distinct CPL signal upon forming a supramolecular gel in toluene. However, upon the application of mechanical force, the gel rapidly transformed into a faintly emissive suspension with a silent CPL signal, along with a notable morphological alteration. Furthermore, by implementing the circularly polarized Förster resonance energy transfer (CP-FRET) strategy, the mechano-responsiveness was effectively imparted to binary systems through the incorporation of dyes Nile red (NR) and coumarin 7 (C7), thus realizing mechanical force-switchable green and red CPL systems. It was particularly noteworthy that by adjusting the ratio of CCPy, C7 and NR, a ternary mechanical force-induced CPL ON-OFF switch that emitted a standard white emission was achieved through sequential CP-FRET. Following this, an information encryption experiment was performed. This work provided a paradigm for fabricating smart multi-color and white-light CPL materials.
Achieving rational control over polarization states and color of circularly polarized luminescence (CPL) through simple modulation poses a challenging yet highly practical problem. To address this issue, we developed a mechano-responsive chiral supramolecular system based on a cyclohexanediamide-derived gelator CCPy. This molecule exhibited a strong blue fluorescence accompanied by a distinct CPL signal upon forming a supramolecular gel in toluene. However, upon the application of mechanical force, the gel rapidly transformed into a faintly emissive suspension with a silent CPL signal, along with a notable morphological alteration. Furthermore, by implementing the circularly polarized Förster resonance energy transfer (CP-FRET) strategy, the mechano-responsiveness was effectively imparted to binary systems through the incorporation of dyes Nile red (NR) and coumarin 7 (C7), thus realizing mechanical force-switchable green and red CPL systems. It was particularly noteworthy that by adjusting the ratio of CCPy, C7 and NR, a ternary mechanical force-induced CPL ON-OFF switch that emitted a standard white emission was achieved through sequential CP-FRET. Following this, an information encryption experiment was performed. This work provided a paradigm for fabricating smart multi-color and white-light CPL materials.
2026, 37(2): 111097
doi: 10.1016/j.cclet.2025.111097
摘要:
Photoreforming poly(lactic acid) (PLA) plastics into pyruvic acid (PA) coupled with hydrogen evolution is of great significance for sustainable development. However, a significant challenge lies in α-OH bond cleaving of lactic acid (LA). Herein, CdS/Bi4Ti3O12 composite is fabricated, bridged by Bi−S bonds, through in-situ growth of CdS nanoparticles on Bi4Ti3O12 nanoflowers for the successive removal of hydrogen from α-C in LA. In-situ X-ray photoelectron spectroscopy confirms the S-scheme carriers transfer route and interfacial Bi−S bond in CdS/Bi4Ti3O12. Consequently, the photo-electrons and holes with extended lifetimes and strong redox potential accumulate in the CdS conduction band and Bi4Ti3O12 valence band, respectively, as evidenced by in-situ electron spin resonance and time-resolved photoluminescence. This facilitates the generation of •OH radicals, which further participate in the successive dehydrogenation reaction of LA. Consequently, the photoreforming efficiencies of converting PLA into PA and H2 by CdS/Bi4Ti3O12 are 1.7 and 3.16 mmol g–1 h–1, which are respectively 2.8 and 22 times higher than that by pristine Bi4Ti3O12. The present work provides a new approach for designing S-scheme to achieve hydrogen production and value-added conversion of plastics.
Photoreforming poly(lactic acid) (PLA) plastics into pyruvic acid (PA) coupled with hydrogen evolution is of great significance for sustainable development. However, a significant challenge lies in α-OH bond cleaving of lactic acid (LA). Herein, CdS/Bi4Ti3O12 composite is fabricated, bridged by Bi−S bonds, through in-situ growth of CdS nanoparticles on Bi4Ti3O12 nanoflowers for the successive removal of hydrogen from α-C in LA. In-situ X-ray photoelectron spectroscopy confirms the S-scheme carriers transfer route and interfacial Bi−S bond in CdS/Bi4Ti3O12. Consequently, the photo-electrons and holes with extended lifetimes and strong redox potential accumulate in the CdS conduction band and Bi4Ti3O12 valence band, respectively, as evidenced by in-situ electron spin resonance and time-resolved photoluminescence. This facilitates the generation of •OH radicals, which further participate in the successive dehydrogenation reaction of LA. Consequently, the photoreforming efficiencies of converting PLA into PA and H2 by CdS/Bi4Ti3O12 are 1.7 and 3.16 mmol g–1 h–1, which are respectively 2.8 and 22 times higher than that by pristine Bi4Ti3O12. The present work provides a new approach for designing S-scheme to achieve hydrogen production and value-added conversion of plastics.
2026, 37(2): 111109
doi: 10.1016/j.cclet.2025.111109
摘要:
The implementation of multiple pathogen testing is essential for a rapid response to future outbreaks and for reducing disease transmission. This study introduces a 96-channel microfluidic chip, fabricated through a molding process, which enables the batch detection of pathogens. It explores the rapid lysis and elution processes of pathogens within the microfluidic chips to ensure that nucleic acid extraction, elution, and amplification are completed entirely within the chip. This chip can extract nucleic acids from samples in just 10 min, achieving an extraction efficiency comparable to that of traditional in-tube methods. An oil phase is pre-loaded into the chip to effectively prevent aerosol contamination. This approach allows for the simultaneous detection of 21 common respiratory pathogens, with a detection limit of 10 copies per reaction. Furthermore, applications involving clinical samples demonstrate significant practicality. Compared to many traditional in-tube pathogen detection methods and molecular biology technologies that utilize microfluidic chips, this detection chip not only enables simultaneous detection of multiple pathogens but also demonstrates high sensitivity.
The implementation of multiple pathogen testing is essential for a rapid response to future outbreaks and for reducing disease transmission. This study introduces a 96-channel microfluidic chip, fabricated through a molding process, which enables the batch detection of pathogens. It explores the rapid lysis and elution processes of pathogens within the microfluidic chips to ensure that nucleic acid extraction, elution, and amplification are completed entirely within the chip. This chip can extract nucleic acids from samples in just 10 min, achieving an extraction efficiency comparable to that of traditional in-tube methods. An oil phase is pre-loaded into the chip to effectively prevent aerosol contamination. This approach allows for the simultaneous detection of 21 common respiratory pathogens, with a detection limit of 10 copies per reaction. Furthermore, applications involving clinical samples demonstrate significant practicality. Compared to many traditional in-tube pathogen detection methods and molecular biology technologies that utilize microfluidic chips, this detection chip not only enables simultaneous detection of multiple pathogens but also demonstrates high sensitivity.
2026, 37(2): 111117
doi: 10.1016/j.cclet.2025.111117
摘要:
Constructing nanofibers with specific therapeutic effects against cancer is a challenge. Here, we present the synthesis approach and application prospects of supramolecular nanofibers, which are based on cucurbit[8]uril (CB[8]) as the host and terpyridine lanthanum ions metal complex as the guest, constructed by layer-by-layer self-assembly through supramolecular interaction. Moreover, nanofibers with lanthanide luminescence properties exhibit surprising pH-responsive deformation properties and antibacterial behavior. In the tumor micro-environment, the dramatic reduction in the size of the nanofibers enables specific and hierarchical release of anticancer drugs in tumor cells to exert an advanced therapeutic effect. In addition, the synergistic therapeutic efficacy was achieved by reducing the excess of Gram-positive and Gram-negative bacteria surrounding tumor cells. The novel supramolecular nanofibers with sequential drug release and combined therapeutic mode provide new guidance for the synthesis of drug carrier materials and direction for the promotion of nanomaterial-mediated cancer therapy.
Constructing nanofibers with specific therapeutic effects against cancer is a challenge. Here, we present the synthesis approach and application prospects of supramolecular nanofibers, which are based on cucurbit[8]uril (CB[8]) as the host and terpyridine lanthanum ions metal complex as the guest, constructed by layer-by-layer self-assembly through supramolecular interaction. Moreover, nanofibers with lanthanide luminescence properties exhibit surprising pH-responsive deformation properties and antibacterial behavior. In the tumor micro-environment, the dramatic reduction in the size of the nanofibers enables specific and hierarchical release of anticancer drugs in tumor cells to exert an advanced therapeutic effect. In addition, the synergistic therapeutic efficacy was achieved by reducing the excess of Gram-positive and Gram-negative bacteria surrounding tumor cells. The novel supramolecular nanofibers with sequential drug release and combined therapeutic mode provide new guidance for the synthesis of drug carrier materials and direction for the promotion of nanomaterial-mediated cancer therapy.
2026, 37(2): 111121
doi: 10.1016/j.cclet.2025.111121
摘要:
Asplactones A–E (1–5), five unique diphenyl ether hybrids, along with two rare spiro-diphenyl ethers, aspviolaceols A (6) and B (7), were isolated and characterized from Aspergillus sp. F1–8A, an endophytic fungus associated with the parotoid glands of Bufo gargarizans Cantor. Compounds 1–5 represent the first examples of diphenyl ether hybrids fused with unusual moieties, including conjugated γ-butyrolactone and cyclopentenone. Compounds 6 and 7 are the first known natural spiro-diphenyl ethers, with 6 featuring an uncommon 6/6/6/6-membered carbon skeleton, and 7 possessing a distinct 6/6/6/6/6/6-membered diphenyl ether spiro-heterodimer carbon framework. Structural elucidation was performed using a combination of spectroscopic techniques, X-ray crystallography, and quantum-chemical calculations, and plausible biosynthetic pathways were proposed. Biologically, compounds 1, 2, 4, 6, and 7 exhibited antioxidant activity comparable to or surpassing that of vitamin C in 1,1-diphenyl-2-picrylhydrazyl (DPPH) and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS), and ferric reducing power assays. They also significantly improved cell viability in H2O2-induced oxidative injury assays using A549 cells.
Asplactones A–E (1–5), five unique diphenyl ether hybrids, along with two rare spiro-diphenyl ethers, aspviolaceols A (6) and B (7), were isolated and characterized from Aspergillus sp. F1–8A, an endophytic fungus associated with the parotoid glands of Bufo gargarizans Cantor. Compounds 1–5 represent the first examples of diphenyl ether hybrids fused with unusual moieties, including conjugated γ-butyrolactone and cyclopentenone. Compounds 6 and 7 are the first known natural spiro-diphenyl ethers, with 6 featuring an uncommon 6/6/6/6-membered carbon skeleton, and 7 possessing a distinct 6/6/6/6/6/6-membered diphenyl ether spiro-heterodimer carbon framework. Structural elucidation was performed using a combination of spectroscopic techniques, X-ray crystallography, and quantum-chemical calculations, and plausible biosynthetic pathways were proposed. Biologically, compounds 1, 2, 4, 6, and 7 exhibited antioxidant activity comparable to or surpassing that of vitamin C in 1,1-diphenyl-2-picrylhydrazyl (DPPH) and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS), and ferric reducing power assays. They also significantly improved cell viability in H2O2-induced oxidative injury assays using A549 cells.
2026, 37(2): 111136
doi: 10.1016/j.cclet.2025.111136
摘要:
Successfully generating reactive oxygen species (ROS) in a targeted and efficient manner for the detoxification of chlorinated organic pollutants (CPs) is a significant and demanding challenge. Herein, we present an in-situ photoreduction strategy to fabricate a composite of palladium (Pd) nanoparticles anchored few-layer carbon nitride nanosheets (Pd-CN). This innovative Pd-CN is then leveraged to activate peroxymonosulfate (PMS) in pursuit of our objective. The incorporation of Pd nanoparticles enhances PMS absorption and targets its terminal oxygen, thereby aiding in the cleavage of the O-O bond. This process generates crucial intermediates, including adsorbed hydroxyl radicals (*OH) and adsorbed atomic oxygen (O*), which are essential for the production of 1O2. Consequently, the Pd-CN catalyst demonstrates strong preference for 1O2 generation during the PMS activation process, successfully degrading over 95% of pollutants such as 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), and 2,4,6-trichlorophenol (2,4,6-TCP) within just 20 min. Additionally, the catalyst exhibits total organic carbon (TOC) removal rates ranging from 49.4% to 31.4%, while the rates for de-chlorination fall between 68.6% and 72.7%. A subsequent continuous-flow treatment experiment has confirmed the application potential of this system, demonstrating consistent catalytic activity for up to 8 h. This promising technique presents an efficient strategy for addressing the high toxicity of chlorinated organic pollutants in contaminated water.
Successfully generating reactive oxygen species (ROS) in a targeted and efficient manner for the detoxification of chlorinated organic pollutants (CPs) is a significant and demanding challenge. Herein, we present an in-situ photoreduction strategy to fabricate a composite of palladium (Pd) nanoparticles anchored few-layer carbon nitride nanosheets (Pd-CN). This innovative Pd-CN is then leveraged to activate peroxymonosulfate (PMS) in pursuit of our objective. The incorporation of Pd nanoparticles enhances PMS absorption and targets its terminal oxygen, thereby aiding in the cleavage of the O-O bond. This process generates crucial intermediates, including adsorbed hydroxyl radicals (*OH) and adsorbed atomic oxygen (O*), which are essential for the production of 1O2. Consequently, the Pd-CN catalyst demonstrates strong preference for 1O2 generation during the PMS activation process, successfully degrading over 95% of pollutants such as 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), and 2,4,6-trichlorophenol (2,4,6-TCP) within just 20 min. Additionally, the catalyst exhibits total organic carbon (TOC) removal rates ranging from 49.4% to 31.4%, while the rates for de-chlorination fall between 68.6% and 72.7%. A subsequent continuous-flow treatment experiment has confirmed the application potential of this system, demonstrating consistent catalytic activity for up to 8 h. This promising technique presents an efficient strategy for addressing the high toxicity of chlorinated organic pollutants in contaminated water.
2026, 37(2): 111148
doi: 10.1016/j.cclet.2025.111148
摘要:
Chiral benzylic amines are important motifs in medicines. A dicationic nickel complex of chiral diphosphine (R)-Ph-BPE promotes highly enantioselective reductive amination of aryl alkyl ketones with arylamines using isopropanol as hydrogen source. The reaction is easily scaled up in a gram-scale synthesis using 1 mol% nickel catalyst and it is applied to an asymmetric synthesis of (S)-rivastigmine. Building on this success, we achieved rare examples of asymmetric hydrogen borrowing reactions with arylamines using an Earth-abundant 3d metal, nickel.
Chiral benzylic amines are important motifs in medicines. A dicationic nickel complex of chiral diphosphine (R)-Ph-BPE promotes highly enantioselective reductive amination of aryl alkyl ketones with arylamines using isopropanol as hydrogen source. The reaction is easily scaled up in a gram-scale synthesis using 1 mol% nickel catalyst and it is applied to an asymmetric synthesis of (S)-rivastigmine. Building on this success, we achieved rare examples of asymmetric hydrogen borrowing reactions with arylamines using an Earth-abundant 3d metal, nickel.
2026, 37(2): 111155
doi: 10.1016/j.cclet.2025.111155
摘要:
Understanding the photoluminescence (PL) mechanism of metal nanoclusters from both molecular and supramolecular perspectives is crucial for developing highly emissive cluster-based nanomaterials. In this study, we synthesized two structurally similar Ag14 nanoclusters with different phosphine stabilizers, which demonstrated opposite PL behaviors in solution and crystalline states. The Ag14 nanocluster stabilized by P(Ph-OMe)3 ligands exhibited a higher PL intensity compared to the one stabilized by P(Ph-F)3 ligands, which was attributed to the stronger electron-donating ability of the P(Ph-OMe)3 ligand that improved ligand-to-metal charge transfer efficiency. In contrast, the P(Ph-F)3 stabilized Ag14 crystals displayed greater PL intensity than the Ag14 cluster crystal with a -OMe surface, which was due to stronger intermolecular interactions within the cluster lattice of the former that limited non-radiative energy loss and thus enhanced PL. Overall, this work aims to promote a comprehensive understanding of the fluorescence in cluster-based nanomaterials, which will be beneficial for their downstream applications.
Understanding the photoluminescence (PL) mechanism of metal nanoclusters from both molecular and supramolecular perspectives is crucial for developing highly emissive cluster-based nanomaterials. In this study, we synthesized two structurally similar Ag14 nanoclusters with different phosphine stabilizers, which demonstrated opposite PL behaviors in solution and crystalline states. The Ag14 nanocluster stabilized by P(Ph-OMe)3 ligands exhibited a higher PL intensity compared to the one stabilized by P(Ph-F)3 ligands, which was attributed to the stronger electron-donating ability of the P(Ph-OMe)3 ligand that improved ligand-to-metal charge transfer efficiency. In contrast, the P(Ph-F)3 stabilized Ag14 crystals displayed greater PL intensity than the Ag14 cluster crystal with a -OMe surface, which was due to stronger intermolecular interactions within the cluster lattice of the former that limited non-radiative energy loss and thus enhanced PL. Overall, this work aims to promote a comprehensive understanding of the fluorescence in cluster-based nanomaterials, which will be beneficial for their downstream applications.
2026, 37(2): 111196
doi: 10.1016/j.cclet.2025.111196
摘要:
Sulfoxides and sulfide compounds have broad-spectrum biological properties and have received considerable attention in the past few decades. Herein we reported two metal and oxidant-free, practical and efficient methods for the synthesis of highly synthetically useful and structurally diverse ortho-aminoaryl sulfoxides and 3,4,5-trisubstituted oxazolones from readily accessible N-arylhydroxylamines and N-thiophthalimides. This rapid transformation occurred smoothly to achieve chemo- and regioselective cascade rearrangements due to the differences of the protecting-groups of the nitrogen atom of N-arylhydroxyamines. DFT studies suggested that the competing S-O and S-C bond formations via SN2 nucleophilic substitution are crucial for the observed protecting-group-dependent chemoselectivity. Subsequent applications have shown that these two protocols might be powerful tools for the construction of sulfur-containing complex molecules under simple conditions.
Sulfoxides and sulfide compounds have broad-spectrum biological properties and have received considerable attention in the past few decades. Herein we reported two metal and oxidant-free, practical and efficient methods for the synthesis of highly synthetically useful and structurally diverse ortho-aminoaryl sulfoxides and 3,4,5-trisubstituted oxazolones from readily accessible N-arylhydroxylamines and N-thiophthalimides. This rapid transformation occurred smoothly to achieve chemo- and regioselective cascade rearrangements due to the differences of the protecting-groups of the nitrogen atom of N-arylhydroxyamines. DFT studies suggested that the competing S-O and S-C bond formations via SN2 nucleophilic substitution are crucial for the observed protecting-group-dependent chemoselectivity. Subsequent applications have shown that these two protocols might be powerful tools for the construction of sulfur-containing complex molecules under simple conditions.
2026, 37(2): 111203
doi: 10.1016/j.cclet.2025.111203
摘要:
Freshwater scarcity is exacerbated by uneven distribution of limited freshwater resources and high energy costs of desalination technologies. Atmospheric water vapor, a vast and geographically unrestricted reservoir, could become a sustainable alternative. Sorption-based atmospheric water harvesting (SAWH) has emerged as an available solution, yet conventional desorption methods relying on energy-intensive electrical heating hinder its scalability. Herein, a photothermal hygroscopic sponge has been developed for solar-driven atmospheric water harvesting. The composites combine a malleable melamine sponge skeleton, lithium chloride as a hygroscopic agent, and hydrangea-like molybdenum disulfide as a photothermal component, forming a multiscale "pore-film" cross-linked structure by an eco-friendly immersion-freeze-drying method. The optimized sample achieves exceptional hygroscopic capacity (3.92 g/g at 90% RH) and freshwater production efficiency (87.77%), which is attributed to synergistic effects of porous skeleton based crosslinked structures and "pore-film" structures, and outstanding photothermal conversion efficiency of MoS2. The unique structure could stabilize LiCl to prevent leakage, increase mass transfer effectiveness of whole SWAH process, and enable flexibility for diverse applications. We carried out outdoor experiments to demonstrate a solar-driven water production rate of 4.22 L m-2 d-1 without external energy input. This work provides insights into sustainable freshwater generation and promotes green energy utilization in addressing global water scarcity.
Freshwater scarcity is exacerbated by uneven distribution of limited freshwater resources and high energy costs of desalination technologies. Atmospheric water vapor, a vast and geographically unrestricted reservoir, could become a sustainable alternative. Sorption-based atmospheric water harvesting (SAWH) has emerged as an available solution, yet conventional desorption methods relying on energy-intensive electrical heating hinder its scalability. Herein, a photothermal hygroscopic sponge has been developed for solar-driven atmospheric water harvesting. The composites combine a malleable melamine sponge skeleton, lithium chloride as a hygroscopic agent, and hydrangea-like molybdenum disulfide as a photothermal component, forming a multiscale "pore-film" cross-linked structure by an eco-friendly immersion-freeze-drying method. The optimized sample achieves exceptional hygroscopic capacity (3.92 g/g at 90% RH) and freshwater production efficiency (87.77%), which is attributed to synergistic effects of porous skeleton based crosslinked structures and "pore-film" structures, and outstanding photothermal conversion efficiency of MoS2. The unique structure could stabilize LiCl to prevent leakage, increase mass transfer effectiveness of whole SWAH process, and enable flexibility for diverse applications. We carried out outdoor experiments to demonstrate a solar-driven water production rate of 4.22 L m-2 d-1 without external energy input. This work provides insights into sustainable freshwater generation and promotes green energy utilization in addressing global water scarcity.
2026, 37(2): 111209
doi: 10.1016/j.cclet.2025.111209
摘要:
The coexistence of emerging containments, such as antibiotic resistant bacteria (ARB), antibiotic-resistant genes (ARGs) and antibiotics, potentially influence elimination efficiencies in UV light-emitting diode (UV-LED) alone and UV-LED/H2O2 system as their complex interactions. Tetracycline (TC) degradation efficiency (kF) correlated closely with its UV molar absorbance (R2 = 0.831) in UV-LED alone system and with •OH yield (R2 = 0.999) in UV-LED/H2O2 system across studied wavelengths (265, 280 and 310 nm). The kF values for intracellular DNA (i-ARGs) also exhibited a high correlation with UV-LED wavelengths in both systems (R2 = 0.997–0.999). The coexistence of TC and ARB/ARGs resulted in a mutual inhibition of their degradation efficiencies due to competition for photons and •OH, along with the consequent reduction in intracellular ROS within ARB, with their degradation efficiencies exhibiting marked dependence on wavelength in both systems. Notably, the UV-LED/H2O2 system at 265 nm effectively achieved the simultaneous removal of TC, ARB and ARGs with minimal energy consumption, and successfully fragmented ARGs. The degradation pathway of TC was analyzed, and the biotoxicity of its degradation intermediates demonstrated the environmental friendliness and safety of UV-LED/H2O2 technology. This study elucidated the competitive interactions between antibiotics and ARB/ARGs within UV-LED/H2O2 system, providing a promising approach for their simultaneous removal while ensuring energy efficiency.
The coexistence of emerging containments, such as antibiotic resistant bacteria (ARB), antibiotic-resistant genes (ARGs) and antibiotics, potentially influence elimination efficiencies in UV light-emitting diode (UV-LED) alone and UV-LED/H2O2 system as their complex interactions. Tetracycline (TC) degradation efficiency (kF) correlated closely with its UV molar absorbance (R2 = 0.831) in UV-LED alone system and with •OH yield (R2 = 0.999) in UV-LED/H2O2 system across studied wavelengths (265, 280 and 310 nm). The kF values for intracellular DNA (i-ARGs) also exhibited a high correlation with UV-LED wavelengths in both systems (R2 = 0.997–0.999). The coexistence of TC and ARB/ARGs resulted in a mutual inhibition of their degradation efficiencies due to competition for photons and •OH, along with the consequent reduction in intracellular ROS within ARB, with their degradation efficiencies exhibiting marked dependence on wavelength in both systems. Notably, the UV-LED/H2O2 system at 265 nm effectively achieved the simultaneous removal of TC, ARB and ARGs with minimal energy consumption, and successfully fragmented ARGs. The degradation pathway of TC was analyzed, and the biotoxicity of its degradation intermediates demonstrated the environmental friendliness and safety of UV-LED/H2O2 technology. This study elucidated the competitive interactions between antibiotics and ARB/ARGs within UV-LED/H2O2 system, providing a promising approach for their simultaneous removal while ensuring energy efficiency.
2026, 37(2): 111210
doi: 10.1016/j.cclet.2025.111210
摘要:
Hard carbon (HC) in sodium-ion batteries is searched by numerous investigations, which can offer the excellent performance of reversible Na+ insertion and extraction. The covalent heteroatom doping in HC is recently worth concentrating, which can dilate the interlayer spacing of graphite to adjust the electrochemical storage performance in carbon anodes. However, the reported doping strategies of the modified HC have only resulted in limited improvement, especially unobvious effects on tuning porous structure. In this study, tannin extract and K2SO4 are respectively utilized as carbon source and sulfur source for the fabrication of HC, in which K2SO4 can contribute to the heteroatom doping, and the pore forming as well. The tannin-derived sulfur-doped carbon anode shows the excellent cycle stability, achieving a high reversible capacity of 520.5 mAh/g at a current density of 100 mA/g. Even after 500 cycles at a current density of 3 A/g, a high specific capacity of 236.7 mAh/g and a capacity retention rate of 92.6% can be reserved. Compared with the initial carbon, the adsorption energy of Na+ is multifold times higher, whereas Na+ diffusion energy barriers manyfold decrease. Moreover, the full battery assembled with Na3V2(PO4)3/tannin-based HC demonstrates a stable cycling performance. This work can manifest the potentiality of the tannin-based electrode as anode for a high-performance sodium-ion batteries (SIBs), which could especially offer an explanation of Na+ storage and solid-electrolyte interface (SEI) stability to the electrochemical performance.
Hard carbon (HC) in sodium-ion batteries is searched by numerous investigations, which can offer the excellent performance of reversible Na+ insertion and extraction. The covalent heteroatom doping in HC is recently worth concentrating, which can dilate the interlayer spacing of graphite to adjust the electrochemical storage performance in carbon anodes. However, the reported doping strategies of the modified HC have only resulted in limited improvement, especially unobvious effects on tuning porous structure. In this study, tannin extract and K2SO4 are respectively utilized as carbon source and sulfur source for the fabrication of HC, in which K2SO4 can contribute to the heteroatom doping, and the pore forming as well. The tannin-derived sulfur-doped carbon anode shows the excellent cycle stability, achieving a high reversible capacity of 520.5 mAh/g at a current density of 100 mA/g. Even after 500 cycles at a current density of 3 A/g, a high specific capacity of 236.7 mAh/g and a capacity retention rate of 92.6% can be reserved. Compared with the initial carbon, the adsorption energy of Na+ is multifold times higher, whereas Na+ diffusion energy barriers manyfold decrease. Moreover, the full battery assembled with Na3V2(PO4)3/tannin-based HC demonstrates a stable cycling performance. This work can manifest the potentiality of the tannin-based electrode as anode for a high-performance sodium-ion batteries (SIBs), which could especially offer an explanation of Na+ storage and solid-electrolyte interface (SEI) stability to the electrochemical performance.
2026, 37(2): 111218
doi: 10.1016/j.cclet.2025.111218
摘要:
High-sensitive quantitative determination of alpha-fetoprotein (AFP) is of crucial importance for early clinical diagnosis of cancers. Herein, an AuNPs-free electrochemical immunosensor (Ab1-Fc-COF) was prepared from a carboxylic group enriched COF by post-functionalization with detecting antibody (Ab1) and ferrocene (Fc), and used for electrochemical detection of AFP. Due to the small, homogeneous pore size of the COF, Ab1 with a big size was immobilized on the surface of the COF, while Fc with a small size was covalently modified both on the surface and in the pores of COF. The covalently immobilized Ab1 was quite stable and beneficial to specifically detect AFP biomarkers. Meanwhile, the enriched Fc molecules not only improved the conductivity of the COF, but also effectively transferred and amplified the electrochemical signal. This proposed immunosensor exhibited high sensitivity in detecting AFP with a detection limit of 0.39 pg/mL (S/N of 3:1) and a wide linear response range spanning from 1 pg/mL to 100 ng/mL when plotted against logarithmic concentrations. Furthermore, this immunosensor showed excellent selectivity, stability and reproducibility in the testing of real samples. This study presents an innovative prototype for construction of a precious metal-free, antibody-directly-immobilized, simple and stable electrochemical immunoprobe.
High-sensitive quantitative determination of alpha-fetoprotein (AFP) is of crucial importance for early clinical diagnosis of cancers. Herein, an AuNPs-free electrochemical immunosensor (Ab1-Fc-COF) was prepared from a carboxylic group enriched COF by post-functionalization with detecting antibody (Ab1) and ferrocene (Fc), and used for electrochemical detection of AFP. Due to the small, homogeneous pore size of the COF, Ab1 with a big size was immobilized on the surface of the COF, while Fc with a small size was covalently modified both on the surface and in the pores of COF. The covalently immobilized Ab1 was quite stable and beneficial to specifically detect AFP biomarkers. Meanwhile, the enriched Fc molecules not only improved the conductivity of the COF, but also effectively transferred and amplified the electrochemical signal. This proposed immunosensor exhibited high sensitivity in detecting AFP with a detection limit of 0.39 pg/mL (S/N of 3:1) and a wide linear response range spanning from 1 pg/mL to 100 ng/mL when plotted against logarithmic concentrations. Furthermore, this immunosensor showed excellent selectivity, stability and reproducibility in the testing of real samples. This study presents an innovative prototype for construction of a precious metal-free, antibody-directly-immobilized, simple and stable electrochemical immunoprobe.
2026, 37(2): 111281
doi: 10.1016/j.cclet.2025.111281
摘要:
Plant-related organic compound (PROC) may interact with redox-active metals like iron while they are present in soil or aquatic environment, but their effects on the photoreduction of Fe(Ⅲ) remain largely unexplored. This study investigates the photochemical behavior of Fe(Ⅲ)-PROC complexes using alkaline lignin (AL), betaine hydrochloride (BH), and phytic acid (PA) as representative proxies for PROC. The reductive agent AL demonstrated the ability to directly reduce Fe(Ⅲ) to Fe(Ⅱ). In contrast, BH, being unable to form strong complexes with Fe(Ⅲ), was able to quench •OH, thereby resulting in a shift of the redox equilibrium towards Fe(Ⅱ). PA exhibited a strong binding affinity for Fe(Ⅲ), effectively inhibiting its photoreduction. Electron paramagnetic resonance (EPR) analysis, utilizing 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin trap, revealed that the DMPO-OH signal detected in photolyzed Fe(Ⅲ)-PROC solutions originated from various pathways. Specifically, uncomplexed Fe(Ⅲ) in AL or BH solutions was shown to oxidize DMPO directly, leading to the formation of a false DMPO-OH adduct. The addition of ethanol to the photolyzed Fe(Ⅲ)-AL and Fe(Ⅲ)-BH systems resulted in the generation of the DMPO-CH(CH3)OH adduct, thereby confirming the presence of authentic •OH in these systems. The photolysis of the Fe(Ⅲ)-PA complex may proceed via a photodissociation mechanism, where the resulting loosely bound Fe(Ⅲ) can oxidize DMPO, followed by a nucleophilic attack from water. This research highlights the multifaceted roles of PROC in facilitating the redox cycling of iron within soil and aquatic ecosystems.
Plant-related organic compound (PROC) may interact with redox-active metals like iron while they are present in soil or aquatic environment, but their effects on the photoreduction of Fe(Ⅲ) remain largely unexplored. This study investigates the photochemical behavior of Fe(Ⅲ)-PROC complexes using alkaline lignin (AL), betaine hydrochloride (BH), and phytic acid (PA) as representative proxies for PROC. The reductive agent AL demonstrated the ability to directly reduce Fe(Ⅲ) to Fe(Ⅱ). In contrast, BH, being unable to form strong complexes with Fe(Ⅲ), was able to quench •OH, thereby resulting in a shift of the redox equilibrium towards Fe(Ⅱ). PA exhibited a strong binding affinity for Fe(Ⅲ), effectively inhibiting its photoreduction. Electron paramagnetic resonance (EPR) analysis, utilizing 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) as a spin trap, revealed that the DMPO-OH signal detected in photolyzed Fe(Ⅲ)-PROC solutions originated from various pathways. Specifically, uncomplexed Fe(Ⅲ) in AL or BH solutions was shown to oxidize DMPO directly, leading to the formation of a false DMPO-OH adduct. The addition of ethanol to the photolyzed Fe(Ⅲ)-AL and Fe(Ⅲ)-BH systems resulted in the generation of the DMPO-CH(CH3)OH adduct, thereby confirming the presence of authentic •OH in these systems. The photolysis of the Fe(Ⅲ)-PA complex may proceed via a photodissociation mechanism, where the resulting loosely bound Fe(Ⅲ) can oxidize DMPO, followed by a nucleophilic attack from water. This research highlights the multifaceted roles of PROC in facilitating the redox cycling of iron within soil and aquatic ecosystems.
2026, 37(2): 111289
doi: 10.1016/j.cclet.2025.111289
摘要:
In the pharmaceutical field, machine learning can play an important role in drug development, production and treatment. Co-crystallization techniques have shown promising potential to enhance the properties of active pharmaceutical ingredients (APIs) such as solubility, permeability, and bioavailability, all without altering their chemical structure. This approach opens new avenues for developing natural products into effective drugs, especially those previously challenging in formulation. Emodin, an anthraquinone-based natural product, is a notable example due to its diverse biological activities; however, its physicochemical limitations, such as poor solubility and easy sublimation, restricted its clinical application. While various methods have improved emodin's physicochemical properties, research on its bioavailability remains limited. In our study, we summarize cocrystals and salts produced through co-crystallization technology and identify piperazine as a favorable coformer. Conflicting conclusions from computational chemistry and molecular modeling method and machine learning method regarding the formation of an emodin-piperazine cocrystal or salt led us to experimentally validate these possibilities. Ultimately, we successfully obtained the emodin-piperazine cocrystal, which were characterized and evaluated by several in vitro methods and pharmacokinetic studies. In addition, experiments have shown that emodin has a certain therapeutic effect on sepsis, so we also evaluated emodin-piperazine biological activity in a sepsis model. The results demonstrate that co-crystallization significantly enhances emodin's solubility, permeability, and bioavailability. Pharmacodynamic studies indicate that the emodin-piperazine cocrystal improves sepsis symptoms and provides protective effects against liver and kidney damage associated with sepsis. This study offers renewed hope for natural products with broad biological activities yet hindered by physicochemical limitations by advancing co-crystallization as a viable development approach.
In the pharmaceutical field, machine learning can play an important role in drug development, production and treatment. Co-crystallization techniques have shown promising potential to enhance the properties of active pharmaceutical ingredients (APIs) such as solubility, permeability, and bioavailability, all without altering their chemical structure. This approach opens new avenues for developing natural products into effective drugs, especially those previously challenging in formulation. Emodin, an anthraquinone-based natural product, is a notable example due to its diverse biological activities; however, its physicochemical limitations, such as poor solubility and easy sublimation, restricted its clinical application. While various methods have improved emodin's physicochemical properties, research on its bioavailability remains limited. In our study, we summarize cocrystals and salts produced through co-crystallization technology and identify piperazine as a favorable coformer. Conflicting conclusions from computational chemistry and molecular modeling method and machine learning method regarding the formation of an emodin-piperazine cocrystal or salt led us to experimentally validate these possibilities. Ultimately, we successfully obtained the emodin-piperazine cocrystal, which were characterized and evaluated by several in vitro methods and pharmacokinetic studies. In addition, experiments have shown that emodin has a certain therapeutic effect on sepsis, so we also evaluated emodin-piperazine biological activity in a sepsis model. The results demonstrate that co-crystallization significantly enhances emodin's solubility, permeability, and bioavailability. Pharmacodynamic studies indicate that the emodin-piperazine cocrystal improves sepsis symptoms and provides protective effects against liver and kidney damage associated with sepsis. This study offers renewed hope for natural products with broad biological activities yet hindered by physicochemical limitations by advancing co-crystallization as a viable development approach.
2026, 37(2): 111301
doi: 10.1016/j.cclet.2025.111301
摘要:
Nowadays, higher requirements are put forward to the storage and utilization of energy, and supercapacitor is a kind of energy storage electronic devices. The resulting CA-N, with a specific surface area of 320.6 m2/g and a pore volume of 0.28 cm3/g, demonstrated a remarkable supercapacitance of 283.3 F/g. As a mesoporous material, CA-N offers numerous channels for the diffusion and absorption of electrolyte ions. Furthermore, it exhibited an impressive capacity retention rate of 98.48% after 5000 charge-discharge cycles. These outstanding electrochemical properties highlight the potential of CA-N for applications in energy storage.
Nowadays, higher requirements are put forward to the storage and utilization of energy, and supercapacitor is a kind of energy storage electronic devices. The resulting CA-N, with a specific surface area of 320.6 m2/g and a pore volume of 0.28 cm3/g, demonstrated a remarkable supercapacitance of 283.3 F/g. As a mesoporous material, CA-N offers numerous channels for the diffusion and absorption of electrolyte ions. Furthermore, it exhibited an impressive capacity retention rate of 98.48% after 5000 charge-discharge cycles. These outstanding electrochemical properties highlight the potential of CA-N for applications in energy storage.
2026, 37(2): 111306
doi: 10.1016/j.cclet.2025.111306
摘要:
Oxidative magnetization has attracted great attention as an efficient strategy for modulating physiochemical properties of magnetic biochar. In this paper, a K2FeO4-involving hydrothermal oxidative magnetization was explored to regulate multiple micro-structures for manufacture magnetic hydrochar (MHC) for Fenton-like degradation of tetracycline in aqueous solution. Diverse shapes of Fe3O4 and nano zero-valent iron (nZVI) were doped with abundant oxygen containing groups and persistent free radicals (PFRs). Multiple catalysis sites including iron species, PFRs, oxygen containing groups, and graphite defects contributed to accelerate the Fenton-like degradation with synergistic effect. Notably, MHC achieved a tetracycline removal rate of 99% within 60 min at 50 mg/L, with a total organic carbon (TOC) removal rate of 35%. Furthermore, after four cycles of reuse, the degradation efficiency slightly decreased to 93%. This study highlights the potential of magnetic hydrochar with multiple catalytic sites in the effective and sustainable degradation of pollutants.
Oxidative magnetization has attracted great attention as an efficient strategy for modulating physiochemical properties of magnetic biochar. In this paper, a K2FeO4-involving hydrothermal oxidative magnetization was explored to regulate multiple micro-structures for manufacture magnetic hydrochar (MHC) for Fenton-like degradation of tetracycline in aqueous solution. Diverse shapes of Fe3O4 and nano zero-valent iron (nZVI) were doped with abundant oxygen containing groups and persistent free radicals (PFRs). Multiple catalysis sites including iron species, PFRs, oxygen containing groups, and graphite defects contributed to accelerate the Fenton-like degradation with synergistic effect. Notably, MHC achieved a tetracycline removal rate of 99% within 60 min at 50 mg/L, with a total organic carbon (TOC) removal rate of 35%. Furthermore, after four cycles of reuse, the degradation efficiency slightly decreased to 93%. This study highlights the potential of magnetic hydrochar with multiple catalytic sites in the effective and sustainable degradation of pollutants.
2026, 37(2): 111323
doi: 10.1016/j.cclet.2025.111323
摘要:
Simultaneous identification and quantitative detection of phenylenediamine (PDA) isomers, including o-phenylenediamine (OPD), m-phenylenediamine (MPD), and p-phenylenediamine (PPD), are essential for environmental risk assessment and human health protection. However, current visual detection methods can only distinguish individual PDA isomers and failed to identify binary or ternary mixtures. Herein, a highly active and ultrastable peroxidase (POD)–like CoPt graphitic nanozyme was used for naked-eye identification and colorimetric/fluorescent (FL) dual-mode quantitative detection of PDA isomers. The CoPt@G nanozyme effectively catalyzed the oxidation of OPD, MPD, PPD, OPD + PPD, OPD + MPD, MPD + PPD and OPD + MPD + PPD into yellow, colorless, lilac, yellow, yellow, wine red and reddish-brown products, respectively, in the presence of H2O2. Thus, the MPD, PPD, MPD + PPD and OPD + MPD + PPD were easily identified based on the distinct color of their oxidation products, and the OPD, OPD + PPD, OPD + MPD could be further identified by the additional addition of MPD or PPD. Subsequently, CoPt@G/H2O2-, a 3,3′,5,5′-tetramethylbenzidine (TMB)/CoPt@G/H2O2-, and MPD/CoPt@G/H2O2-enabled colorimetric/FL dual-mode platforms for the quantitative detection of OPD, MPD and PPD were proposed. The experimental results illustrated that the constructed sensing platforms exhibit satisfactory sensitivity, comparable to that reported in previous studies. Finally, the evaluation of PDAs in water samples was realized, yielding satisfactory recoveries. This work expanded the application prospects of nanozymes in assessing environmental risks and protection of human security.
Simultaneous identification and quantitative detection of phenylenediamine (PDA) isomers, including o-phenylenediamine (OPD), m-phenylenediamine (MPD), and p-phenylenediamine (PPD), are essential for environmental risk assessment and human health protection. However, current visual detection methods can only distinguish individual PDA isomers and failed to identify binary or ternary mixtures. Herein, a highly active and ultrastable peroxidase (POD)–like CoPt graphitic nanozyme was used for naked-eye identification and colorimetric/fluorescent (FL) dual-mode quantitative detection of PDA isomers. The CoPt@G nanozyme effectively catalyzed the oxidation of OPD, MPD, PPD, OPD + PPD, OPD + MPD, MPD + PPD and OPD + MPD + PPD into yellow, colorless, lilac, yellow, yellow, wine red and reddish-brown products, respectively, in the presence of H2O2. Thus, the MPD, PPD, MPD + PPD and OPD + MPD + PPD were easily identified based on the distinct color of their oxidation products, and the OPD, OPD + PPD, OPD + MPD could be further identified by the additional addition of MPD or PPD. Subsequently, CoPt@G/H2O2-, a 3,3′,5,5′-tetramethylbenzidine (TMB)/CoPt@G/H2O2-, and MPD/CoPt@G/H2O2-enabled colorimetric/FL dual-mode platforms for the quantitative detection of OPD, MPD and PPD were proposed. The experimental results illustrated that the constructed sensing platforms exhibit satisfactory sensitivity, comparable to that reported in previous studies. Finally, the evaluation of PDAs in water samples was realized, yielding satisfactory recoveries. This work expanded the application prospects of nanozymes in assessing environmental risks and protection of human security.
2026, 37(2): 111333
doi: 10.1016/j.cclet.2025.111333
摘要:
Small extracellular vesicles (sEVs) membrane protein profile (sEVpp) is a novel biomarker for cancer, and it can reveal the in-depth phenotype information. The point-of-care testing (POCT) of sEVpp holds great significance for mass screening of cancer, so the cost-effective and simple detection methods of sEVpp are urgently demanded. Herein, we constructed a paper-based multichannel sEVpp POCT device (sEVpp-PAD) enabled by functional DNA probes and metal-organic framework (MOF). The core components are aptamer/MOF-modified paper chips. The modified aptamers can immunocapture the sEV expressing corresponding proteins, while the modified MOF can provide abundant sites for aptamer-modification, reduce the nonspecific protein absorption, and act as reference for ratiometric detection. Simply powered by two syringes, the sEVpp-PAD can efficiently capture sEVs expressing corresponding protein from cell culture media and sera. Furthermore, a detection probe (DP) consisted of CD63 aptamer and G-quadruplex was developed for the colorimetric detection of captured sEVs. Utilizing this device, the sEVpp in various hepatocellular carcinoma cell culture medium and, more importantly, in human sera can be accurately determined, only with ＄2 device, ＄0.2 detection reagents and 1.8 h procedure. This simple strategy for sEVpp detection can innovatively promote the POCT and subtyping of cancer based on sEV-related liquid biopsy.
Small extracellular vesicles (sEVs) membrane protein profile (sEVpp) is a novel biomarker for cancer, and it can reveal the in-depth phenotype information. The point-of-care testing (POCT) of sEVpp holds great significance for mass screening of cancer, so the cost-effective and simple detection methods of sEVpp are urgently demanded. Herein, we constructed a paper-based multichannel sEVpp POCT device (sEVpp-PAD) enabled by functional DNA probes and metal-organic framework (MOF). The core components are aptamer/MOF-modified paper chips. The modified aptamers can immunocapture the sEV expressing corresponding proteins, while the modified MOF can provide abundant sites for aptamer-modification, reduce the nonspecific protein absorption, and act as reference for ratiometric detection. Simply powered by two syringes, the sEVpp-PAD can efficiently capture sEVs expressing corresponding protein from cell culture media and sera. Furthermore, a detection probe (DP) consisted of CD63 aptamer and G-quadruplex was developed for the colorimetric detection of captured sEVs. Utilizing this device, the sEVpp in various hepatocellular carcinoma cell culture medium and, more importantly, in human sera can be accurately determined, only with ＄2 device, ＄0.2 detection reagents and 1.8 h procedure. This simple strategy for sEVpp detection can innovatively promote the POCT and subtyping of cancer based on sEV-related liquid biopsy.
2026, 37(2): 111335
doi: 10.1016/j.cclet.2025.111335
摘要:
Doxorubicin (DOX) is known to elicit potent antitumor immune responses through the induction of immunogenic cell death (ICD). However, its therapeutic efficacy is undermined by the adaptive upregulation of programmed cell death ligand 1 (PD-L1), which hijacked the antitumor immunity. In this study, we developed a reactive oxygen species (ROS)-responsive dihydroartemisinin (DHA) prodrug to facilitate the delivery of DOX via hydrophobic and electrostatic interactions. Upon internalization by tumor cells, the nanoparticles (NPs) preferentially accumulated in endoplasmic reticulum (ER), exacerbating ER stress and amplifying ICD to enhance tumor immunogenicity. Simultaneously, the oxidative intracellular environment trigged the degradation of NPs, releasing DHA, which downregulated PD-L1 by disrupting signal transducer and activator of transcription 3 (STAT3) phosphorylation and inactivating the nuclear factor kappa-B (NF-κB) pathway. Consequently, the effective PD-L1 blockade and robust ICD response, synergistically inhibited breast cancer progression, significantly enhancing the chemo-immunotherapy efficacy of doxorubicin.
Doxorubicin (DOX) is known to elicit potent antitumor immune responses through the induction of immunogenic cell death (ICD). However, its therapeutic efficacy is undermined by the adaptive upregulation of programmed cell death ligand 1 (PD-L1), which hijacked the antitumor immunity. In this study, we developed a reactive oxygen species (ROS)-responsive dihydroartemisinin (DHA) prodrug to facilitate the delivery of DOX via hydrophobic and electrostatic interactions. Upon internalization by tumor cells, the nanoparticles (NPs) preferentially accumulated in endoplasmic reticulum (ER), exacerbating ER stress and amplifying ICD to enhance tumor immunogenicity. Simultaneously, the oxidative intracellular environment trigged the degradation of NPs, releasing DHA, which downregulated PD-L1 by disrupting signal transducer and activator of transcription 3 (STAT3) phosphorylation and inactivating the nuclear factor kappa-B (NF-κB) pathway. Consequently, the effective PD-L1 blockade and robust ICD response, synergistically inhibited breast cancer progression, significantly enhancing the chemo-immunotherapy efficacy of doxorubicin.
2026, 37(2): 111342
doi: 10.1016/j.cclet.2025.111342
摘要:
Raw water temperature can fluctuate significantly throughout the year, with peaks above 30 ℃ in summer and below 15 ℃ in winter. Traditional desalination systems (e.g., reverse osmosis, RO) face challenges under these varying temperature conditions. Specifically, while the RO system performs well under high temperatures, its efficiency decreases sharply at lower temperatures. Membrane capacitive deionization (MCDI) is considered as an emergent and promising technology for brackish water desalination. While plenty of studies have been devoted to investigating the impacts of raw water properties (e.g., salinity, coexisting ions, and natural organic matter) on MCDI performance, the role of water temperatures during the desalination remains under-explored. In this study, we first tested and determined the optimized MCDI operation parameters, such as the cell voltage and feedwater flow rate. Key findings showed that MCDI's salt removal efficiency remains unaffected by feedwater temperature fluctuations. However, as feedwater temperature increases from 15 ℃ to 40 ℃, the specific energy consumption for desalination slightly rises by 16.3%, and current efficiency drops by 14.1%. Compared to RO systems, the resilience of MCDI to temperature fluctuations makes it a preferable choice for brackish water treatment in areas with a large temperature difference.
Raw water temperature can fluctuate significantly throughout the year, with peaks above 30 ℃ in summer and below 15 ℃ in winter. Traditional desalination systems (e.g., reverse osmosis, RO) face challenges under these varying temperature conditions. Specifically, while the RO system performs well under high temperatures, its efficiency decreases sharply at lower temperatures. Membrane capacitive deionization (MCDI) is considered as an emergent and promising technology for brackish water desalination. While plenty of studies have been devoted to investigating the impacts of raw water properties (e.g., salinity, coexisting ions, and natural organic matter) on MCDI performance, the role of water temperatures during the desalination remains under-explored. In this study, we first tested and determined the optimized MCDI operation parameters, such as the cell voltage and feedwater flow rate. Key findings showed that MCDI's salt removal efficiency remains unaffected by feedwater temperature fluctuations. However, as feedwater temperature increases from 15 ℃ to 40 ℃, the specific energy consumption for desalination slightly rises by 16.3%, and current efficiency drops by 14.1%. Compared to RO systems, the resilience of MCDI to temperature fluctuations makes it a preferable choice for brackish water treatment in areas with a large temperature difference.
2026, 37(2): 111355
doi: 10.1016/j.cclet.2025.111355
摘要:
Peroxymonosulfate (PMS)-based advanced oxidation technology has been proven to be a viable option for the decontamination of organic pollutants from water bodies. Advanced catalyst design is essential to this technology. Herein, a vanadium-doped LaFeO3 perovskite (LFO-V) featuring asymmetric Fe-O-V sites was rationally designed. Thanks to orbital electron interaction between Fe and V atoms, the modified electronic structure elevated electron density near the Fermi energy level while reducing the energy barrier toward effective PMS activation. This facilitated concurrent PMS reduction at the Fe sites to generate SO4•- and •OH (57.7%), and PMS oxidation at V sites to produce 1O2 (42.3%). The LFO-V/PMS system demonstrated excellent tetracycline (TC) degradation performance with a 2-fold enhancement in rate constant compared to that of pristine LFO. Further, the LFO-V maintained long-term stability, and the toxicity of degradation intermediates was evaluated through microbial metabolomics. This work establishes an effective route to regulate the PMS activation pathways through precise electronic structure modulation, advancing the rational design of advanced Fenton-like catalysts.
Peroxymonosulfate (PMS)-based advanced oxidation technology has been proven to be a viable option for the decontamination of organic pollutants from water bodies. Advanced catalyst design is essential to this technology. Herein, a vanadium-doped LaFeO3 perovskite (LFO-V) featuring asymmetric Fe-O-V sites was rationally designed. Thanks to orbital electron interaction between Fe and V atoms, the modified electronic structure elevated electron density near the Fermi energy level while reducing the energy barrier toward effective PMS activation. This facilitated concurrent PMS reduction at the Fe sites to generate SO4•- and •OH (57.7%), and PMS oxidation at V sites to produce 1O2 (42.3%). The LFO-V/PMS system demonstrated excellent tetracycline (TC) degradation performance with a 2-fold enhancement in rate constant compared to that of pristine LFO. Further, the LFO-V maintained long-term stability, and the toxicity of degradation intermediates was evaluated through microbial metabolomics. This work establishes an effective route to regulate the PMS activation pathways through precise electronic structure modulation, advancing the rational design of advanced Fenton-like catalysts.
2026, 37(2): 111357
doi: 10.1016/j.cclet.2025.111357
摘要:
The limited redox capability of photocatalysts often leads to harmful NO2 byproduct formation during photocatalytic NO oxidation. Herein, Bi4Ti3O12 nanosheets modified with plasmonic metallic bismuth and abundant oxygen vacancies were synthesized via an in-situ reduction method. The optimized catalyst (BTOR2, with a molar ratio of 40% NaBH4 to Bi4Ti3O12) achieved a maximum NO removal efficiency of 62.3%, significantly higher than pristine Bi4Ti3O12 (40.5%) while minimizing NO2 production. The results reveal that the synergistic effects of Bi's plasmonic resonance and oxygen vacancies enhanced visible light absorption and charge separation. The density functional theory (DFT) analysis showed electrons can transfer from Bi4Ti3O12 to Bi, promoting O2 activation to •O2- radicals. In-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) confirmed that light-induced H2O adsorption was strengthened, improving •OH radical generation. These radicals promoted the selective conversion of activated NO- to NO3-, rather than NO2. This work provides valuable insights for advancing research into efficient photocatalysts for air pollution control.
The limited redox capability of photocatalysts often leads to harmful NO2 byproduct formation during photocatalytic NO oxidation. Herein, Bi4Ti3O12 nanosheets modified with plasmonic metallic bismuth and abundant oxygen vacancies were synthesized via an in-situ reduction method. The optimized catalyst (BTOR2, with a molar ratio of 40% NaBH4 to Bi4Ti3O12) achieved a maximum NO removal efficiency of 62.3%, significantly higher than pristine Bi4Ti3O12 (40.5%) while minimizing NO2 production. The results reveal that the synergistic effects of Bi's plasmonic resonance and oxygen vacancies enhanced visible light absorption and charge separation. The density functional theory (DFT) analysis showed electrons can transfer from Bi4Ti3O12 to Bi, promoting O2 activation to •O2- radicals. In-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) confirmed that light-induced H2O adsorption was strengthened, improving •OH radical generation. These radicals promoted the selective conversion of activated NO- to NO3-, rather than NO2. This work provides valuable insights for advancing research into efficient photocatalysts for air pollution control.
2026, 37(2): 111372
doi: 10.1016/j.cclet.2025.111372
摘要:
Machine learning (ML) is recognized as a potent tool for the inverse design of environmental functional material, particularly for complex entities like biochar-based catalysts (BCs). Thus, the tailored BCs can have a distinct ability to trigger the nonradical pathway in advance oxidation processes (AOPs), promising a stable, rapid and selective degradation of persistent contaminants. However, due to the inherent "black box" nature and limitations of input features, results and conclusions derived from ML may not always be intuitively understood or comprehensively validated. To tackle this challenge, we linked the front-point interpretable analysis approaches with back-point density functional theory (DFT) calculations to form a chained learning strategy for deeper sight into the intrinsic activation mechanism of BCs in AOPs. At the front point, we conducted an easy-to-interpret meta-analysis to validate two strategies for enhancing nonradical pathways by increasing oxygen content and specific surface area (SSA), and prepared oxidized biochar (OBC500) and SSA-increased biochar (SBC900) by controlling pyrolysis conditions and modification methods. Subsequently, experimental results showed that OBC500 and SBC900 had distinct dominant degradation pathways for 1O2 generation and electron transfer, respectively. Finally, at the end point, DFT calculations revealed their active sites and degradation mechanisms. This chained learning strategy elucidates fundamental principles for BC inverse design and showcases the exceptional capacity to integrate computational techniques to accelerate catalyst inverse design.
Machine learning (ML) is recognized as a potent tool for the inverse design of environmental functional material, particularly for complex entities like biochar-based catalysts (BCs). Thus, the tailored BCs can have a distinct ability to trigger the nonradical pathway in advance oxidation processes (AOPs), promising a stable, rapid and selective degradation of persistent contaminants. However, due to the inherent "black box" nature and limitations of input features, results and conclusions derived from ML may not always be intuitively understood or comprehensively validated. To tackle this challenge, we linked the front-point interpretable analysis approaches with back-point density functional theory (DFT) calculations to form a chained learning strategy for deeper sight into the intrinsic activation mechanism of BCs in AOPs. At the front point, we conducted an easy-to-interpret meta-analysis to validate two strategies for enhancing nonradical pathways by increasing oxygen content and specific surface area (SSA), and prepared oxidized biochar (OBC500) and SSA-increased biochar (SBC900) by controlling pyrolysis conditions and modification methods. Subsequently, experimental results showed that OBC500 and SBC900 had distinct dominant degradation pathways for 1O2 generation and electron transfer, respectively. Finally, at the end point, DFT calculations revealed their active sites and degradation mechanisms. This chained learning strategy elucidates fundamental principles for BC inverse design and showcases the exceptional capacity to integrate computational techniques to accelerate catalyst inverse design.
2026, 37(2): 111373
doi: 10.1016/j.cclet.2025.111373
摘要:
Chlorinated antibiotics pose great challenges in efficient removal, while for the first time, this work greatly enhanced their electrocatalytic dechlorination performance by construction of non-noble metal Co3O4/g-C3N4 heterojunctions to improve process cost-effectiveness. The Co3O4/g-C3N4 heterojunction demonstrated an effective removal of 93.6% thiamphenicol (TAP) within 45 min, with the rate constant (0.0584 min-1) that was 2.4 and 2.8 times that of Co3O4 and g-C3N4 alone, respectively. The formation of heterojunctions facilitated electron transfer, enriched the electron density on Co3O4, and enhanced the adsorption of pollutants as well as the desorption of degradation intermediates. The enhanced production of atomic hydrogen (H*) of Co3O4/g-C3N4, which increased by 13.6–28.2 times, contributed more to pollutant removal (64.0%), much higher than that of Co3O4 (37.3%) and g-C3N4 (6.1%). The energy barrier for H2 formation on Co3O4/g-C3N4 (0.75 eV) was higher than that on Co3O4 (-1.84 eV), supporting that it could stabilize H* and inhibit the formation of H2. The Co3O4/g-C3N4 heterojunction exhibited stable performance with less impact by pH and co-existing ions, and posed effectiveness for the dechlorination of typical chlorinated antibiotics. This study offers an efficient and sustainable strategy for constructing heterojunctions to enhance the performance of non-noble metal catalysts in electrocatalytic dechlorination.
Chlorinated antibiotics pose great challenges in efficient removal, while for the first time, this work greatly enhanced their electrocatalytic dechlorination performance by construction of non-noble metal Co3O4/g-C3N4 heterojunctions to improve process cost-effectiveness. The Co3O4/g-C3N4 heterojunction demonstrated an effective removal of 93.6% thiamphenicol (TAP) within 45 min, with the rate constant (0.0584 min-1) that was 2.4 and 2.8 times that of Co3O4 and g-C3N4 alone, respectively. The formation of heterojunctions facilitated electron transfer, enriched the electron density on Co3O4, and enhanced the adsorption of pollutants as well as the desorption of degradation intermediates. The enhanced production of atomic hydrogen (H*) of Co3O4/g-C3N4, which increased by 13.6–28.2 times, contributed more to pollutant removal (64.0%), much higher than that of Co3O4 (37.3%) and g-C3N4 (6.1%). The energy barrier for H2 formation on Co3O4/g-C3N4 (0.75 eV) was higher than that on Co3O4 (-1.84 eV), supporting that it could stabilize H* and inhibit the formation of H2. The Co3O4/g-C3N4 heterojunction exhibited stable performance with less impact by pH and co-existing ions, and posed effectiveness for the dechlorination of typical chlorinated antibiotics. This study offers an efficient and sustainable strategy for constructing heterojunctions to enhance the performance of non-noble metal catalysts in electrocatalytic dechlorination.
2026, 37(2): 111379
doi: 10.1016/j.cclet.2025.111379
摘要:
A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed. This transition metal-free protocol, using 9-mesityl-10-methylacridinium perchlorate as the photocatalyst, represents a masterly tactic for the synthesis of sulfonated dihydroisoquinolino[1,2-b]quinazolinones featuring mild conditions, facile operation, and broad substrate scope.
A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed. This transition metal-free protocol, using 9-mesityl-10-methylacridinium perchlorate as the photocatalyst, represents a masterly tactic for the synthesis of sulfonated dihydroisoquinolino[1,2-b]quinazolinones featuring mild conditions, facile operation, and broad substrate scope.
2026, 37(2): 111380
doi: 10.1016/j.cclet.2025.111380
摘要:
ADPr-ATP is a natural nucleotide with three sugar rings and five pentavalent phosphorus, and can be produced through TIR-catalyzed ADP-ribosylation reactions for plant immunity. Here, we report the first total synthesis of ADPr-ATP (1) with a total yield of 6.4% through 14 steps, featuring late-stage P(V)−N activation reaction of pyrophosphate (4) and 5′-phosphoromorpholidate (25). The protected adenosine 5′-phosphoromorpholidate (24) was prepared on the basis of a scalable to adenosine 5′′-monophosphate (2). The construction of P(V)−N bond in phosphoramidate is esteemed as a critical step as they are sufficiently stable in deprotection reactions. The chemical synthesis of ADPr-ATP can offer an appealing alternative to traditional enzymatic synthesis and fractionation methods. Furthermore, the pRib-AMP and its prodrug are also synthesized to evaluate cytotoxicity and anti-influenza activity in vitro.
ADPr-ATP is a natural nucleotide with three sugar rings and five pentavalent phosphorus, and can be produced through TIR-catalyzed ADP-ribosylation reactions for plant immunity. Here, we report the first total synthesis of ADPr-ATP (1) with a total yield of 6.4% through 14 steps, featuring late-stage P(V)−N activation reaction of pyrophosphate (4) and 5′-phosphoromorpholidate (25). The protected adenosine 5′-phosphoromorpholidate (24) was prepared on the basis of a scalable to adenosine 5′′-monophosphate (2). The construction of P(V)−N bond in phosphoramidate is esteemed as a critical step as they are sufficiently stable in deprotection reactions. The chemical synthesis of ADPr-ATP can offer an appealing alternative to traditional enzymatic synthesis and fractionation methods. Furthermore, the pRib-AMP and its prodrug are also synthesized to evaluate cytotoxicity and anti-influenza activity in vitro.
2026, 37(2): 111423
doi: 10.1016/j.cclet.2025.111423
摘要:
Lysine-targeting reversible covalent inhibitors, particularly salicylaldehyde-based compounds such as the Food and Drug Administration (FDA)-approved drug Voxelotor, exhibit significant therapeutic potential but are limited by challenges including instability and off-target effects. To overcome these limitations in kinase inhibitor A5, we devised a pH-responsive prodrug strategy by masking its reactive aldehyde group with an acid-labile hydrazone linkage and enhancing intracellular delivery through conjugation with FK506. The optimized prodrug demonstrated robust antitumor efficacy in K562 tumor-bearing mice. Furthermore, the incorporation of the photosensitizer chlorin e6 (Ce6) led to the formation of self-assembled nanoparticles (AKNP), which not only improved physiological stability and prolonged tumor retention but also enabled light-triggered release of A5 in conjunction with photodynamic therapy (PDT). Our study thus presents a promising prodrug self-assembly strategy that combines the on-demand release of a novel lysine-targeting, reversible covalent kinase inhibitor with PDT in clinical cancer therapy.
Lysine-targeting reversible covalent inhibitors, particularly salicylaldehyde-based compounds such as the Food and Drug Administration (FDA)-approved drug Voxelotor, exhibit significant therapeutic potential but are limited by challenges including instability and off-target effects. To overcome these limitations in kinase inhibitor A5, we devised a pH-responsive prodrug strategy by masking its reactive aldehyde group with an acid-labile hydrazone linkage and enhancing intracellular delivery through conjugation with FK506. The optimized prodrug demonstrated robust antitumor efficacy in K562 tumor-bearing mice. Furthermore, the incorporation of the photosensitizer chlorin e6 (Ce6) led to the formation of self-assembled nanoparticles (AKNP), which not only improved physiological stability and prolonged tumor retention but also enabled light-triggered release of A5 in conjunction with photodynamic therapy (PDT). Our study thus presents a promising prodrug self-assembly strategy that combines the on-demand release of a novel lysine-targeting, reversible covalent kinase inhibitor with PDT in clinical cancer therapy.
2026, 37(2): 111424
doi: 10.1016/j.cclet.2025.111424
摘要:
Light-energy-driven semiconductor catalysis offers attractive ways to address environmental and energy crises. TiO2 is the most promising catalyst for photocatalysis, but the lack of charge-carrier separation efficiency severely limits its catalytic performance. In this study, we carried out crystal phase engineering to prepare in situ Z-scheme hetero-phase homojunction of anatase-rutile and clarified the structure-performance relationship. The efficiency of sulfamerazine removal by hetero-phase homojunction TiO2 nanotube arrays in a single-compartment photocatalytic fuel cell system was improved by 1.93 times compared to conventional anatase TiO2 nanotube arrays and the degradation pathways were revealed by the Fukui function combined with HP-LCMS. The successful construction of Z-scheme hetero-phase homojunction was confirmed by Raman, X-ray diffraction (XRD), and electron spin resonance (ESR), which combined with density functional theory (DFT) calculations revealed the key role of crystal phase engineering in the construction of hetero-phase homojunction. This work provides a novel strategy for the scientific design of titanium dioxide photocatalysts.
Light-energy-driven semiconductor catalysis offers attractive ways to address environmental and energy crises. TiO2 is the most promising catalyst for photocatalysis, but the lack of charge-carrier separation efficiency severely limits its catalytic performance. In this study, we carried out crystal phase engineering to prepare in situ Z-scheme hetero-phase homojunction of anatase-rutile and clarified the structure-performance relationship. The efficiency of sulfamerazine removal by hetero-phase homojunction TiO2 nanotube arrays in a single-compartment photocatalytic fuel cell system was improved by 1.93 times compared to conventional anatase TiO2 nanotube arrays and the degradation pathways were revealed by the Fukui function combined with HP-LCMS. The successful construction of Z-scheme hetero-phase homojunction was confirmed by Raman, X-ray diffraction (XRD), and electron spin resonance (ESR), which combined with density functional theory (DFT) calculations revealed the key role of crystal phase engineering in the construction of hetero-phase homojunction. This work provides a novel strategy for the scientific design of titanium dioxide photocatalysts.
2026, 37(2): 111428
doi: 10.1016/j.cclet.2025.111428
摘要:
The preparation of a novel nanoscale imazalil (IMZ)-based coordination polymer [Zn(HBTC)(IMZ)2]n (PDCP1) (H3BTC = 1,3,5-benzenetricarboxylic acid), and its antifungal application within a sustainable delivery system was reported. The intermolecular interactions presented in the structure, and their contributions to crystal packing were studied by Hirshfeld, Fingerprint plot and Mayer bond order. The obtained PDCP1 had a relatively high loading rate of IMZ (68.5%). PDCP1 exhibited notable antifungal activities against Colletotrichum gloeosporioides, Magnaporthe Oryzae, and Alternaria Nees strains, with EC50 values of 0.72, 0.92, and 0.56 µg/mL, respectively. The key benefits of the application of PDCP1 as a control release pesticide include high fungicide loading and offer nearly complete release, pH-responsive release, enhanced UV stability, exhibits favorable biosafety profiles. The remarkable inhibition of C. gloeosporioides growth by PDCP1 underscores a promising strategy for agrochemical material development, high loading of active ingredients and readily delivery fosters more efficient pesticides utilization in agricultural processes.
The preparation of a novel nanoscale imazalil (IMZ)-based coordination polymer [Zn(HBTC)(IMZ)2]n (PDCP1) (H3BTC = 1,3,5-benzenetricarboxylic acid), and its antifungal application within a sustainable delivery system was reported. The intermolecular interactions presented in the structure, and their contributions to crystal packing were studied by Hirshfeld, Fingerprint plot and Mayer bond order. The obtained PDCP1 had a relatively high loading rate of IMZ (68.5%). PDCP1 exhibited notable antifungal activities against Colletotrichum gloeosporioides, Magnaporthe Oryzae, and Alternaria Nees strains, with EC50 values of 0.72, 0.92, and 0.56 µg/mL, respectively. The key benefits of the application of PDCP1 as a control release pesticide include high fungicide loading and offer nearly complete release, pH-responsive release, enhanced UV stability, exhibits favorable biosafety profiles. The remarkable inhibition of C. gloeosporioides growth by PDCP1 underscores a promising strategy for agrochemical material development, high loading of active ingredients and readily delivery fosters more efficient pesticides utilization in agricultural processes.
2026, 37(2): 111434
doi: 10.1016/j.cclet.2025.111434
摘要:
Polyethylene oxide (PEO)-based solid polymer electrolytes (SPEs) have long faced limitations due to low ionic conductivity at ambient temperature and poor interfacial stability with lithium metal anodes. Here, we present a structural engineering strategy to address these challenges through shear-induced crystallization of concentrated PEO-LiTFSI solutions, which self-assemble into flower-like spherulites with radially aligned lamellar crystals. This unique structure creates continuous Li+ transport highways through densely packed crystalline domains, achieving a record-high ionic conductivity of 1.70 × 10–4 S/cm at 25 ℃ for pristine PEO-based systems. Strategic incorporation of lithium montmorillonite (MMTli, 10 wt%) further optimizes the composite electrolyte, balancing high ionic conductivity (1.47 × 10–4 S/cm) with enhanced electrochemical stability (4.99 V vs. Li+/Li), elevated Li+ transference number (0.62), and mechanical robustness. The composite electrolyte enables stable Li plating/stripping over 800 h in symmetric Li||Li cells and powers LiFePO4||Li solid-state batteries with 82% capacity retention after 200 cycles at 0.2 C under ambient conditions. This work pioneers a scalable processing paradigm for crystalline polymer electrolytes, offering new insights into ion transport mechanisms and validating clay minerals as multifunctional additives for next-generation energy storage systems.
Polyethylene oxide (PEO)-based solid polymer electrolytes (SPEs) have long faced limitations due to low ionic conductivity at ambient temperature and poor interfacial stability with lithium metal anodes. Here, we present a structural engineering strategy to address these challenges through shear-induced crystallization of concentrated PEO-LiTFSI solutions, which self-assemble into flower-like spherulites with radially aligned lamellar crystals. This unique structure creates continuous Li+ transport highways through densely packed crystalline domains, achieving a record-high ionic conductivity of 1.70 × 10–4 S/cm at 25 ℃ for pristine PEO-based systems. Strategic incorporation of lithium montmorillonite (MMTli, 10 wt%) further optimizes the composite electrolyte, balancing high ionic conductivity (1.47 × 10–4 S/cm) with enhanced electrochemical stability (4.99 V vs. Li+/Li), elevated Li+ transference number (0.62), and mechanical robustness. The composite electrolyte enables stable Li plating/stripping over 800 h in symmetric Li||Li cells and powers LiFePO4||Li solid-state batteries with 82% capacity retention after 200 cycles at 0.2 C under ambient conditions. This work pioneers a scalable processing paradigm for crystalline polymer electrolytes, offering new insights into ion transport mechanisms and validating clay minerals as multifunctional additives for next-generation energy storage systems.
2026, 37(2): 111452
doi: 10.1016/j.cclet.2025.111452
摘要:
Albumin, owing to its high abundance and excellent biocompatibility, is widely used as a drug carrier to enhance delivery efficiency and reduce systemic toxicity. The Michael addition between albumin thiols and maleimide-functionalized prodrugs is a common in situ macromolecular prodrug strategy. However, the resulting reversible adducts are susceptible to retro-Michael reactions in vivo, leading to premature drug release and off-target effects. To address this limitation, a gemcitabine prodrug (GAB) bearing a chloroacetamide group was designed to form irreversible covalent bonds with albumin via nucleophilic substitution. A maleimide-based prodrug (GAM) was synthesized as a control. Compared to GAM, GAB showed faster and stronger albumin binding in plasma, enhanced blood circulation time, improved tumor accumulation, and superior in vivo antitumor efficacy. Moreover, GAB exhibited a better safety profile, with reduced cytotoxicity in normal tissues and no observable systemic toxicity. These advantages are attributed to the stable albumin-drug conjugate formed by GAB, which improves drug retention and targeted delivery. This study presents an effective and generalizable albumin-hitchhiking strategy for constructing irreversible prodrugs, offering a promising approach to enhance the therapeutic index of chemotherapeutic agents.
Albumin, owing to its high abundance and excellent biocompatibility, is widely used as a drug carrier to enhance delivery efficiency and reduce systemic toxicity. The Michael addition between albumin thiols and maleimide-functionalized prodrugs is a common in situ macromolecular prodrug strategy. However, the resulting reversible adducts are susceptible to retro-Michael reactions in vivo, leading to premature drug release and off-target effects. To address this limitation, a gemcitabine prodrug (GAB) bearing a chloroacetamide group was designed to form irreversible covalent bonds with albumin via nucleophilic substitution. A maleimide-based prodrug (GAM) was synthesized as a control. Compared to GAM, GAB showed faster and stronger albumin binding in plasma, enhanced blood circulation time, improved tumor accumulation, and superior in vivo antitumor efficacy. Moreover, GAB exhibited a better safety profile, with reduced cytotoxicity in normal tissues and no observable systemic toxicity. These advantages are attributed to the stable albumin-drug conjugate formed by GAB, which improves drug retention and targeted delivery. This study presents an effective and generalizable albumin-hitchhiking strategy for constructing irreversible prodrugs, offering a promising approach to enhance the therapeutic index of chemotherapeutic agents.
2026, 37(2): 111487
doi: 10.1016/j.cclet.2025.111487
摘要:
Fluorinated motifs are prevalent in both pharmaceuticals and agrochemicals. The incorporation of fluorine-containing moieties to drug candidates has emerged as a potent strategy for lead optimization in pharmaceutical research and development. While extensive research has been devoted to constructing molecules that incorporate a trifluoromethylthio (SCF3−) group on a stereogenic carbon, the synthesis of trifluoromethylthiolated alkanes featuring a SCF3-substituted stereogenic carbon at non-activated site remains understudied. Herein, we report a Cu-catalyzed regio- and enantioselective hydroallylation of 1-trifluoromethylthiolated alkenes. Important to the process is the regio- and enantioselective Cu-H insertion to SCF3-substituted alkene to form chiral α-SCF3 alkyl copper intermediates, outcompeting unproductive insertion to the coupling partner, and eventually proceed to afford optically active homoallylic trifluoromethylthiolated products.
Fluorinated motifs are prevalent in both pharmaceuticals and agrochemicals. The incorporation of fluorine-containing moieties to drug candidates has emerged as a potent strategy for lead optimization in pharmaceutical research and development. While extensive research has been devoted to constructing molecules that incorporate a trifluoromethylthio (SCF3−) group on a stereogenic carbon, the synthesis of trifluoromethylthiolated alkanes featuring a SCF3-substituted stereogenic carbon at non-activated site remains understudied. Herein, we report a Cu-catalyzed regio- and enantioselective hydroallylation of 1-trifluoromethylthiolated alkenes. Important to the process is the regio- and enantioselective Cu-H insertion to SCF3-substituted alkene to form chiral α-SCF3 alkyl copper intermediates, outcompeting unproductive insertion to the coupling partner, and eventually proceed to afford optically active homoallylic trifluoromethylthiolated products.
2026, 37(2): 111491
doi: 10.1016/j.cclet.2025.111491
摘要:
The formation of Zn dendrites and the occurrence of the hydrogen evolution reaction (HER) at Zn anodes represent two major obstacles that significantly impede the widespread commercialization of aqueous Zn-ion batteries. In this work, we propose sorbitan oleate (Span 80) as a novel amphiphilic electrolyte additive for 2 mol/L ZnSO4, demonstrating multifunctional performance. The unique ultra-long hydrophobic carbon chains of Span 80 effectively reduce free water molecules at the Zn anode-electrolyte interface, forming a robust hydrophobic interfacial layer that significantly suppresses HER and corrosion reactions. Simultaneously, carbon chains can enhance the desolvation effect of [Zn(H2O)6]2+, leading to improve rate performance. Additionally, the hydrophilic sorbitan groups in Span 80 selectively adsorb onto active sites of the Zn anode, promoting uniform Zn2+ deposition and suppressing dendrite growth. The optimized Zn||Zn symmetric cell exhibits outstanding cycling stability, sustaining reversible plating/stripping for 570 h at 50 mA/cm2 and the Zn||V2O5 full cell retains exceptional stability over 2000 cycles at 1 A/g. Our work presents a promising strategy for suppressing interfacial side reactions by constructing a hydrophobic protective layer through the use of ultra-long carbon chain surfactants. This approach offers new insights into enhancing the performance of aqueous Zn-ion batteries.
The formation of Zn dendrites and the occurrence of the hydrogen evolution reaction (HER) at Zn anodes represent two major obstacles that significantly impede the widespread commercialization of aqueous Zn-ion batteries. In this work, we propose sorbitan oleate (Span 80) as a novel amphiphilic electrolyte additive for 2 mol/L ZnSO4, demonstrating multifunctional performance. The unique ultra-long hydrophobic carbon chains of Span 80 effectively reduce free water molecules at the Zn anode-electrolyte interface, forming a robust hydrophobic interfacial layer that significantly suppresses HER and corrosion reactions. Simultaneously, carbon chains can enhance the desolvation effect of [Zn(H2O)6]2+, leading to improve rate performance. Additionally, the hydrophilic sorbitan groups in Span 80 selectively adsorb onto active sites of the Zn anode, promoting uniform Zn2+ deposition and suppressing dendrite growth. The optimized Zn||Zn symmetric cell exhibits outstanding cycling stability, sustaining reversible plating/stripping for 570 h at 50 mA/cm2 and the Zn||V2O5 full cell retains exceptional stability over 2000 cycles at 1 A/g. Our work presents a promising strategy for suppressing interfacial side reactions by constructing a hydrophobic protective layer through the use of ultra-long carbon chain surfactants. This approach offers new insights into enhancing the performance of aqueous Zn-ion batteries.
2026, 37(2): 111503
doi: 10.1016/j.cclet.2025.111503
摘要:
The demand for 238Pu (nuclear battery heat source) drives the separation of its precursor, 237Np, from spent nuclear fuel (SNF). However, the co-existence of multi-valence states (Ⅳ/Ⅴ/Ⅵ) of Np and similar redox behavior with Pu(Ⅳ) hinder the effective separation of Np. N-Butyraldehyde (n-C3H7CHO) selectively reduces Np(Ⅵ) to Np(Ⅴ) without reducing Pu(Ⅳ). Herein, we examined the reduction mechanisms of Np(Ⅵ) and Pu(Ⅳ) by n-C3H7CHO using relativistic density functional theory. Based on the results of the potential energy profiles, the reductions of both Np(Ⅵ) and Pu(Ⅳ) by n-C3H7CHO are thermodynamically feasible, whereas only the former is kinetically achievable. It uncovers that n-C3H7CHO can only reduce Np(Ⅵ) to Np(Ⅴ) owing to kinetically controlled selective reduction. The analyses of spin density and bond distance indicate that the reduction nature for the first Np(Ⅵ)/Pu(Ⅳ) belongs to hydrogen atom transfer, whereas that for the second one involves outer-sphere electron transfer. Localized molecular orbitals (LMOs) analysis discloses the bonding evolution during the reduction process of Np(Ⅵ)/Pu(Ⅳ). This study elucidates the reason behind the kinetically controlled selective reduction of Np(Ⅵ)/Pu(Ⅳ) by n-C3H7CHO at the molecular level and offers in-depth perspectives on the isolation of specific metal ions from the view of kinetic control.
The demand for 238Pu (nuclear battery heat source) drives the separation of its precursor, 237Np, from spent nuclear fuel (SNF). However, the co-existence of multi-valence states (Ⅳ/Ⅴ/Ⅵ) of Np and similar redox behavior with Pu(Ⅳ) hinder the effective separation of Np. N-Butyraldehyde (n-C3H7CHO) selectively reduces Np(Ⅵ) to Np(Ⅴ) without reducing Pu(Ⅳ). Herein, we examined the reduction mechanisms of Np(Ⅵ) and Pu(Ⅳ) by n-C3H7CHO using relativistic density functional theory. Based on the results of the potential energy profiles, the reductions of both Np(Ⅵ) and Pu(Ⅳ) by n-C3H7CHO are thermodynamically feasible, whereas only the former is kinetically achievable. It uncovers that n-C3H7CHO can only reduce Np(Ⅵ) to Np(Ⅴ) owing to kinetically controlled selective reduction. The analyses of spin density and bond distance indicate that the reduction nature for the first Np(Ⅵ)/Pu(Ⅳ) belongs to hydrogen atom transfer, whereas that for the second one involves outer-sphere electron transfer. Localized molecular orbitals (LMOs) analysis discloses the bonding evolution during the reduction process of Np(Ⅵ)/Pu(Ⅳ). This study elucidates the reason behind the kinetically controlled selective reduction of Np(Ⅵ)/Pu(Ⅳ) by n-C3H7CHO at the molecular level and offers in-depth perspectives on the isolation of specific metal ions from the view of kinetic control.
2026, 37(2): 111506
doi: 10.1016/j.cclet.2025.111506
摘要:
Hard carbon is a vital anode material for sodium-ion batteries; however, the nonuniform growth of solid electrolyte interphase (SEI) film substantially diminishes its initial coulombic efficiency (ICE) and cycle life. The chemical and morphological properties of surface highly influence the electrode/electrolyte interfacial reactions. In this study, we have tuned orbital hybridization states forming an interface enriched with sp2 hybridized carbon (sp2–C), which decreases the binding energy to solvent molecules and inhibits excessive solvent decomposition during SEI formation. Benefiting from successfully constructed inorganic-rich SEI, the ICE increased to 91% and sodium storage capacity reached 346 mAh/g. Besides, the capacity retention rate was 90.7% after 700 cycles at 1 A/g higher than pristine electrode (83.8%).
Hard carbon is a vital anode material for sodium-ion batteries; however, the nonuniform growth of solid electrolyte interphase (SEI) film substantially diminishes its initial coulombic efficiency (ICE) and cycle life. The chemical and morphological properties of surface highly influence the electrode/electrolyte interfacial reactions. In this study, we have tuned orbital hybridization states forming an interface enriched with sp2 hybridized carbon (sp2–C), which decreases the binding energy to solvent molecules and inhibits excessive solvent decomposition during SEI formation. Benefiting from successfully constructed inorganic-rich SEI, the ICE increased to 91% and sodium storage capacity reached 346 mAh/g. Besides, the capacity retention rate was 90.7% after 700 cycles at 1 A/g higher than pristine electrode (83.8%).
2026, 37(2): 111507
doi: 10.1016/j.cclet.2025.111507
摘要:
One-dimensional (1D) organic-inorganic halide perovskites have produced significant research interest due to their unique structure and superior tunable luminescence properties. Here, we successfully achieved a unique color-tunable phenomenon of Mn-doped 1D post-perovskite (TDMP)PbBr4 (TDMP = trans-2,5-dimethylpiperazine) (TPBM-14) under high pressure. Which exhibited tunable photoluminescence (PL) emission from red to yellow orange. Meanwhile, the band gap continued to decrease below 20.0 GPa, accompanied by piezochromism, which was associated the shrinkage and distortion of inorganic, which enhances the crystal field splitting energy and reduces the energy gap of the 4T1 to 6A1 transition. The unique octahedral corner- and edge-sharing structure of (TDMP)PbBr4, the synergistic effect of Mn doping and pressure induces local lattice distortion in TPBM-14, leading to a significant enhancement of the STE emission at 8.1 GPa. Our research explores the intrinsic connection between the band structure and optical properties of TPBM-14 under high pressure and offers valuable insights for performance optimization.
One-dimensional (1D) organic-inorganic halide perovskites have produced significant research interest due to their unique structure and superior tunable luminescence properties. Here, we successfully achieved a unique color-tunable phenomenon of Mn-doped 1D post-perovskite (TDMP)PbBr4 (TDMP = trans-2,5-dimethylpiperazine) (TPBM-14) under high pressure. Which exhibited tunable photoluminescence (PL) emission from red to yellow orange. Meanwhile, the band gap continued to decrease below 20.0 GPa, accompanied by piezochromism, which was associated the shrinkage and distortion of inorganic, which enhances the crystal field splitting energy and reduces the energy gap of the 4T1 to 6A1 transition. The unique octahedral corner- and edge-sharing structure of (TDMP)PbBr4, the synergistic effect of Mn doping and pressure induces local lattice distortion in TPBM-14, leading to a significant enhancement of the STE emission at 8.1 GPa. Our research explores the intrinsic connection between the band structure and optical properties of TPBM-14 under high pressure and offers valuable insights for performance optimization.
2026, 37(2): 111607
doi: 10.1016/j.cclet.2025.111607
摘要:
Although the combination of chemotherapy and immunotherapy can improve the treatment of breast cancer, traditional drugs are highly toxic because they do not specifically target tumors. In this study, we developed a self-driving bacteria/nanoparticle biohybrid called Bif@PDA-aPD1/DOX-Lip by attaching polydopamine (PDA) coated doxorubicin (DOX) liposomes and the immune checkpoint inhibitor anti-programmed cell death protein 1 antibody (aPD-1) to Bifidobacterium infantis (B. infantis, Bif). Using the homing abilities of bacteria, Bif@PDA-aPD1/DOX-Lip could actively accumulate in tumor tissue, releasing DOX and aPD-1 in the acidic environment to have a synergistic anti-tumor effect. Results show that the concentration of DOX in tumors of the Bif@PDA-aPD1/DOX-Lip group was 6.31 times higher than in the free DOX group. The combination of DOX and aPD-1 not only killed tumor cells but also promoted immune normalization by maturing dendritic cells (DCs), increasing M1 macrophage ratio, and enhancing infiltration of CD8+ and CD4+ T cells in tumors and spleen. Therefore, Bif@PDA-aPD1/DOX-Lip therapy significantly inhibited tumor growth and increased the average survival time of mice to over 80 days. The Bif@PDA-aPD1/DOX-Lip biomotors offer a highly effective method for enhancing chemo-immunotherapy in solid tumors.
Although the combination of chemotherapy and immunotherapy can improve the treatment of breast cancer, traditional drugs are highly toxic because they do not specifically target tumors. In this study, we developed a self-driving bacteria/nanoparticle biohybrid called Bif@PDA-aPD1/DOX-Lip by attaching polydopamine (PDA) coated doxorubicin (DOX) liposomes and the immune checkpoint inhibitor anti-programmed cell death protein 1 antibody (aPD-1) to Bifidobacterium infantis (B. infantis, Bif). Using the homing abilities of bacteria, Bif@PDA-aPD1/DOX-Lip could actively accumulate in tumor tissue, releasing DOX and aPD-1 in the acidic environment to have a synergistic anti-tumor effect. Results show that the concentration of DOX in tumors of the Bif@PDA-aPD1/DOX-Lip group was 6.31 times higher than in the free DOX group. The combination of DOX and aPD-1 not only killed tumor cells but also promoted immune normalization by maturing dendritic cells (DCs), increasing M1 macrophage ratio, and enhancing infiltration of CD8+ and CD4+ T cells in tumors and spleen. Therefore, Bif@PDA-aPD1/DOX-Lip therapy significantly inhibited tumor growth and increased the average survival time of mice to over 80 days. The Bif@PDA-aPD1/DOX-Lip biomotors offer a highly effective method for enhancing chemo-immunotherapy in solid tumors.
2026, 37(2): 111613
doi: 10.1016/j.cclet.2025.111613
摘要:
Organic ambipolar emitting materials hold immense potential for application in integrated optoelectrical devices yet challenging to design and synthesize. Cocrystals exhibit significant superiority in designing such materials because the properties of emission and transport can be flexibly tailored through the strategic pairing of donor and acceptor units. In this study, we report a new cocrystal system, DPA-5FDPA, derived from two high-mobility emissive molecules, 2,6-diphenylanthracene (DPA) and 2,6-diperfluorophenyl anthracene (5FDPA). This cocrystal system exhibits outstanding emission and ambipolar semiconducting properties. Notably, the single-crystal field-effect transistor devices based on DPA-5FDPA achieve maximum hole and electron mobilities of 0.298 cm2 V-1 s-1 and 0.009 cm2 V-1 s-1, respectively. In comparison, the reference compound of 2-perfluorophenyl-6-phenylanthracene (5FBA) exhibits unipolar p-type transport with the hole mobility of 0.008 cm2 V-1 s-1. In addition, DPA-5FDPA exhibits excellent optical waveguide behavior with a small optical loss coefficient of 0.079 dB/µm at 508 nm, which is lower than most reported cocrystal systems. These results underscore the promise of co-crystallization as a versatile strategy for developing advanced ambipolar emissive semiconductors and provide deeper insights into the relationships among molecular structures, packing modes, intermolecular interactions, and charge-transport properties.
Organic ambipolar emitting materials hold immense potential for application in integrated optoelectrical devices yet challenging to design and synthesize. Cocrystals exhibit significant superiority in designing such materials because the properties of emission and transport can be flexibly tailored through the strategic pairing of donor and acceptor units. In this study, we report a new cocrystal system, DPA-5FDPA, derived from two high-mobility emissive molecules, 2,6-diphenylanthracene (DPA) and 2,6-diperfluorophenyl anthracene (5FDPA). This cocrystal system exhibits outstanding emission and ambipolar semiconducting properties. Notably, the single-crystal field-effect transistor devices based on DPA-5FDPA achieve maximum hole and electron mobilities of 0.298 cm2 V-1 s-1 and 0.009 cm2 V-1 s-1, respectively. In comparison, the reference compound of 2-perfluorophenyl-6-phenylanthracene (5FBA) exhibits unipolar p-type transport with the hole mobility of 0.008 cm2 V-1 s-1. In addition, DPA-5FDPA exhibits excellent optical waveguide behavior with a small optical loss coefficient of 0.079 dB/µm at 508 nm, which is lower than most reported cocrystal systems. These results underscore the promise of co-crystallization as a versatile strategy for developing advanced ambipolar emissive semiconductors and provide deeper insights into the relationships among molecular structures, packing modes, intermolecular interactions, and charge-transport properties.
2026, 37(2): 111634
doi: 10.1016/j.cclet.2025.111634
摘要:
Improving the optoelectronic behavior and stress-deformation stability of conjugated materials is crucial for the realization of their potential applications in flexible optoelectronics. To tune the emission behavior and mechanical property of molecular crystals simultaneously via supramolecular salt strategy is rarely reported, which is very important to improve their photophysical behavior and softness for the fabrication of flexible light-emitting device. Herein, supramolecular salt approach has been successfully applied to synthesize two elastic organic fluorescent crystals (CMOH-Py-Cl and CMOH-Py-Br) derived from non-emissive and brittle pyridine-substituted coumarin derivative (CMOH-Py). Their elastic properties can be attributed to the prevalent presence of numerous weak interactions introduced by halogen atoms, which are beneficial to the absorption and release of mechanical energy. Furthermore, density functional theory (DFT) calculations demonstrated a narrowing of the HOMO–LUMO energy gaps from CMOH-Py to CMOH-Py-Cl/CMOH-Py-Br via supramolecular salt approach. Finally, the application of flexible crystal materials in the field of optical waveguides has been investigated. The transformation of crystals in terms of photophysical and mechanical properties, achieved by the supramolecular salt approach, offers novel insights into the design and construction of flexible crystalline materials, providing a new path for the development of next-generation smart materials.
Improving the optoelectronic behavior and stress-deformation stability of conjugated materials is crucial for the realization of their potential applications in flexible optoelectronics. To tune the emission behavior and mechanical property of molecular crystals simultaneously via supramolecular salt strategy is rarely reported, which is very important to improve their photophysical behavior and softness for the fabrication of flexible light-emitting device. Herein, supramolecular salt approach has been successfully applied to synthesize two elastic organic fluorescent crystals (CMOH-Py-Cl and CMOH-Py-Br) derived from non-emissive and brittle pyridine-substituted coumarin derivative (CMOH-Py). Their elastic properties can be attributed to the prevalent presence of numerous weak interactions introduced by halogen atoms, which are beneficial to the absorption and release of mechanical energy. Furthermore, density functional theory (DFT) calculations demonstrated a narrowing of the HOMO–LUMO energy gaps from CMOH-Py to CMOH-Py-Cl/CMOH-Py-Br via supramolecular salt approach. Finally, the application of flexible crystal materials in the field of optical waveguides has been investigated. The transformation of crystals in terms of photophysical and mechanical properties, achieved by the supramolecular salt approach, offers novel insights into the design and construction of flexible crystalline materials, providing a new path for the development of next-generation smart materials.
2026, 37(2): 111676
doi: 10.1016/j.cclet.2025.111676
摘要:
Possessing excellent mechanical properties, a high-coverage slide-ring conductive gel is constructed by in situ polymerization of α-cyclodextrin (α-CD) polyrotaxane (PR) and 1-vinyl-3-ethylimidazolium bromide ([VEIM]Br) ionic liquid (IL), using 1-ethyl-3-methylimidazolium bromide ([EMIM]Br) IL as solvent. Benefiting from the compatibility of ILs and alkene-PR, the cross-linked network slide-ring gel not only maintains excellent conductivity (1.52 × 10−2 S/m), but also has effectively improved mechanical properties (513% fracture strain, 0.713 MPa fracture stress, 211 kPa elastic modulus and 1366 kJ/m3 toughness) and adhesive properties (472.3 ± 25.9 kPa). The supramolecular gel can be used as a strain sensor to efficiently monitor deformation signals in real-time at least 200 times. Especially, the slide-ring gel can self-power generated by triboelectric effect and electrostatic induction between the skin layer and the polydimethylsiloxane (PDMS) layer that encapsulates the gel, achieving reversible and durable motion sensing, which provides a convenient pathway for constructing supramolecular self-powered flexible electronic materials.
Possessing excellent mechanical properties, a high-coverage slide-ring conductive gel is constructed by in situ polymerization of α-cyclodextrin (α-CD) polyrotaxane (PR) and 1-vinyl-3-ethylimidazolium bromide ([VEIM]Br) ionic liquid (IL), using 1-ethyl-3-methylimidazolium bromide ([EMIM]Br) IL as solvent. Benefiting from the compatibility of ILs and alkene-PR, the cross-linked network slide-ring gel not only maintains excellent conductivity (1.52 × 10−2 S/m), but also has effectively improved mechanical properties (513% fracture strain, 0.713 MPa fracture stress, 211 kPa elastic modulus and 1366 kJ/m3 toughness) and adhesive properties (472.3 ± 25.9 kPa). The supramolecular gel can be used as a strain sensor to efficiently monitor deformation signals in real-time at least 200 times. Especially, the slide-ring gel can self-power generated by triboelectric effect and electrostatic induction between the skin layer and the polydimethylsiloxane (PDMS) layer that encapsulates the gel, achieving reversible and durable motion sensing, which provides a convenient pathway for constructing supramolecular self-powered flexible electronic materials.
2026, 37(2): 111677
doi: 10.1016/j.cclet.2025.111677
摘要:
Boron (B) doping serves as a promising strategy to enhance the quantum yield, photostability and environmental robustness of graphene quantum dots (GQDs). In this study, we reported a light-driven strategy for the facile synthesis of boron-doped graphene quantum dots (B-GQDs). Specifically, under continuous stirring at room temperature, ultraviolet irradiation induces the progressive polymerization of o-phenylenediamine (o-PDA) precursors, resulting in the formation of GQDs; meanwhile, 2-hydroxyphenylboronic acid (2-HPBA), acting as the B source, participates in the polymerization reaction with o-PDA intermediates, ultimately yielding B-GQDs. This approach significantly improves the technology of preparing QDs, yielding B-GQDs with a remarkably high fluorescence quantum yield of 71.2%. Detailed investigations reveal that the abundant surface functional groups on B-GQDs facilitate hydrogen-bonding interactions with water molecules, enabling their application as fluorescent probes for the quantitative detection of water content in various organic solvents. By integrating B-GQDs, a paper-based fluorescent sensor was successfully designed, achieving ultra-portable water content detection with excellent performance (0%-100%).
Boron (B) doping serves as a promising strategy to enhance the quantum yield, photostability and environmental robustness of graphene quantum dots (GQDs). In this study, we reported a light-driven strategy for the facile synthesis of boron-doped graphene quantum dots (B-GQDs). Specifically, under continuous stirring at room temperature, ultraviolet irradiation induces the progressive polymerization of o-phenylenediamine (o-PDA) precursors, resulting in the formation of GQDs; meanwhile, 2-hydroxyphenylboronic acid (2-HPBA), acting as the B source, participates in the polymerization reaction with o-PDA intermediates, ultimately yielding B-GQDs. This approach significantly improves the technology of preparing QDs, yielding B-GQDs with a remarkably high fluorescence quantum yield of 71.2%. Detailed investigations reveal that the abundant surface functional groups on B-GQDs facilitate hydrogen-bonding interactions with water molecules, enabling their application as fluorescent probes for the quantitative detection of water content in various organic solvents. By integrating B-GQDs, a paper-based fluorescent sensor was successfully designed, achieving ultra-portable water content detection with excellent performance (0%-100%).
2026, 37(2): 111710
doi: 10.1016/j.cclet.2025.111710
摘要:
Azobenzene-winged phenanthrolines (L1 and L2) were designed, synthesized, and fully characterized. Ligand L1 forms an in-situ cobalt complex, which has been effectively employed as a circular dichroism (CD)-active chiral sensor. The resulting ternary complex (L1–Co2+–amino alcohol) exhibits pronounced exciton-coupled circular dichroism (ECCD) signals at the characteristic azobenzene absorption bands. These signals arise from efficient chirality transfer from the chiral amino alcohol to the azobenzene chromophores, enabling the determination of the absolute configuration of chiral amino alcohols. Accordingly, the L1–Co2+ coordination system demonstrates considerably potential in chirality sensing applications. Remarkably, the induced ECCD signals are highly responsive to multiple external stimuli, including photoirradiation, solvent polarity, temperature, and redox conditions. In particular, temperature and redox changes can induce a reversible inversion of the ECCD signal, thereby establishing this system as a multifunctional, stimuli-responsive chiroptical molecular switch.
Azobenzene-winged phenanthrolines (L1 and L2) were designed, synthesized, and fully characterized. Ligand L1 forms an in-situ cobalt complex, which has been effectively employed as a circular dichroism (CD)-active chiral sensor. The resulting ternary complex (L1–Co2+–amino alcohol) exhibits pronounced exciton-coupled circular dichroism (ECCD) signals at the characteristic azobenzene absorption bands. These signals arise from efficient chirality transfer from the chiral amino alcohol to the azobenzene chromophores, enabling the determination of the absolute configuration of chiral amino alcohols. Accordingly, the L1–Co2+ coordination system demonstrates considerably potential in chirality sensing applications. Remarkably, the induced ECCD signals are highly responsive to multiple external stimuli, including photoirradiation, solvent polarity, temperature, and redox conditions. In particular, temperature and redox changes can induce a reversible inversion of the ECCD signal, thereby establishing this system as a multifunctional, stimuli-responsive chiroptical molecular switch.
2026, 37(2): 111815
doi: 10.1016/j.cclet.2025.111815
摘要:
Polymer-electrolyte-based solid-state Li metal batteries with high-voltage Ni-rich cathodes are promising energy storage technologies owing to their favorable security and high energy densities. However, operating in wide temperature range and at high voltage is a tough challenge for them. Herein, F/N donating fluorinated-amide-based plasticizers regulated polymer electrolyte capable of enabling high-voltage Li||LiNi0.8Co0.1Mn0.1O2 (NCM811) batteries with excellent performance in wide temperature range is developed. F/N donating fluorinated-amide-based plasticizers significantly improve ionic conductivity (1.52 mS/cm at 30 ℃), enhance oxidation stability (5.0 V vs. Li+/Li) and fabricate robust LiF/Li3N-rich electrode-electrolyte interphases, which significantly improve the interface stability of Li metal anode and NCM811 cathode. The designed polymer electrolyte is nonflammable and has excellent dimensional stability at 200 ℃. Capitalizing on these advantageous attributes, the Li||NCM811 cells show excellent cycle stability and rate capability from −20 ℃ to 60 ℃ at high voltages (~4.6 V), and under high-loading full cell condition, which display impressive capacity retention of 84.4% after 1000 cycles and ultrahigh capacity of 154.8 mAh/g at 10 C. This work provides a rational design strategy of polymer electrolytes for wide-temperature high-energy solid-state Li metal batteries.
Polymer-electrolyte-based solid-state Li metal batteries with high-voltage Ni-rich cathodes are promising energy storage technologies owing to their favorable security and high energy densities. However, operating in wide temperature range and at high voltage is a tough challenge for them. Herein, F/N donating fluorinated-amide-based plasticizers regulated polymer electrolyte capable of enabling high-voltage Li||LiNi0.8Co0.1Mn0.1O2 (NCM811) batteries with excellent performance in wide temperature range is developed. F/N donating fluorinated-amide-based plasticizers significantly improve ionic conductivity (1.52 mS/cm at 30 ℃), enhance oxidation stability (5.0 V vs. Li+/Li) and fabricate robust LiF/Li3N-rich electrode-electrolyte interphases, which significantly improve the interface stability of Li metal anode and NCM811 cathode. The designed polymer electrolyte is nonflammable and has excellent dimensional stability at 200 ℃. Capitalizing on these advantageous attributes, the Li||NCM811 cells show excellent cycle stability and rate capability from −20 ℃ to 60 ℃ at high voltages (~4.6 V), and under high-loading full cell condition, which display impressive capacity retention of 84.4% after 1000 cycles and ultrahigh capacity of 154.8 mAh/g at 10 C. This work provides a rational design strategy of polymer electrolytes for wide-temperature high-energy solid-state Li metal batteries.
2026, 37(2): 111824
doi: 10.1016/j.cclet.2025.111824
摘要:
Organic pollutants, a pivotal factor in water pollution, have persistently menaced the aquatic ecosystem, as well as the sustainable development of human health, economy, and society. Consequently, there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water. Here, we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions. These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants, characterized by high apparent adsorption rate constants (kobs) and maximum adsorption capacities (qmax, e). Notably, Compound NCCP-1 demonstrated a remarkable qmax, e of 459 mg/g for bisphenol A (BPA), ranking among the highest values reported for organic polymer adsorbents. In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them, primarily mediated by the hydrophobic effect. Furthermore, NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles, highlighting its potential for practical applications in water treatment.
Organic pollutants, a pivotal factor in water pollution, have persistently menaced the aquatic ecosystem, as well as the sustainable development of human health, economy, and society. Consequently, there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water. Here, we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions. These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants, characterized by high apparent adsorption rate constants (kobs) and maximum adsorption capacities (qmax, e). Notably, Compound NCCP-1 demonstrated a remarkable qmax, e of 459 mg/g for bisphenol A (BPA), ranking among the highest values reported for organic polymer adsorbents. In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them, primarily mediated by the hydrophobic effect. Furthermore, NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles, highlighting its potential for practical applications in water treatment.
2026, 37(2): 111875
doi: 10.1016/j.cclet.2025.111875
摘要:
Pseudomonas aeruginosa is an opportunistic pathogen responsible for severe nosocomial infections. This multidrug-resistant bacterium can cause pneumonia and cystic fibrosis, both of which are associated with high morbidity and mortality rates. The lipopolysaccharide of P. aeruginosa serves as an attractive target for the development of effective glycoconjugate vaccines. In this article, we report the first chemical synthesis of the highly challenging tetrasaccharide repeating unit of the P. aeruginosa serotype O3 O-antigen using a two-directional [1+(2 + 1)] glycosylation strategy. The synthesis is particularly challenging due to the poor nucleophilicity of the axial C4 hydroxyl group of L-galactose and the steric hindrance imposed by the 3S-hydroxybutyryl (Hb) chain. Furthermore, the presence of an acetyl group at the ortho position relative to the glycosylation site on L-galactose can lead to undesirable acetyl migration. Additionally, it is noteworthy that the selective removal of a 2-naphthylmethyl ether (Nap) during the late stages of synthesis, particularly in the presence of multiple benzyl groups, can be somewhat challenging to predict. Through the careful selection of synthetic strategies, building blocks, and optimized reaction conditions, we achieved the stereoselective glycosylations, selective oxidation of primary alcohols, remarkable enhancement of acceptor activity, and efficient introduction of the 3S-Hb group. The synthetic methodology presented in this work serves as a valuable reference for the preparation of structurally related oligosaccharides. By incorporating an aminopropyl linker, the target tetrasaccharide facilitates glycan microarray preparation and in vivo immunological assessments, thereby accelerating progress toward a synthetic glycoconjugate vaccine for P. aeruginosa.
Pseudomonas aeruginosa is an opportunistic pathogen responsible for severe nosocomial infections. This multidrug-resistant bacterium can cause pneumonia and cystic fibrosis, both of which are associated with high morbidity and mortality rates. The lipopolysaccharide of P. aeruginosa serves as an attractive target for the development of effective glycoconjugate vaccines. In this article, we report the first chemical synthesis of the highly challenging tetrasaccharide repeating unit of the P. aeruginosa serotype O3 O-antigen using a two-directional [1+(2 + 1)] glycosylation strategy. The synthesis is particularly challenging due to the poor nucleophilicity of the axial C4 hydroxyl group of L-galactose and the steric hindrance imposed by the 3S-hydroxybutyryl (Hb) chain. Furthermore, the presence of an acetyl group at the ortho position relative to the glycosylation site on L-galactose can lead to undesirable acetyl migration. Additionally, it is noteworthy that the selective removal of a 2-naphthylmethyl ether (Nap) during the late stages of synthesis, particularly in the presence of multiple benzyl groups, can be somewhat challenging to predict. Through the careful selection of synthetic strategies, building blocks, and optimized reaction conditions, we achieved the stereoselective glycosylations, selective oxidation of primary alcohols, remarkable enhancement of acceptor activity, and efficient introduction of the 3S-Hb group. The synthetic methodology presented in this work serves as a valuable reference for the preparation of structurally related oligosaccharides. By incorporating an aminopropyl linker, the target tetrasaccharide facilitates glycan microarray preparation and in vivo immunological assessments, thereby accelerating progress toward a synthetic glycoconjugate vaccine for P. aeruginosa.
2026, 37(2): 111891
doi: 10.1016/j.cclet.2025.111891
摘要:
Portable ratiometric fluorescent platforms have emerged as promising tools for multifarious detection, yet remain unexplored for point-of-care monitoring doxorubicin (DOX), one of clinically antineoplastic drugs. To this end, we herein develop a portable self-calibrating platform namely carbon dots (C-dots)-embedded hydrogel sensors with a smartphone-assisted high-throughput imaging device, for DOX sensing. The prepared green-emitting (λem = 508 nm) and negatively-charged C-dots (−11.40 ± 1.21 mV), which have sufficient spectral overlap with the absorption band of DOX (~500 nm), can strongly bind with positively-charged DOX molecules by electrostatic attraction effects. As a result, DOX molecules are selectively and rapid (20 s) determined with a detection limit of 10.26 nmol/L via Förster resonance energy transfer processes, demonstrating a remarkably chromatic shift from green to red. Further integrated with a 3D-printed smartphone-assisted device, the platform enabled high-throughput quantification, achieving recoveries of 96.40%–101.85% in human urine/serum (RSDs < 2.94%, n = 3). Notably, the dual linear detection ranges of the platform align with the reported clinical DOX concentrations in urine and plasma (0–4 h post-administration), validating their capability for direct quantification of DOX in clinical samples without special pre-treatment processes. By virtue of attractive analytical performances and robust feasibility, this platform bridges laboratory precision and point-of-care testing needs, offering promising potential for personalized chemotherapy and multiplexed analyte screening.
Portable ratiometric fluorescent platforms have emerged as promising tools for multifarious detection, yet remain unexplored for point-of-care monitoring doxorubicin (DOX), one of clinically antineoplastic drugs. To this end, we herein develop a portable self-calibrating platform namely carbon dots (C-dots)-embedded hydrogel sensors with a smartphone-assisted high-throughput imaging device, for DOX sensing. The prepared green-emitting (λem = 508 nm) and negatively-charged C-dots (−11.40 ± 1.21 mV), which have sufficient spectral overlap with the absorption band of DOX (~500 nm), can strongly bind with positively-charged DOX molecules by electrostatic attraction effects. As a result, DOX molecules are selectively and rapid (20 s) determined with a detection limit of 10.26 nmol/L via Förster resonance energy transfer processes, demonstrating a remarkably chromatic shift from green to red. Further integrated with a 3D-printed smartphone-assisted device, the platform enabled high-throughput quantification, achieving recoveries of 96.40%–101.85% in human urine/serum (RSDs < 2.94%, n = 3). Notably, the dual linear detection ranges of the platform align with the reported clinical DOX concentrations in urine and plasma (0–4 h post-administration), validating their capability for direct quantification of DOX in clinical samples without special pre-treatment processes. By virtue of attractive analytical performances and robust feasibility, this platform bridges laboratory precision and point-of-care testing needs, offering promising potential for personalized chemotherapy and multiplexed analyte screening.
2026, 37(2): 111917
doi: 10.1016/j.cclet.2025.111917
摘要:
The hydrogen evolution reaction (HER) is crucial for hydrogen production and sustainable energy storage. Molybdenum disulfide (MoS2), a representative transition metal dichalcogenides (TMDs), shows potential as an HER catalyst but suffers from limited performance due to poor charge transfer and interfacial effects. Here, we report a salt-assisted chemical vapor deposition (CVD) method for synthesizing high-quality tungsten ditelluride (WTe2) with tunable morphologies using alkali halides (NaCl, KCl and LiCl). The prepared WTe2 nanoribbons and hexagonal nanosheets exhibit morphology-dependent electrical conductivity, with nanosheets showing superior performance. To evaluate WTe2 as a contact electrode, WTe2−MoS2 heterostructures were fabricated and compared with graphene-MoS2 counterparts. The WTe2−MoS2 heterostructure exhibits a superior Tafel slope of 111.57 mV/dec and an overpotential of 298 mV at -10 mA/cm2, significantly outperforming graphene-based electrodes. This improvement is attributed to the excellent conductivity of WTe2 and reduced interfacial Schottky barriers. Moreover, we systematically investigate the influence of WTe2 thickness on HER performance and assess the electrochemical durability and structural stability of the heterostructure, further confirming the effectiveness of WTe2 as a contact electrode for enhancing the HER activity of MoS2. This study offers a novel approach for enhancing the HER performance of MoS2 through controlled WTe2 growth and application as a contact electrode. Our findings provide valuable insights into the synthesis of high-quality WTe2 and broaden the potential applications of two-dimensional materials in energy catalysis.
The hydrogen evolution reaction (HER) is crucial for hydrogen production and sustainable energy storage. Molybdenum disulfide (MoS2), a representative transition metal dichalcogenides (TMDs), shows potential as an HER catalyst but suffers from limited performance due to poor charge transfer and interfacial effects. Here, we report a salt-assisted chemical vapor deposition (CVD) method for synthesizing high-quality tungsten ditelluride (WTe2) with tunable morphologies using alkali halides (NaCl, KCl and LiCl). The prepared WTe2 nanoribbons and hexagonal nanosheets exhibit morphology-dependent electrical conductivity, with nanosheets showing superior performance. To evaluate WTe2 as a contact electrode, WTe2−MoS2 heterostructures were fabricated and compared with graphene-MoS2 counterparts. The WTe2−MoS2 heterostructure exhibits a superior Tafel slope of 111.57 mV/dec and an overpotential of 298 mV at -10 mA/cm2, significantly outperforming graphene-based electrodes. This improvement is attributed to the excellent conductivity of WTe2 and reduced interfacial Schottky barriers. Moreover, we systematically investigate the influence of WTe2 thickness on HER performance and assess the electrochemical durability and structural stability of the heterostructure, further confirming the effectiveness of WTe2 as a contact electrode for enhancing the HER activity of MoS2. This study offers a novel approach for enhancing the HER performance of MoS2 through controlled WTe2 growth and application as a contact electrode. Our findings provide valuable insights into the synthesis of high-quality WTe2 and broaden the potential applications of two-dimensional materials in energy catalysis.
2026, 37(2): 111920
doi: 10.1016/j.cclet.2025.111920
摘要:
Cu electrocatalysts have been demonstrated to have unique ability to reduce CO2 to various high value-added C2 products like ethylene and alcohols. However, realizing high selectivity of C2 products are still a main challenge due to complex CO2 electroreduction pathways and small opportunity of C–C coupling reactions. Here, we found the origin of enhanced CO2 electroreduction reaction activity and product selectivity towards C2 products and C–C coupling mechanism at halogen atoms-adsorbed Cu/H2O interfaces, the corresponding CO2 electroreduction evolution mechanisms at the halogen atoms-modified Cu/H2O interfaces are systematically studied via theoretical modeling and calculations. The calculated results indicate that halide anions modifications are beneficial to CO dimerization into OCCO dimer, especially Cl−-adsorbed Cu(111)/H2O interface has the optimum activity and selectivity towards OCCO dimer, subsequent Cl-adsorbed Cu(111)/H2O interface can selectively reduce CO2 into C2H4 product. The function relationship between adsorption free energy of Cl atom and electrode potential explain why the adsorption of Cl− can enhance selectivity of C2H4 product. The determinations of onset potentials indicate that electroreduction pathways of CO2 towards C2H4 product are facile to take place and further explain the origin of the significantly enhanced CO production activity and C2H4 product selectivity. This work on selective realization of CO2 electroreduction towards C2H4 product via Cl−-modified Cu(111)/H2O interface provide a theoretical guideline for how to selectively realize other high value-added C2 products.
Cu electrocatalysts have been demonstrated to have unique ability to reduce CO2 to various high value-added C2 products like ethylene and alcohols. However, realizing high selectivity of C2 products are still a main challenge due to complex CO2 electroreduction pathways and small opportunity of C–C coupling reactions. Here, we found the origin of enhanced CO2 electroreduction reaction activity and product selectivity towards C2 products and C–C coupling mechanism at halogen atoms-adsorbed Cu/H2O interfaces, the corresponding CO2 electroreduction evolution mechanisms at the halogen atoms-modified Cu/H2O interfaces are systematically studied via theoretical modeling and calculations. The calculated results indicate that halide anions modifications are beneficial to CO dimerization into OCCO dimer, especially Cl−-adsorbed Cu(111)/H2O interface has the optimum activity and selectivity towards OCCO dimer, subsequent Cl-adsorbed Cu(111)/H2O interface can selectively reduce CO2 into C2H4 product. The function relationship between adsorption free energy of Cl atom and electrode potential explain why the adsorption of Cl− can enhance selectivity of C2H4 product. The determinations of onset potentials indicate that electroreduction pathways of CO2 towards C2H4 product are facile to take place and further explain the origin of the significantly enhanced CO production activity and C2H4 product selectivity. This work on selective realization of CO2 electroreduction towards C2H4 product via Cl−-modified Cu(111)/H2O interface provide a theoretical guideline for how to selectively realize other high value-added C2 products.
2026, 37(2): 111933
doi: 10.1016/j.cclet.2025.111933
摘要:
Charge-transfer complexes (CTCs) have emerged as promising n-type organic thermoelectric (TE) materials due to their inherent high electrical conductivity and tunable transport polarities. In this study, we performed a comprehensive first-principles investigation on the TE properties of nine CTCs comprised of 2,7-dialkyl[1]benzothieno[3,2-b][1]benzothiophenes (CnBTBT, n = 4, 8, 12) as donors and fluorinated derivatives of tetracyanoquinodimethane (FmTCNQ, m = 0, 2, 4) as acceptors, aiming to identify high-performance n-type organic TE materials and elucidate the underlying structure–property relationships. Our calculation results, based on the Boltzmann transport equation and deformation potential theory, reveal that the length of the alkyl side chains and the number of fluorine substitutions significantly impact their electronic structures and TE properties. Notably, the CnBTBT–FmTCNQ CTCs with shorter alkyl chains and more fluorine substitution demonstrate superior n-type characteristics, particularly C4BTBT–F4TCNQ, which achieves an excellent power factor of 671 µW cm-1 K-2 at an optimal charge carrier concentration. Our findings not only clarify the critical role of molecular engineering in CTC-based TE materials but also provide valuable guidance for developing high-efficiency organic TE materials with versatile practical applications.
Charge-transfer complexes (CTCs) have emerged as promising n-type organic thermoelectric (TE) materials due to their inherent high electrical conductivity and tunable transport polarities. In this study, we performed a comprehensive first-principles investigation on the TE properties of nine CTCs comprised of 2,7-dialkyl[1]benzothieno[3,2-b][1]benzothiophenes (CnBTBT, n = 4, 8, 12) as donors and fluorinated derivatives of tetracyanoquinodimethane (FmTCNQ, m = 0, 2, 4) as acceptors, aiming to identify high-performance n-type organic TE materials and elucidate the underlying structure–property relationships. Our calculation results, based on the Boltzmann transport equation and deformation potential theory, reveal that the length of the alkyl side chains and the number of fluorine substitutions significantly impact their electronic structures and TE properties. Notably, the CnBTBT–FmTCNQ CTCs with shorter alkyl chains and more fluorine substitution demonstrate superior n-type characteristics, particularly C4BTBT–F4TCNQ, which achieves an excellent power factor of 671 µW cm-1 K-2 at an optimal charge carrier concentration. Our findings not only clarify the critical role of molecular engineering in CTC-based TE materials but also provide valuable guidance for developing high-efficiency organic TE materials with versatile practical applications.
2026, 37(2): 111945
doi: 10.1016/j.cclet.2025.111945
摘要:
We report an immobilized enzyme-catalyzed batch and continuous-flow synthesis of optically pure ethyl (R)-pantothenate ((R)-PaOEt), the direct precursor of D-pantothenic acid. Firstly, a ketoreductase mutant designated as M2, carrying two-point mutations of F97L and M242F relative to the wild-type SSCR, was constructed by site-directed mutagenesis, exhibited simultaneously improved activity toward ethyl 2′-ketopantothenate (K-PaOEt) and isopropanol, and could effectively catalyze the stereoselective reduction of K-PaOEt to (R)-PaOEt by using isopropanol as the sacrificial co-substrate to regenerate NADPH. After screening six commercially available carriers, an amino resin LXTE-700 was identified as the best solid support for the immobilization of M2 via the glutaraldehyde activation method. Upon optimization of the immobilization process and reaction conditions, the fabricated immobilized enzyme M2@amino resin demonstrated excellent recyclability and reusability, with the complete conversion of K-PaOEt to (R)-PaOEt being still realized after 12 cycles of reuse. Finally, M2@amino resin-catalyzed synthesis of (R)-PaOEt was successfully implemented in continuous-flow, accomplishing a 6.3 times higher space-time yield than that with the batch synthesis (529.2 versus 84 g L-1 d-1). Our developed flow biocatalysis system also features an outstanding operational stability, as evidenced by the 100% conversion rate achieved after 15 consecutive days of operation.
We report an immobilized enzyme-catalyzed batch and continuous-flow synthesis of optically pure ethyl (R)-pantothenate ((R)-PaOEt), the direct precursor of D-pantothenic acid. Firstly, a ketoreductase mutant designated as M2, carrying two-point mutations of F97L and M242F relative to the wild-type SSCR, was constructed by site-directed mutagenesis, exhibited simultaneously improved activity toward ethyl 2′-ketopantothenate (K-PaOEt) and isopropanol, and could effectively catalyze the stereoselective reduction of K-PaOEt to (R)-PaOEt by using isopropanol as the sacrificial co-substrate to regenerate NADPH. After screening six commercially available carriers, an amino resin LXTE-700 was identified as the best solid support for the immobilization of M2 via the glutaraldehyde activation method. Upon optimization of the immobilization process and reaction conditions, the fabricated immobilized enzyme M2@amino resin demonstrated excellent recyclability and reusability, with the complete conversion of K-PaOEt to (R)-PaOEt being still realized after 12 cycles of reuse. Finally, M2@amino resin-catalyzed synthesis of (R)-PaOEt was successfully implemented in continuous-flow, accomplishing a 6.3 times higher space-time yield than that with the batch synthesis (529.2 versus 84 g L-1 d-1). Our developed flow biocatalysis system also features an outstanding operational stability, as evidenced by the 100% conversion rate achieved after 15 consecutive days of operation.
2026, 37(2): 111946
doi: 10.1016/j.cclet.2025.111946
摘要:
Developing advanced polymeric materials with enhanced mechanical properties and functionalities has been a long-standing goal in materials science. Recently, supramolecular polymeric materials (SPMs) have drawn increased attention due to their unique properties and potential applications in self-healing, shape memory, sensors, and flexible electronics. Here, we develop an ionic cluster-optimized microphase separation strategy to enhance the toughening and energy dissipation capabilities of polydisulfide-based supramolecular polymers. The mechanical properties, including Young’s modulus and toughness, are significantly improved by integrating the quadruple H-bonding 2-ureido-4-pyrimidone (UPy) induced microphase separation with iron(Ⅲ)-to-carboxylate ionic clusters. By combining established chemical approaches with adjustable polymer phase ratios, it is revealed that the synergistic effect of these factors expands the interchain spacing, facilitates the formation of microphase domains, and enhances the tolerance of polythioctic acid-based polymers to external mechanical and thermal stimuli, meeting the practical requirements for industrial plastic applications. Moreover, the UPy-functionalized polymers incorporating iron carboxylate clusters exhibit good one-way shape memory behavior with practical applicability at a relatively low recovery temperature. Our work demonstrates a novel strategy for constructing industrially viable shape memory dynamic SPMs and paves the way for future innovations in developing SPMs.
Developing advanced polymeric materials with enhanced mechanical properties and functionalities has been a long-standing goal in materials science. Recently, supramolecular polymeric materials (SPMs) have drawn increased attention due to their unique properties and potential applications in self-healing, shape memory, sensors, and flexible electronics. Here, we develop an ionic cluster-optimized microphase separation strategy to enhance the toughening and energy dissipation capabilities of polydisulfide-based supramolecular polymers. The mechanical properties, including Young’s modulus and toughness, are significantly improved by integrating the quadruple H-bonding 2-ureido-4-pyrimidone (UPy) induced microphase separation with iron(Ⅲ)-to-carboxylate ionic clusters. By combining established chemical approaches with adjustable polymer phase ratios, it is revealed that the synergistic effect of these factors expands the interchain spacing, facilitates the formation of microphase domains, and enhances the tolerance of polythioctic acid-based polymers to external mechanical and thermal stimuli, meeting the practical requirements for industrial plastic applications. Moreover, the UPy-functionalized polymers incorporating iron carboxylate clusters exhibit good one-way shape memory behavior with practical applicability at a relatively low recovery temperature. Our work demonstrates a novel strategy for constructing industrially viable shape memory dynamic SPMs and paves the way for future innovations in developing SPMs.
2026, 37(2): 111949
doi: 10.1016/j.cclet.2025.111949
摘要:
As a common electronic adhesive, ultraviolet (UV) curing polyurethane acrylate adhesive has both flexibility and wear resistance of polyurethane, excellent weather resistance and optical properties of acrylate. Despite the extensive applications, it is still difficult to solve the problems caused by the shrinkage of adhesive. Here, a new type of photosensitive adhesive for bonding electronic components based on supramolecular interaction was designed and synthesized. The supramolecular interaction of cyclodextrin and adamantane moieties introduced into the adhesive polymer entitles the viscosity of the adhesive to rise rapidly during use, thereby preventing adhesive loss and dislocation of electronic components. UV light could further cure the adhesive and position the electronic components. The adhesive shrunk < 2% when cured by UV light, so it can be used for electronic packaging and high-resolution, defect-free lithography.
As a common electronic adhesive, ultraviolet (UV) curing polyurethane acrylate adhesive has both flexibility and wear resistance of polyurethane, excellent weather resistance and optical properties of acrylate. Despite the extensive applications, it is still difficult to solve the problems caused by the shrinkage of adhesive. Here, a new type of photosensitive adhesive for bonding electronic components based on supramolecular interaction was designed and synthesized. The supramolecular interaction of cyclodextrin and adamantane moieties introduced into the adhesive polymer entitles the viscosity of the adhesive to rise rapidly during use, thereby preventing adhesive loss and dislocation of electronic components. UV light could further cure the adhesive and position the electronic components. The adhesive shrunk < 2% when cured by UV light, so it can be used for electronic packaging and high-resolution, defect-free lithography.
2026, 37(2): 111959
doi: 10.1016/j.cclet.2025.111959
摘要:
Shape memory polymers used in 4D printing only had one permanent shape after molding, which limited their applications in requiring multiple reconstructions and multifunctional shapes. Furthermore, the inherent stability of the triazine ring structure within cyanate ester (CE) crosslinked networks after molding posed significant challenges for both recycling, repairing, and degradation of resin. To address these obstacles, dynamic thiocyanate ester (TCE) bonds and photocurable group were incorporated into CE, obtaining the recyclable and 3D printable CE covalent adaptable networks (CANs), denoted as PTCE1.5. This material exhibits a Young’s modulus of 810 MPa and a tensile strength of 50.8 MPa. Notably, damaged printed PTCE1.5 objects can be readily repaired through reprinting and interface rejoining by thermal treatment. Leveraging the solid-state plasticity, PTCE1.5 also demonstrated attractive shape memory ability and permanent shape reconfigurability, enabling its reconfigurable 4D printing. The printed PTCE1.5 hinges and a main body were assembled into a deployable and retractable satellite model, validating its potential application as a controllable component in the aerospace field. Moreover, printed PTCE1.5 can be fully degraded into thiol-modified intermediate products. Overall, this material not only enriches the application range of CE resin, but also provides a reliable approach to addressing environmental issue.
Shape memory polymers used in 4D printing only had one permanent shape after molding, which limited their applications in requiring multiple reconstructions and multifunctional shapes. Furthermore, the inherent stability of the triazine ring structure within cyanate ester (CE) crosslinked networks after molding posed significant challenges for both recycling, repairing, and degradation of resin. To address these obstacles, dynamic thiocyanate ester (TCE) bonds and photocurable group were incorporated into CE, obtaining the recyclable and 3D printable CE covalent adaptable networks (CANs), denoted as PTCE1.5. This material exhibits a Young’s modulus of 810 MPa and a tensile strength of 50.8 MPa. Notably, damaged printed PTCE1.5 objects can be readily repaired through reprinting and interface rejoining by thermal treatment. Leveraging the solid-state plasticity, PTCE1.5 also demonstrated attractive shape memory ability and permanent shape reconfigurability, enabling its reconfigurable 4D printing. The printed PTCE1.5 hinges and a main body were assembled into a deployable and retractable satellite model, validating its potential application as a controllable component in the aerospace field. Moreover, printed PTCE1.5 can be fully degraded into thiol-modified intermediate products. Overall, this material not only enriches the application range of CE resin, but also provides a reliable approach to addressing environmental issue.
2026, 37(2): 111989
doi: 10.1016/j.cclet.2025.111989
摘要:
Cyclo[n]Thiophenes (CnTs) are a distinctive class of π-conjugated macrocyclic molecules that have attracted growing attention owing to their structural aesthetics and organic electronic characteristics. However, the development of CnTs has been largely impeded by inefficient synthetic route. In this work, we employ a bridge strategy using bipyridine as bridge to link two quaterthiophene units resulting in Φ-shaped bicyclosystem. This strain-retaining approach improves the synthesis efficiency of the macrocycles. Two new macrocyclic molecules, (4T-2hexyl-2Me)2-DPBP and (4T-2hexyl)2-DPBP, were successfully synthesized in total yield 17% and 16%, respectively. Single-crystal structure of (4T-2hexyl-2Me)2-DPBP reveals that the bipyridine bridge is orthogonally strapped by two quaterthiophene units. Notably, both compounds exhibit aggregation-induced emission enhancement (AIEE) behavior-an unprecedented feature among CnT-based macrocycles. Theoretical calculations reveal that this AIE phenomenon originates from the restriction of intramolecular motion (RIM) in the aggregated state, which suppresses the non-radiative decay channels. These results demonstrate a generalized strategy for the synthesis of functional π-conjugated macrocyclic molecules based fluorescent materials.
Cyclo[n]Thiophenes (CnTs) are a distinctive class of π-conjugated macrocyclic molecules that have attracted growing attention owing to their structural aesthetics and organic electronic characteristics. However, the development of CnTs has been largely impeded by inefficient synthetic route. In this work, we employ a bridge strategy using bipyridine as bridge to link two quaterthiophene units resulting in Φ-shaped bicyclosystem. This strain-retaining approach improves the synthesis efficiency of the macrocycles. Two new macrocyclic molecules, (4T-2hexyl-2Me)2-DPBP and (4T-2hexyl)2-DPBP, were successfully synthesized in total yield 17% and 16%, respectively. Single-crystal structure of (4T-2hexyl-2Me)2-DPBP reveals that the bipyridine bridge is orthogonally strapped by two quaterthiophene units. Notably, both compounds exhibit aggregation-induced emission enhancement (AIEE) behavior-an unprecedented feature among CnT-based macrocycles. Theoretical calculations reveal that this AIE phenomenon originates from the restriction of intramolecular motion (RIM) in the aggregated state, which suppresses the non-radiative decay channels. These results demonstrate a generalized strategy for the synthesis of functional π-conjugated macrocyclic molecules based fluorescent materials.
2026, 37(2): 112022
doi: 10.1016/j.cclet.2025.112022
摘要:
Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction (HER). Here, we reported PtNi nanoparticles with a refined size of 2.71 nm and regular strains loaded on carbon black, synthesized using the high-temperature liquid shock (HTLS) method. This approach offers significant advantages over conventional synthesis methods, including high scalability, rapid reaction rates, and precise control over the size and shape of nanocrystals. Importantly, the synthesized PtNi electrocatalysts demonstrate outstanding catalytic activity and long-term stability for HER, achieving low overpotentials of 19 and 203 mV at current densities of 10 and 1000 mA/cm2, respectively. The superior performance can be attributed to the combination of a refined particle size, lattice strains, and synergistic effects between Pt and Ni. This rapid liquid-state synthesis demonstrated here holds great potential for scalable and industrial manufacturing of micro-/nano-catalysts.
Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction (HER). Here, we reported PtNi nanoparticles with a refined size of 2.71 nm and regular strains loaded on carbon black, synthesized using the high-temperature liquid shock (HTLS) method. This approach offers significant advantages over conventional synthesis methods, including high scalability, rapid reaction rates, and precise control over the size and shape of nanocrystals. Importantly, the synthesized PtNi electrocatalysts demonstrate outstanding catalytic activity and long-term stability for HER, achieving low overpotentials of 19 and 203 mV at current densities of 10 and 1000 mA/cm2, respectively. The superior performance can be attributed to the combination of a refined particle size, lattice strains, and synergistic effects between Pt and Ni. This rapid liquid-state synthesis demonstrated here holds great potential for scalable and industrial manufacturing of micro-/nano-catalysts.
2026, 37(2): 112039
doi: 10.1016/j.cclet.2025.112039
摘要:
Chiral amino acids (AAs) serve as essential building blocks of proteins and play vital physiological roles in living organisms. To achieve accurate, rapid, and high-throughput analysis of chiral AAs, this work proposed a methylbenzyl isocyanate (MBIC) derivatization strategy coupled with ultra-high performance liquid chromatography-mass spectrometry or trapped ion mobility spectrometry-mass spectrometry. The integration of a chiral carbon atom with a rigid urea-based structure can significantly enhance the separation of chiral MBIC-labeled AA enantiomers. This phenomenon can be attributed to the labeled l-AAs allow the carboxyl group to form intramolecular hydrogen bonds with the amino group in the rigid urea-based structure, whereas labeled d-AAs are unable to form such bonds. The method based on MBIC derivatization coupled with ultra-performance liquid chromatography-tandem mass spectrometry achieved simultaneous separation of 19 pairs of chiral AAs using only a C18 column within 30 min, enabling quantitatively detect twelve types of chiral AAs in the serum of healthy humans and Parkinson's patients. The distribution of twenty-four chiral AAs is observed in mouse brain using MBIC labeling-based matrix-assisted laser desorption/ionization-trapped ion mobility spectrometry-mass spectrometry imaging without prior separation. Our work elucidates the principles governing the separation of chiral AAs using derivatization methods, providing valuable guidance for the separation of chiral compounds.
Chiral amino acids (AAs) serve as essential building blocks of proteins and play vital physiological roles in living organisms. To achieve accurate, rapid, and high-throughput analysis of chiral AAs, this work proposed a methylbenzyl isocyanate (MBIC) derivatization strategy coupled with ultra-high performance liquid chromatography-mass spectrometry or trapped ion mobility spectrometry-mass spectrometry. The integration of a chiral carbon atom with a rigid urea-based structure can significantly enhance the separation of chiral MBIC-labeled AA enantiomers. This phenomenon can be attributed to the labeled l-AAs allow the carboxyl group to form intramolecular hydrogen bonds with the amino group in the rigid urea-based structure, whereas labeled d-AAs are unable to form such bonds. The method based on MBIC derivatization coupled with ultra-performance liquid chromatography-tandem mass spectrometry achieved simultaneous separation of 19 pairs of chiral AAs using only a C18 column within 30 min, enabling quantitatively detect twelve types of chiral AAs in the serum of healthy humans and Parkinson's patients. The distribution of twenty-four chiral AAs is observed in mouse brain using MBIC labeling-based matrix-assisted laser desorption/ionization-trapped ion mobility spectrometry-mass spectrometry imaging without prior separation. Our work elucidates the principles governing the separation of chiral AAs using derivatization methods, providing valuable guidance for the separation of chiral compounds.
2026, 37(2): 112051
doi: 10.1016/j.cclet.2025.112051
摘要:
The structural principles of traditional Chinese mortise-and-tenon joints have inspired breakthroughs in supramolecular engineering. Nevertheless, substantial challenges remain in constructing nanoscale supramolecular architectures with precisely controlled giant dimensions. Herein, we report a precision-guided synthetic strategy for constructing giant 2D and 3D supramolecular architectures with rhomboidal motifs, which was achieved through a dovetail joint strategy. Initial assembly of bis-mortise ligand L1 with dovetail tenon ligand L2 in the presence of Cd2+ ions yielded the fundamental bis-rhombic supramolecule R1. Subsequent structural elaboration of the dovetail tenon motif enabled the development of multitopic ligands L3 and L4, which facilitated the construction of expanded architectures of the giant bis-propeller supramolecule R2 and tris-propeller supramolecule R3. The synthesized supramolecules R1–R3 were fully characterized multidimensional NMR spectroscopy, electrospray ionization mass spectrometry (ESI-MS), traveling wave ion mobility mass spectrometry (TWIM-MS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). This work develops an innovative dovetail-joint assembly strategy for constructing rigid giant supramolecular architectures, establishing a new paradigm for precision engineering of complex 3D molecular systems.
The structural principles of traditional Chinese mortise-and-tenon joints have inspired breakthroughs in supramolecular engineering. Nevertheless, substantial challenges remain in constructing nanoscale supramolecular architectures with precisely controlled giant dimensions. Herein, we report a precision-guided synthetic strategy for constructing giant 2D and 3D supramolecular architectures with rhomboidal motifs, which was achieved through a dovetail joint strategy. Initial assembly of bis-mortise ligand L1 with dovetail tenon ligand L2 in the presence of Cd2+ ions yielded the fundamental bis-rhombic supramolecule R1. Subsequent structural elaboration of the dovetail tenon motif enabled the development of multitopic ligands L3 and L4, which facilitated the construction of expanded architectures of the giant bis-propeller supramolecule R2 and tris-propeller supramolecule R3. The synthesized supramolecules R1–R3 were fully characterized multidimensional NMR spectroscopy, electrospray ionization mass spectrometry (ESI-MS), traveling wave ion mobility mass spectrometry (TWIM-MS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). This work develops an innovative dovetail-joint assembly strategy for constructing rigid giant supramolecular architectures, establishing a new paradigm for precision engineering of complex 3D molecular systems.
2026, 37(2): 112099
doi: 10.1016/j.cclet.2025.112099
摘要:
PEGylation, the controlled covalent conjugation of polyethylene glycol to therapeutics, enhances therapeutic efficacy through optimized pharmacokinetics. However, to date no high-molecular-weight PEGylated small-molecule prodrugs have received regulatory approval. This technological gap can be partially attributed to the exponential proliferation of metabolic intermediates resulting from multi-payload conjugation strategies, which introduces unprecedented analytical complexities in metabolite profiling and pharmacokinetic characterization. To address this challenge, we developed a liquid chromatography-triple-quadrupole/time-of-flight mass spectrometry platform for PEG20k-(irinotecan)3, a Phase Ⅲ clinical candidate. Our methodology employs payload stoichiometry-based chromatographic resolution for clustering isomeric PEG species. Complementarily, diagnostic product ions at m/z 699.83, 569.27, and 587.28 enable systematic differentiation between double-loaded, single-loaded, and released irinotecan payload. This approach successfully identifies eight metabolic clusters spanning from PEG-conjugates, cleaved PEG segments, and released small-molecule species. Its demonstrated capacity to deconvolute complex metabolic profiles—through payload-stoichiometry based chromatographic resolution coupled with diagnostic ion analysis—positions this workflow as an attractive tool for accelerating the development of PEGylated small-molecule therapeutics.
PEGylation, the controlled covalent conjugation of polyethylene glycol to therapeutics, enhances therapeutic efficacy through optimized pharmacokinetics. However, to date no high-molecular-weight PEGylated small-molecule prodrugs have received regulatory approval. This technological gap can be partially attributed to the exponential proliferation of metabolic intermediates resulting from multi-payload conjugation strategies, which introduces unprecedented analytical complexities in metabolite profiling and pharmacokinetic characterization. To address this challenge, we developed a liquid chromatography-triple-quadrupole/time-of-flight mass spectrometry platform for PEG20k-(irinotecan)3, a Phase Ⅲ clinical candidate. Our methodology employs payload stoichiometry-based chromatographic resolution for clustering isomeric PEG species. Complementarily, diagnostic product ions at m/z 699.83, 569.27, and 587.28 enable systematic differentiation between double-loaded, single-loaded, and released irinotecan payload. This approach successfully identifies eight metabolic clusters spanning from PEG-conjugates, cleaved PEG segments, and released small-molecule species. Its demonstrated capacity to deconvolute complex metabolic profiles—through payload-stoichiometry based chromatographic resolution coupled with diagnostic ion analysis—positions this workflow as an attractive tool for accelerating the development of PEGylated small-molecule therapeutics.
2026, 37(2): 110606
doi: 10.1016/j.cclet.2024.110606
摘要:
As the chemical industry expands, the use of benzene, toluene, and xylene (collectively known as BTX) in industrial production has increased greatly. Meanwhile, the toxic nature and potential health hazards of BTX gases cannot be ignored due to low-concentration leaks underline the critical need for rapid and real-time monitoring of these gases. Chemiresistive metal oxide semiconductor (MOS)-based gas sensors, which are extensively used for gas detection in both industrial settings and everyday life, emerge as one of the optimal solutions for trace BTX detection. These sensors are highly valued for their high sensitivity and low detection limits. Nevertheless, the improvement of selectivity towards specific BTX gases to achieve efficient and precise detection still remains challenging. This review summarizes the chemiresistive MOS-based gas sensors designed for BTX detection, categorizing them based on the components of sensing materials-basically into three groups: single-component, single heterojunction, and multiple heterojunctions gas sensing materials. Further, the review proposes the future application prospects of chemiresistive MOS-based BTX gas sensors, with specific emphasis on their significance in promoting industrial safety and environmental monitoring.
As the chemical industry expands, the use of benzene, toluene, and xylene (collectively known as BTX) in industrial production has increased greatly. Meanwhile, the toxic nature and potential health hazards of BTX gases cannot be ignored due to low-concentration leaks underline the critical need for rapid and real-time monitoring of these gases. Chemiresistive metal oxide semiconductor (MOS)-based gas sensors, which are extensively used for gas detection in both industrial settings and everyday life, emerge as one of the optimal solutions for trace BTX detection. These sensors are highly valued for their high sensitivity and low detection limits. Nevertheless, the improvement of selectivity towards specific BTX gases to achieve efficient and precise detection still remains challenging. This review summarizes the chemiresistive MOS-based gas sensors designed for BTX detection, categorizing them based on the components of sensing materials-basically into three groups: single-component, single heterojunction, and multiple heterojunctions gas sensing materials. Further, the review proposes the future application prospects of chemiresistive MOS-based BTX gas sensors, with specific emphasis on their significance in promoting industrial safety and environmental monitoring.
2026, 37(2): 110960
doi: 10.1016/j.cclet.2025.110960
摘要:
Cancer is the second leading cause of death globally. Its treatment remains a major challenge due to the disease's complexity, heterogeneity, and adaptive nature. Among the array of available treatments, targeted therapy emerges as a paramount approach to address this substantial unmet clinical need, owing to its precise tumor targeting capabilities and potential for mitigating tumor progression risks. Drug conjugates are in high demand for targeted therapy due to their unique ligand specificity and potent cytotoxicity, thereby significantly enhancing therapeutic efficacy and reducing the incidence of adverse effects. Therefore, as a burgeoning field in biomedical research, it is timely to outline the latest advances in drug conjugates-driven cancer treatment. Herein, we aim to present the emerging breakthroughs in this exciting field at the intersection of target ligands, linkers, payloads, and cancer treatments. This review focuses on several drug conjugates-related strategies, including antibody-drug conjugates (ADCs), peptide-drug conjugates (PDCs), small molecule-drug conjugates (SMDCs), aptamer-drug conjugates (ApDCs) and radionuclide-drug conjugates (RDCs). Finally, we discuss the fundamentals behind drug conjugate-based anticancer therapeutics, along with their inherent advantages and associated challenges, as well as recent research advances.
Cancer is the second leading cause of death globally. Its treatment remains a major challenge due to the disease's complexity, heterogeneity, and adaptive nature. Among the array of available treatments, targeted therapy emerges as a paramount approach to address this substantial unmet clinical need, owing to its precise tumor targeting capabilities and potential for mitigating tumor progression risks. Drug conjugates are in high demand for targeted therapy due to their unique ligand specificity and potent cytotoxicity, thereby significantly enhancing therapeutic efficacy and reducing the incidence of adverse effects. Therefore, as a burgeoning field in biomedical research, it is timely to outline the latest advances in drug conjugates-driven cancer treatment. Herein, we aim to present the emerging breakthroughs in this exciting field at the intersection of target ligands, linkers, payloads, and cancer treatments. This review focuses on several drug conjugates-related strategies, including antibody-drug conjugates (ADCs), peptide-drug conjugates (PDCs), small molecule-drug conjugates (SMDCs), aptamer-drug conjugates (ApDCs) and radionuclide-drug conjugates (RDCs). Finally, we discuss the fundamentals behind drug conjugate-based anticancer therapeutics, along with their inherent advantages and associated challenges, as well as recent research advances.
2026, 37(2): 110990
doi: 10.1016/j.cclet.2025.110990
摘要:
The stimulator of interferon genes (STING), as a critical innate immune sensor, has been widely and continually explored in immune-related disease treatment. As lipid bilayer-closed particles derived from cells, extracellular vesicles (EVs) inherently function in target-guided intercellular communication. To incorporate the native merits of EVs into STING pathways, i.e., engineered EV@STING, poor bioavailability and off-target issues that STING activators possess could be significantly overcome. In this review, emerged STING activators such as nitrogen-containing heterocyclic structures and the universal STING activation strategy (uniSTING) are firstly summarized. Diverse EVs sources from mesenchymal stem cells (MSCs) and innate and adaptive immune cells may evoke distinct regulatory results. Concurrently, how the EVs contents including double-stranded DNA (dsDNA), microRNA (miRNA), cyclic GMP-AMP synthase (cGAS) and 2′3′-cyclic GMP-AMP (2′3′-cGAMP) proteins participate in the regulation of STING activation are widely studied. After mastering the two pivotal aspects of EV@STING, their immunomodulatory roles including in pathogen infection, inflammatory diseases, and cancer therapy are comprehensively summed up and discussed. Finally, in cancer study field, therapeutic challenges and clinical translational opportunities of EV@STING are thoroughly evaluated.
The stimulator of interferon genes (STING), as a critical innate immune sensor, has been widely and continually explored in immune-related disease treatment. As lipid bilayer-closed particles derived from cells, extracellular vesicles (EVs) inherently function in target-guided intercellular communication. To incorporate the native merits of EVs into STING pathways, i.e., engineered EV@STING, poor bioavailability and off-target issues that STING activators possess could be significantly overcome. In this review, emerged STING activators such as nitrogen-containing heterocyclic structures and the universal STING activation strategy (uniSTING) are firstly summarized. Diverse EVs sources from mesenchymal stem cells (MSCs) and innate and adaptive immune cells may evoke distinct regulatory results. Concurrently, how the EVs contents including double-stranded DNA (dsDNA), microRNA (miRNA), cyclic GMP-AMP synthase (cGAS) and 2′3′-cyclic GMP-AMP (2′3′-cGAMP) proteins participate in the regulation of STING activation are widely studied. After mastering the two pivotal aspects of EV@STING, their immunomodulatory roles including in pathogen infection, inflammatory diseases, and cancer therapy are comprehensively summed up and discussed. Finally, in cancer study field, therapeutic challenges and clinical translational opportunities of EV@STING are thoroughly evaluated.
2026, 37(2): 111032
doi: 10.1016/j.cclet.2025.111032
摘要:
Pulmonary diseases have long posed a severe threat to human life and health. The incidence and mortality rates of pulmonary diseases have shown a rising trend year by year, highlighting the urgency of developing safe and effective therapeutic approaches. In recent years, to address the challenges faced by traditional treatment strategies for pulmonary diseases, the interdisciplinary integration has greatly promoted the rapid development of biomedical polymer materials in the field of pulmonary disease treatment. This review provides a detailed description of the structural characteristics of lung tissue, types of pulmonary diseases, traditional treatment methods, the categories and properties of biomedical polymer materials applied to pulmonary diseases. We systematically elaborate on the applications of biomedical polymer materials in the treatment of different pulmonary diseases and thoroughly discuss their functional roles in pulmonary diseases, particularly in the delivery of therapeutic agents to diseased sites, the formation of pulmonary aerosol formulations, and the facilitation of the effective accumulation of therapeutic agents. The latest research progresses of biomedical polymer materials are also introduced in pulmonary disease treatment. We have highlighted the current challenges and development opportunities of biomedical polymer materials in the treatment of pulmonary diseases, and provide future research directions for biomedical polymer materials in this field. This review will provide valuable reference for the basic research and clinical application of biomedical polymer materials in pulmonary disease treatment.
Pulmonary diseases have long posed a severe threat to human life and health. The incidence and mortality rates of pulmonary diseases have shown a rising trend year by year, highlighting the urgency of developing safe and effective therapeutic approaches. In recent years, to address the challenges faced by traditional treatment strategies for pulmonary diseases, the interdisciplinary integration has greatly promoted the rapid development of biomedical polymer materials in the field of pulmonary disease treatment. This review provides a detailed description of the structural characteristics of lung tissue, types of pulmonary diseases, traditional treatment methods, the categories and properties of biomedical polymer materials applied to pulmonary diseases. We systematically elaborate on the applications of biomedical polymer materials in the treatment of different pulmonary diseases and thoroughly discuss their functional roles in pulmonary diseases, particularly in the delivery of therapeutic agents to diseased sites, the formation of pulmonary aerosol formulations, and the facilitation of the effective accumulation of therapeutic agents. The latest research progresses of biomedical polymer materials are also introduced in pulmonary disease treatment. We have highlighted the current challenges and development opportunities of biomedical polymer materials in the treatment of pulmonary diseases, and provide future research directions for biomedical polymer materials in this field. This review will provide valuable reference for the basic research and clinical application of biomedical polymer materials in pulmonary disease treatment.
2026, 37(2): 111275
doi: 10.1016/j.cclet.2025.111275
摘要:
Human health is seriously jeopardized by infections caused by pathogenic microorganisms. The current traditional disinfection technologies have many defects, such as producing harmful by-products, being affected by water turbidity, and high energy consumption. The growing concern for microbial safety has brought non-thermal plasma (NTP) disinfection technology into the spotlight. NTP is a promising disinfection technology with advantages such as environmental protection, safety, room temperature disinfection, short disinfection cycle, and wide applicability. Researchers are continuously optimizing NTP reactions to improve disinfection efficiency. This paper provides an integrated analysis of both plasma disinfection in water and plasma-activated water (PAW) disinfection on object surfaces. NTP can directly treat bacterial contaminated water, and can also be employed to produce PAW as a disinfectant for treating bacteria on surfaces. This review introduces the fundamental concepts and commonly used equipment related to NTP technology, analyzes the influencing factors and mechanisms of disinfection, and concludes by outlining the future directions of NTP technology in the field of disinfection. We hope to provide a reference for the research and practice of bacterial pollution issues.
Human health is seriously jeopardized by infections caused by pathogenic microorganisms. The current traditional disinfection technologies have many defects, such as producing harmful by-products, being affected by water turbidity, and high energy consumption. The growing concern for microbial safety has brought non-thermal plasma (NTP) disinfection technology into the spotlight. NTP is a promising disinfection technology with advantages such as environmental protection, safety, room temperature disinfection, short disinfection cycle, and wide applicability. Researchers are continuously optimizing NTP reactions to improve disinfection efficiency. This paper provides an integrated analysis of both plasma disinfection in water and plasma-activated water (PAW) disinfection on object surfaces. NTP can directly treat bacterial contaminated water, and can also be employed to produce PAW as a disinfectant for treating bacteria on surfaces. This review introduces the fundamental concepts and commonly used equipment related to NTP technology, analyzes the influencing factors and mechanisms of disinfection, and concludes by outlining the future directions of NTP technology in the field of disinfection. We hope to provide a reference for the research and practice of bacterial pollution issues.
2026, 37(2): 111305
doi: 10.1016/j.cclet.2025.111305
摘要:
Pyrimidine is a widely used compound in pesticides and medicine, with over 60 commercial pesticides containing a pyrimidine structure. Examples include the insecticide flufenerim, herbicide nicosulfuron, fungicide mepanipyrim, antiviral agent ningnanmycin, and plant growth regulator ancymidol. This paper reviews the characteristics from 2014 to 2024 of highly active pyrimidine-containing compounds and their biological activities, focusing on insecticidal, herbicidal, antibacterial, antiviral, and plant growth regulation properties. The goal is to provide insights for the design and synthesis of new pyrimidine-based pesticide candidates.
Pyrimidine is a widely used compound in pesticides and medicine, with over 60 commercial pesticides containing a pyrimidine structure. Examples include the insecticide flufenerim, herbicide nicosulfuron, fungicide mepanipyrim, antiviral agent ningnanmycin, and plant growth regulator ancymidol. This paper reviews the characteristics from 2014 to 2024 of highly active pyrimidine-containing compounds and their biological activities, focusing on insecticidal, herbicidal, antibacterial, antiviral, and plant growth regulation properties. The goal is to provide insights for the design and synthesis of new pyrimidine-based pesticide candidates.
2026, 37(2): 111315
doi: 10.1016/j.cclet.2025.111315
摘要:
Among various advanced oxidation processes (AOPs), heterogeneous catalytic ozonation has garnered extensive attention in wastewater treatment owing to its broad pH range applicability and the elimination of the need for additional energy input. Enhancing catalyst activity by introducing oxygen vacancies has been used extensively in heterogeneous catalytic ozonation. This paper reviews prevalent methods for the construction and characterization of oxygen vacancies. Based on a thorough examination of existing research, the role of oxygen vacancies is categorized according to their primary mechanisms of action in heterogeneous catalytic ozonation. For example, modulation of the catalyst electronic structure to enhance electron transfer; participation in the reaction as an active site to generate radicals and non-radicals; and exposure of more metal sites to enhance the reaction. Lastly, the paper delineates the limitations and future research directions concerning the role of oxygen vacancies in catalytic ozonation. This review addresses the gap in existing literature concerning the role of oxygen vacancies in catalytic ozone systems, establishes a comprehensive theoretical framework to aid in the design of efficient ozone catalysts, and delves into the functionality of oxygen vacancies in heterogeneous catalytic ozone reactions.
Among various advanced oxidation processes (AOPs), heterogeneous catalytic ozonation has garnered extensive attention in wastewater treatment owing to its broad pH range applicability and the elimination of the need for additional energy input. Enhancing catalyst activity by introducing oxygen vacancies has been used extensively in heterogeneous catalytic ozonation. This paper reviews prevalent methods for the construction and characterization of oxygen vacancies. Based on a thorough examination of existing research, the role of oxygen vacancies is categorized according to their primary mechanisms of action in heterogeneous catalytic ozonation. For example, modulation of the catalyst electronic structure to enhance electron transfer; participation in the reaction as an active site to generate radicals and non-radicals; and exposure of more metal sites to enhance the reaction. Lastly, the paper delineates the limitations and future research directions concerning the role of oxygen vacancies in catalytic ozonation. This review addresses the gap in existing literature concerning the role of oxygen vacancies in catalytic ozone systems, establishes a comprehensive theoretical framework to aid in the design of efficient ozone catalysts, and delves into the functionality of oxygen vacancies in heterogeneous catalytic ozone reactions.
2026, 37(2): 111371
doi: 10.1016/j.cclet.2025.111371
摘要:
Vacuum-ultraviolet (VUV) radiation is high-energy UV radiation with a wavelength of 100–200 nm capable of decomposing/mineralizing hazardous emerging organic pollutants (EPs) in water through direct photolysis and/or by generating reactive free radicals (RFRs) during photolysis. However, due to the unsatisfactory photoelectric conversion rate, strong absorption by oxygen and water molecules, and other characteristics of VUV radiation, its application and development are hindered, leading to misconceptions regarding high energy consumption and insufficient free radical yield. The objectives of our assessment in this review are as follows: The illumination of the photochemical characteristics of VUV and the reactivity of aqueous solutions. Summarization of accurate UV dose and energy evaluation criteria. Comparison and analysis of the photochemical mechanisms and reaction kinetics of different types of EPs via VUV direct photolysis, as well as the interference origins of typical substrates in water for VUV decontamination. We found that quantities typically reported in VUV photochemical reactions of engineered systems are underreported in low-pressure mercury lamp (LPUV) photochemical reactions, especially a quantitative indicator of the species or energy that induces a chemical reaction. The absence of these quantities has made it difficult to assess the fundamental performance of VUV photolysis fully compared with that of UV-C. Some studies have sought to optimize VUV-advanced reduction processes (VUV-ARP) or VUV reactor treatment of these contaminants; however, an abundant evaluation of the reaction origins and processes between VUV-derived main RFRs and reactants (H2O, O2, organic matter, inorganic ions, etc.) is essential, cause these scientific elements will provide the possibility to break the application gap for VUV in the field of EPs treating. Overall, the data compilation, analysis, and research recommendations provided in this review will form the basis for all photochemical reactions initiated by VUV radiation with water as the backing agent.
Vacuum-ultraviolet (VUV) radiation is high-energy UV radiation with a wavelength of 100–200 nm capable of decomposing/mineralizing hazardous emerging organic pollutants (EPs) in water through direct photolysis and/or by generating reactive free radicals (RFRs) during photolysis. However, due to the unsatisfactory photoelectric conversion rate, strong absorption by oxygen and water molecules, and other characteristics of VUV radiation, its application and development are hindered, leading to misconceptions regarding high energy consumption and insufficient free radical yield. The objectives of our assessment in this review are as follows: The illumination of the photochemical characteristics of VUV and the reactivity of aqueous solutions. Summarization of accurate UV dose and energy evaluation criteria. Comparison and analysis of the photochemical mechanisms and reaction kinetics of different types of EPs via VUV direct photolysis, as well as the interference origins of typical substrates in water for VUV decontamination. We found that quantities typically reported in VUV photochemical reactions of engineered systems are underreported in low-pressure mercury lamp (LPUV) photochemical reactions, especially a quantitative indicator of the species or energy that induces a chemical reaction. The absence of these quantities has made it difficult to assess the fundamental performance of VUV photolysis fully compared with that of UV-C. Some studies have sought to optimize VUV-advanced reduction processes (VUV-ARP) or VUV reactor treatment of these contaminants; however, an abundant evaluation of the reaction origins and processes between VUV-derived main RFRs and reactants (H2O, O2, organic matter, inorganic ions, etc.) is essential, cause these scientific elements will provide the possibility to break the application gap for VUV in the field of EPs treating. Overall, the data compilation, analysis, and research recommendations provided in this review will form the basis for all photochemical reactions initiated by VUV radiation with water as the backing agent.
2026, 37(2): 111556
doi: 10.1016/j.cclet.2025.111556
摘要:
The Smiles rearrangement is an exceptionally versatile method in organic synthesis, providing a broad canvas for designing cascade reactions that construct new Csp2-Y (Y = C, O, N, S, CO, etc.) bonds. Among the various types of Smiles rearrangement, the radical-type variant has emerged as a more powerful, mild, efficient, and modern synthetic technique compared to its traditional ionic counterpart. This approach excels in generating new (hetero)aromatic migration products, enabling significant advancements in recent years. This tutorial review focuses on the recent progress, since 2016, in the development and application of radical Smiles rearrangement in organic chemistry. Special attention is paid to novel transformations achieved through photochemical, electrochemical, and transition metal catalysis methods.
The Smiles rearrangement is an exceptionally versatile method in organic synthesis, providing a broad canvas for designing cascade reactions that construct new Csp2-Y (Y = C, O, N, S, CO, etc.) bonds. Among the various types of Smiles rearrangement, the radical-type variant has emerged as a more powerful, mild, efficient, and modern synthetic technique compared to its traditional ionic counterpart. This approach excels in generating new (hetero)aromatic migration products, enabling significant advancements in recent years. This tutorial review focuses on the recent progress, since 2016, in the development and application of radical Smiles rearrangement in organic chemistry. Special attention is paid to novel transformations achieved through photochemical, electrochemical, and transition metal catalysis methods.
2026, 37(2): 111593
doi: 10.1016/j.cclet.2025.111593
摘要:
Polyimide-linkage covalent organic frameworks (PI-COFs), as a subclass of the COFs material family, featuring the unique combination of excellent thermal stability of polyimide, tunable pore sizes, as well as high crystallinity and surface area of COFs, are expected to be a novel type of promising crystalline porous material with potential applications in adsorption and separation, catalysis, chemical sensing, and energy storage. Therefore, it is increasingly important to summarize polyimide-linkage in COFs and related applications and provide in-depth insight to accelerate future development. In this review, we offer a comprehensive overview of recent advancements in PI-COFs, emphasizing their synthesis methods, design principles and applications. Finally, our brief outlooks on the current challenges and future developments of PI-COFs are provided. Overall, this review aims to guide the recent and future development of PI-COFs.
Polyimide-linkage covalent organic frameworks (PI-COFs), as a subclass of the COFs material family, featuring the unique combination of excellent thermal stability of polyimide, tunable pore sizes, as well as high crystallinity and surface area of COFs, are expected to be a novel type of promising crystalline porous material with potential applications in adsorption and separation, catalysis, chemical sensing, and energy storage. Therefore, it is increasingly important to summarize polyimide-linkage in COFs and related applications and provide in-depth insight to accelerate future development. In this review, we offer a comprehensive overview of recent advancements in PI-COFs, emphasizing their synthesis methods, design principles and applications. Finally, our brief outlooks on the current challenges and future developments of PI-COFs are provided. Overall, this review aims to guide the recent and future development of PI-COFs.
2026, 37(2): 111608
doi: 10.1016/j.cclet.2025.111608
摘要:
Adjuvants enhance and prolong the immune response to therapeutic agents, such as drugs and vaccines. However, conventional adjuvants have limitations in terms of immune specificity and duration. Nanoadjuvants can leverage their nanoscale size to increase the capture efficacy of antigens by antigen-presenting cells and improve immunogen presentation for targeted delivery. Furthermore, noninvasive visualization of bifunctional nanoadjuvants with integrated efficacy and imaging postdelivery can provide insights into in vivo distribution and performance, aiding in the optimization and design of new dosage forms. This review systematically summarizes the structure, assembly, and function of nanoadjuvants alongside contrast agents. It delves into the impact of complex structures formed by nanoadjuvant-contrast agent interactions on antigen presentation, migration, imaging tracking, and visualization of immune cell recruitment. It also discusses how imaging can determine optimal immune intervals, vaccine safety, and toxicity while enabling diagnostic and therapeutic integration. Moreover, this paper discusses potential applications of novel adjuvants and promising imaging technologies that could have implications for future vaccine and drug development endeavors.
Adjuvants enhance and prolong the immune response to therapeutic agents, such as drugs and vaccines. However, conventional adjuvants have limitations in terms of immune specificity and duration. Nanoadjuvants can leverage their nanoscale size to increase the capture efficacy of antigens by antigen-presenting cells and improve immunogen presentation for targeted delivery. Furthermore, noninvasive visualization of bifunctional nanoadjuvants with integrated efficacy and imaging postdelivery can provide insights into in vivo distribution and performance, aiding in the optimization and design of new dosage forms. This review systematically summarizes the structure, assembly, and function of nanoadjuvants alongside contrast agents. It delves into the impact of complex structures formed by nanoadjuvant-contrast agent interactions on antigen presentation, migration, imaging tracking, and visualization of immune cell recruitment. It also discusses how imaging can determine optimal immune intervals, vaccine safety, and toxicity while enabling diagnostic and therapeutic integration. Moreover, this paper discusses potential applications of novel adjuvants and promising imaging technologies that could have implications for future vaccine and drug development endeavors.
2026, 37(2): 111629
doi: 10.1016/j.cclet.2025.111629
摘要:
Carbon-rich cycloarene macrocycles can adopt multiple atropisomeric forms due to steric hindrance restricting σ-bond rotation. These distinct conformations exhibit variations in cavity structure, electronic properties, and functional site distribution, leading to diverse molecular recognition and self-assembly behaviors. In recent years, research on carbon-rich cycloarene macrocyclic compounds has emerged as a cutting-edge and interdisciplinary focus in the fields of carbon-rich functional molecules and macrocyclic chemistry. This review provides a comprehensive overview of the development of atropisomers in carbon-rich cycloarene macrocycles, spanning their design and synthesis, optoelectronic properties, and supramolecular chemistry.
Carbon-rich cycloarene macrocycles can adopt multiple atropisomeric forms due to steric hindrance restricting σ-bond rotation. These distinct conformations exhibit variations in cavity structure, electronic properties, and functional site distribution, leading to diverse molecular recognition and self-assembly behaviors. In recent years, research on carbon-rich cycloarene macrocyclic compounds has emerged as a cutting-edge and interdisciplinary focus in the fields of carbon-rich functional molecules and macrocyclic chemistry. This review provides a comprehensive overview of the development of atropisomers in carbon-rich cycloarene macrocycles, spanning their design and synthesis, optoelectronic properties, and supramolecular chemistry.
2026, 37(2): 111678
doi: 10.1016/j.cclet.2025.111678
摘要:
Peptides play important roles in chemistry, medicinal chemistry and life science, due to their high efficiency and specificity, unusual biological and therapeutic properties. As naturally occurring peptides often face with their intrinsic limitations including metabolic instability and low membrane permeability, the strategies for synthesizing unnatural amino acids and peptides are explored. Among the methods for modifying amino acids and peptides, chemo- and site-selective approaches are preferred because of the ability to fine-tuning structural features. Recently, transition metal-catalyzed C-H activation has been employed for the functionalization of amino acids and peptides. Through domino C-H activation/annulation, a series of structurally complex and diverse amino acids and peptides is constructed. This review highlights recent advances in the synthesis of unnatural amino acids and peptides via transition metal-catalyzed C-H activation/annulation.
Peptides play important roles in chemistry, medicinal chemistry and life science, due to their high efficiency and specificity, unusual biological and therapeutic properties. As naturally occurring peptides often face with their intrinsic limitations including metabolic instability and low membrane permeability, the strategies for synthesizing unnatural amino acids and peptides are explored. Among the methods for modifying amino acids and peptides, chemo- and site-selective approaches are preferred because of the ability to fine-tuning structural features. Recently, transition metal-catalyzed C-H activation has been employed for the functionalization of amino acids and peptides. Through domino C-H activation/annulation, a series of structurally complex and diverse amino acids and peptides is constructed. This review highlights recent advances in the synthesis of unnatural amino acids and peptides via transition metal-catalyzed C-H activation/annulation.
2026, 37(2): 111728
doi: 10.1016/j.cclet.2025.111728
摘要:
The application of DNA hybridization technology, grounded in Watson-Crick base pairing, has facilitated the rational design of framework nucleic acids (FNAs) featuring adaptable shapes and dimensions. These nanostructures exhibit remarkable stability and reproducibility, making them promising candidates for biomedical applications. Among various FNAs, tetrahedral FNAs (tFNAs), first introduced by Turberfield, are nanoscale assemblies of oligonucleotides that possess unique physical, chemical, and biological properties. Previous studies have demonstrated that tFNAs exhibit excellent cellular uptake, enhanced tissue permeability, and strong capabilities to promote cell migration, proliferation, and differentiation. Moreover, the intrinsic ability of tFNAs to efficiently penetrate cell membranes allows tFNAs to serve as versatile carriers for small-molecule drugs or functional oligonucleotides, thereby exerting significant anti-inflammatory, antioxidant, antibacterial, and immunomodulatory effects. These features highlight the therapeutic potential of tFNA-based complexes in skin, mucosal, and barrier tissue repair and regeneration. This review provides a comprehensive analysis of recent advances in the application of tFNAs for the prevention and treatment of skin, mucosal, and barrier tissue diseases, with a focus on their mechanisms of action and future prospects in regenerative medicine and targeted therapies.
The application of DNA hybridization technology, grounded in Watson-Crick base pairing, has facilitated the rational design of framework nucleic acids (FNAs) featuring adaptable shapes and dimensions. These nanostructures exhibit remarkable stability and reproducibility, making them promising candidates for biomedical applications. Among various FNAs, tetrahedral FNAs (tFNAs), first introduced by Turberfield, are nanoscale assemblies of oligonucleotides that possess unique physical, chemical, and biological properties. Previous studies have demonstrated that tFNAs exhibit excellent cellular uptake, enhanced tissue permeability, and strong capabilities to promote cell migration, proliferation, and differentiation. Moreover, the intrinsic ability of tFNAs to efficiently penetrate cell membranes allows tFNAs to serve as versatile carriers for small-molecule drugs or functional oligonucleotides, thereby exerting significant anti-inflammatory, antioxidant, antibacterial, and immunomodulatory effects. These features highlight the therapeutic potential of tFNA-based complexes in skin, mucosal, and barrier tissue repair and regeneration. This review provides a comprehensive analysis of recent advances in the application of tFNAs for the prevention and treatment of skin, mucosal, and barrier tissue diseases, with a focus on their mechanisms of action and future prospects in regenerative medicine and targeted therapies.
2026, 37(2): 111834
doi: 10.1016/j.cclet.2025.111834
摘要:
Carbenes as one of the most important class of intermediates have been widely utilized in various organic synthetic transformations. Carbene insertion-initiated ring-opening reactions of cyclic ethers offer a valuable strategy for constructing new carbon-oxygen bonds. In comparison with traditional thermal or metal-mediated carbene transfer reactions, visible-light-promoted multi-component reaction strategy provides a mild and eco-friendly approach to access densely functionalized molecules. Recently, visible-light-induced multi-component carbene transfer reactions of diazo compounds have been rapidly developed and attracted a great deal of research interest of chemists owing to their advantages of simple operation, mild condition, high atom economy and rich structural diversity. This paper summarizes the recent research progress on the visible-light-promoted multi-component carbene transfer reactions of diazo compounds via ring-opening of cyclic ethers with various nucleophiles. The reaction patterns of different nucleophiles and their corresponding mechanism are described in this review. The future research direction and challenges in this area are also discussed.
Carbenes as one of the most important class of intermediates have been widely utilized in various organic synthetic transformations. Carbene insertion-initiated ring-opening reactions of cyclic ethers offer a valuable strategy for constructing new carbon-oxygen bonds. In comparison with traditional thermal or metal-mediated carbene transfer reactions, visible-light-promoted multi-component reaction strategy provides a mild and eco-friendly approach to access densely functionalized molecules. Recently, visible-light-induced multi-component carbene transfer reactions of diazo compounds have been rapidly developed and attracted a great deal of research interest of chemists owing to their advantages of simple operation, mild condition, high atom economy and rich structural diversity. This paper summarizes the recent research progress on the visible-light-promoted multi-component carbene transfer reactions of diazo compounds via ring-opening of cyclic ethers with various nucleophiles. The reaction patterns of different nucleophiles and their corresponding mechanism are described in this review. The future research direction and challenges in this area are also discussed.
2026, 37(2): 111859
doi: 10.1016/j.cclet.2025.111859
摘要:
Catalytic CO2-to-methanol conversion presents a synergistic approach for concurrent greenhouse gas abatement and sustainable energy carrier synthesis. Single-atom catalysts (SACs) with maximized atomic utilization, tailored electronic configurations and unique metal-support interactions, exhibit superior performance in CO2 activation and methanol synthesis. This review systematically compares reaction mechanisms and pathways across thermal, photocatalytic and electrocatalytic systems, emphasizing structure-activity relationships governed by active sites, coordination microenvironments and support functionalities. Through case studies of representative SACs, we elucidate how metal-support synergies dictate intermediate binding energetics and methanol selectivity. A critical analysis of reaction parameters (e.g., temperature, pressure) reveals condition-dependent catalytic behaviors in thermal system, with fewer studies in photo/electrocatalytic systems identified as key knowledge gaps. While thermal catalysis achieves industrially viable methanol yields, the scalability is constrained by energy-intensive operation and catalyst sintering. Conversely, photo/electrocatalytic routes offer renewable energy integration but suffer from inefficient charge dynamics and mass transport limitations. To address the challenges, we propose strategic research priorities on precise design of active sites, synergy of multiple technological pathways, development of intelligent catalytic systems and diverse CO2 feedstock compatibility. These insights establish a framework for developing next-generation SACs, offering both theoretical foundations and technological blueprints for developing carbon-negative catalytic technologies.
Catalytic CO2-to-methanol conversion presents a synergistic approach for concurrent greenhouse gas abatement and sustainable energy carrier synthesis. Single-atom catalysts (SACs) with maximized atomic utilization, tailored electronic configurations and unique metal-support interactions, exhibit superior performance in CO2 activation and methanol synthesis. This review systematically compares reaction mechanisms and pathways across thermal, photocatalytic and electrocatalytic systems, emphasizing structure-activity relationships governed by active sites, coordination microenvironments and support functionalities. Through case studies of representative SACs, we elucidate how metal-support synergies dictate intermediate binding energetics and methanol selectivity. A critical analysis of reaction parameters (e.g., temperature, pressure) reveals condition-dependent catalytic behaviors in thermal system, with fewer studies in photo/electrocatalytic systems identified as key knowledge gaps. While thermal catalysis achieves industrially viable methanol yields, the scalability is constrained by energy-intensive operation and catalyst sintering. Conversely, photo/electrocatalytic routes offer renewable energy integration but suffer from inefficient charge dynamics and mass transport limitations. To address the challenges, we propose strategic research priorities on precise design of active sites, synergy of multiple technological pathways, development of intelligent catalytic systems and diverse CO2 feedstock compatibility. These insights establish a framework for developing next-generation SACs, offering both theoretical foundations and technological blueprints for developing carbon-negative catalytic technologies.
2026, 37(2): 111957
doi: 10.1016/j.cclet.2025.111957
摘要:
Carbon dots (CDs), a class of emerging fluorescent nanomaterials, have garnered notable attention in the biomedical field owing to their outstanding photoluminescence properties, excellent biocompatibility, and ease of synthesis and functionalization. Recently, numerous CDs have been developed that allow precise subcellular localization through surface modifications or covalent conjugation with targeting ligands such as peptides, small molecules, Golgi-specific agents, and cell membrane-specific agents. This review begins with an overview of the synthesis strategies of CDs, highlighting their exceptional optical properties, stability, biocompatibility, and significance for subcellular imaging. The mechanisms by which CDs target specific organelles, including the nucleus, mitochondrion, lysosomes, Golgi apparatus, and cell membrane, are discussed. These mechanisms include specific targeting molecules, pH-sensitive targeting, charge-driven interactions, and hydrophobic and hydrophilic dynamics. Furthermore, we summarize their applications in subcellular imaging, such as the long-term dynamic monitoring of organelles, sensing, reactive oxygen species scavenging, and therapy. By presenting a comprehensive review of CDs in subcellular imaging, we aim to pave the way for further development of CDs in bioimaging and related biomedical applications.
Carbon dots (CDs), a class of emerging fluorescent nanomaterials, have garnered notable attention in the biomedical field owing to their outstanding photoluminescence properties, excellent biocompatibility, and ease of synthesis and functionalization. Recently, numerous CDs have been developed that allow precise subcellular localization through surface modifications or covalent conjugation with targeting ligands such as peptides, small molecules, Golgi-specific agents, and cell membrane-specific agents. This review begins with an overview of the synthesis strategies of CDs, highlighting their exceptional optical properties, stability, biocompatibility, and significance for subcellular imaging. The mechanisms by which CDs target specific organelles, including the nucleus, mitochondrion, lysosomes, Golgi apparatus, and cell membrane, are discussed. These mechanisms include specific targeting molecules, pH-sensitive targeting, charge-driven interactions, and hydrophobic and hydrophilic dynamics. Furthermore, we summarize their applications in subcellular imaging, such as the long-term dynamic monitoring of organelles, sensing, reactive oxygen species scavenging, and therapy. By presenting a comprehensive review of CDs in subcellular imaging, we aim to pave the way for further development of CDs in bioimaging and related biomedical applications.
2026, 37(2): 111990
doi: 10.1016/j.cclet.2025.111990
摘要:
In 2024, the MOE Key Laboratory of Macromolecular Synthesis and Functionalization at Zhejiang University continued its impactful researches across five core areas. In controllable catalytic polymerization, organoboron catalysts were developed for CO2 copolymerization and novel photoresist materials. Studies in microstructure and rheology elucidated universal deformation modes in graphene-based 2D membranes and improved graphene fiber properties through shear alignment engineering, defect control, and enhanced interlayer entanglement. For separating functional polymers, Janus membranes and channels were created for multiphase separation, liquid-phase molecular layer-by-layer deposition technique was developed to fabricate aromatic polyamide nanofilms, and the harmonic amide bond density was established as a valuable parameter for polyamide structural analysis. In biomedical functional polymers, a sustainable carboxyl-ester transesterification strategy was proposed for upcycling poly(ethylene terephthalate) (PET) waste into biodegradable plastics. Additionally, immunocompatible biomaterials were designed utilizing zwitterionic polypeptides and albumin-derived coatings, and Cu2+-phenolic nanoflower was designed to combat fungal infections by combining cuproptosis and cell wall digestion. Further, the researchers developed a gelatin-DOPA-knob/fibrinogen hydrogel to achieve rapid and robust hemostatic sealing, utilized a double-network polyelectrolyte-coated hydrogel for enhancing endothelialization of left atrial appendage (LAA) occluders, and the researchers also demonstrated that image-guided high-intensity focused ultrasound enables manipulation of shape-memory polymers. Finally, in the realm of photo-electro-magnetic functional polymers, precise control of through-space conjugation was shown to enhance organic luminescence. Topologically structured hydrogels were revealed to exhibit autonomous actuation. Also, solar-driven photothermal ion pumps were developed for selective lithium extraction from seawater, and high-performance non-solvated C60 single-crystal films were prepared via facile bar coating. Lastly, the researchers demonstrated outstanding dielectric properties of polyethylene (PE) lamellar single crystals. The relevant works are reviewed in this paper.
In 2024, the MOE Key Laboratory of Macromolecular Synthesis and Functionalization at Zhejiang University continued its impactful researches across five core areas. In controllable catalytic polymerization, organoboron catalysts were developed for CO2 copolymerization and novel photoresist materials. Studies in microstructure and rheology elucidated universal deformation modes in graphene-based 2D membranes and improved graphene fiber properties through shear alignment engineering, defect control, and enhanced interlayer entanglement. For separating functional polymers, Janus membranes and channels were created for multiphase separation, liquid-phase molecular layer-by-layer deposition technique was developed to fabricate aromatic polyamide nanofilms, and the harmonic amide bond density was established as a valuable parameter for polyamide structural analysis. In biomedical functional polymers, a sustainable carboxyl-ester transesterification strategy was proposed for upcycling poly(ethylene terephthalate) (PET) waste into biodegradable plastics. Additionally, immunocompatible biomaterials were designed utilizing zwitterionic polypeptides and albumin-derived coatings, and Cu2+-phenolic nanoflower was designed to combat fungal infections by combining cuproptosis and cell wall digestion. Further, the researchers developed a gelatin-DOPA-knob/fibrinogen hydrogel to achieve rapid and robust hemostatic sealing, utilized a double-network polyelectrolyte-coated hydrogel for enhancing endothelialization of left atrial appendage (LAA) occluders, and the researchers also demonstrated that image-guided high-intensity focused ultrasound enables manipulation of shape-memory polymers. Finally, in the realm of photo-electro-magnetic functional polymers, precise control of through-space conjugation was shown to enhance organic luminescence. Topologically structured hydrogels were revealed to exhibit autonomous actuation. Also, solar-driven photothermal ion pumps were developed for selective lithium extraction from seawater, and high-performance non-solvated C60 single-crystal films were prepared via facile bar coating. Lastly, the researchers demonstrated outstanding dielectric properties of polyethylene (PE) lamellar single crystals. The relevant works are reviewed in this paper.
2026, 37(2): 112054
doi: 10.1016/j.cclet.2025.112054
摘要:
In recent years, AgBiS2 nanocrystals (NCs) have emerged as a research hotspot in the field of solar cells due to their excellent optoelectronic properties and environmentally friendly characteristics. Although the theoretical power conversion efficiency (PCE) of AgBiS2 NC solar cells can reach up to 26%, the current best device only achieved a PCE of 10.84%. Such an enormous efficiency gap is primarily caused by the complex surface defects, severe carrier recombination, and undesirable energy-level mismatches. Therefore, this review comprehensively summarizes recent advancements in AgBiS2 NCs, including their crystal structures, optoelectronic properties, synthesis methods, ligand engineering, and device optimization. By fine-tuning synthesis conditions (e.g., temperature, precursor ratios) and employing ligand exchange strategies (solid-state/liquid-state), significant improvements in material performance have been realized. Furthermore, device structure optimization (e.g., transport layer selection, interface modification) and energy-level alignment engineering have further enhanced efficiency. Despite decent stabilities of AgBiS2 NCs, several challenges such as large-area uniformity and long-term device durability remain unraveled, which may be the major obstacles for their further commercialization. Future advancements in defect control, the development of novel ligands, and encapsulation technologies are expected to expand the applications of AgBiS2 NCs in flexible electronics, aerospace, and wearable devices.
In recent years, AgBiS2 nanocrystals (NCs) have emerged as a research hotspot in the field of solar cells due to their excellent optoelectronic properties and environmentally friendly characteristics. Although the theoretical power conversion efficiency (PCE) of AgBiS2 NC solar cells can reach up to 26%, the current best device only achieved a PCE of 10.84%. Such an enormous efficiency gap is primarily caused by the complex surface defects, severe carrier recombination, and undesirable energy-level mismatches. Therefore, this review comprehensively summarizes recent advancements in AgBiS2 NCs, including their crystal structures, optoelectronic properties, synthesis methods, ligand engineering, and device optimization. By fine-tuning synthesis conditions (e.g., temperature, precursor ratios) and employing ligand exchange strategies (solid-state/liquid-state), significant improvements in material performance have been realized. Furthermore, device structure optimization (e.g., transport layer selection, interface modification) and energy-level alignment engineering have further enhanced efficiency. Despite decent stabilities of AgBiS2 NCs, several challenges such as large-area uniformity and long-term device durability remain unraveled, which may be the major obstacles for their further commercialization. Future advancements in defect control, the development of novel ligands, and encapsulation technologies are expected to expand the applications of AgBiS2 NCs in flexible electronics, aerospace, and wearable devices.
2026, 37(2): 112116
doi: 10.1016/j.cclet.2025.112116
摘要:
Sustainable development for our life is important task, which is driven by key materials and technologies. In this roadmap, we discuss three main aspects in addressing environmental questions, green chemical processes and energy challenges. They are included, such as gas treatment and separation, wastewater treatment, waste gas treatment, solid waste treatment, lithium extraction, hydrogen production, water splitting, CO2 reduction, photocatalytic clean technologies, plastic degradation, fuel cells, lithium batteries, sodium batteries, aqueous batteries, solid state batteries, metal air batteries and supercapacitors. Their status, challenges, progress and future perspectives are also discussed. We hope that this paper can give clear views on sustainable development in materials and technologies.
Sustainable development for our life is important task, which is driven by key materials and technologies. In this roadmap, we discuss three main aspects in addressing environmental questions, green chemical processes and energy challenges. They are included, such as gas treatment and separation, wastewater treatment, waste gas treatment, solid waste treatment, lithium extraction, hydrogen production, water splitting, CO2 reduction, photocatalytic clean technologies, plastic degradation, fuel cells, lithium batteries, sodium batteries, aqueous batteries, solid state batteries, metal air batteries and supercapacitors. Their status, challenges, progress and future perspectives are also discussed. We hope that this paper can give clear views on sustainable development in materials and technologies.
2026, 37(2): 111925
doi: 10.1016/j.cclet.2025.111925
摘要:
2026, 37(2): 112045
doi: 10.1016/j.cclet.2025.112045
摘要:
2026, 37(1): 110064
doi: 10.1016/j.cclet.2024.110064
摘要:
This research explores the influence of crystallinity on gas chromatographic (GC) separation using covalent organic frameworks (COFs) as stationary phases. Three COF materials (CTF-DCBs) with varying crystallinity were synthesized and characterized. CTF-DCB-1, with superior crystallinity, demonstrated high-selectivity GC separation of benzene isomers as well as styrene/phenylacetylene mixtures, while CTF-DCB-2 and CTF-DCB-3 exhibited lower crystallinity and worse separation performance. Thermodynamic and kinetic tests showed that CTF-DCB-1 had the worst thermodynamic adsorption but low diffusion mass transfer resistance, which resulted in the best separation. Therefore, optimizing the crystallinity of COFs is necessary for balancing the kinetic diffusion and thermodynamic interactions towards the analytes, achieving high-performance GC stationary phases.
This research explores the influence of crystallinity on gas chromatographic (GC) separation using covalent organic frameworks (COFs) as stationary phases. Three COF materials (CTF-DCBs) with varying crystallinity were synthesized and characterized. CTF-DCB-1, with superior crystallinity, demonstrated high-selectivity GC separation of benzene isomers as well as styrene/phenylacetylene mixtures, while CTF-DCB-2 and CTF-DCB-3 exhibited lower crystallinity and worse separation performance. Thermodynamic and kinetic tests showed that CTF-DCB-1 had the worst thermodynamic adsorption but low diffusion mass transfer resistance, which resulted in the best separation. Therefore, optimizing the crystallinity of COFs is necessary for balancing the kinetic diffusion and thermodynamic interactions towards the analytes, achieving high-performance GC stationary phases.
2026, 37(1): 110071
doi: 10.1016/j.cclet.2024.110071
摘要:
Regulation of apoptosis represents a key parameter in all living organisms. In this paper, an input-induced logic-gated modular nanocalculator is designed to regulate cancer cell apoptosis by programmatically combining and connecting logic gate modules with different functions. Via rational design of the various logic gate modules of the nanocalculator, different apoptosis related operations including cancer cell targeting, apoptosis induction, and apoptosis monitoring could be performed. Importantly, each of these logic gate modules could independently perform apoptosis related YES logic operations when ran separately. After combining each YES logic gate module into a logic circuit and connecting it to the GO scaffold to construct a logic-gated nanocalculator, the input-induced logic-gated modular nanocalculator could selectively enter cancer cells and control the drug release to logically apoptosis (output), by performing AND logic gate operations when inputs (nucleolin and H+) were included at the same time. Moreover, evidence suggests that these efficient logical calculations proceed in cancer cell apoptosis regulation without the general limiations of lithography in nanotechnology. As such, this work provides a new vision for the construction of a logic-gated modular nanocalculator with logical calculation proficiency potentially useful in cancer therapy and the regulation of life.
Regulation of apoptosis represents a key parameter in all living organisms. In this paper, an input-induced logic-gated modular nanocalculator is designed to regulate cancer cell apoptosis by programmatically combining and connecting logic gate modules with different functions. Via rational design of the various logic gate modules of the nanocalculator, different apoptosis related operations including cancer cell targeting, apoptosis induction, and apoptosis monitoring could be performed. Importantly, each of these logic gate modules could independently perform apoptosis related YES logic operations when ran separately. After combining each YES logic gate module into a logic circuit and connecting it to the GO scaffold to construct a logic-gated nanocalculator, the input-induced logic-gated modular nanocalculator could selectively enter cancer cells and control the drug release to logically apoptosis (output), by performing AND logic gate operations when inputs (nucleolin and H+) were included at the same time. Moreover, evidence suggests that these efficient logical calculations proceed in cancer cell apoptosis regulation without the general limiations of lithography in nanotechnology. As such, this work provides a new vision for the construction of a logic-gated modular nanocalculator with logical calculation proficiency potentially useful in cancer therapy and the regulation of life.
2026, 37(1): 110414
doi: 10.1016/j.cclet.2024.110414
摘要:
Magnesium hydride (MgH2) demonstrates immense potential as a solid-state hydrogen storage material, while its commercial utilization is impeded by the elevated operating temperature and sluggish reaction kinetics. Herein, a MOF derived multi-phase FeNi3-S catalyst was specially designed for efficient hydrogen storage in MgH2. Experiments confirmed that the incorporation of FeNi3-S into MgH2 significantly lowered the desorption temperature and accelerated the kinetics of hydrogen desorption and reabsorption. The initial dehydrogenation temperature of the MgH2 + 10 wt% FeNi3-S composite was 202 °C, which was 123 °C lower than that of pure MgH2. At 325 °C, the MgH2 + 10 wt% FeNi3-S composite released 6.57 wt% H2 (fully dehydrogenated) within 1000 s. Remarkably, MgH2 + 10 wt% FeNi3-S composite initiated rehydrogenation at room temperature and rapidly absorbed 2.49 wt% H2 within 30 min at 100 °C. Moreover, 6.3 wt% H2 was still retained after 20 cycles at 300 °C, demonstrating the superior cycling performance of the MgH2 + 10 wt% FeNi3-S composite. The activation energy fitting calculations further evidenced the addition of FeNi3-S enhanced the de/resorption kinetics of MgH2 (Ea = 98.6 kJ/mol and 43.3 kJ/mol, respectively). Through phase and microstructural analysis, it was determined that the exceptional hydrogen storage performance of the composite was attributed to the in-situ formation of Mg/Mg2Ni + Fe/MgS and MgH2/Mg2NiH4 + Fe/MgS hydrogen storage systems. Further mechanistic analysis revealed that Mg2Ni/Mg2NiH4 served as “hydrogen pump” and Fe/MgS served as “hydrogen diffusion channel”, thus accelerating the dissociation and recombination of hydrogen molecules. In conclusion, this work offers insight into catalysts combining transition metal alloys and transition metal sulfide for exerting muti-phase synergistic effect on boosting the dehydrogenation/hydrogenation reactions of MgH2, which can also inspire future pioneering work on designing and fabricating high efficient catalysts in other energy storage related areas.
Magnesium hydride (MgH2) demonstrates immense potential as a solid-state hydrogen storage material, while its commercial utilization is impeded by the elevated operating temperature and sluggish reaction kinetics. Herein, a MOF derived multi-phase FeNi3-S catalyst was specially designed for efficient hydrogen storage in MgH2. Experiments confirmed that the incorporation of FeNi3-S into MgH2 significantly lowered the desorption temperature and accelerated the kinetics of hydrogen desorption and reabsorption. The initial dehydrogenation temperature of the MgH2 + 10 wt% FeNi3-S composite was 202 °C, which was 123 °C lower than that of pure MgH2. At 325 °C, the MgH2 + 10 wt% FeNi3-S composite released 6.57 wt% H2 (fully dehydrogenated) within 1000 s. Remarkably, MgH2 + 10 wt% FeNi3-S composite initiated rehydrogenation at room temperature and rapidly absorbed 2.49 wt% H2 within 30 min at 100 °C. Moreover, 6.3 wt% H2 was still retained after 20 cycles at 300 °C, demonstrating the superior cycling performance of the MgH2 + 10 wt% FeNi3-S composite. The activation energy fitting calculations further evidenced the addition of FeNi3-S enhanced the de/resorption kinetics of MgH2 (Ea = 98.6 kJ/mol and 43.3 kJ/mol, respectively). Through phase and microstructural analysis, it was determined that the exceptional hydrogen storage performance of the composite was attributed to the in-situ formation of Mg/Mg2Ni + Fe/MgS and MgH2/Mg2NiH4 + Fe/MgS hydrogen storage systems. Further mechanistic analysis revealed that Mg2Ni/Mg2NiH4 served as “hydrogen pump” and Fe/MgS served as “hydrogen diffusion channel”, thus accelerating the dissociation and recombination of hydrogen molecules. In conclusion, this work offers insight into catalysts combining transition metal alloys and transition metal sulfide for exerting muti-phase synergistic effect on boosting the dehydrogenation/hydrogenation reactions of MgH2, which can also inspire future pioneering work on designing and fabricating high efficient catalysts in other energy storage related areas.
2026, 37(1): 110572
doi: 10.1016/j.cclet.2024.110572
摘要:
The rate-limited activation of NN triple bonds with high bond energies has been a bottleneck in photoctalytic nitrogen fixation. Here, polymeric carbon nitride with frustrated Lewis pairs (FLPs) was constructed by inserting electron-deficient magnesium into g-C3N4 (CN). The synergistic interactions between Mg and amino groups in CN led to a 7.2 fold increase in the photoreactivity of nitrogen (N2) fixation by carbon nitride.
The rate-limited activation of NN triple bonds with high bond energies has been a bottleneck in photoctalytic nitrogen fixation. Here, polymeric carbon nitride with frustrated Lewis pairs (FLPs) was constructed by inserting electron-deficient magnesium into g-C3N4 (CN). The synergistic interactions between Mg and amino groups in CN led to a 7.2 fold increase in the photoreactivity of nitrogen (N2) fixation by carbon nitride.
2026, 37(1): 110576
doi: 10.1016/j.cclet.2024.110576
摘要:
Photocatalytic fuel cells provide promising opportunities for sustainable wastewater treatment and energy conversion. However, their applications are challenged by the sluggish oxygen reducton reaction (ORR) kinetics at cathodes owning to the low O2 solubility and diffusion rate. Herein, we proposed a photo-biocatalytic fuel cell (PBFC) with a novel hybrid biocathode based on artificially engineered algal cells coated by ZIF-8 confined carbon dots/bilirubin oxidase (ZIF-8/CDs/BOD@algae). Microalgae absorbed CO2 and provided O2 in situ for BOD catalysts. Due to effective absorption of O2 by imidazole and confinement of hydrophobic porous ZIF-8, oxygen diffusion has been accelerated in MOF/enzyme systems. Importantly, the introduction of CDs alleviated the poor conductivity of ZIF-8 and improved the electron transfer rate of BOD. Thus, the biocathode exhibited a high current density of 1767 µA/cm2, a 2.26-fold increase compared with that of CDs/BOD/algae biocathode. Also, it displayed enduring operational stability for up to 60 h since the firmly wrapped ZIF-8 shells could encapsulate proteins and protect algae from the external stimulation. When coupled with Mo: BiVO4 photoanodes, the PBFC exhibited a remarkable power output of 131.8 µW/cm2 using tetracycline hydrochloride (TCH) as a fuel and an increased degradation rate of TCH. Therefore, this work not only establishs an effective confinement strategy for enzyme to enrich oxygen, but also unveils new possibilities for modified microalgal cells aiding photoelectrocatalytic systems to recover energy from wastewater treatment.
Photocatalytic fuel cells provide promising opportunities for sustainable wastewater treatment and energy conversion. However, their applications are challenged by the sluggish oxygen reducton reaction (ORR) kinetics at cathodes owning to the low O2 solubility and diffusion rate. Herein, we proposed a photo-biocatalytic fuel cell (PBFC) with a novel hybrid biocathode based on artificially engineered algal cells coated by ZIF-8 confined carbon dots/bilirubin oxidase (ZIF-8/CDs/BOD@algae). Microalgae absorbed CO2 and provided O2 in situ for BOD catalysts. Due to effective absorption of O2 by imidazole and confinement of hydrophobic porous ZIF-8, oxygen diffusion has been accelerated in MOF/enzyme systems. Importantly, the introduction of CDs alleviated the poor conductivity of ZIF-8 and improved the electron transfer rate of BOD. Thus, the biocathode exhibited a high current density of 1767 µA/cm2, a 2.26-fold increase compared with that of CDs/BOD/algae biocathode. Also, it displayed enduring operational stability for up to 60 h since the firmly wrapped ZIF-8 shells could encapsulate proteins and protect algae from the external stimulation. When coupled with Mo: BiVO4 photoanodes, the PBFC exhibited a remarkable power output of 131.8 µW/cm2 using tetracycline hydrochloride (TCH) as a fuel and an increased degradation rate of TCH. Therefore, this work not only establishs an effective confinement strategy for enzyme to enrich oxygen, but also unveils new possibilities for modified microalgal cells aiding photoelectrocatalytic systems to recover energy from wastewater treatment.
2026, 37(1): 110752
doi: 10.1016/j.cclet.2024.110752
摘要:
Converting CO2 into methanol (CH3OH), a high-value-added liquid-phase product, through efficient and highly selective photocatalysis remains a significant challenge. Herein, we present a straightforward cation exchange strategy for the in-situ growth of BiVO4 on an InVO4 substrate to generate a Z-scheme heterojunction of InVO4/BiVO4. This in-situ partial transformation approach endows the InVO4/BiVO4 heterojunction with a tightly connected interface, resulting in a significant improvement in charge separation efficiency between InVO4 and BiVO4. Moreover, the construction of the heterojunction reduces the formation energy barrier of the *COOH intermediate during the photoreduction of CO2 and increases the desorption energy barrier of the *CO intermediate, facilitating the deep reduction of *CO. Consequently, the InVO4/BiVO4 heterojunction is capable of photocatalytic CO2 reduction to CH3OH with high efficiency and selectivity. Under conditions where water serves as the electron source and a light intensity of 100 mW/cm2, the yield of CH3OH reaches 130.5 µmol g−1 h−1 with a selectivity of 92 %, outperforming photocatalysts reported under similar conditions.
Converting CO2 into methanol (CH3OH), a high-value-added liquid-phase product, through efficient and highly selective photocatalysis remains a significant challenge. Herein, we present a straightforward cation exchange strategy for the in-situ growth of BiVO4 on an InVO4 substrate to generate a Z-scheme heterojunction of InVO4/BiVO4. This in-situ partial transformation approach endows the InVO4/BiVO4 heterojunction with a tightly connected interface, resulting in a significant improvement in charge separation efficiency between InVO4 and BiVO4. Moreover, the construction of the heterojunction reduces the formation energy barrier of the *COOH intermediate during the photoreduction of CO2 and increases the desorption energy barrier of the *CO intermediate, facilitating the deep reduction of *CO. Consequently, the InVO4/BiVO4 heterojunction is capable of photocatalytic CO2 reduction to CH3OH with high efficiency and selectivity. Under conditions where water serves as the electron source and a light intensity of 100 mW/cm2, the yield of CH3OH reaches 130.5 µmol g−1 h−1 with a selectivity of 92 %, outperforming photocatalysts reported under similar conditions.
2026, 37(1): 110903
doi: 10.1016/j.cclet.2025.110903
摘要:
Many labdane-related diterpenoids (LRDs) exhibit high values in drug development. Their diversity in structure and bioactivity, to a large extent, arise from oxidative modifications which are mainly catalyzed by cytochrome P450s (CYPs). The medicinal plant Euphorbia fischeriana Steud. is rich in LRDs with distinct scaffolds. Herein, we characterized three cytochrome P450s involved in LRD biosynthesis from this plant. Notably, CYP71D450 and CYP701A148 are two substrate-promiscuity CYPs. The former is the first example of CYPs which can oxidize C-3 of ent–atisane skeleton and ent–isopimara-7(8),15-diene, and the latter is the first example of CYPs which can oxidize C-19 of ent–abietane and ent–pimarane skeletons. This study expands the toolkit for bioproduction of diverse LRDs.
Many labdane-related diterpenoids (LRDs) exhibit high values in drug development. Their diversity in structure and bioactivity, to a large extent, arise from oxidative modifications which are mainly catalyzed by cytochrome P450s (CYPs). The medicinal plant Euphorbia fischeriana Steud. is rich in LRDs with distinct scaffolds. Herein, we characterized three cytochrome P450s involved in LRD biosynthesis from this plant. Notably, CYP71D450 and CYP701A148 are two substrate-promiscuity CYPs. The former is the first example of CYPs which can oxidize C-3 of ent–atisane skeleton and ent–isopimara-7(8),15-diene, and the latter is the first example of CYPs which can oxidize C-19 of ent–abietane and ent–pimarane skeletons. This study expands the toolkit for bioproduction of diverse LRDs.
2026, 37(1): 110919
doi: 10.1016/j.cclet.2025.110919
摘要:
Owing to their intricate molecular frameworks and copious chiral centers, the structural identification and configurational assignment of natural products are challenging tasks. Comprehensive spectral data analysis is crucial for the confirmation of absolute configurations. Ignoring critical parameters will lead to false structure, which may confuse the total synthesis and drug development. Herein, the configurations of seven heterogeneous Pallavicinia diterpenoids (PDs) isolated from Pallavicinia liverworts are revised using a combination of single-crystal X-ray diffraction and electronic circular dichroism (ECD) calculations. Meanwhile, identification of five unprecedented PD heterodimers PD-dimers A–E (18–22) along with eleven previously undescribed PDs (5–9, 13–17, 23) obtained by the reinvestigation of the Chinese liverwort Pallavicinia subciliata have resulted in corrections and support the revised conclusions.
Owing to their intricate molecular frameworks and copious chiral centers, the structural identification and configurational assignment of natural products are challenging tasks. Comprehensive spectral data analysis is crucial for the confirmation of absolute configurations. Ignoring critical parameters will lead to false structure, which may confuse the total synthesis and drug development. Herein, the configurations of seven heterogeneous Pallavicinia diterpenoids (PDs) isolated from Pallavicinia liverworts are revised using a combination of single-crystal X-ray diffraction and electronic circular dichroism (ECD) calculations. Meanwhile, identification of five unprecedented PD heterodimers PD-dimers A–E (18–22) along with eleven previously undescribed PDs (5–9, 13–17, 23) obtained by the reinvestigation of the Chinese liverwort Pallavicinia subciliata have resulted in corrections and support the revised conclusions.
2026, 37(1): 110956
doi: 10.1016/j.cclet.2025.110956
摘要:
Overproduction of reactive oxygen species (ROS) following ischemic injury triggers an inflammatory response, significantly impeding neurological functional recovery. Nanozymes with potent antioxidative and anti-inflammatory effects thus offer great potential for ischemic stroke treatment. In this study, we developed an ischemia-homing nanozyme by combining melatonin (MT)-loaded honeycomb manganese dioxide (MnO2) nanoflowers with M2-type microglia membranes to rescue the ischemic penumbra. The surface-engineered M2-type microglia membranes provided intrinsic ischemia-homing and blood-brain barrier (BBB)-crossing properties to the biomimetic nanozymes. This nanozyme can not only transforms harmfulsuperoxide anion radicals (•O2–) and hydrogen peroxide (H2O2) into harmless water and oxygen but also scavenges highly toxic hydroxyl radicals (•OH), dramatically lowering intracellular ROS levels. More importantly, the biomimetic nanoparticles reduce cerebral infarct areas and provide significant neuroprotection against ischemic stroke by lowering oxidative stress, inhibiting cell apoptosis, and decreasing inflammation. This study may offer a viable approach for the use of nanozymes in treating ischemic stroke.
Overproduction of reactive oxygen species (ROS) following ischemic injury triggers an inflammatory response, significantly impeding neurological functional recovery. Nanozymes with potent antioxidative and anti-inflammatory effects thus offer great potential for ischemic stroke treatment. In this study, we developed an ischemia-homing nanozyme by combining melatonin (MT)-loaded honeycomb manganese dioxide (MnO2) nanoflowers with M2-type microglia membranes to rescue the ischemic penumbra. The surface-engineered M2-type microglia membranes provided intrinsic ischemia-homing and blood-brain barrier (BBB)-crossing properties to the biomimetic nanozymes. This nanozyme can not only transforms harmfulsuperoxide anion radicals (•O2–) and hydrogen peroxide (H2O2) into harmless water and oxygen but also scavenges highly toxic hydroxyl radicals (•OH), dramatically lowering intracellular ROS levels. More importantly, the biomimetic nanoparticles reduce cerebral infarct areas and provide significant neuroprotection against ischemic stroke by lowering oxidative stress, inhibiting cell apoptosis, and decreasing inflammation. This study may offer a viable approach for the use of nanozymes in treating ischemic stroke.
2026, 37(1): 110959
doi: 10.1016/j.cclet.2025.110959
摘要:
Metal ion homeostasis plays a pivotal role in maintaining cellular functions, and its disruption can initiate regulated cell death pathways. Despite its therapeutic potential, metal ion therapy for breast cancer has been hampered by inefficient ion delivery and the intrinsic resistance mechanisms of cancer cells. In this work, a cuproptosis amplifier of copper-telaglenastat coordinate (denoted as Cu-CB) is developed to trigger cell ferroptosis for synergistic breast cancer treatment. Telaglenastat (CB-839), a glutaminase inhibitor, is identified as an effective copper ionophore that facilitates the formation of Cu-CB. Specially, Cu-CB can promote the aggregation of lipoylated proteins to initiate cuproptosis, while also inhibiting glutathione (GSH) synthesis and downregulating glutathione peroxidase 4 (GPX4) to trigger ferroptosis. The interplay between these cuproptosis and apoptosis pathways, mediated by Cu-CB, significantly amplifies reactive oxygen species (ROS) production and lipid peroxidation, culminating in the synergistic suppression of breast cancer. Both in vitro and in vivo studies validate the superior antitumor effects of Cu-CB through the induction of cuproptosis and ferroptosis, which may provide a new insight for metal ion delivery systems and metal ion-based tumor therapies.
Metal ion homeostasis plays a pivotal role in maintaining cellular functions, and its disruption can initiate regulated cell death pathways. Despite its therapeutic potential, metal ion therapy for breast cancer has been hampered by inefficient ion delivery and the intrinsic resistance mechanisms of cancer cells. In this work, a cuproptosis amplifier of copper-telaglenastat coordinate (denoted as Cu-CB) is developed to trigger cell ferroptosis for synergistic breast cancer treatment. Telaglenastat (CB-839), a glutaminase inhibitor, is identified as an effective copper ionophore that facilitates the formation of Cu-CB. Specially, Cu-CB can promote the aggregation of lipoylated proteins to initiate cuproptosis, while also inhibiting glutathione (GSH) synthesis and downregulating glutathione peroxidase 4 (GPX4) to trigger ferroptosis. The interplay between these cuproptosis and apoptosis pathways, mediated by Cu-CB, significantly amplifies reactive oxygen species (ROS) production and lipid peroxidation, culminating in the synergistic suppression of breast cancer. Both in vitro and in vivo studies validate the superior antitumor effects of Cu-CB through the induction of cuproptosis and ferroptosis, which may provide a new insight for metal ion delivery systems and metal ion-based tumor therapies.
2026, 37(1): 110964
doi: 10.1016/j.cclet.2025.110964
摘要:
Alzheimer’s disease (AD) is a common neurodegenerative disorder among the elderly population. There are currently no effective therapeutic drugs available, the multi-target-directed ligands (MTDLs) strategy has been considered as the promising approach. Given the structural diversity of natural products, Rivastigmine’s pharmacophore was integrated with diverse natural product scaffolds to construct a combinatorial compound library. This library was subsequently screened and optimized to identify a novel butyrylcholinesterase (BuChE) inhibitor, compound 3c. The results showed that compound 3c exhibited favorable BuChE inhibitory activity (half-maximal inhibitory concentration (IC50) = 0.43 µmol/L), potential anti-inflammatory potency, good Aβ1–42 aggregation inhibitory capacity and remarkable neuroprotective effects. The in vivo study exhibited that 3c significantly ameliorated AlCl3-induced zebrafish AD model and scopolamine-induced memory impairment. Collectively, compound 3c was the artificial intelligence (AI)-driven promising multifunctional agent with BuChE inhibition for the treatment of AD.
Alzheimer’s disease (AD) is a common neurodegenerative disorder among the elderly population. There are currently no effective therapeutic drugs available, the multi-target-directed ligands (MTDLs) strategy has been considered as the promising approach. Given the structural diversity of natural products, Rivastigmine’s pharmacophore was integrated with diverse natural product scaffolds to construct a combinatorial compound library. This library was subsequently screened and optimized to identify a novel butyrylcholinesterase (BuChE) inhibitor, compound 3c. The results showed that compound 3c exhibited favorable BuChE inhibitory activity (half-maximal inhibitory concentration (IC50) = 0.43 µmol/L), potential anti-inflammatory potency, good Aβ1–42 aggregation inhibitory capacity and remarkable neuroprotective effects. The in vivo study exhibited that 3c significantly ameliorated AlCl3-induced zebrafish AD model and scopolamine-induced memory impairment. Collectively, compound 3c was the artificial intelligence (AI)-driven promising multifunctional agent with BuChE inhibition for the treatment of AD.
2026, 37(1): 110966
doi: 10.1016/j.cclet.2025.110966
摘要:
The study of target proteins is crucial for understanding molecular interactions and developing analytical platforms, therapeutic agents and functional tools. Herein, we present a novel nanoplatform activated by near-infrared (NIR) light for triple-modal proteins study, which enabling target protein labeling, enrichment and visualization. Azido-naphthalimide-coated upconversion nanoparticles (UCNPs) serve as NIR light-responsive nanoplatforms, showing promising applications in studying interactions between various bioactive molecules and proteins in living systems. Under NIR light irradiation, azido-naphthalimides are activated by ultraviolet (UV) and blue light emitted from UCNPs and the resulting amino-naphthalimides intermediate not only crosslink nearby target proteins but also enable imaging performance. We demonstrate that this nanoplatform is capable of selective protein labeling and imaging in complex protein environments, achieving specific labeling and imaging of both intracellular and extracellular proteins in mammalian cells as well as bacteria. Furthermore, in vivo protein labeling has been achieved using this novel NIR light-activatable nanoplatform. This technique will open new avenues for discoveries and mechanistic interrogation in chemical biology.
The study of target proteins is crucial for understanding molecular interactions and developing analytical platforms, therapeutic agents and functional tools. Herein, we present a novel nanoplatform activated by near-infrared (NIR) light for triple-modal proteins study, which enabling target protein labeling, enrichment and visualization. Azido-naphthalimide-coated upconversion nanoparticles (UCNPs) serve as NIR light-responsive nanoplatforms, showing promising applications in studying interactions between various bioactive molecules and proteins in living systems. Under NIR light irradiation, azido-naphthalimides are activated by ultraviolet (UV) and blue light emitted from UCNPs and the resulting amino-naphthalimides intermediate not only crosslink nearby target proteins but also enable imaging performance. We demonstrate that this nanoplatform is capable of selective protein labeling and imaging in complex protein environments, achieving specific labeling and imaging of both intracellular and extracellular proteins in mammalian cells as well as bacteria. Furthermore, in vivo protein labeling has been achieved using this novel NIR light-activatable nanoplatform. This technique will open new avenues for discoveries and mechanistic interrogation in chemical biology.
2026, 37(1): 110970
doi: 10.1016/j.cclet.2025.110970
摘要:
The field of nanomedicine has been revolutionized by the concept of immunogenic cell death (ICD)-enhanced cancer therapy, which holds immense promise for the efficient treatment of cancer. However, precise delivery of ICD inducer is severely hindered by complex biological barriers. How to design and build intelligent nanoplatform for adaptive and dynamic cancer therapy remains a big challenge. Herein, this article presents the design and preparation of CD44-targeting and ZIF-8 gated gold nanocage (Au@ZH) for programmed delivery of the 1,2-diaminocyclohexane-Pt(Ⅱ) (DACHPt) as ICD inducer. After actively targeting the CD44 on the surface of 4T1 tumor cell, this Pt-Au@ZH can be effectively endocytosed by the 4T1 cell and release the DACHPt in tumor acidic environment, resulting in ICD effect and superior antitumor efficacy both in vitro and in vivo in the presence of mild 808 nm laser irradiation. By integration of internal and external stimuli intelligently, this programmed nanoplatform is poised to become a cornerstone in the pursuit of effective and targeted cancer therapy in the foreseeable future.
The field of nanomedicine has been revolutionized by the concept of immunogenic cell death (ICD)-enhanced cancer therapy, which holds immense promise for the efficient treatment of cancer. However, precise delivery of ICD inducer is severely hindered by complex biological barriers. How to design and build intelligent nanoplatform for adaptive and dynamic cancer therapy remains a big challenge. Herein, this article presents the design and preparation of CD44-targeting and ZIF-8 gated gold nanocage (Au@ZH) for programmed delivery of the 1,2-diaminocyclohexane-Pt(Ⅱ) (DACHPt) as ICD inducer. After actively targeting the CD44 on the surface of 4T1 tumor cell, this Pt-Au@ZH can be effectively endocytosed by the 4T1 cell and release the DACHPt in tumor acidic environment, resulting in ICD effect and superior antitumor efficacy both in vitro and in vivo in the presence of mild 808 nm laser irradiation. By integration of internal and external stimuli intelligently, this programmed nanoplatform is poised to become a cornerstone in the pursuit of effective and targeted cancer therapy in the foreseeable future.
2026, 37(1): 110971
doi: 10.1016/j.cclet.2025.110971
摘要:
Fluorescent probes based on intramolecular charge transfer (ICT) have obvious advantages for accurate quantitative analysis. To obtain high-performance ratiometric probes requires distinct photophysical properties during recognition reaction process, which is closely related to their ICT characteristics. 1,8-Naphthalimide is known as a typical fluorophore with desirable ICT property when functionalized with an electron-donating moiety at the para-position of the naphthalene chromophore. Although the photophysical properties of para-substituted 1,8-naphthalimide have been well studied, its meta-substituted counterpart has not been fully evaluated since the meta-position is conventionally thought to be weakly conjugated. Herein, combined experimental and theoretical studies are performed which consistently indicate that stronger charge transfer (CT) is exhibited by the meta-amino substituted 1,8-naphthalimide (m-NH2) compared to the para-amino substituted one (p-NH2). The ratiometric response of fluorescence with significant changes in wavelength and intensity upon acetylation (m-NAc and p-NAc) can be attributed to the larger ICT and stronger -NH2 vibrations. This observation is further demonstrated by deuterium oxide experiments, viscosity experiments and quantum chemical calculations. The practical application of meta-amino-1,8-naphthalimide ICT-based probes is also confirmed. This research is expected to bring an in-depth understanding of π-conjugated systems with ICT characteristics, and facilitates the design of sensitive ICT fluorescent probes with meta-amino substitution.
Fluorescent probes based on intramolecular charge transfer (ICT) have obvious advantages for accurate quantitative analysis. To obtain high-performance ratiometric probes requires distinct photophysical properties during recognition reaction process, which is closely related to their ICT characteristics. 1,8-Naphthalimide is known as a typical fluorophore with desirable ICT property when functionalized with an electron-donating moiety at the para-position of the naphthalene chromophore. Although the photophysical properties of para-substituted 1,8-naphthalimide have been well studied, its meta-substituted counterpart has not been fully evaluated since the meta-position is conventionally thought to be weakly conjugated. Herein, combined experimental and theoretical studies are performed which consistently indicate that stronger charge transfer (CT) is exhibited by the meta-amino substituted 1,8-naphthalimide (m-NH2) compared to the para-amino substituted one (p-NH2). The ratiometric response of fluorescence with significant changes in wavelength and intensity upon acetylation (m-NAc and p-NAc) can be attributed to the larger ICT and stronger -NH2 vibrations. This observation is further demonstrated by deuterium oxide experiments, viscosity experiments and quantum chemical calculations. The practical application of meta-amino-1,8-naphthalimide ICT-based probes is also confirmed. This research is expected to bring an in-depth understanding of π-conjugated systems with ICT characteristics, and facilitates the design of sensitive ICT fluorescent probes with meta-amino substitution.
2026, 37(1): 110979
doi: 10.1016/j.cclet.2025.110979
摘要:
Sulfur dioxide (SO2) and its derivatives have been recognized as harmful environmental pollutants. However, they are often produced during the processing of traditional Chinese medicines, potentially compromising the quality of these medicinal materials and contributing to various health issues. Due to a lack of effective monitoring and imaging tools, the physiological effects of excessive SO2 residues in traditional Chinese medicine remain unclear. Therefore, developing a rapid and effective tool for detecting SO2 is crucial for understanding its metabolic pathways and effects in vivo. In this study, we developed a near infrared (NIR) and ratiometric fluorescent probe, NIR-RS, which exhibits high sensitivity, selectivity, and rapid response for SO2 detection. Notably, NIR-RS accurately quantifies SO2 contents in Pinelliae rhizoma (P. rhizoma) samples, with recovery rates from 98.46% to 102.40%, and relative standard deviations (RSDs) < 5.0%. For bioimaging applications, NIR-RS has low cytotoxicity and good mitochondrial-targeting ability, making it suitable for imaging exogenous and endogenous SO2 in mitochondria. Additionally, NIR-RS was successfully applied to image SO2 content of P. rhizoma samples within cells, revealing that high SO2 residue elevated mitochondria adenosine triphosphate (ATP) content, these findings reveal that P. rhizoma with excessive SO2 can affect the organism's growth mechanisms through alterations in ATP pathways. In vivo, SO2 was found to predominantly accumulate in the liver following gavage with P. rhizoma solution, with accumulation levels increasing in proportion to SO2 residue concentration. High SO2 concentrations in P. rhizoma can cause pulmonary fibrosis and gastric mucosal damage. This work provides a valuable tool for regulating SO2 content in P. rhizoma and may help researcher better understand the metabolism of SO2 derivatives and explore their physiological roles in biological systems.
Sulfur dioxide (SO2) and its derivatives have been recognized as harmful environmental pollutants. However, they are often produced during the processing of traditional Chinese medicines, potentially compromising the quality of these medicinal materials and contributing to various health issues. Due to a lack of effective monitoring and imaging tools, the physiological effects of excessive SO2 residues in traditional Chinese medicine remain unclear. Therefore, developing a rapid and effective tool for detecting SO2 is crucial for understanding its metabolic pathways and effects in vivo. In this study, we developed a near infrared (NIR) and ratiometric fluorescent probe, NIR-RS, which exhibits high sensitivity, selectivity, and rapid response for SO2 detection. Notably, NIR-RS accurately quantifies SO2 contents in Pinelliae rhizoma (P. rhizoma) samples, with recovery rates from 98.46% to 102.40%, and relative standard deviations (RSDs) < 5.0%. For bioimaging applications, NIR-RS has low cytotoxicity and good mitochondrial-targeting ability, making it suitable for imaging exogenous and endogenous SO2 in mitochondria. Additionally, NIR-RS was successfully applied to image SO2 content of P. rhizoma samples within cells, revealing that high SO2 residue elevated mitochondria adenosine triphosphate (ATP) content, these findings reveal that P. rhizoma with excessive SO2 can affect the organism's growth mechanisms through alterations in ATP pathways. In vivo, SO2 was found to predominantly accumulate in the liver following gavage with P. rhizoma solution, with accumulation levels increasing in proportion to SO2 residue concentration. High SO2 concentrations in P. rhizoma can cause pulmonary fibrosis and gastric mucosal damage. This work provides a valuable tool for regulating SO2 content in P. rhizoma and may help researcher better understand the metabolism of SO2 derivatives and explore their physiological roles in biological systems.
2026, 37(1): 110981
doi: 10.1016/j.cclet.2025.110981
摘要:
Poor solubility often results in low efficacy of antitumor drugs. Nevertheless, limited research has been conducted on the potential decrease in drug efficacy following the self-assembly of hydrophobic pure drugs into nanodrugs, and solutions to this problem are even rarer. Loading water-insoluble antitumor drugs into nanocarriers offers a promising solution. However, intricate carrier preparation, limited drug loading capacity, and carrier-associated safety remain key challenges. In this study, based on the discovery that hydrophobic gambogic acid (GA) self-assembles into nanostructures with diminished antitumor efficacy in aqueous environments, we developed a carrier-free nanodrug system, designated as GA-S-S-AS nanoparticles (NPs), characterized by straightforward preparation, high drug loading, fluorescence imaging, tumor-targeting, and responsive drug release in reducing environments. Specifically, the hydrophobic GA was covalently linked to the hydrophilic aptamer through a disulfide bond and then self-assembled into the nanodrugs. About 92% of drug was encapsulated in self-assembled NPs, demonstrating remarkable stability under physiological conditions and controlled release of GA in the high-glutathione environment characteristic of tumor sites. Furthermore, by utilizing the synergistic interaction between the enhanced permeability and retention (EPR) effect and ligand-receptor active targeting mechanisms, the nanodrugs significantly increased the accumulation of GA at tumor locations. Consequently, the nanodrugs exhibited optimal therapeutic efficacy against the tumor both in vitro and in vivo, significantly inhibiting tumor growth. Furthermore, the nanodrugs demonstrated enhanced biosafety compared to free GA, effectively reducing GA-induced hepatotoxicity. Taken together, these findings underscore the significant potential of this multifunctional carrier-free nanodrugs for the targeted delivery of GA, thereby laying a foundation for future endeavors aimed at developing novel formulations of hydrophobic antitumor drugs.
Poor solubility often results in low efficacy of antitumor drugs. Nevertheless, limited research has been conducted on the potential decrease in drug efficacy following the self-assembly of hydrophobic pure drugs into nanodrugs, and solutions to this problem are even rarer. Loading water-insoluble antitumor drugs into nanocarriers offers a promising solution. However, intricate carrier preparation, limited drug loading capacity, and carrier-associated safety remain key challenges. In this study, based on the discovery that hydrophobic gambogic acid (GA) self-assembles into nanostructures with diminished antitumor efficacy in aqueous environments, we developed a carrier-free nanodrug system, designated as GA-S-S-AS nanoparticles (NPs), characterized by straightforward preparation, high drug loading, fluorescence imaging, tumor-targeting, and responsive drug release in reducing environments. Specifically, the hydrophobic GA was covalently linked to the hydrophilic aptamer through a disulfide bond and then self-assembled into the nanodrugs. About 92% of drug was encapsulated in self-assembled NPs, demonstrating remarkable stability under physiological conditions and controlled release of GA in the high-glutathione environment characteristic of tumor sites. Furthermore, by utilizing the synergistic interaction between the enhanced permeability and retention (EPR) effect and ligand-receptor active targeting mechanisms, the nanodrugs significantly increased the accumulation of GA at tumor locations. Consequently, the nanodrugs exhibited optimal therapeutic efficacy against the tumor both in vitro and in vivo, significantly inhibiting tumor growth. Furthermore, the nanodrugs demonstrated enhanced biosafety compared to free GA, effectively reducing GA-induced hepatotoxicity. Taken together, these findings underscore the significant potential of this multifunctional carrier-free nanodrugs for the targeted delivery of GA, thereby laying a foundation for future endeavors aimed at developing novel formulations of hydrophobic antitumor drugs.
2026, 37(1): 111042
doi: 10.1016/j.cclet.2025.111042
摘要:
Mangicol-type sesterterpenoids possess potent anti-inflammatory activity, characterized by a 5–5–6–5 tetracyclic carbon skeleton formed by mangicdiene synthase FgMS. Two proposed mechanisms for mangicdiene formation involve either C6-C10 cyclization (path a) or C2-C10 cyclization (path b) after the C10 carbocation formation, but neither has been experimentally validated. Here, we have identified a second mangicdiene synthase ManD, which is derived from Fusarium sp. JNU-XJ070152–01 and shares high amino acid sequence identity with FgMS. Through heterologous expression of manD in Aspergillus oryzae NSAR1, we observed production not only of mangicdiene (1) and variecoltetraene (2), previously identified by expression of FgMS in Escherichia coli, but also two novel sesterterpene skeletons fusadiene (3) and fusatriene (4). The identification of fusadiene and fusatriene supports the occurrence of two key carbocation intermediates in path b, thus experimentally confirming that mangicdiene is built via path b for the first time, consistent with previous density functional theory (DFT) calculation results.
Mangicol-type sesterterpenoids possess potent anti-inflammatory activity, characterized by a 5–5–6–5 tetracyclic carbon skeleton formed by mangicdiene synthase FgMS. Two proposed mechanisms for mangicdiene formation involve either C6-C10 cyclization (path a) or C2-C10 cyclization (path b) after the C10 carbocation formation, but neither has been experimentally validated. Here, we have identified a second mangicdiene synthase ManD, which is derived from Fusarium sp. JNU-XJ070152–01 and shares high amino acid sequence identity with FgMS. Through heterologous expression of manD in Aspergillus oryzae NSAR1, we observed production not only of mangicdiene (1) and variecoltetraene (2), previously identified by expression of FgMS in Escherichia coli, but also two novel sesterterpene skeletons fusadiene (3) and fusatriene (4). The identification of fusadiene and fusatriene supports the occurrence of two key carbocation intermediates in path b, thus experimentally confirming that mangicdiene is built via path b for the first time, consistent with previous density functional theory (DFT) calculation results.
2026, 37(1): 111072
doi: 10.1016/j.cclet.2025.111072
摘要:
Bicyclo[2.1.1]hexanes (BCHs) are structurally unique C(sp3)-rich bicyclic hydrocarbons that are gaining prominence in the field of medicinal chemistry as bioisosteres of benzenoids. The nitrile is an important functionality in drug development due to its ability to improve physicochemical and pharmacokinetic properties and facilitate potential noncovalent interactions with drug targets. Consequently, cyano-arene motifs are commonly found in drug development. The introduction of cyano-BCHs as potential bioisosteres of cyano-arenes shows great promise; however, there are currently no catalytic methods available for their synthesis. Herein, we report a palladium-catalyzed enantioselective [2σ + 2π] cycloadditions of bicyclo[1.1.0]butanes with arylidenemalononitriles for the preparation of chiral cyano-BCHs. This method accommodated a wide range of substrates and tolerated various functional groups. The cyano-BCH products could be transformed to molecules with diverse functionality. Control experiments suggest that the reaction proceeds via a zwitterionic intermediate generated by palladium-mediated ring opening of vinyl-carbonyl bicyclo[1.1.0]butanes followed by stereoselective 1,2-addition and intramolecular allylic substitution reactions.
Bicyclo[2.1.1]hexanes (BCHs) are structurally unique C(sp3)-rich bicyclic hydrocarbons that are gaining prominence in the field of medicinal chemistry as bioisosteres of benzenoids. The nitrile is an important functionality in drug development due to its ability to improve physicochemical and pharmacokinetic properties and facilitate potential noncovalent interactions with drug targets. Consequently, cyano-arene motifs are commonly found in drug development. The introduction of cyano-BCHs as potential bioisosteres of cyano-arenes shows great promise; however, there are currently no catalytic methods available for their synthesis. Herein, we report a palladium-catalyzed enantioselective [2σ + 2π] cycloadditions of bicyclo[1.1.0]butanes with arylidenemalononitriles for the preparation of chiral cyano-BCHs. This method accommodated a wide range of substrates and tolerated various functional groups. The cyano-BCH products could be transformed to molecules with diverse functionality. Control experiments suggest that the reaction proceeds via a zwitterionic intermediate generated by palladium-mediated ring opening of vinyl-carbonyl bicyclo[1.1.0]butanes followed by stereoselective 1,2-addition and intramolecular allylic substitution reactions.
2026, 37(1): 111082
doi: 10.1016/j.cclet.2025.111082
摘要:
The large volume expansion and rapid capacity attenuation of tin-based electrodes are the main factors limiting their commercial application. The reasonable design of electrode material structure is particularly important for improving its electrochemical performance. Herein, phosphorus-modified graphene encapsulated Sn6O4(OH)4 nanoparticles composite (P-Sn6O4(OH)4@RGO) with crystalline-amorphous heterostructure has been successfully designed and prepared. The design of crystalline-amorphous structure has largely enhanced the active sites, and the construction of a graphene encapsulation structure has greatly alleviated volume expansion. Notably, P-Sn6O4(OH)4@RGO obtained an excellent high-rate long-term cycling performance for lithium-ion batteries anode, reaching a high specific capacity of 970 mAh/g at 1.0 A/g after 1450 cycles. This work demonstrates that restructuring the electrode material's structure and phase through phosphorus modification can effectively improve the electrochemical performance of tin-based electrode materials.
The large volume expansion and rapid capacity attenuation of tin-based electrodes are the main factors limiting their commercial application. The reasonable design of electrode material structure is particularly important for improving its electrochemical performance. Herein, phosphorus-modified graphene encapsulated Sn6O4(OH)4 nanoparticles composite (P-Sn6O4(OH)4@RGO) with crystalline-amorphous heterostructure has been successfully designed and prepared. The design of crystalline-amorphous structure has largely enhanced the active sites, and the construction of a graphene encapsulation structure has greatly alleviated volume expansion. Notably, P-Sn6O4(OH)4@RGO obtained an excellent high-rate long-term cycling performance for lithium-ion batteries anode, reaching a high specific capacity of 970 mAh/g at 1.0 A/g after 1450 cycles. This work demonstrates that restructuring the electrode material's structure and phase through phosphorus modification can effectively improve the electrochemical performance of tin-based electrode materials.
2026, 37(1): 111085
doi: 10.1016/j.cclet.2025.111085
摘要:
Ln@MOFs by anchoring rare metal ions (Ln) into metal–organic frameworks (MOFs) are proved to have great potential in the field of luminescent molecular thermometer. Nevertheless, the current research indicated that the poor structural stability and low sensitivity hindered their application scope. In this work, a new MOF Zn-450 luminescent thermometer with multiple emission fluorescence characteristics was synthesized by the combination of 3,3′,5,5′-biphenyl tetracarboxylic acid (H4L) and Zn2+ ion under solvothermal conditions. Interestingly, a high relative sensitivity of 1.43 % K−1 was found within 80–300 K based on Zn-450. Subsequently, two high-sensitivity luminescent Ln@MOFs (Ln = Eu and Tb) were further fabricated by doping rare earth ions into Zn-450 based on the post-synthesis strategy. Among them, the Eu@Zn-450 demonstrates various luminous behaviors while achieving an increased relative sensitivity of 1.63 % K−1. In addition, the continuously visible red, pink, and purple luminescent emissions at the same temperature range were observed, suggesting that the Eu@Zn-450 could be utilized as a luminescent colorimetric molecular thermometer. Importantly, this work can present new possibilities for the development of rare earth-doped luminescence and its temperature sensing properties.
Ln@MOFs by anchoring rare metal ions (Ln) into metal–organic frameworks (MOFs) are proved to have great potential in the field of luminescent molecular thermometer. Nevertheless, the current research indicated that the poor structural stability and low sensitivity hindered their application scope. In this work, a new MOF Zn-450 luminescent thermometer with multiple emission fluorescence characteristics was synthesized by the combination of 3,3′,5,5′-biphenyl tetracarboxylic acid (H4L) and Zn2+ ion under solvothermal conditions. Interestingly, a high relative sensitivity of 1.43 % K−1 was found within 80–300 K based on Zn-450. Subsequently, two high-sensitivity luminescent Ln@MOFs (Ln = Eu and Tb) were further fabricated by doping rare earth ions into Zn-450 based on the post-synthesis strategy. Among them, the Eu@Zn-450 demonstrates various luminous behaviors while achieving an increased relative sensitivity of 1.63 % K−1. In addition, the continuously visible red, pink, and purple luminescent emissions at the same temperature range were observed, suggesting that the Eu@Zn-450 could be utilized as a luminescent colorimetric molecular thermometer. Importantly, this work can present new possibilities for the development of rare earth-doped luminescence and its temperature sensing properties.
2026, 37(1): 111095
doi: 10.1016/j.cclet.2025.111095
摘要:
In this study, we meticulously designed a layered carbon-based catalytic material to induce the degradation of a series of organic pollutants by activating peroxymonosulfate (PMS) in the PMS-based advanced oxidation processes (AOPs). Results indicated that the silicon and oxygen elements from the montmorillonite were incorporated into the catalyst matrix to form the Si-O-C structure. It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array, achieving over 90% removal rate of most pollutants within 60 min. It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array. The salt bridge system confirmed that pollutants can provide electrons to the Si-O-C/PMS system, and we verified that the electron transfer process (ETP) mechanism was the main pathway for the degradation of pollutants in the Si-O-C/PMS system via the open-circuit potential analysis. In combination with the structural properties of different pollutants, we discovered that electron-donating pollutants can supply more electrons to the Si-O-C/PMS system, thereby enhancing the ETP process. The findings of this study are anticipated to advance the development and practical application of layered carbonaceous materials-based catalysts and support the design and implementation of nanoconfined catalysts in the field of AOPs.
In this study, we meticulously designed a layered carbon-based catalytic material to induce the degradation of a series of organic pollutants by activating peroxymonosulfate (PMS) in the PMS-based advanced oxidation processes (AOPs). Results indicated that the silicon and oxygen elements from the montmorillonite were incorporated into the catalyst matrix to form the Si-O-C structure. It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array, achieving over 90% removal rate of most pollutants within 60 min. It was notable that the layered carbonaceous material with Si-O-C structure exhibited an outstanding catalytic effect on the synthesized layered catalytic material array. The salt bridge system confirmed that pollutants can provide electrons to the Si-O-C/PMS system, and we verified that the electron transfer process (ETP) mechanism was the main pathway for the degradation of pollutants in the Si-O-C/PMS system via the open-circuit potential analysis. In combination with the structural properties of different pollutants, we discovered that electron-donating pollutants can supply more electrons to the Si-O-C/PMS system, thereby enhancing the ETP process. The findings of this study are anticipated to advance the development and practical application of layered carbonaceous materials-based catalysts and support the design and implementation of nanoconfined catalysts in the field of AOPs.
2026, 37(1): 111116
doi: 10.1016/j.cclet.2025.111116
摘要:
Photocatalysis uses solar energy to convert nitrogen and water directly into ammonia, helping reduce dependence on fossil fuels and offering a way to integrate the nitrogen cycle into a clean energy network. Ohmic junctions between metals and semiconductors have demonstrated significant advantages in enhancing stability and reducing carrier recombination, but their application in photocatalytic nitrogen fixation is limited due to the difficulty of work function matching and the complexity of fabrication processes. In this study, density functional theory (DFT) calculations were used to confirm the work function matching between Bi and Bi2Ti2O7 (BTO), ensuring the formation of an Ohmic junction. A Bi-Bi2Ti2O7 (B-BTO) composite was successfully synthesized via a one-step hydrothermal method, using bismuth nitrate and titanium sulfate as precursors. Compared to pure BTO, the B-BTO heterojunction, driven by dual electron injection from both metal Bi and BTO, significantly increased the ammonia synthesis rate to 686.95 µmol g−1 h−1, making it the most active nitrogen fixation material among similar pyrochlore-based catalysts to date. The differential charge density calculations, photocurrent (i-t) measurements, and photoluminescence (PL) tests further validate the role of Ohmic contacts in enhancing charge transfer and prolonging carrier lifetimes. This research provides valuable insight into the application of Ohmic junctions in photocatalytic nitrogen fixation and contributes to advancements in this field.
Photocatalysis uses solar energy to convert nitrogen and water directly into ammonia, helping reduce dependence on fossil fuels and offering a way to integrate the nitrogen cycle into a clean energy network. Ohmic junctions between metals and semiconductors have demonstrated significant advantages in enhancing stability and reducing carrier recombination, but their application in photocatalytic nitrogen fixation is limited due to the difficulty of work function matching and the complexity of fabrication processes. In this study, density functional theory (DFT) calculations were used to confirm the work function matching between Bi and Bi2Ti2O7 (BTO), ensuring the formation of an Ohmic junction. A Bi-Bi2Ti2O7 (B-BTO) composite was successfully synthesized via a one-step hydrothermal method, using bismuth nitrate and titanium sulfate as precursors. Compared to pure BTO, the B-BTO heterojunction, driven by dual electron injection from both metal Bi and BTO, significantly increased the ammonia synthesis rate to 686.95 µmol g−1 h−1, making it the most active nitrogen fixation material among similar pyrochlore-based catalysts to date. The differential charge density calculations, photocurrent (i-t) measurements, and photoluminescence (PL) tests further validate the role of Ohmic contacts in enhancing charge transfer and prolonging carrier lifetimes. This research provides valuable insight into the application of Ohmic junctions in photocatalytic nitrogen fixation and contributes to advancements in this field.
2026, 37(1): 111131
doi: 10.1016/j.cclet.2025.111131
摘要:
The development of catalytic multicomponent reactions for constructing complex organic scaffolds from readily accessible commodity chemicals is a key pursuit in contemporary synthetic chemistry. Current methods for synthesizing thioesters primarily rely on the acylation of thiols, which produces substantial waste and requires malodorous, unstable sulfur sources. In this work, we introduce a photocatalyzed hydrogen transfer strategy that enables a three-component synthesis of thioesters using abundant primary alcohols, easily available alkenes and elemental sulfur under mild conditions. This protocol demonstrates broad applicability and high chemo- and regioselectivity for both primary alcohols and alkenes, highlighting the advantage and potential of photo-mediated hydrogen transfer in facilitating multicomponent reactions using primary alcohol and elemental sulfur feedstocks.
The development of catalytic multicomponent reactions for constructing complex organic scaffolds from readily accessible commodity chemicals is a key pursuit in contemporary synthetic chemistry. Current methods for synthesizing thioesters primarily rely on the acylation of thiols, which produces substantial waste and requires malodorous, unstable sulfur sources. In this work, we introduce a photocatalyzed hydrogen transfer strategy that enables a three-component synthesis of thioesters using abundant primary alcohols, easily available alkenes and elemental sulfur under mild conditions. This protocol demonstrates broad applicability and high chemo- and regioselectivity for both primary alcohols and alkenes, highlighting the advantage and potential of photo-mediated hydrogen transfer in facilitating multicomponent reactions using primary alcohol and elemental sulfur feedstocks.
2026, 37(1): 111132
doi: 10.1016/j.cclet.2025.111132
摘要:
The deuterium labeling has garnered significant interest in drug discovery due to its critical role on improving pharmacokinetic and metabolic properties. However, despite its pharmaceutical value, the general and rapid syntheses of aromatic scaffolds that contains deuterium remain an important yet elusive task. State-of-the-art approaches mainly relied on the transition metal-catalyzed C–H deuteration via the assistance of directing groups (DGs), which often suffered from over-deuteration and lengthy step counts required for installation and/or removal of DG. Herein, we report a generalizable synthetic linchpin strategy for the facile preparation of the ortho-deuterated aromatic core. Through capture of aryne-derived 1,3-zwitterion with heavy water, we synthesized an array of ortho-deuterated aryl sulfonium salts. These novel linchpins not only participated the transition metal catalyzed cross-coupling reaction as nucleophiles, but also served as aryl radical reservoirs under photochemical or electrochemical conditions, enabling facile and precise access to structurally diverse deuterated aromatics. Moreover, we have disclosed a novel EDA complex enabled direct arylation of phosphines under visible-light irradiation, further expanding the utility of our platform approach.
The deuterium labeling has garnered significant interest in drug discovery due to its critical role on improving pharmacokinetic and metabolic properties. However, despite its pharmaceutical value, the general and rapid syntheses of aromatic scaffolds that contains deuterium remain an important yet elusive task. State-of-the-art approaches mainly relied on the transition metal-catalyzed C–H deuteration via the assistance of directing groups (DGs), which often suffered from over-deuteration and lengthy step counts required for installation and/or removal of DG. Herein, we report a generalizable synthetic linchpin strategy for the facile preparation of the ortho-deuterated aromatic core. Through capture of aryne-derived 1,3-zwitterion with heavy water, we synthesized an array of ortho-deuterated aryl sulfonium salts. These novel linchpins not only participated the transition metal catalyzed cross-coupling reaction as nucleophiles, but also served as aryl radical reservoirs under photochemical or electrochemical conditions, enabling facile and precise access to structurally diverse deuterated aromatics. Moreover, we have disclosed a novel EDA complex enabled direct arylation of phosphines under visible-light irradiation, further expanding the utility of our platform approach.
2026, 37(1): 111134
doi: 10.1016/j.cclet.2025.111134
摘要:
The recovery of gold from waste electronic and electric equipment (WEEE) has gained great attention with the increased number of WEEE, because it can largely alleviate the pressure on the environment and resources. Covalent organic frameworks (COFs) are ideal adsorbents for gold recovery owing to their large surface area, good stability, easily functionalized ability, periodic structures, and definitive nanopores. Herein, a cyano-functionalized COF (COF-CN) with high crystallinity was large-scale prepared under mild conditions for the recovery of gold. The introduction of cyano groups enable COF-CN to exhibit excellent gold recovery performance, which possesses fast adsorption kinetics, high cycling stability, and adsorption capacity up to 663.67 mg/g. Excitingly, COF-CN showed extremely high selectivity for gold ions, even in the presence of various competing cations and anions. The COF-CN maintained excellent selectivity and removal efficiency in gold recovery experiments from WEEE. The facile synthesis of COF-CN and its outstanding selectivity in actual samples make it an attractive opportunity for practical gold recovery.
The recovery of gold from waste electronic and electric equipment (WEEE) has gained great attention with the increased number of WEEE, because it can largely alleviate the pressure on the environment and resources. Covalent organic frameworks (COFs) are ideal adsorbents for gold recovery owing to their large surface area, good stability, easily functionalized ability, periodic structures, and definitive nanopores. Herein, a cyano-functionalized COF (COF-CN) with high crystallinity was large-scale prepared under mild conditions for the recovery of gold. The introduction of cyano groups enable COF-CN to exhibit excellent gold recovery performance, which possesses fast adsorption kinetics, high cycling stability, and adsorption capacity up to 663.67 mg/g. Excitingly, COF-CN showed extremely high selectivity for gold ions, even in the presence of various competing cations and anions. The COF-CN maintained excellent selectivity and removal efficiency in gold recovery experiments from WEEE. The facile synthesis of COF-CN and its outstanding selectivity in actual samples make it an attractive opportunity for practical gold recovery.
2026, 37(1): 111142
doi: 10.1016/j.cclet.2025.111142
摘要:
Triclosan (TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects. Therefore, developing an efficient and sustainable technology to degrade TCS is urgently needed. Herein, cobalt oxyhydroxide @covalent organic frameworks (CoOOH@COFs) S−scheme heterojunction was synthesized, which combined the visible-light-driven photocatalysis and peroxymonosulfate (PMS) activation to synergistically generate abundant reactive oxygen species (ROSs) for TCS degradation. The degradation efficiency of TCS reached 100% within 8 min in the Vis-CoOOH@COFs/PMS system, and the reaction rate constant was 0.456 min−1, which was nearly 1.90 and 2.85 times that of single CoOOH and COFs, and 2.36 times that under dark condition, respectively. The density functional theory (DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to CoOOH. Both experimental and theoretical analyses indicated that CoOOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation, enhanced interfacial electron transfer, accelerated PMS activation, and generated multiple ROSs. In particular, photogenerated electrons (e−) accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle, while the PMS captured the e−, which significantly decreased the charge combination of CoOOH@COFs. Radicals (O2•−, •OH, and SO4•−) and non-radicals (such as 1O2, h+, and e−) were both presented in the Vis-CoOOH@COFs/PMS system, with O2− playing a dominant role in TCS degradation. Furthermore, the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification. Importantly, the environmentally friendly CoOOH@COFs S−scheme heterojunction exhibited excellent stability and reusability. In conclusion, this study innovatively designed an S−scheme heterojunction in the photocatalytic-PMS activation system, providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.
Triclosan (TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects. Therefore, developing an efficient and sustainable technology to degrade TCS is urgently needed. Herein, cobalt oxyhydroxide @covalent organic frameworks (CoOOH@COFs) S−scheme heterojunction was synthesized, which combined the visible-light-driven photocatalysis and peroxymonosulfate (PMS) activation to synergistically generate abundant reactive oxygen species (ROSs) for TCS degradation. The degradation efficiency of TCS reached 100% within 8 min in the Vis-CoOOH@COFs/PMS system, and the reaction rate constant was 0.456 min−1, which was nearly 1.90 and 2.85 times that of single CoOOH and COFs, and 2.36 times that under dark condition, respectively. The density functional theory (DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to CoOOH. Both experimental and theoretical analyses indicated that CoOOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation, enhanced interfacial electron transfer, accelerated PMS activation, and generated multiple ROSs. In particular, photogenerated electrons (e−) accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle, while the PMS captured the e−, which significantly decreased the charge combination of CoOOH@COFs. Radicals (O2•−, •OH, and SO4•−) and non-radicals (such as 1O2, h+, and e−) were both presented in the Vis-CoOOH@COFs/PMS system, with O2− playing a dominant role in TCS degradation. Furthermore, the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification. Importantly, the environmentally friendly CoOOH@COFs S−scheme heterojunction exhibited excellent stability and reusability. In conclusion, this study innovatively designed an S−scheme heterojunction in the photocatalytic-PMS activation system, providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.
2026, 37(1): 111146
doi: 10.1016/j.cclet.2025.111146
摘要:
Developing a chiral material as versatile and universal chiral stationary phase (CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance. In this study, we demonstrated for the first time that a chiral metal-organic cage (MOC), [Zn6M4], as a universal chiral recognition material for both multi-mode high-performance liquid chromatography (HPLC) and capillary gas chromatography (GC) enantioseparation. Two novel HPLC CSPs with different bonding arms (CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn6M4] onto thiolated silica via thiol-ene click chemistry. Meanwhile, a capillary GC column statically coated with the chiral MOC [Zn6M4] was also fabricated. The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC (NP-HPLC) and reversed phase (RP-HPLC) but also in GC, and various racemates were well separated, including alcohols, diols, esters, ketones, ethers, amines, and epoxides. Importantly, CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation, which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns, suggesting the great potential of the two prepared CSPs in enantioseparation. This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC, and also paves the way to expand the potential applications of MOCs.
Developing a chiral material as versatile and universal chiral stationary phase (CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance. In this study, we demonstrated for the first time that a chiral metal-organic cage (MOC), [Zn6M4], as a universal chiral recognition material for both multi-mode high-performance liquid chromatography (HPLC) and capillary gas chromatography (GC) enantioseparation. Two novel HPLC CSPs with different bonding arms (CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn6M4] onto thiolated silica via thiol-ene click chemistry. Meanwhile, a capillary GC column statically coated with the chiral MOC [Zn6M4] was also fabricated. The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC (NP-HPLC) and reversed phase (RP-HPLC) but also in GC, and various racemates were well separated, including alcohols, diols, esters, ketones, ethers, amines, and epoxides. Importantly, CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation, which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns, suggesting the great potential of the two prepared CSPs in enantioseparation. This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC, and also paves the way to expand the potential applications of MOCs.
2026, 37(1): 111147
doi: 10.1016/j.cclet.2025.111147
摘要:
Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials. Herein, we report photo-responsive reversible multicolor supramolecular hydrogel with near-infrared emission, which is constructed by cucurbit[7]uril (CB[7]), cyanostilbene derivative (DAC) and Laponite XLG (LP) via supramolecular cascade assembly. Compared with the free guest molecule DAC, the confinement of macrocycle CB[7] achieve effective near-infrared fluorescence in the aqueous phase from scratch, and the subsequent cascade assembly with LP further restrict the molecular rotation of the DAC, which not only result in a substantial enhancement of the fluorescence intensity, but is also endowed with light-controlled fluorescence on/off both in the solution and hydrogel states. Further, 8–hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt (HPTS) is introduced in the cascade assembly to fabricated photo-controllable reversible multicolor luminescence supramolecular hydrogel between red and green induced by Förster resonance energy transfer, which is successfully employed in reversible multiple information encryption.
Photo-responsive supramolecular assembly especially supramolecular hydrogels with tunable luminescence show a promising application potential in writable information recording and display materials. Herein, we report photo-responsive reversible multicolor supramolecular hydrogel with near-infrared emission, which is constructed by cucurbit[7]uril (CB[7]), cyanostilbene derivative (DAC) and Laponite XLG (LP) via supramolecular cascade assembly. Compared with the free guest molecule DAC, the confinement of macrocycle CB[7] achieve effective near-infrared fluorescence in the aqueous phase from scratch, and the subsequent cascade assembly with LP further restrict the molecular rotation of the DAC, which not only result in a substantial enhancement of the fluorescence intensity, but is also endowed with light-controlled fluorescence on/off both in the solution and hydrogel states. Further, 8–hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt (HPTS) is introduced in the cascade assembly to fabricated photo-controllable reversible multicolor luminescence supramolecular hydrogel between red and green induced by Förster resonance energy transfer, which is successfully employed in reversible multiple information encryption.
2026, 37(1): 111153
doi: 10.1016/j.cclet.2025.111153
摘要:
The brain's functions are governed by molecular metabolic networks. However, due to the sophisticated spatial organization and diverse activities of the brain, characterizing both the minute and large-scale metabolic activity across the entire brain and its numerous micro-regions remains incredibly challenging. Here, we offer a high-definition spatially resolved metabolomics technique to better understand the metabolic specialization and interconnection throughout the mouse brain using improved ambient mass spectrometry imaging. This method allows for the simultaneous mapping of thousands of metabolites at a 30 µm spatial resolution across the mouse brain, ranging from structural lipids to functional neurotransmitters. This approach effectively reveals the distribution patterns of delicate microregions and their distinctive metabolic characteristics. Using an integrated database, we annotated 259 metabolites, demonstrating that the metabolome and metabolic pathways are unique to each brain microregion. The distribution of metabolites, closely linked to functionally connected brain regions and their interactions, offers profound insights into the complexity of chemical processes and their roles in brain function. An initial dataset for future metabolomics research might be obtained from the high-definition mouse brain's spatial metabolome atlas.
The brain's functions are governed by molecular metabolic networks. However, due to the sophisticated spatial organization and diverse activities of the brain, characterizing both the minute and large-scale metabolic activity across the entire brain and its numerous micro-regions remains incredibly challenging. Here, we offer a high-definition spatially resolved metabolomics technique to better understand the metabolic specialization and interconnection throughout the mouse brain using improved ambient mass spectrometry imaging. This method allows for the simultaneous mapping of thousands of metabolites at a 30 µm spatial resolution across the mouse brain, ranging from structural lipids to functional neurotransmitters. This approach effectively reveals the distribution patterns of delicate microregions and their distinctive metabolic characteristics. Using an integrated database, we annotated 259 metabolites, demonstrating that the metabolome and metabolic pathways are unique to each brain microregion. The distribution of metabolites, closely linked to functionally connected brain regions and their interactions, offers profound insights into the complexity of chemical processes and their roles in brain function. An initial dataset for future metabolomics research might be obtained from the high-definition mouse brain's spatial metabolome atlas.
2026, 37(1): 111154
doi: 10.1016/j.cclet.2025.111154
摘要:
RNA binding proteins (RBPs) are a crucial class of proteins that interact with RNA and play a key role in various biological process. Deficiencies or abnormalities of RBPs are closely linked to the occurrence and progression of numerous diseases, making RBPs potential therapeutic targets. However, the limited tissue penetration of 254 nm UV irradiation makes it difficult to efficiently crosslink weak and dynamic RNA–protein interactions in mammal tissues. Additionally, RNA degradation in metal catalyzed click reaction further hinders the enrichment of RNA-protein complexes (RPCs). Due to these inherent limitations, globally profiling the RNA binding proteome in mammal organs has long been a challenge. Herein, we proposed a novel method, which utilized a dual crosslinking with formaldehyde and 254 nm UV irradiation, metabolic labeling and metal-free thiol-yne click reaction to enable large-scale enrichment and identification of RBPs in mouse liver, called FTYc_UV. In this method, formaldehyde is first used to crosslink the crude RNA-protein complexes (cRPCs) in situ to address the problem of poor tissue penetration of 254 nm UV irradiation. Furthermore, this method integrates metabolic labeling with a metal-free thiol-yne click reaction to achieve non-destructive RNA tagging. After specifically RNA-RBPs crosslinking by 254 nm UV irradiation in tissue lysates, formaldehyde decrosslinking is employed to remove non-specific proteins, leading to effective enrichment of RPCs from mouse liver and thereby overcoming the poor specificity of formaldehyde crosslinking. Application of FTYc_UV in mouse liver successfully identified over 1600 RBPs covering approximately 75% of previously reported RBPs. Furthermore, 420 candidate RBPs, including 151 metabolic enzymes, were also obtained, demonstrating the sensitivity of FTYc_UV and the potential of this method for in-depth exploration of RNA–protein interactions in biological and clinical research.
RNA binding proteins (RBPs) are a crucial class of proteins that interact with RNA and play a key role in various biological process. Deficiencies or abnormalities of RBPs are closely linked to the occurrence and progression of numerous diseases, making RBPs potential therapeutic targets. However, the limited tissue penetration of 254 nm UV irradiation makes it difficult to efficiently crosslink weak and dynamic RNA–protein interactions in mammal tissues. Additionally, RNA degradation in metal catalyzed click reaction further hinders the enrichment of RNA-protein complexes (RPCs). Due to these inherent limitations, globally profiling the RNA binding proteome in mammal organs has long been a challenge. Herein, we proposed a novel method, which utilized a dual crosslinking with formaldehyde and 254 nm UV irradiation, metabolic labeling and metal-free thiol-yne click reaction to enable large-scale enrichment and identification of RBPs in mouse liver, called FTYc_UV. In this method, formaldehyde is first used to crosslink the crude RNA-protein complexes (cRPCs) in situ to address the problem of poor tissue penetration of 254 nm UV irradiation. Furthermore, this method integrates metabolic labeling with a metal-free thiol-yne click reaction to achieve non-destructive RNA tagging. After specifically RNA-RBPs crosslinking by 254 nm UV irradiation in tissue lysates, formaldehyde decrosslinking is employed to remove non-specific proteins, leading to effective enrichment of RPCs from mouse liver and thereby overcoming the poor specificity of formaldehyde crosslinking. Application of FTYc_UV in mouse liver successfully identified over 1600 RBPs covering approximately 75% of previously reported RBPs. Furthermore, 420 candidate RBPs, including 151 metabolic enzymes, were also obtained, demonstrating the sensitivity of FTYc_UV and the potential of this method for in-depth exploration of RNA–protein interactions in biological and clinical research.
2026, 37(1): 111165
doi: 10.1016/j.cclet.2025.111165
摘要:
Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives. However, it is challenging to develop environmentally friendly catalytic systems, especially in constructing efficient and recyclable catalysts under water or solvent-free conditions. Here, we designed two novel coordination polymers Cd–CPs and Fe–CPs to investigate their catalytic performance in water. Gratifyingly, it was observed that Cd-CPs as a multifunctional catalyst was successfully applied to establish a universal pathway for direct fabrication of 1,8-naphthyridine derivatives under water conditions, while it was effective for the synthesis of 1,3,5-triazines through acceptorless dehydrogenative coupling strategies. The features of broad substrate, high atom efficiency, and good catalyst reusability highlight the feasibility of this transformation. In additional, we demonstrated the spindle-like structures Fe-P, derived from the Fe–CPs via phosphorylation, which can be used as an efficient electrocatalyst for oxygen evolution reaction with good stability. This work provides two highly efficient non-noble metal catalysts for functionalized 1,8-naphthyridine derivatives production and oxygen evolution reaction, and opens a new avenue to further fabricate diverse metal catalysts with high catalytic performance in water.
Acceptorless dehydrogenative coupling of pyridinemethanol with ketones is one of the most reliable methodologies to access functionalized 1,8-naphthyridine derivatives. However, it is challenging to develop environmentally friendly catalytic systems, especially in constructing efficient and recyclable catalysts under water or solvent-free conditions. Here, we designed two novel coordination polymers Cd–CPs and Fe–CPs to investigate their catalytic performance in water. Gratifyingly, it was observed that Cd-CPs as a multifunctional catalyst was successfully applied to establish a universal pathway for direct fabrication of 1,8-naphthyridine derivatives under water conditions, while it was effective for the synthesis of 1,3,5-triazines through acceptorless dehydrogenative coupling strategies. The features of broad substrate, high atom efficiency, and good catalyst reusability highlight the feasibility of this transformation. In additional, we demonstrated the spindle-like structures Fe-P, derived from the Fe–CPs via phosphorylation, which can be used as an efficient electrocatalyst for oxygen evolution reaction with good stability. This work provides two highly efficient non-noble metal catalysts for functionalized 1,8-naphthyridine derivatives production and oxygen evolution reaction, and opens a new avenue to further fabricate diverse metal catalysts with high catalytic performance in water.
2026, 37(1): 111168
doi: 10.1016/j.cclet.2025.111168
摘要:
Fractal assembly in discrete structures, especially for artificial supramolecular species, has attracted significantly increased interest over the past two decades. In this study, we present the precisely controlled fractal expanding synthesis of a novel triangular prism supramolecule featuring Sierpiński triangular face, which was achieved through a module-intervened self-expansion strategy. The homoleptic S1 was firstly synthesized through the assembly of ligand L1 with Zn2+ ions. Based on the triangular-faced prism S1, we further introduced Sierpiński triangular faces on the section of the heteroleptic supramolecular cage S2 with an expanded inner cavity and more abundant active sites for photocatalytic properties. The topotactic architectures for both S1 and S2 were fully characterized by nuclear magnetic resonance spectroscopy, high-resolution electrospray ionization mass spectrometry, transmission electron microscopy, and atomic force microscopy. Furthermore, the enhanced photocatalytic activity of the fractal expanded S2 was performed via the superior amine oxidative efficiency over S1. This study proposes the unprecedented fractal expanding strategy for three-dimensional supramolecular species with higher complexity, potentially opening new avenues for structural regulation of artificial fractal molecules.
Fractal assembly in discrete structures, especially for artificial supramolecular species, has attracted significantly increased interest over the past two decades. In this study, we present the precisely controlled fractal expanding synthesis of a novel triangular prism supramolecule featuring Sierpiński triangular face, which was achieved through a module-intervened self-expansion strategy. The homoleptic S1 was firstly synthesized through the assembly of ligand L1 with Zn2+ ions. Based on the triangular-faced prism S1, we further introduced Sierpiński triangular faces on the section of the heteroleptic supramolecular cage S2 with an expanded inner cavity and more abundant active sites for photocatalytic properties. The topotactic architectures for both S1 and S2 were fully characterized by nuclear magnetic resonance spectroscopy, high-resolution electrospray ionization mass spectrometry, transmission electron microscopy, and atomic force microscopy. Furthermore, the enhanced photocatalytic activity of the fractal expanded S2 was performed via the superior amine oxidative efficiency over S1. This study proposes the unprecedented fractal expanding strategy for three-dimensional supramolecular species with higher complexity, potentially opening new avenues for structural regulation of artificial fractal molecules.
2026, 37(1): 111177
doi: 10.1016/j.cclet.2025.111177
摘要:
The Jellium closed-shell model, a cornerstone of cluster science, has long guided the design of superatoms by dictating electron-counting rules. However, its reliance on precise control of cluster composition and electron shell occupancy presents significant experimental challenges. Here, we introduce a ligation strategy that circumvents these limitations by demonstrating that the adiabatic electron affinity (AEA) of aluminum-based clusters, whether with filled or partially filled electron shells, can be dramatically enhanced through the attachment of organic Lewis acid ligands. It was evidenced that the AEA of PAl12 can be significantly increased by 2.17 eV after the ligation of two ligands, indicating a remarkable improvement in its electron-accepting ability. This approach yields superhalogen species, offering a versatile and practical means to tune the electronic properties of clusters while preserving their superatomic states, independent of shell occupancy. Remarkably, this ligand-induced modulation is not confined to naked clusters but also extends to nano-confined systems, hinting at its broader applicability. Given the indispensable role of ligands in cluster synthesis, this strategy holds promise for advancing the field of condensed-phase superatom synthesis, potentially complementing traditional electron-counting rules in a broader range of applications.
The Jellium closed-shell model, a cornerstone of cluster science, has long guided the design of superatoms by dictating electron-counting rules. However, its reliance on precise control of cluster composition and electron shell occupancy presents significant experimental challenges. Here, we introduce a ligation strategy that circumvents these limitations by demonstrating that the adiabatic electron affinity (AEA) of aluminum-based clusters, whether with filled or partially filled electron shells, can be dramatically enhanced through the attachment of organic Lewis acid ligands. It was evidenced that the AEA of PAl12 can be significantly increased by 2.17 eV after the ligation of two ligands, indicating a remarkable improvement in its electron-accepting ability. This approach yields superhalogen species, offering a versatile and practical means to tune the electronic properties of clusters while preserving their superatomic states, independent of shell occupancy. Remarkably, this ligand-induced modulation is not confined to naked clusters but also extends to nano-confined systems, hinting at its broader applicability. Given the indispensable role of ligands in cluster synthesis, this strategy holds promise for advancing the field of condensed-phase superatom synthesis, potentially complementing traditional electron-counting rules in a broader range of applications.
2026, 37(1): 111184
doi: 10.1016/j.cclet.2025.111184
摘要:
DNA methylation is an important promising biomarker for cancer diagnosis and monitoring. Therefore, the assessment of DNA methylation levels is helpful for the prognosis and diagnosis of cancer. However, it is still a huge challenge to sensitively and accurately quantify the levels of DNA methylation in clinical sample. In this work, we proposed a protospacer adjacent motif (PAM)-free mediated CRISPR-Cas12a ultra-sensitive and quantitative DNA methylation detection method. Through recognizing the dsDNA with toehold region, CRISPR-Cas12a not only got rid of the limitation of PAM, but also improved its distinction ability for single CpG site methylation, nearly 5-fold that of conventional PAM-containing dsDNA. We further introduced assist-strand and design an artificial mismatch to greatly improve the ability to distinguish single CpG methylation site. Our results showed that the discrimination factor was > 200. Then, we constructed toe-dsDNA by using "heating and freezing", which made our method universally applicable and feasible. In addition, we greatly simplified the difficulty of primer design. Our method detected four highly methylated genes acyl carrier protein (ACP), CLV3/ESR-related (CLE), Disabled (DAB) and Homeobox (HOX) with a detection limit of 0.01% and excellent linearity in DNA methylation standards. Then, we verified the clinical utility of this method in 29 hepatocellular carcinomas, 11 ovarian cancers and 4 health people. In conclusion, we have successfully constructed a PAM-free CRISPR-Cas12a DNA methylation quantification method, which achieves high congruence in sensitivity, specificity and universality, fully demonstrating its significant clinical application value.
DNA methylation is an important promising biomarker for cancer diagnosis and monitoring. Therefore, the assessment of DNA methylation levels is helpful for the prognosis and diagnosis of cancer. However, it is still a huge challenge to sensitively and accurately quantify the levels of DNA methylation in clinical sample. In this work, we proposed a protospacer adjacent motif (PAM)-free mediated CRISPR-Cas12a ultra-sensitive and quantitative DNA methylation detection method. Through recognizing the dsDNA with toehold region, CRISPR-Cas12a not only got rid of the limitation of PAM, but also improved its distinction ability for single CpG site methylation, nearly 5-fold that of conventional PAM-containing dsDNA. We further introduced assist-strand and design an artificial mismatch to greatly improve the ability to distinguish single CpG methylation site. Our results showed that the discrimination factor was > 200. Then, we constructed toe-dsDNA by using "heating and freezing", which made our method universally applicable and feasible. In addition, we greatly simplified the difficulty of primer design. Our method detected four highly methylated genes acyl carrier protein (ACP), CLV3/ESR-related (CLE), Disabled (DAB) and Homeobox (HOX) with a detection limit of 0.01% and excellent linearity in DNA methylation standards. Then, we verified the clinical utility of this method in 29 hepatocellular carcinomas, 11 ovarian cancers and 4 health people. In conclusion, we have successfully constructed a PAM-free CRISPR-Cas12a DNA methylation quantification method, which achieves high congruence in sensitivity, specificity and universality, fully demonstrating its significant clinical application value.
2026, 37(1): 111186
doi: 10.1016/j.cclet.2025.111186
摘要:
Metal organic framework (MOF) assembled with coordination bonds has the disadvantage of poor stability that limits its application in the field of stationary phase, while covalent organic framework (COF) assembled through covalent bonds exhibits excellent structural stability. It has been shown that the stationary phases prepared by combining MOF and COF can make up for the poor stability of MOF@SiO2, and the MOF/COF composites have superior chromatographic separation performance. However, the traditional methods for preparing COF/MOF based stationary phases are generally solvent thermal synthesis. In this study, a green and low-cost synthesis method was proposed for the preparation of MOF/COF@SiO2 stationary phase. Firstly, COF@SiO2 was prepared in a choline chloride/ethylene glycol based deep eutectic solvent (DES). Secondly, another acid-base tunable DES prepared by mixing p-toluenesulfonic acid (PTSA) and 2-methylimidazole in different proportions was introduced as the reaction solvent and reactant for rapid synthesis of MOF/COF@SiO2. Compared with the toxic transition metal-based MOFs selected in most previous studies, a lightweight and non-toxic S-zone metal (calcium) based MOF was employed in this study. PTSA and calcium will form the calcium/oxygen-containing organic acid framework in acidic DES, which assembles with terephthalic acid dissolved in basic DES to form MOF. The strong hydrogen bonding effect of DES can facilitate rapid assembly of Ca-MOF. The obtained Ca-MOF/COF@SiO2 can be used for multi-mode chromatography to efficiently separate multiple isomeric/hydrophilic/hydrophobic analytes. The synthesis method of Ca-MOF/COF@SiO2 is green and mild, especially the use of acid-base tunable DES promotes the rapid synthesis of non-toxic Ca-MOF/COF@silica composites, which offers an innovative approach of greenly synthesizing novel MOF/COF stationary phases and extends their applications in the field of chromatography.
Metal organic framework (MOF) assembled with coordination bonds has the disadvantage of poor stability that limits its application in the field of stationary phase, while covalent organic framework (COF) assembled through covalent bonds exhibits excellent structural stability. It has been shown that the stationary phases prepared by combining MOF and COF can make up for the poor stability of MOF@SiO2, and the MOF/COF composites have superior chromatographic separation performance. However, the traditional methods for preparing COF/MOF based stationary phases are generally solvent thermal synthesis. In this study, a green and low-cost synthesis method was proposed for the preparation of MOF/COF@SiO2 stationary phase. Firstly, COF@SiO2 was prepared in a choline chloride/ethylene glycol based deep eutectic solvent (DES). Secondly, another acid-base tunable DES prepared by mixing p-toluenesulfonic acid (PTSA) and 2-methylimidazole in different proportions was introduced as the reaction solvent and reactant for rapid synthesis of MOF/COF@SiO2. Compared with the toxic transition metal-based MOFs selected in most previous studies, a lightweight and non-toxic S-zone metal (calcium) based MOF was employed in this study. PTSA and calcium will form the calcium/oxygen-containing organic acid framework in acidic DES, which assembles with terephthalic acid dissolved in basic DES to form MOF. The strong hydrogen bonding effect of DES can facilitate rapid assembly of Ca-MOF. The obtained Ca-MOF/COF@SiO2 can be used for multi-mode chromatography to efficiently separate multiple isomeric/hydrophilic/hydrophobic analytes. The synthesis method of Ca-MOF/COF@SiO2 is green and mild, especially the use of acid-base tunable DES promotes the rapid synthesis of non-toxic Ca-MOF/COF@silica composites, which offers an innovative approach of greenly synthesizing novel MOF/COF stationary phases and extends their applications in the field of chromatography.
2026, 37(1): 111187
doi: 10.1016/j.cclet.2025.111187
摘要:
Cuprous oxide (Cu2O) is one of the most promising catalysts for electrochemical conversion of CO2 into value-added C2 products. The efficiency of CO2-to-C2 conversion is highly dependent on the Cu2O crystal plane orientation and the corresponding adsorbed *CO species. Herein, we constructed high-index crystal planes (311) in Cu2O (CO–Cu2O) via a facile self-selective CO-induced strategy under a CO atmosphere, which was verified by high-resolution transmission electron microscopy (HR-TEM) and atomic force microscopy (AFM) results. By exploiting the high surface energy of the high index crystal planes, *CO species are stabilized in CO–Cu2O during CO2RR, resulting in exceptional catalytic performance for CO2-to-C2 products. In situ infrared spectroscopy revealed that both atop-type (*COatop) and hollow-type (*COhollow) adsorption of *CO species occurred on the CO–Cu2O. The asymmetric C–C coupling energy barrier between *COatop and *COhollow in (311) crystal plane decreases by 47.8% compared to the symmetric coupling of *COatop in conventional (100) crystal planes. Consequently, the Faradaic efficiency of C2 products generated with CO–Cu2O was increased by as high as 100% compared to that with pristine Cu2O.
Cuprous oxide (Cu2O) is one of the most promising catalysts for electrochemical conversion of CO2 into value-added C2 products. The efficiency of CO2-to-C2 conversion is highly dependent on the Cu2O crystal plane orientation and the corresponding adsorbed *CO species. Herein, we constructed high-index crystal planes (311) in Cu2O (CO–Cu2O) via a facile self-selective CO-induced strategy under a CO atmosphere, which was verified by high-resolution transmission electron microscopy (HR-TEM) and atomic force microscopy (AFM) results. By exploiting the high surface energy of the high index crystal planes, *CO species are stabilized in CO–Cu2O during CO2RR, resulting in exceptional catalytic performance for CO2-to-C2 products. In situ infrared spectroscopy revealed that both atop-type (*COatop) and hollow-type (*COhollow) adsorption of *CO species occurred on the CO–Cu2O. The asymmetric C–C coupling energy barrier between *COatop and *COhollow in (311) crystal plane decreases by 47.8% compared to the symmetric coupling of *COatop in conventional (100) crystal planes. Consequently, the Faradaic efficiency of C2 products generated with CO–Cu2O was increased by as high as 100% compared to that with pristine Cu2O.
2026, 37(1): 111197
doi: 10.1016/j.cclet.2025.111197
摘要:
The direct transformation of dinitrogen (N2) into nitrogen-containing organic compounds holds substantial importance. In this work, we report a titanium-promoted method for the conversion of N2 to N-methylimides. Initially, the N2-bridging end-on dititanium side-on dipotassium complex [{(TrenTMS)Ti}2(μ-η1:η1:η2:η2-N2K2)] underwent simultaneous disproportionation and N-methylation reactions in the presence of methyl trifluoromethanesulfonate (MeOTf), yielding [{(NMe, TMSNN2TMS)Ti}(μ-NMe)]2 with complete cleavage of the N≡N bond. The nucleophilicity of the N-methylated intermediate allowed it to react with electrophilic reagents such as trimethylchlorosilane (TMSCl) to form heptamethyldisilazane, or with acyl chlorides to generate N-methylimides. Moreover, nitrogen-15 (15N) labeled experiments provided a novel approach to synthesizing 15N-labeled methylimides.
The direct transformation of dinitrogen (N2) into nitrogen-containing organic compounds holds substantial importance. In this work, we report a titanium-promoted method for the conversion of N2 to N-methylimides. Initially, the N2-bridging end-on dititanium side-on dipotassium complex [{(TrenTMS)Ti}2(μ-η1:η1:η2:η2-N2K2)] underwent simultaneous disproportionation and N-methylation reactions in the presence of methyl trifluoromethanesulfonate (MeOTf), yielding [{(NMe, TMSNN2TMS)Ti}(μ-NMe)]2 with complete cleavage of the N≡N bond. The nucleophilicity of the N-methylated intermediate allowed it to react with electrophilic reagents such as trimethylchlorosilane (TMSCl) to form heptamethyldisilazane, or with acyl chlorides to generate N-methylimides. Moreover, nitrogen-15 (15N) labeled experiments provided a novel approach to synthesizing 15N-labeled methylimides.
2026, 37(1): 111207
doi: 10.1016/j.cclet.2025.111207
摘要:
The excessive use of pesticides has exacerbated environmental pollution due to herbicide residues, while their persistent toxicity poses serious challenges to global ecological security. A magnetically recyclable CoFe2O4/BiOBr S-scheme heterojunctions was prepared by microwave-assisted co-precipitation method for photocatalytic degradation of Diuron (DUR) in water. The formation of S-scheme heterojunction enhances electron transfer and charge separation, which was demonstrated by free radical trapping, electrochemical experiments, and DFT calculations. The magnetic CoFe2O4/BiOBr catalysts can achieve 99.9% removal of diuron in 50 min under visible light irradiation. Furthermore, the system maintains stable performance across a broad pH range (3–9), enabling adaptation to diverse water environments, effective elimination of multiple pollutants, and strong resistance to ionic interference. Using magnetic recovery, CoFe2O4/BiOBr exhibits a high removal rate of 99% and a markedly low ion leaching rate (< 20 µg/L) after six cycles photocatalytic process, confirming its excellent stability and durability. According to HPLC-QTOF-MS and DFT calculation, the main ways of DUR degradation include dechlorinated hydroxylation, dealkylation and hydroxylation of aromatic ring and side chain. Toxicity analysis showed that the toxicity of the intermediates generated during degradation was generally lower than that of DUR. The magnetic CoFe2O4/BiOBr S-scheme heterojunction developed in this study exhibits excellent photocatalytic performance, high applicability, good stability, and durability, providing an effective magnetic for the removal of refractory pollutants.
The excessive use of pesticides has exacerbated environmental pollution due to herbicide residues, while their persistent toxicity poses serious challenges to global ecological security. A magnetically recyclable CoFe2O4/BiOBr S-scheme heterojunctions was prepared by microwave-assisted co-precipitation method for photocatalytic degradation of Diuron (DUR) in water. The formation of S-scheme heterojunction enhances electron transfer and charge separation, which was demonstrated by free radical trapping, electrochemical experiments, and DFT calculations. The magnetic CoFe2O4/BiOBr catalysts can achieve 99.9% removal of diuron in 50 min under visible light irradiation. Furthermore, the system maintains stable performance across a broad pH range (3–9), enabling adaptation to diverse water environments, effective elimination of multiple pollutants, and strong resistance to ionic interference. Using magnetic recovery, CoFe2O4/BiOBr exhibits a high removal rate of 99% and a markedly low ion leaching rate (< 20 µg/L) after six cycles photocatalytic process, confirming its excellent stability and durability. According to HPLC-QTOF-MS and DFT calculation, the main ways of DUR degradation include dechlorinated hydroxylation, dealkylation and hydroxylation of aromatic ring and side chain. Toxicity analysis showed that the toxicity of the intermediates generated during degradation was generally lower than that of DUR. The magnetic CoFe2O4/BiOBr S-scheme heterojunction developed in this study exhibits excellent photocatalytic performance, high applicability, good stability, and durability, providing an effective magnetic for the removal of refractory pollutants.
2026, 37(1): 111219
doi: 10.1016/j.cclet.2025.111219
摘要:
Albeit notable endeavors in the construction of organophosphorodithioates, the direct catalytic enantioselective synthesis of organophosphorodithioates still stands for a long-lasting challenge. Herein, an efficient organocatalytic enantioselective nucleophilic addition of vinylidene ortho-quinone methide with phosphinothioic thioanhydride as nucleophilic reagent has been achieved by the dual catalysis of cinchona alkaloid-derived squaramide and 4-dimethylaminopyridine. This protocol provides a straightforward approach for accessing a variety of axially chiral phosphorodithiolated styrenes in good yields (up to 98% yield) with high stereoselectivities (up to 97% ee and >99:1 E/Z).
Albeit notable endeavors in the construction of organophosphorodithioates, the direct catalytic enantioselective synthesis of organophosphorodithioates still stands for a long-lasting challenge. Herein, an efficient organocatalytic enantioselective nucleophilic addition of vinylidene ortho-quinone methide with phosphinothioic thioanhydride as nucleophilic reagent has been achieved by the dual catalysis of cinchona alkaloid-derived squaramide and 4-dimethylaminopyridine. This protocol provides a straightforward approach for accessing a variety of axially chiral phosphorodithiolated styrenes in good yields (up to 98% yield) with high stereoselectivities (up to 97% ee and >99:1 E/Z).
2026, 37(1): 111222
doi: 10.1016/j.cclet.2025.111222
摘要:
T-cell acute lymphoblastic leukemia (T-ALL) is a common yet severe pediatric cancer treated with L-asparaginase (ASP). To boost the treatment's effectiveness and lessen its toxicity, enzyme@MOF nanoparticles were engineered with a hyaluronic acid (HA)-targeted polyethylene glycol (PEG) surface. These nanoparticles, termed ASP@MOF/PEG-HA, showed efficient uptake by drug-resistant T-ALL cells. The pH-sensitive zeolitic imidazolate framework-8 (ZIF-8) based metal-organic framework (MOF) nanoparticles allowed the encapsulated ASP to significantly increase cytotoxicity against T-ALL cells. Furthermore, HA's ability to bind to T-ALL cells with elevated CD44 expression further induced apoptosis in CD44+ T-ALL cells with poor prognosis. In animal models, the nanoparticles improved survival rates and reduced the burden of leukemia, demonstrating substantial anti-leukemia effects. Thus, these nanoparticles offer an effective treatment approach for drug-resistant T-ALL cells characterized by increased CD44 expression.
T-cell acute lymphoblastic leukemia (T-ALL) is a common yet severe pediatric cancer treated with L-asparaginase (ASP). To boost the treatment's effectiveness and lessen its toxicity, enzyme@MOF nanoparticles were engineered with a hyaluronic acid (HA)-targeted polyethylene glycol (PEG) surface. These nanoparticles, termed ASP@MOF/PEG-HA, showed efficient uptake by drug-resistant T-ALL cells. The pH-sensitive zeolitic imidazolate framework-8 (ZIF-8) based metal-organic framework (MOF) nanoparticles allowed the encapsulated ASP to significantly increase cytotoxicity against T-ALL cells. Furthermore, HA's ability to bind to T-ALL cells with elevated CD44 expression further induced apoptosis in CD44+ T-ALL cells with poor prognosis. In animal models, the nanoparticles improved survival rates and reduced the burden of leukemia, demonstrating substantial anti-leukemia effects. Thus, these nanoparticles offer an effective treatment approach for drug-resistant T-ALL cells characterized by increased CD44 expression.
2026, 37(1): 111237
doi: 10.1016/j.cclet.2025.111237
摘要:
Hepatic fibrosis is regulated by the synergistic actions of various cells and cytokines, with the activation and proliferation of hepatic stellate cells (HSCs) being considered the central event in this process. To achieve specific targeting of activated hepatic stellate cells (aHSCs) and precise treatment of hepatic fibrosis, this study developed a dual-functional drug delivery system (SIL/cRGD-PEG-PPS PMs) with both targeting and responsive release capabilities. It aims to target the αvβ3 receptor specifically expressed on the surface of aHSCs using the cyclic peptide c(RGDyk), and to exploit the high reactive oxygen species (ROS) level in the cellular microenvironment to achieve concentrated burst release of drugs at the pathological sites of hepatic fibrosis. Based on multiple assessments, SIL/cRGD-PEG-PPS PMs specifically enhanced the targeted delivery of silybin (SIL) to aHSCs, inhibited the proliferation and migration of aHSCs, and exhibited good biosafety. Additionally, it demonstrated excellent anti-fibrotic activity in fibrotic mice. In summary, this study shows great potential in targeted treatment of hepatic fibrosis and provides a multifunctional tool for advancing the research and therapeutic strategies of hepatic fibrosis.
Hepatic fibrosis is regulated by the synergistic actions of various cells and cytokines, with the activation and proliferation of hepatic stellate cells (HSCs) being considered the central event in this process. To achieve specific targeting of activated hepatic stellate cells (aHSCs) and precise treatment of hepatic fibrosis, this study developed a dual-functional drug delivery system (SIL/cRGD-PEG-PPS PMs) with both targeting and responsive release capabilities. It aims to target the αvβ3 receptor specifically expressed on the surface of aHSCs using the cyclic peptide c(RGDyk), and to exploit the high reactive oxygen species (ROS) level in the cellular microenvironment to achieve concentrated burst release of drugs at the pathological sites of hepatic fibrosis. Based on multiple assessments, SIL/cRGD-PEG-PPS PMs specifically enhanced the targeted delivery of silybin (SIL) to aHSCs, inhibited the proliferation and migration of aHSCs, and exhibited good biosafety. Additionally, it demonstrated excellent anti-fibrotic activity in fibrotic mice. In summary, this study shows great potential in targeted treatment of hepatic fibrosis and provides a multifunctional tool for advancing the research and therapeutic strategies of hepatic fibrosis.
2026, 37(1): 111251
doi: 10.1016/j.cclet.2025.111251
摘要:
Nanofiltration (NF) technology, with its capacity for nanoscale filtration and controllable selectivity, holds significant promise in diverse applications. However, the current upper bound of permeance and selectivity of NF membranes is intrinsically constrained by the morphology and structure of the polyamide (PA) selective layer. This issue arises because NF membranes typically exhibit relatively smooth nodular structures, which theoretically impede efficient water transport. In this study, we enhanced the formation of nanobubbles by synergistically regulating with surfactant and low temperatures, resulting in the fabrication of PA NF membranes with a crumpled morphology. We observed that lower temperatures promote enhanced gas solubility in the aqueous phase, facilitating increased nanobubble formation through the foaming effect of surfactant sodium dodecylbenzene sulfonate (SDBS). Consequently, this resulted in the creation of PA NF membranes with more crumpled structures and superior performance, with pure water permeance reaching 36.25 ± 0.42 L m-2 h-1 bar-1, representing an improvement of 14.47 L m-2 h-1 bar-1 compared to the control group. Additionally, it maintains a high Na2SO4 rejection rate of 97.00% ± 0.58%. The PA NF membranes produced by eliminating nanobubbles and free interfaces exhibited a smooth structure, whereas introducing nanobubbles (through NaHCO3 addition, N2 pressurization, and ultrasonication) resulted in the formation of crumpled membranes. This emphasized that the large amount of nanobubbles generated by SDBS and low temperature in the interfacial process played a critical role in shaping crumpled PA NF membranes and enhancing membrane performance. This approach has the potential to provide valuable insights into customizing the structural design of TFC PA NF membranes, contributing to further advancements in this field.
Nanofiltration (NF) technology, with its capacity for nanoscale filtration and controllable selectivity, holds significant promise in diverse applications. However, the current upper bound of permeance and selectivity of NF membranes is intrinsically constrained by the morphology and structure of the polyamide (PA) selective layer. This issue arises because NF membranes typically exhibit relatively smooth nodular structures, which theoretically impede efficient water transport. In this study, we enhanced the formation of nanobubbles by synergistically regulating with surfactant and low temperatures, resulting in the fabrication of PA NF membranes with a crumpled morphology. We observed that lower temperatures promote enhanced gas solubility in the aqueous phase, facilitating increased nanobubble formation through the foaming effect of surfactant sodium dodecylbenzene sulfonate (SDBS). Consequently, this resulted in the creation of PA NF membranes with more crumpled structures and superior performance, with pure water permeance reaching 36.25 ± 0.42 L m-2 h-1 bar-1, representing an improvement of 14.47 L m-2 h-1 bar-1 compared to the control group. Additionally, it maintains a high Na2SO4 rejection rate of 97.00% ± 0.58%. The PA NF membranes produced by eliminating nanobubbles and free interfaces exhibited a smooth structure, whereas introducing nanobubbles (through NaHCO3 addition, N2 pressurization, and ultrasonication) resulted in the formation of crumpled membranes. This emphasized that the large amount of nanobubbles generated by SDBS and low temperature in the interfacial process played a critical role in shaping crumpled PA NF membranes and enhancing membrane performance. This approach has the potential to provide valuable insights into customizing the structural design of TFC PA NF membranes, contributing to further advancements in this field.
2026, 37(1): 111252
doi: 10.1016/j.cclet.2025.111252
摘要:
As an important class of phenanthroline derivatives containing soft N and hard O donor atoms, the laborious syntheses of unsymmetrical 1, 10-phenanthroline-derived diamide ligands (DAPhen) have hindered its extensive study. In this work, we first report a convenient synthetic method for the construction of DAPhen using Friedländer reaction by two facile steps (vs. previous 12 steps). A variety of DAPhen ligands are readily available, especially unsymmetrical ones, which give us a platform to systematically study the substituent effect on f-block elements extraction performance. The performance of unsymmetrical extractants is experimentally confirmed to falls between that of their corresponding symmetrical extractants by extracting UO22+ as the representative f-block element. This work provides a direct and versatile method to synthesize symmetrical and unsymmetrical DAPhen, which paves way for the investigations on their coordination properties with metal ions and other applications.
As an important class of phenanthroline derivatives containing soft N and hard O donor atoms, the laborious syntheses of unsymmetrical 1, 10-phenanthroline-derived diamide ligands (DAPhen) have hindered its extensive study. In this work, we first report a convenient synthetic method for the construction of DAPhen using Friedländer reaction by two facile steps (vs. previous 12 steps). A variety of DAPhen ligands are readily available, especially unsymmetrical ones, which give us a platform to systematically study the substituent effect on f-block elements extraction performance. The performance of unsymmetrical extractants is experimentally confirmed to falls between that of their corresponding symmetrical extractants by extracting UO22+ as the representative f-block element. This work provides a direct and versatile method to synthesize symmetrical and unsymmetrical DAPhen, which paves way for the investigations on their coordination properties with metal ions and other applications.
2026, 37(1): 111253
doi: 10.1016/j.cclet.2025.111253
摘要:
Integration of single-atom catalysts (SACs) onto metal-organic frameworks (MOFs) with porous channels has garnered significant interest in the field of CO2 reduction. However, MOFs are usually bulky can impede the diffusion of intermediates with substrates and maximizing catalytic site utilization remains a challenge. In this study, we utilized firstly the post-synthetic single-atom chelation sites on zirconium-based metal-organic cages (Zr-MOCs) to anchor cobalt (Co) atom to synthesize single-dispersible ZrT-1-NH2-IS-Co molecular cages for CO2 photoreduction. Experimental results demonstrate that ZrT-1-NH2-IS-Co exhibits impressive catalytic performance, achieving syngas yields of up to 30.9 mmol g-1 h-1, ranking among the highest values of reported crystalline porous catalysts. Mechanistic insights reveal the newly introduced metal serving as the catalytic site and *COOH acts as a crucial intermediate in the CO2 reduction process. Furthermore, the successful synthesis of ZrT-1-NH2-IS-Ni and ZrT-1-NH2-IS-Mn show the universality of the modification strategies, with their CO2 catalytic activity surpassing that of ZrT-1-NH2.
Integration of single-atom catalysts (SACs) onto metal-organic frameworks (MOFs) with porous channels has garnered significant interest in the field of CO2 reduction. However, MOFs are usually bulky can impede the diffusion of intermediates with substrates and maximizing catalytic site utilization remains a challenge. In this study, we utilized firstly the post-synthetic single-atom chelation sites on zirconium-based metal-organic cages (Zr-MOCs) to anchor cobalt (Co) atom to synthesize single-dispersible ZrT-1-NH2-IS-Co molecular cages for CO2 photoreduction. Experimental results demonstrate that ZrT-1-NH2-IS-Co exhibits impressive catalytic performance, achieving syngas yields of up to 30.9 mmol g-1 h-1, ranking among the highest values of reported crystalline porous catalysts. Mechanistic insights reveal the newly introduced metal serving as the catalytic site and *COOH acts as a crucial intermediate in the CO2 reduction process. Furthermore, the successful synthesis of ZrT-1-NH2-IS-Ni and ZrT-1-NH2-IS-Mn show the universality of the modification strategies, with their CO2 catalytic activity surpassing that of ZrT-1-NH2.
2026, 37(1): 111260
doi: 10.1016/j.cclet.2025.111260
摘要:
Ferroptosis has exhibited great potential in therapies and intracellular reducing agents of sulfur species (RSSs) in the thiol-dependent redox systems are crucial in ferroptosis. This makes the simultaneous detection of multiple RSSs significant for evaluating ferroptosis therapy. However, the traditional techniques, including fluorescent (FL) imaging and electrospray ionization-based mass spectrometry (MS) detection, cannot achieve the discrimination of different RSSs. Herein, simultaneous MS detection of multiple RSSs, including cysteine (Cys), homocysteine (Hcy), glutathione (GSH) and hydrogen sulfide (H2S), was obtained upon enhancing ionization efficiency by a fluorescent probe (NBD-O-1). Based on the interaction between NBD-O-1 and RSSs, the complex of RSSs with a fragment of NBD-O-1 can be generated, which can be easily ionized for MS detection in the negative mode. Therefore, the intracellular RSSs can be well detected upon the incubation of HeLa cells with the probe of NBD-O-1, exhibiting the total RSS levels by the FL imaging and further providing expression of each RSS by enhanced MS detection. Furthermore, the RSSs during ferroptosis in HeLa cells have been evaluated using the present strategy, demonstrating the potential for ferroptosis examinations. This work has made an unconventional application of a fluorescent probe to enhance the detection of multiple RSSs by MS, providing significant molecular information for addressing the ferroptosis mechanism.
Ferroptosis has exhibited great potential in therapies and intracellular reducing agents of sulfur species (RSSs) in the thiol-dependent redox systems are crucial in ferroptosis. This makes the simultaneous detection of multiple RSSs significant for evaluating ferroptosis therapy. However, the traditional techniques, including fluorescent (FL) imaging and electrospray ionization-based mass spectrometry (MS) detection, cannot achieve the discrimination of different RSSs. Herein, simultaneous MS detection of multiple RSSs, including cysteine (Cys), homocysteine (Hcy), glutathione (GSH) and hydrogen sulfide (H2S), was obtained upon enhancing ionization efficiency by a fluorescent probe (NBD-O-1). Based on the interaction between NBD-O-1 and RSSs, the complex of RSSs with a fragment of NBD-O-1 can be generated, which can be easily ionized for MS detection in the negative mode. Therefore, the intracellular RSSs can be well detected upon the incubation of HeLa cells with the probe of NBD-O-1, exhibiting the total RSS levels by the FL imaging and further providing expression of each RSS by enhanced MS detection. Furthermore, the RSSs during ferroptosis in HeLa cells have been evaluated using the present strategy, demonstrating the potential for ferroptosis examinations. This work has made an unconventional application of a fluorescent probe to enhance the detection of multiple RSSs by MS, providing significant molecular information for addressing the ferroptosis mechanism.
Beyond superhalogen assembly: Field-driven hyperhalogen design via dual-external-field cooperativity
2026, 37(1): 111265
doi: 10.1016/j.cclet.2025.111265
摘要:
Traditional strategies for designing hyperhalogens, superatoms with exceptional electron-withdrawing capacity, rely on complex superhalogen assembly, posing significant experimental challenges. Here, we introduce a non-invasive dual external field (DEF) approach combining solvent effects and an oriented external electric field (OEEF) to construct hyperhalogens, as demonstrated by density functional theory (DFT) calculations. Our DEF strategy proves versatile, successfully designing hyperhalogens not only in simplified Agn− model systems but also in the experimentally synthesized Ag25 nanocluster. Using the 3D Ag19− structure as a model, we further reveal the DEF's pivotal role in O2 activation, where solvent-OEEF synergy induces tunable O–O bond elongation and charge transfer, proportional to field strength. Our findings establish a field-driven paradigm for hyperhalogen design that preserves native cluster composition, providing a theoretical foundation for tailoring high-performance catalysts through precise active-site modulation.
Traditional strategies for designing hyperhalogens, superatoms with exceptional electron-withdrawing capacity, rely on complex superhalogen assembly, posing significant experimental challenges. Here, we introduce a non-invasive dual external field (DEF) approach combining solvent effects and an oriented external electric field (OEEF) to construct hyperhalogens, as demonstrated by density functional theory (DFT) calculations. Our DEF strategy proves versatile, successfully designing hyperhalogens not only in simplified Agn− model systems but also in the experimentally synthesized Ag25 nanocluster. Using the 3D Ag19− structure as a model, we further reveal the DEF's pivotal role in O2 activation, where solvent-OEEF synergy induces tunable O–O bond elongation and charge transfer, proportional to field strength. Our findings establish a field-driven paradigm for hyperhalogen design that preserves native cluster composition, providing a theoretical foundation for tailoring high-performance catalysts through precise active-site modulation.
2026, 37(1): 111270
doi: 10.1016/j.cclet.2025.111270
摘要:
This study investigates the properties of high-purity starches extracted from Polygonum multiflorum (PMS) and Smilax glabra (SGS). The starches were characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, high-performance anion-exchange chromatography, and differential scanning calorimetry. Significant differences were observed in their morphological, physicochemical, and functional properties. PMS had a smaller particle size (13.68 µm), irregular polygonal shape, A-type, lower water absorption (62.67%), and higher oil absorption (51.17%). In contrast, SGS exhibited larger particles (31.75 µm), a nearly spherical shape, B-type, higher crystallinity (50.66%), and greater amylose content (21.54%), with superior thermal stability, shear resistance, and gelatinization enthalpy. SGS also contained higher resistant starch (83.28%) and longer average chain length (20.58%), but showed lower solubility, swelling power, light transmittance, and freeze-thaw stability. The physicochemical properties differences in crystal pattern and particle morphology between PMS and SGS lead to distinct behaviors during in vitro digestion and fermentation. These findings highlight the potential of medicinal plant starches in functional ingredients and industrial processes.
This study investigates the properties of high-purity starches extracted from Polygonum multiflorum (PMS) and Smilax glabra (SGS). The starches were characterized by scanning electron microscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, high-performance anion-exchange chromatography, and differential scanning calorimetry. Significant differences were observed in their morphological, physicochemical, and functional properties. PMS had a smaller particle size (13.68 µm), irregular polygonal shape, A-type, lower water absorption (62.67%), and higher oil absorption (51.17%). In contrast, SGS exhibited larger particles (31.75 µm), a nearly spherical shape, B-type, higher crystallinity (50.66%), and greater amylose content (21.54%), with superior thermal stability, shear resistance, and gelatinization enthalpy. SGS also contained higher resistant starch (83.28%) and longer average chain length (20.58%), but showed lower solubility, swelling power, light transmittance, and freeze-thaw stability. The physicochemical properties differences in crystal pattern and particle morphology between PMS and SGS lead to distinct behaviors during in vitro digestion and fermentation. These findings highlight the potential of medicinal plant starches in functional ingredients and industrial processes.
2026, 37(1): 111283
doi: 10.1016/j.cclet.2025.111283
摘要:
To enhance the anti-resistance efficacy of our previously disclosed naphthyl-triazine 5, structure-based drug design strategy was rationally conducted to design a series of novel biphenyl-piperidine-triazine-containing non-nucleoside reverse transcriptase inhibitors. Remarkably, several of these compounds demonstrated single-digit nanomolar antiviral potency against both wild-type (WT) human immunodeficiency virus-1 (HIV-1) and five clinically relevant mutant strains. Among these, compound 11s emerged as the most potent inhibitor, showing remarkable efficacy against WT HIV-1 (50% effective concentration (EC50) = 2 nmol/L) and five mutant strains (EC50 = 0.003–0.073 µmol/L), which was significantly superior to that of compound 5. This optimized derivative demonstrated substantially improved pharmacological properties compared to existing drugs etravirine (ETR) and rilpivirine (RPV), showing a 4-fold reduction in cytotoxicity alongside 6-fold enhancement in selectivity index (50% cytotoxic concentration (CC50) = 19.69 µmol/L, selectivity index (SI) = 7438). The compound’s metabolic profile revealed exceptional stability, with an elimination half-life (t1/2 = 41.4 min) more than double that of RPV (t1/2 = 16.03 min). Comprehensive safety evaluation indicated minimal cytochrome P450 (CYP) enzymes interference, low cardiac ion channel activity, and no observable acute toxicity, collectively suggesting a reduced risk profile for therapeutic applications. These promising characteristics significantly advance the development potential of biphenyl-piperidine-triazine derivatives as next-generation non-nucleoside reverse transcriptase inhibitors (NNRTIs), offering enhanced efficacy, improved safety, and favorable pharmacokinetic properties for antiretroviral therapy.
To enhance the anti-resistance efficacy of our previously disclosed naphthyl-triazine 5, structure-based drug design strategy was rationally conducted to design a series of novel biphenyl-piperidine-triazine-containing non-nucleoside reverse transcriptase inhibitors. Remarkably, several of these compounds demonstrated single-digit nanomolar antiviral potency against both wild-type (WT) human immunodeficiency virus-1 (HIV-1) and five clinically relevant mutant strains. Among these, compound 11s emerged as the most potent inhibitor, showing remarkable efficacy against WT HIV-1 (50% effective concentration (EC50) = 2 nmol/L) and five mutant strains (EC50 = 0.003–0.073 µmol/L), which was significantly superior to that of compound 5. This optimized derivative demonstrated substantially improved pharmacological properties compared to existing drugs etravirine (ETR) and rilpivirine (RPV), showing a 4-fold reduction in cytotoxicity alongside 6-fold enhancement in selectivity index (50% cytotoxic concentration (CC50) = 19.69 µmol/L, selectivity index (SI) = 7438). The compound’s metabolic profile revealed exceptional stability, with an elimination half-life (t1/2 = 41.4 min) more than double that of RPV (t1/2 = 16.03 min). Comprehensive safety evaluation indicated minimal cytochrome P450 (CYP) enzymes interference, low cardiac ion channel activity, and no observable acute toxicity, collectively suggesting a reduced risk profile for therapeutic applications. These promising characteristics significantly advance the development potential of biphenyl-piperidine-triazine derivatives as next-generation non-nucleoside reverse transcriptase inhibitors (NNRTIs), offering enhanced efficacy, improved safety, and favorable pharmacokinetic properties for antiretroviral therapy.
2026, 37(1): 111307
doi: 10.1016/j.cclet.2025.111307
摘要:
Electrochemical CO2 reduction reaction (CO2RR) into valuable formate provides a strategy for carbon neutrality. Bismuth (Bi) catalysts, attributed to their appropriate energy barrier of OCHO* intermediate, have demonstrated substantial potential for the advancement of electrocatalytic CO2 reduction to formate. However, due to the weak bonding of protons (H*) of Bi, the available protonate of CO2 on Bi is insufficient, which limits the formation of OCHO*. Prediction by theoretical calculation, chlorine doping can effectively promote the dissociation of H2O and thus achieve effective proton supply. We prepare chlorine-doped Bi (Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO2. An obvious improvement of faradaic efficiency (FE) of formate (96.7% at −0.95 V vs. RHE) can be achieved on Cl-Bi, higher than that of Bi (89.4%). Meanwhile, Cl-Bi has the highest formate production rate of 275 µmol h−1 cm−2 at −0.95 V vs. RHE, which is 1.2 times higher than that of Bi (224 µmol h−1 cm−2). In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H2O and supply sufficient protons to promote the protonation of CO2 to OCHO*, which is consistent with theoretical calculation. The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.
Electrochemical CO2 reduction reaction (CO2RR) into valuable formate provides a strategy for carbon neutrality. Bismuth (Bi) catalysts, attributed to their appropriate energy barrier of OCHO* intermediate, have demonstrated substantial potential for the advancement of electrocatalytic CO2 reduction to formate. However, due to the weak bonding of protons (H*) of Bi, the available protonate of CO2 on Bi is insufficient, which limits the formation of OCHO*. Prediction by theoretical calculation, chlorine doping can effectively promote the dissociation of H2O and thus achieve effective proton supply. We prepare chlorine-doped Bi (Cl-Bi) via an electrochemical conversion strategy for electroreduction of CO2. An obvious improvement of faradaic efficiency (FE) of formate (96.7% at −0.95 V vs. RHE) can be achieved on Cl-Bi, higher than that of Bi (89.4%). Meanwhile, Cl-Bi has the highest formate production rate of 275 µmol h−1 cm−2 at −0.95 V vs. RHE, which is 1.2 times higher than that of Bi (224 µmol h−1 cm−2). In situ characterizations and kinetic analysis reveal that chlorine doping promotes the activation of H2O and supply sufficient protons to promote the protonation of CO2 to OCHO*, which is consistent with theoretical calculation. The study presents an effective strategy for rational design of highly efficient electrocatalysts to promote green chemical production.
2026, 37(1): 111308
doi: 10.1016/j.cclet.2025.111308
摘要:
The hydrogen evolution reaction (HER) is a key process in electrocatalytic water splitting for hydrogen production, yet it is often limited by sluggish H*-OH adsorption and H* binding kinetics. We obtained Ru-modified NiO nanoparticles (Ru-NiO/NF) with enhanced HER properties by substituting ruthenium (Ru) for Ni atoms in the NiO (200) crystalline facets on nickel foam by a one-step electrodeposition technique. This novel catalyst exhibits a significantly reduced H*-OH adsorption energy and improved kinetics, with an overpotential of only 60 mV at 10 mA/cm2 and a Tafel slope of 26.19 mV/dec. The Ru-NiO/NF maintains its activity for over 115 h, outperforming NiO/NF by reducing the overpotential by 177 mV. DFT calculations confirm that the addition of Ru to NiO enhances the HER kinetics by modifying the electronic structure, optimizing the surface chemistry, stabilizing the intermediates, lowering the energy barriers, and facilitating efficient charge transfer through a robust three-dimensional structure, resulting in a change in the rate-limiting step and a significant reduction in the Gibbs free energy. This study presents a highly efficient HER catalyst and offers insights into designing advanced NiO-based electrocatalysts by reducing reaction energy barriers.
The hydrogen evolution reaction (HER) is a key process in electrocatalytic water splitting for hydrogen production, yet it is often limited by sluggish H*-OH adsorption and H* binding kinetics. We obtained Ru-modified NiO nanoparticles (Ru-NiO/NF) with enhanced HER properties by substituting ruthenium (Ru) for Ni atoms in the NiO (200) crystalline facets on nickel foam by a one-step electrodeposition technique. This novel catalyst exhibits a significantly reduced H*-OH adsorption energy and improved kinetics, with an overpotential of only 60 mV at 10 mA/cm2 and a Tafel slope of 26.19 mV/dec. The Ru-NiO/NF maintains its activity for over 115 h, outperforming NiO/NF by reducing the overpotential by 177 mV. DFT calculations confirm that the addition of Ru to NiO enhances the HER kinetics by modifying the electronic structure, optimizing the surface chemistry, stabilizing the intermediates, lowering the energy barriers, and facilitating efficient charge transfer through a robust three-dimensional structure, resulting in a change in the rate-limiting step and a significant reduction in the Gibbs free energy. This study presents a highly efficient HER catalyst and offers insights into designing advanced NiO-based electrocatalysts by reducing reaction energy barriers.
2026, 37(1): 111321
doi: 10.1016/j.cclet.2025.111321
摘要:
The first hemiterpene-quassinoid adducts, bruquass A and B (1 and 2), were rapidly isolated and identified from Brucea javanica using an integrated analytical strategy. They possessed unusual carbon skeletons formed by the coupling of quassinoids with hemiterpene units via vinylogous aldol reactions. Their structural configurations were determined through comprehensive spectroscopic analysis and electronic circular dichroism (ECD) calculations. Plausible biosynthetic pathways for 1 and 2 were proposed, and guided by these biogenetic insights, the biomimetic synthesis of compound 1 was successfully achieved. Furthermore, compounds 1 and 2 exhibited significant antifeedant activity against Plutella xylostella. The bioactivity assessment results open up the prospects of 1 and 2 as a promising new class of botanical insecticide.
The first hemiterpene-quassinoid adducts, bruquass A and B (1 and 2), were rapidly isolated and identified from Brucea javanica using an integrated analytical strategy. They possessed unusual carbon skeletons formed by the coupling of quassinoids with hemiterpene units via vinylogous aldol reactions. Their structural configurations were determined through comprehensive spectroscopic analysis and electronic circular dichroism (ECD) calculations. Plausible biosynthetic pathways for 1 and 2 were proposed, and guided by these biogenetic insights, the biomimetic synthesis of compound 1 was successfully achieved. Furthermore, compounds 1 and 2 exhibited significant antifeedant activity against Plutella xylostella. The bioactivity assessment results open up the prospects of 1 and 2 as a promising new class of botanical insecticide.
2026, 37(1): 111353
doi: 10.1016/j.cclet.2025.111353
摘要:
Two supramolecular organic frameworks (SOFs) have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water. Dynamic light scattering and 1H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature. One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice, which improves by 40% compared with the highest value of the reported SOFs. In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrug-resistant MDR A549/ADR tumor cells to realize intracellular delivery, leading to enhanced antitumor efficacy. Moreover, it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism. As the first examples that undergo room-temperature reversible assembly and disassembly, the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
Two supramolecular organic frameworks (SOFs) have been constructed from the co-assembly of biimidazolium-derived octacationic components and cucurbit[8]uril in water. Dynamic light scattering and 1H NMR experiments reveal that both SOFs can undergo reversible assembly and disassembly at room temperature. One of the SOFs displays unprecedently high maximum tolerated dose of 120 mg/kg with mice, which improves by 40% compared with the highest value of the reported SOFs. In vitro and in vivo tests show that the SOF can adsorb doxorubicin and overcome the resistance of multidrug-resistant MDR A549/ADR tumor cells to realize intracellular delivery, leading to enhanced antitumor efficacy. Moreover, it can also completely inhibit the posttreatment phototoxicity of photofrin and fully neutralize the anticoagulation of both unfractionated heparin and low molecular weight heparins through efficient inclusion and elimination or sequestration mechanism. As the first examples that undergo room-temperature reversible assembly and disassembly, the new SOFs in principle allow for quantitative analysis of the molecular components in the body that is prerequisite for preclinical evaluation in the future.
2026, 37(1): 111385
doi: 10.1016/j.cclet.2025.111385
摘要:
Achieving non-centrosymmetric (NCS) configurations in ABX3-type hybrid halides remains a critical challenge for nonlinear optical (NLO) materials due to the conflicting requirements of high second-harmonic generation (SHG) response, wide bandgap, and phase-matching capabilities. Herein, we propose a triple-site modulation strategy by synergistically tailoring the A-site cations (2-methylimidazole cation/1-ethyl-3-methylimidazole cation), B-site metals (Sn2+/Pb2+), and X-site halogens (Cl/Br), which effectively disrupts lattice symmetry and enables NCS crystallization. Our results demonstrate a strong SHG response, an expanded optical bandgap and increased birefringence. The optimized compound C6H11N2PbCl3 exhibits a moderately strong SHG efficiency of 3.8 × KDP, a wide bandgap (3.87 eV), and enhanced birefringence (0.139@1064 nm), surpassing majority hybrid NLO materials. The innovative anionic framework introduced here broadens the scope of hybrid NLO crystals, facilitating the integration of various aromatic heterocyclic cations. This research provides a robust strategic framework for the development of advanced NLO materials.
Achieving non-centrosymmetric (NCS) configurations in ABX3-type hybrid halides remains a critical challenge for nonlinear optical (NLO) materials due to the conflicting requirements of high second-harmonic generation (SHG) response, wide bandgap, and phase-matching capabilities. Herein, we propose a triple-site modulation strategy by synergistically tailoring the A-site cations (2-methylimidazole cation/1-ethyl-3-methylimidazole cation), B-site metals (Sn2+/Pb2+), and X-site halogens (Cl/Br), which effectively disrupts lattice symmetry and enables NCS crystallization. Our results demonstrate a strong SHG response, an expanded optical bandgap and increased birefringence. The optimized compound C6H11N2PbCl3 exhibits a moderately strong SHG efficiency of 3.8 × KDP, a wide bandgap (3.87 eV), and enhanced birefringence (0.139@1064 nm), surpassing majority hybrid NLO materials. The innovative anionic framework introduced here broadens the scope of hybrid NLO crystals, facilitating the integration of various aromatic heterocyclic cations. This research provides a robust strategic framework for the development of advanced NLO materials.
2026, 37(1): 111415
doi: 10.1016/j.cclet.2025.111415
摘要:
Aqueous zinc-ion batteries (AZIBs) have advantages including low economic cost and high safety. Nevertheless, the serious hydrogen evolution reactions (HER) and rampant growth of Zn dendrite hinder their further development. Herein, potassium acetate (KAc) additive with cation/anion synergy effect is added into the ZnSO4 electrolyte to effectively promote the oriented uniform Zn deposition and suppress side reactions. According to density functional theory calculation and experimental results, CH3COO− (Ac−) anions are capable of forming stronger hydrogen bonds with H2O molecules, leading to an expanded electrochemical stability window, reduced the reactivity of H2O, and hence suppressing HER. Meanwhile, Ac− anions can also preferentially adsorb onto the Zn anode, promoting dense deposition towards the (100) crystal plane. Besides, dissociated K+ ions serve as electrostatic shielding cations, which significantly promote uniform Zn deposition and prevent dendrite formation. Thus, the ZnZn symmetric cell demonstrates an impressive cycle lifespan of 3000 h at 1.0 mA/cm2. Furthermore, the ZnMnO2 full battery exhibits superior stability with a capacity retention of 86.95% at 2.0 A/g after 4000 cycles. Therefore, the cation/anion synergy effect in KAc additive offers a viable solution to address HER and hinder dendrite growth at the interface of Zn anodes.
Aqueous zinc-ion batteries (AZIBs) have advantages including low economic cost and high safety. Nevertheless, the serious hydrogen evolution reactions (HER) and rampant growth of Zn dendrite hinder their further development. Herein, potassium acetate (KAc) additive with cation/anion synergy effect is added into the ZnSO4 electrolyte to effectively promote the oriented uniform Zn deposition and suppress side reactions. According to density functional theory calculation and experimental results, CH3COO− (Ac−) anions are capable of forming stronger hydrogen bonds with H2O molecules, leading to an expanded electrochemical stability window, reduced the reactivity of H2O, and hence suppressing HER. Meanwhile, Ac− anions can also preferentially adsorb onto the Zn anode, promoting dense deposition towards the (100) crystal plane. Besides, dissociated K+ ions serve as electrostatic shielding cations, which significantly promote uniform Zn deposition and prevent dendrite formation. Thus, the ZnZn symmetric cell demonstrates an impressive cycle lifespan of 3000 h at 1.0 mA/cm2. Furthermore, the ZnMnO2 full battery exhibits superior stability with a capacity retention of 86.95% at 2.0 A/g after 4000 cycles. Therefore, the cation/anion synergy effect in KAc additive offers a viable solution to address HER and hinder dendrite growth at the interface of Zn anodes.
2026, 37(1): 111425
doi: 10.1016/j.cclet.2025.111425
摘要:
Effective treatment of subcutaneous tumors remains a focal point in cancer therapy. Photothermal therapy, a novel therapeutic approach, has emerged as a promising alternative, offering a less invasive option for the treatment of subcutaneous tumors. This study reports the exploration of novel supramolecular halogen-bonded organic frameworks (XOFs) based on [N···Br+···N] halogen bonds through the ligand exchange strategy and their application in photothermal therapy. Through ligand exchange, XOF(Br)-TPy was successfully prepared, and its structure and properties were thoroughly characterized using NMR, XPS, FT-IR, and XRD techniques. Due to their cationic characteristics, these XOFs serve as effective carriers for the photothermal agent IR820. In vitro experiments demonstrated that the IR820@XOF(Br)-TPy composite exhibits excellent photothermal conversion efficiency under NIR irradiation, effectively inducing tumor cell ablation. Furthermore, in vivo studies confirmed the remarkable antitumor efficacy of the composite material in a subcutaneous tumor model. This work demonstrates that the ligand exchange strategy is a versatile and facile approach for constructing XOFs(Br) and provides a novel strategy for developing advanced photothermal therapeutic agents with significant application potential.
Effective treatment of subcutaneous tumors remains a focal point in cancer therapy. Photothermal therapy, a novel therapeutic approach, has emerged as a promising alternative, offering a less invasive option for the treatment of subcutaneous tumors. This study reports the exploration of novel supramolecular halogen-bonded organic frameworks (XOFs) based on [N···Br+···N] halogen bonds through the ligand exchange strategy and their application in photothermal therapy. Through ligand exchange, XOF(Br)-TPy was successfully prepared, and its structure and properties were thoroughly characterized using NMR, XPS, FT-IR, and XRD techniques. Due to their cationic characteristics, these XOFs serve as effective carriers for the photothermal agent IR820. In vitro experiments demonstrated that the IR820@XOF(Br)-TPy composite exhibits excellent photothermal conversion efficiency under NIR irradiation, effectively inducing tumor cell ablation. Furthermore, in vivo studies confirmed the remarkable antitumor efficacy of the composite material in a subcutaneous tumor model. This work demonstrates that the ligand exchange strategy is a versatile and facile approach for constructing XOFs(Br) and provides a novel strategy for developing advanced photothermal therapeutic agents with significant application potential.
2026, 37(1): 111450
doi: 10.1016/j.cclet.2025.111450
摘要:
Cisplatin (CDDP)-based chemotherapy is an effective strategy for the treatment of advanced nasopharyngeal carcinoma (NPC). However, serious toxic side effects of CDDP limit patient tolerance and treatment compliance, which urgently needs to be addressed in clinical application. Liposomes have been considered ideal vehicles for reducing CDDP toxicity due to their high biocompatibility, low toxicity and passive targeting ability. Nevertheless, CDDP's poor water/lipid solubility usually results in a low liposome drug-lipid ratio, limiting tumor delivery ability. Herein, a CDDP-polyphenol complex liposome was designed to increase the drug loading capacity of CDDP to realize the reduction of toxicity and effective antitumor effect simultaneously. The complex was prepared via complexation reaction of different stoichiometric ratios of CDDP and polyphenolic substances (gallic acid, epigallocatechin gallate and tannic acid), followed by encapsulation of complex in liposomes to improve tumor targeting. Notably, the molecular interaction forces between CDDP and polyphenolic substances were intensively investigated through a binding force disruption assay. In vitro studies demonstrated that the optimal formulation of CDDP-epigallocatechin gallate complex liposome (CDDP-EGCG Lips) showed the highest CDDP encapsulation efficiency, favorable stability, pH-sensitive release, enhanced cellular uptake and apoptosis effect. In vivo studies revealed that CDDP-EGCG Lips retarded the elimination of CDDP to prolong their circulation time, inhibited the growth of tumors, and significantly reduced the toxic side effects compared to CDDP monotherapy. This delivery strategy holds great promise for improving the clinical use of platinum-based drugs.
Cisplatin (CDDP)-based chemotherapy is an effective strategy for the treatment of advanced nasopharyngeal carcinoma (NPC). However, serious toxic side effects of CDDP limit patient tolerance and treatment compliance, which urgently needs to be addressed in clinical application. Liposomes have been considered ideal vehicles for reducing CDDP toxicity due to their high biocompatibility, low toxicity and passive targeting ability. Nevertheless, CDDP's poor water/lipid solubility usually results in a low liposome drug-lipid ratio, limiting tumor delivery ability. Herein, a CDDP-polyphenol complex liposome was designed to increase the drug loading capacity of CDDP to realize the reduction of toxicity and effective antitumor effect simultaneously. The complex was prepared via complexation reaction of different stoichiometric ratios of CDDP and polyphenolic substances (gallic acid, epigallocatechin gallate and tannic acid), followed by encapsulation of complex in liposomes to improve tumor targeting. Notably, the molecular interaction forces between CDDP and polyphenolic substances were intensively investigated through a binding force disruption assay. In vitro studies demonstrated that the optimal formulation of CDDP-epigallocatechin gallate complex liposome (CDDP-EGCG Lips) showed the highest CDDP encapsulation efficiency, favorable stability, pH-sensitive release, enhanced cellular uptake and apoptosis effect. In vivo studies revealed that CDDP-EGCG Lips retarded the elimination of CDDP to prolong their circulation time, inhibited the growth of tumors, and significantly reduced the toxic side effects compared to CDDP monotherapy. This delivery strategy holds great promise for improving the clinical use of platinum-based drugs.
2026, 37(1): 111458
doi: 10.1016/j.cclet.2025.111458
摘要:
Aqueous zinc-ion batteries (AZIBs) are regarded as one of the most promising energy conversion and storage devices. Nevertheless, side reactions and dendrite growth on the zinc metal anode hinder their widespread application. In this study, hemin was employed as a multi-functional artificial interface for the first time to inhibit the disordered growth of zinc dendrites and mitigate side reactions. Theoretical calculations indicate that hemin is preferentially adsorbed onto the zinc anode, thus blocking the interaction between the active zinc anode and electrolyte. Compared with zinc foil, the Hemin@Zn anode demonstrates enhanced corrosion resistance, a decrease in hydrogen evolution, and more orderly deposition of zinc. As expected, the symmetric cell with Hemin@Zn anode can sustain up to 4000 h at 0.2 mA/cm2, 0.2 mAh/cm2. Asymmetric Zn//Cu cells exhibit an average coulombic efficiency exceeding 99.72% during 500 cycles. Moreover, the full cell Hemin@Zn//NH4V4O10 delivers a superior capacity up to 367 mAh/g and the discharge capacity retention reaches 124 mAh/g after 1200 cycles even at a current density of 5 A/g. This work provides a simple and effective method for constructing a robust artificial interface to promote the application of long-life AZIBs.
Aqueous zinc-ion batteries (AZIBs) are regarded as one of the most promising energy conversion and storage devices. Nevertheless, side reactions and dendrite growth on the zinc metal anode hinder their widespread application. In this study, hemin was employed as a multi-functional artificial interface for the first time to inhibit the disordered growth of zinc dendrites and mitigate side reactions. Theoretical calculations indicate that hemin is preferentially adsorbed onto the zinc anode, thus blocking the interaction between the active zinc anode and electrolyte. Compared with zinc foil, the Hemin@Zn anode demonstrates enhanced corrosion resistance, a decrease in hydrogen evolution, and more orderly deposition of zinc. As expected, the symmetric cell with Hemin@Zn anode can sustain up to 4000 h at 0.2 mA/cm2, 0.2 mAh/cm2. Asymmetric Zn//Cu cells exhibit an average coulombic efficiency exceeding 99.72% during 500 cycles. Moreover, the full cell Hemin@Zn//NH4V4O10 delivers a superior capacity up to 367 mAh/g and the discharge capacity retention reaches 124 mAh/g after 1200 cycles even at a current density of 5 A/g. This work provides a simple and effective method for constructing a robust artificial interface to promote the application of long-life AZIBs.
2026, 37(1): 111476
doi: 10.1016/j.cclet.2025.111476
摘要:
Schizophrenia (SCZ) is a severe mental disorder with an unclear pathogenesis. Increasing evidence suggests that oxidative stress (OS) may contribute to the neuropathological processes underlying SCZ. Biothiols, key endogenous antioxidants, have been proposed as potential biomarkers for the disease. However, due to the presence of the blood-brain barrier (BBB), fluorescent probes are rarely used to image biothiols in the brain of SCZ models. In this study, a series of fluorescent probes for biothiols were developed using dicyanoisophorone derivatives as fluorophores known for their excellent optical properties, and carboxylic esters as recognition units. A parallel synthesis and rapid screening strategy was employed to construct and optimize these probes. By introducing trifluoromethyl and benzothiazole groups into the fluorophore, the emission wavelength was successfully shifted into the near-infrared region. Additionally, various trifluoromethyl-substituted aromatic and nitrogen heterocyclic compounds were incorporated to optimize the carboxylic esters, thereby improving the probes' reactivity and lipophilicity. Systematic evaluation of the physicochemical characteristics, and optical performance led to the identification of DCI-BT-11 as the most promising candidate. DCI-BT-11 demonstrated excellent BBB permeability and a good response to biothiols both in vitro and in vivo. Notably, DCI-BT-11 was used for the first time to visualize biothiol flux and assess the therapeutic effects of the antioxidant N-acetylcysteine (NAC) in the brains of SCZ mouse models, offering new insights into the role of OS in the pathogenesis and treatment of SCZ.
Schizophrenia (SCZ) is a severe mental disorder with an unclear pathogenesis. Increasing evidence suggests that oxidative stress (OS) may contribute to the neuropathological processes underlying SCZ. Biothiols, key endogenous antioxidants, have been proposed as potential biomarkers for the disease. However, due to the presence of the blood-brain barrier (BBB), fluorescent probes are rarely used to image biothiols in the brain of SCZ models. In this study, a series of fluorescent probes for biothiols were developed using dicyanoisophorone derivatives as fluorophores known for their excellent optical properties, and carboxylic esters as recognition units. A parallel synthesis and rapid screening strategy was employed to construct and optimize these probes. By introducing trifluoromethyl and benzothiazole groups into the fluorophore, the emission wavelength was successfully shifted into the near-infrared region. Additionally, various trifluoromethyl-substituted aromatic and nitrogen heterocyclic compounds were incorporated to optimize the carboxylic esters, thereby improving the probes' reactivity and lipophilicity. Systematic evaluation of the physicochemical characteristics, and optical performance led to the identification of DCI-BT-11 as the most promising candidate. DCI-BT-11 demonstrated excellent BBB permeability and a good response to biothiols both in vitro and in vivo. Notably, DCI-BT-11 was used for the first time to visualize biothiol flux and assess the therapeutic effects of the antioxidant N-acetylcysteine (NAC) in the brains of SCZ mouse models, offering new insights into the role of OS in the pathogenesis and treatment of SCZ.
2026, 37(1): 111486
doi: 10.1016/j.cclet.2025.111486
摘要:
By using carbohydrates as the biomass carbon sources, Se/C materials could be easily prepared. The materials could catalyze the oxidative deoximation reactions, which are significant transformations in both pharmaceutical industry and fine chemical production. Compared with the reported organoselenium-catalyzed ionic reactions, the Se/C-catalyzed deoximation reactions occurred via unique free radical mechanisms, endowing the Se species high catalytic reactivity. The Se/C catalysts were recyclable and their turnover numbers (TONs) were high (>104), making the reactions practical for industrial grade preparation. The unique free radical mechanisms of the reaction and green and practical features of the catalysts are the characteristics and advantages of the work.
By using carbohydrates as the biomass carbon sources, Se/C materials could be easily prepared. The materials could catalyze the oxidative deoximation reactions, which are significant transformations in both pharmaceutical industry and fine chemical production. Compared with the reported organoselenium-catalyzed ionic reactions, the Se/C-catalyzed deoximation reactions occurred via unique free radical mechanisms, endowing the Se species high catalytic reactivity. The Se/C catalysts were recyclable and their turnover numbers (TONs) were high (>104), making the reactions practical for industrial grade preparation. The unique free radical mechanisms of the reaction and green and practical features of the catalysts are the characteristics and advantages of the work.
2026, 37(1): 111500
doi: 10.1016/j.cclet.2025.111500
摘要:
The detection of amino acid enantiomers holds significant importance in biomedical, chemical, food, and other fields. Traditional chiral recognition methods using fluorescent probes primarily rely on fluorescence intensity changes, which can compromise accuracy and repeatability. In this study, we report a novel fluorescent probe (R)-Z1 that achieves effective enantioselective recognition of chiral amino acids in water by altering emission wavelengths (> 60 nm). This water-soluble probe (R)-Z1 exhibits cyan or yellow-green luminescence upon interaction with amino acid enantiomers, enabling reliable chiral detection of 14 natural amino acids. It also allows for the determination of enantiomeric excess through monitoring changes in luminescent color. Additionally, a logic operation with two inputs and three outputs was constructed based on these optical properties. Notably, amino acid enantiomers were successfully detected via dual-channel analysis at both the food and cellular levels. This study provides a new dynamic luminescence-based tool for the accurate sensing and detection of amino acid enantiomers.
The detection of amino acid enantiomers holds significant importance in biomedical, chemical, food, and other fields. Traditional chiral recognition methods using fluorescent probes primarily rely on fluorescence intensity changes, which can compromise accuracy and repeatability. In this study, we report a novel fluorescent probe (R)-Z1 that achieves effective enantioselective recognition of chiral amino acids in water by altering emission wavelengths (> 60 nm). This water-soluble probe (R)-Z1 exhibits cyan or yellow-green luminescence upon interaction with amino acid enantiomers, enabling reliable chiral detection of 14 natural amino acids. It also allows for the determination of enantiomeric excess through monitoring changes in luminescent color. Additionally, a logic operation with two inputs and three outputs was constructed based on these optical properties. Notably, amino acid enantiomers were successfully detected via dual-channel analysis at both the food and cellular levels. This study provides a new dynamic luminescence-based tool for the accurate sensing and detection of amino acid enantiomers.
2026, 37(1): 111520
doi: 10.1016/j.cclet.2025.111520
摘要:
Metal-support interaction (MSI) is crucial for fine-tuning the active-site structure of supported catalysts and enhancing performance. Here, we present an ammonia-directed reactive gas-metal-support interaction (RGMSI), in which NH3 reduces ZnO and assembles an anti-perovskite Ni3ZnN structure with interstitial nitrogen, significantly boosting hydrogenation efficiency. Nitrogen incorporation expands the lattice parameter, increasing the (111) lattice spacing from 2.04 Å in Ni to 2.18 Å in Ni3ZnN, with an extended Ni-Ni interatomic distance from 2.49 Å to 2.65 Å. Additionally, Ni-N coordination shifts the d-band center downward and induces electron deficiency in Ni via charge transfer. These modifications optimize reactant adsorption on the tailored Ni3ZnN structure compared to Ni, leading to a remarkable increase in 1,3-butadiene hydrogenation selectivity from 30.0% to 92.9%, along with an enhanced TOF from 0.067 s−1 to 0.079 s−1. These findings highlight RGMSI as a versatile and effective strategy for designing supported metal catalysts, offering new insights into selective hydrogenation catalysis.
Metal-support interaction (MSI) is crucial for fine-tuning the active-site structure of supported catalysts and enhancing performance. Here, we present an ammonia-directed reactive gas-metal-support interaction (RGMSI), in which NH3 reduces ZnO and assembles an anti-perovskite Ni3ZnN structure with interstitial nitrogen, significantly boosting hydrogenation efficiency. Nitrogen incorporation expands the lattice parameter, increasing the (111) lattice spacing from 2.04 Å in Ni to 2.18 Å in Ni3ZnN, with an extended Ni-Ni interatomic distance from 2.49 Å to 2.65 Å. Additionally, Ni-N coordination shifts the d-band center downward and induces electron deficiency in Ni via charge transfer. These modifications optimize reactant adsorption on the tailored Ni3ZnN structure compared to Ni, leading to a remarkable increase in 1,3-butadiene hydrogenation selectivity from 30.0% to 92.9%, along with an enhanced TOF from 0.067 s−1 to 0.079 s−1. These findings highlight RGMSI as a versatile and effective strategy for designing supported metal catalysts, offering new insights into selective hydrogenation catalysis.
2026, 37(1): 111551
doi: 10.1016/j.cclet.2025.111551
摘要:
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes (PLEDs). Herein, we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors (PG and PDG) via metal-free CN coupling polymerization for the fabrication of deep-blue PLEDs. The steric, rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state. Due to the different length of electron-deficient diphenyl sulfone monomers, PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films. Interestingly, similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation. Finally, PLEDs based on PG are fabricated with a stable deep-blue emission of CIE (0.15, 0.10), and corresponding EL spectral profile is also completely identical to PL ones of diluted solution, revealed the intrachain emission without obvious interchain excited state, confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes (PLEDs). Herein, we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors (PG and PDG) via metal-free CN coupling polymerization for the fabrication of deep-blue PLEDs. The steric, rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state. Due to the different length of electron-deficient diphenyl sulfone monomers, PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films. Interestingly, similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation. Finally, PLEDs based on PG are fabricated with a stable deep-blue emission of CIE (0.15, 0.10), and corresponding EL spectral profile is also completely identical to PL ones of diluted solution, revealed the intrachain emission without obvious interchain excited state, confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
2026, 37(1): 111582
doi: 10.1016/j.cclet.2025.111582
摘要:
Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications, e.g., encapsulating enzymes to enhance their stability, activity, and reusability. However, precise control and tune the pore size of such frameworks still remains a significant challenge to date. In this study, we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block. First, a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization. Then 2-ureido-4[1H]-pyrimidinone (Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization. Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units, well-ordered supramolecular polymer frameworks were readily obtained. Notably, the pore size was dependent on the chain length of the polyisocyanide arms. Precisely control the chain length of polyisocyanide arms, supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved. These frameworks, with tunable and large pore apertures, demonstrated exceptional capabilities in encapsulating enzymes of different sizes, such as lipase (TL), horseradish peroxidase (HRP), and glucose oxidase (GOx). The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability. Moreover, the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes, enabling efficient dual-enzyme cascade reactions.
Three-dimensional supramolecular organic frameworks with precisely tunable pore sizes are highly demanded for a wide range of applications, e.g., encapsulating enzymes to enhance their stability, activity, and reusability. However, precise control and tune the pore size of such frameworks still remains a significant challenge to date. In this study, we constructed supramolecular polymer frameworks using rigid tetrahedral star polyisocyanides with tunable length and sufficiently narrow distribution as building block. First, a series of tetrahedral four-arm star polyisocyanides with controlled chain lengths and narrow molecular weight distributions was prepared via the Pd(Ⅱ)-catalyzed living isocyanide polymerization. Then 2-ureido-4[1H]-pyrimidinone (Upy) unit was installed onto each chain-end of polyisocyanide arms via post-polymerization functionalization. Leveraging the supramolecular hydrogen bonding interactions between the terminal Upy units, well-ordered supramolecular polymer frameworks were readily obtained. Notably, the pore size was dependent on the chain length of the polyisocyanide arms. Precisely control the chain length of polyisocyanide arms, supramolecular polymer frameworks with pore sizes ranging from 5.06 nm to 9.72 nm were achieved. These frameworks, with tunable and large pore apertures, demonstrated exceptional capabilities in encapsulating enzymes of different sizes, such as lipase (TL), horseradish peroxidase (HRP), and glucose oxidase (GOx). The encapsulated enzymes exhibited significantly enhanced catalytic activity and durability. Moreover, the frameworks' tunable and large pore apertures facilitated the co-encapsulation of multiple enzymes, enabling efficient dual-enzyme cascade reactions.
2026, 37(1): 111609
doi: 10.1016/j.cclet.2025.111609
摘要:
Despite demonstrating significant anti-tumor potential as an artemisinin derivative, artesunate faces delivery efficiency challenges due to low water solubility and insufficient targeting specificity. To improve the delivery efficiency, we engineered three artesunate (ART) derivatives, AC15-L (linear), AC15-B (branched), and AC15-C (cyclic) with distinct aliphatic chain architectures. Unexpectedly, we observed that AC15-C exhibited superior cytotoxicity against 4T1 breast cancer cells, and had the highest binding affinity for Lon protease 1 (LONP1) (−72.6 kcal/mol). Subsequently, disulfide bond-containing lipid-PEG (DSPE-SS-PEG2K) modified chain architecture-engineered ART derivatives nanoassemblies (NAs) were developed to mitigate solubility-related limitations while enhancing targeting precision. Molecular docking and experimental validation demonstrated that ART derivatives inhibited LONP1 through hydrophobic interactions while preserved Fe2+-mediated Fenton-like reaction activity. In vitro and in vivo evaluations demonstrated that AC15-C NAs outperformed free ART and other NAs, suppressing 4T1 tumor growth via dual action: LONP1-directed mitochondrial proteostasis collapse and reactive oxygen species (ROS) amplification through Fe2+-ART interactions. This study elucidated a novel anti-tumor mechanism of ART through the rational design of derivatives with spatially configured aliphatic chains, and developed reduction-responsive NAs to provide an advanced delivery strategy.
Despite demonstrating significant anti-tumor potential as an artemisinin derivative, artesunate faces delivery efficiency challenges due to low water solubility and insufficient targeting specificity. To improve the delivery efficiency, we engineered three artesunate (ART) derivatives, AC15-L (linear), AC15-B (branched), and AC15-C (cyclic) with distinct aliphatic chain architectures. Unexpectedly, we observed that AC15-C exhibited superior cytotoxicity against 4T1 breast cancer cells, and had the highest binding affinity for Lon protease 1 (LONP1) (−72.6 kcal/mol). Subsequently, disulfide bond-containing lipid-PEG (DSPE-SS-PEG2K) modified chain architecture-engineered ART derivatives nanoassemblies (NAs) were developed to mitigate solubility-related limitations while enhancing targeting precision. Molecular docking and experimental validation demonstrated that ART derivatives inhibited LONP1 through hydrophobic interactions while preserved Fe2+-mediated Fenton-like reaction activity. In vitro and in vivo evaluations demonstrated that AC15-C NAs outperformed free ART and other NAs, suppressing 4T1 tumor growth via dual action: LONP1-directed mitochondrial proteostasis collapse and reactive oxygen species (ROS) amplification through Fe2+-ART interactions. This study elucidated a novel anti-tumor mechanism of ART through the rational design of derivatives with spatially configured aliphatic chains, and developed reduction-responsive NAs to provide an advanced delivery strategy.
2026, 37(1): 111622
doi: 10.1016/j.cclet.2025.111622
摘要:
The fluorination strategy has been proven effective in significantly enhancing the photovoltaic performance of organic solar cells (OSCs) based on non-fused ring electron acceptors (NFREAs). However, research on the impact of fluorination positions at side chains on NFREAs device performance remains scant. In this study, we introduce two isomeric NFREAs, designated as GA-2F-E and GA-2F, distinguished by their fluorination positions at the side chains. Both NFREAs share a thiophene[3,2-b]thiophene core, but their side chains differ: GA-2F-E features two (4-butylphenyl)-N-(4-fluorophenyl) amino groups, whereas GA-2F’s side chains consist of bis(4-fluorophenyl)amino and bis(4-butylphenyl)amino groups attached to opposite sides of the core. To delve into the influence of fluorination positions on the optoelectronic properties, aggregation behavior, and overall efficiency of the acceptor molecules, a comprehensive investigation was conducted. The findings reveal that, despite similar photophysical properties and comparable absorption bandwidths, GA-2F-E, with fluorine atoms positioned on both sides of the molecular framework, demonstrates more compact π-π stacking, reduced bimolecular recombination, superior exciton transport, and a more balanced, higher mobility. As a result of these advantages, OSCs optimized with D18:GA-2F-E achieve a remarkable power conversion efficiency (PCE) of 16.45%, surpassing the 15.83% PCE of devices utilizing D18:GA-2F. This research underscores the potential of NFREAs in future applications and highlights the significance of fluorination positions in enhancing OSC performance, paving the way for the development of more efficient NFREAs.
The fluorination strategy has been proven effective in significantly enhancing the photovoltaic performance of organic solar cells (OSCs) based on non-fused ring electron acceptors (NFREAs). However, research on the impact of fluorination positions at side chains on NFREAs device performance remains scant. In this study, we introduce two isomeric NFREAs, designated as GA-2F-E and GA-2F, distinguished by their fluorination positions at the side chains. Both NFREAs share a thiophene[3,2-b]thiophene core, but their side chains differ: GA-2F-E features two (4-butylphenyl)-N-(4-fluorophenyl) amino groups, whereas GA-2F’s side chains consist of bis(4-fluorophenyl)amino and bis(4-butylphenyl)amino groups attached to opposite sides of the core. To delve into the influence of fluorination positions on the optoelectronic properties, aggregation behavior, and overall efficiency of the acceptor molecules, a comprehensive investigation was conducted. The findings reveal that, despite similar photophysical properties and comparable absorption bandwidths, GA-2F-E, with fluorine atoms positioned on both sides of the molecular framework, demonstrates more compact π-π stacking, reduced bimolecular recombination, superior exciton transport, and a more balanced, higher mobility. As a result of these advantages, OSCs optimized with D18:GA-2F-E achieve a remarkable power conversion efficiency (PCE) of 16.45%, surpassing the 15.83% PCE of devices utilizing D18:GA-2F. This research underscores the potential of NFREAs in future applications and highlights the significance of fluorination positions in enhancing OSC performance, paving the way for the development of more efficient NFREAs.
2026, 37(1): 111623
doi: 10.1016/j.cclet.2025.111623
摘要:
Field-effect nanofluidic transistors (FENTs), biomimicking the structure and functionality of neuron, act as biological transistors with the ability to gate switching responses to external stimuli. The switching ratio has been verified to evaluate the performance of FENTs, but until recently, the response time, another crucial indicator, has been ignored. Employing finite-element method, we investigated the relationship among gate charge, switching ratio and response time by divisionally manipulating gate charge, including entrance surface and the surface of confinement space, for ion transport to optimize switching capability. The dual-split gate charge on FENTs exhibits synergistic effect on switching response. Based on the two regional gate charge on FENTs, multivalence ions in lower concentration, high aspect ratio and single channel show higher switching ratio but longer response time compared to monovalent ions. The findings highlight the necessity of balancing these two signals in FENTs and offer insights for optimizing their design and expanding applications to dual-signal-detection iontronics.
Field-effect nanofluidic transistors (FENTs), biomimicking the structure and functionality of neuron, act as biological transistors with the ability to gate switching responses to external stimuli. The switching ratio has been verified to evaluate the performance of FENTs, but until recently, the response time, another crucial indicator, has been ignored. Employing finite-element method, we investigated the relationship among gate charge, switching ratio and response time by divisionally manipulating gate charge, including entrance surface and the surface of confinement space, for ion transport to optimize switching capability. The dual-split gate charge on FENTs exhibits synergistic effect on switching response. Based on the two regional gate charge on FENTs, multivalence ions in lower concentration, high aspect ratio and single channel show higher switching ratio but longer response time compared to monovalent ions. The findings highlight the necessity of balancing these two signals in FENTs and offer insights for optimizing their design and expanding applications to dual-signal-detection iontronics.
2026, 37(1): 111659
doi: 10.1016/j.cclet.2025.111659
摘要:
Magnetic field-driven spin polarization modulation has emerged as an effective way to boost the electrocatalytic oxygen evolution reaction (OER). However, the correlation among catalyst structure, magnetic property, and magnetic field enhanced-electrochemical activity remains to be fully elucidated. Herein, single-domain CoFe2O4 catalysts with tunable oxygen vacancies (CFO-VO) were synthesized to probe how VO mediates magnetism and OER activity under magnetic field. The introduction of VO can simultaneously modulate saturation magnetization (Ms) and coercivity (Hc), where the increased Ms dominates the magnetic field-enhanced OER activity. Under a 14,000 G magnetic field, the optimized CFO-VO exhibits up to 16.1% reduction in overpotential and 365% enhancement in magnetocurrent (MC). Electrochemical analyses and post-OER characterization reveal that the magnetic field synergistically improves OER kinetics through lattice distortion induction, magnetohydrodynamic effect, and spin charge transfer effect. Importantly, the magnetic field promotes additional Co3+ generation to compensate for charge imbalance caused by VO filling, maintaining dynamic equilibrium of VO and effective reactant adsorption-conversion processes. This work unveils the synergistic mechanism of VO and magnetic parameters for enhancing OER performance under the magnetic field, providing new insights into the design of high-efficiency spin-regulated OER catalysts.
Magnetic field-driven spin polarization modulation has emerged as an effective way to boost the electrocatalytic oxygen evolution reaction (OER). However, the correlation among catalyst structure, magnetic property, and magnetic field enhanced-electrochemical activity remains to be fully elucidated. Herein, single-domain CoFe2O4 catalysts with tunable oxygen vacancies (CFO-VO) were synthesized to probe how VO mediates magnetism and OER activity under magnetic field. The introduction of VO can simultaneously modulate saturation magnetization (Ms) and coercivity (Hc), where the increased Ms dominates the magnetic field-enhanced OER activity. Under a 14,000 G magnetic field, the optimized CFO-VO exhibits up to 16.1% reduction in overpotential and 365% enhancement in magnetocurrent (MC). Electrochemical analyses and post-OER characterization reveal that the magnetic field synergistically improves OER kinetics through lattice distortion induction, magnetohydrodynamic effect, and spin charge transfer effect. Importantly, the magnetic field promotes additional Co3+ generation to compensate for charge imbalance caused by VO filling, maintaining dynamic equilibrium of VO and effective reactant adsorption-conversion processes. This work unveils the synergistic mechanism of VO and magnetic parameters for enhancing OER performance under the magnetic field, providing new insights into the design of high-efficiency spin-regulated OER catalysts.
2026, 37(1): 111660
doi: 10.1016/j.cclet.2025.111660
摘要:
Structural instability and sluggish lithium-ion (Li+) kinetics of spinel NiCo2O4 anodes severely hinder their applications in high-energy-density lithium-ion batteries. Mesocrystalline structures exhibit promising potential in balancing structural stability and enhancing reaction kinetics. However, their controlled synthesis mechanisms remain elusive. Herein, a substrate interface engineering strategy is developed to achieve controllable synthesis of mesocrystalline and polycrystalline NiCo2O4 nanorods. Remarkably, mesocrystalline NiCo2O4 exhibits a high capacity retention rate of 85.7% after 500 cycles at 2 A/g, attributed to its porous structure facilitating Li+ transport kinetics and unique stress-buffering effect validated by ex-situ TEM. Theoretical calculations and interfacial chemical analysis reveal that substrate-crystal surface engineering regulates the nucleation-growth pathways: Acid-treated nickel foam enables epitaxial growth via lattice matching, acting as a low-interfacial-energy template to reduce nucleation barriers and promote low-temperature oriented crystallization. In contrast, carbon cloth requires high-temperature thermal activation to overcome surface diffusion barriers induced by elevated interfacial energy. This substrate-driven crystallization kinetic modulation overcomes the limitations of random nucleation in conventional hydrothermal synthesis. The established substrate-crystal interfacial interaction model not only clarifies the kinetic essence of crystal orientation regulation but also provides a universal theoretical framework for lattice-matching design and mesostructural optimization of advanced electrode materials.
Structural instability and sluggish lithium-ion (Li+) kinetics of spinel NiCo2O4 anodes severely hinder their applications in high-energy-density lithium-ion batteries. Mesocrystalline structures exhibit promising potential in balancing structural stability and enhancing reaction kinetics. However, their controlled synthesis mechanisms remain elusive. Herein, a substrate interface engineering strategy is developed to achieve controllable synthesis of mesocrystalline and polycrystalline NiCo2O4 nanorods. Remarkably, mesocrystalline NiCo2O4 exhibits a high capacity retention rate of 85.7% after 500 cycles at 2 A/g, attributed to its porous structure facilitating Li+ transport kinetics and unique stress-buffering effect validated by ex-situ TEM. Theoretical calculations and interfacial chemical analysis reveal that substrate-crystal surface engineering regulates the nucleation-growth pathways: Acid-treated nickel foam enables epitaxial growth via lattice matching, acting as a low-interfacial-energy template to reduce nucleation barriers and promote low-temperature oriented crystallization. In contrast, carbon cloth requires high-temperature thermal activation to overcome surface diffusion barriers induced by elevated interfacial energy. This substrate-driven crystallization kinetic modulation overcomes the limitations of random nucleation in conventional hydrothermal synthesis. The established substrate-crystal interfacial interaction model not only clarifies the kinetic essence of crystal orientation regulation but also provides a universal theoretical framework for lattice-matching design and mesostructural optimization of advanced electrode materials.
2026, 37(1): 111679
doi: 10.1016/j.cclet.2025.111679
摘要:
In this study, electrochemical C-H carboxylation of benzylamines with CO2 was reported. This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids (α-AAs) under mild conditions. Various substituted benzylamines containing diverse functional groups and even highly reactive moieties, such as cyano, amide and alkene groups could be successfully transformed to the carboxylated products. Notably, this method proved to be applicable to the late-stage modification of biorelevant compounds, highlighting its potential for synthetic chemistry. Mechanistic studies such as radical trapping experiments, kinetic isotope effect (KIE) tests and cyclic voltammetry (CV) studies provided useful insight into this transformation.
In this study, electrochemical C-H carboxylation of benzylamines with CO2 was reported. This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids (α-AAs) under mild conditions. Various substituted benzylamines containing diverse functional groups and even highly reactive moieties, such as cyano, amide and alkene groups could be successfully transformed to the carboxylated products. Notably, this method proved to be applicable to the late-stage modification of biorelevant compounds, highlighting its potential for synthetic chemistry. Mechanistic studies such as radical trapping experiments, kinetic isotope effect (KIE) tests and cyclic voltammetry (CV) studies provided useful insight into this transformation.
2026, 37(1): 111721
doi: 10.1016/j.cclet.2025.111721
摘要:
Thermally activated delayed fluorescence (TADF) emitters show great potential in photodynamic therapy (PDT) and bioimaging, leveraging their structural adaptability, efficient reverse intersystem crossing (RISC), robust photosensitizing capability, and high photoluminescence quantum yields (PLQYs). Herein, we developed a new class of donor–acceptor–donor (D-A-D)-type TADF materials by connecting the highly twisted indolizine-benzophenone electron acceptors with a series of electron donors including phenoxazine, phenothiazine and 9,9-dimethyl-9,10-dihydroacridine. These materials exhibit enhanced TADF properties, aggregation-induced emission (AIE), alongside high reactive oxygen species (ROS) generation efficiency, effectively mitigating aggregation-caused quenching observed in traditional fluorophores. Among them, IDP-p-PXZ, incorporating the phenoxazine donor, stands out with the smallest singlet–triplet splitting energy (ΔEST) and the highest spin-orbit coupling matrix elements (SOCMEs). Upon encapsulation into 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000] (DSPE-PEG2000) nanoparticles (NPs), IDP-p-PXZ demonstrates extended delayed fluorescence lifetimes in air, an exceptionally fast intersystem crossing (ISC) rate constant (kISC) of 3.4 × 107 s−1, and a radiative rate constant (kr) of 5.05 × 106 s−1. These NPs exhibit superior biocompatibility, efficient cellular internalization, and potent ROS production, enabling effective simultaneous PDT and confocal fluorescence imaging in HeLa cells.
Thermally activated delayed fluorescence (TADF) emitters show great potential in photodynamic therapy (PDT) and bioimaging, leveraging their structural adaptability, efficient reverse intersystem crossing (RISC), robust photosensitizing capability, and high photoluminescence quantum yields (PLQYs). Herein, we developed a new class of donor–acceptor–donor (D-A-D)-type TADF materials by connecting the highly twisted indolizine-benzophenone electron acceptors with a series of electron donors including phenoxazine, phenothiazine and 9,9-dimethyl-9,10-dihydroacridine. These materials exhibit enhanced TADF properties, aggregation-induced emission (AIE), alongside high reactive oxygen species (ROS) generation efficiency, effectively mitigating aggregation-caused quenching observed in traditional fluorophores. Among them, IDP-p-PXZ, incorporating the phenoxazine donor, stands out with the smallest singlet–triplet splitting energy (ΔEST) and the highest spin-orbit coupling matrix elements (SOCMEs). Upon encapsulation into 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000] (DSPE-PEG2000) nanoparticles (NPs), IDP-p-PXZ demonstrates extended delayed fluorescence lifetimes in air, an exceptionally fast intersystem crossing (ISC) rate constant (kISC) of 3.4 × 107 s−1, and a radiative rate constant (kr) of 5.05 × 106 s−1. These NPs exhibit superior biocompatibility, efficient cellular internalization, and potent ROS production, enabling effective simultaneous PDT and confocal fluorescence imaging in HeLa cells.
2026, 37(1): 111724
doi: 10.1016/j.cclet.2025.111724
摘要:
Herein, we have developed a straightforward wet-chemical method to synthesize a series of Pd-based alloy nanowires (NWs), including PdPt NWs, PdAu NWs, PdIr NWs, and PdRu NWs, which exhibits high mass activity and turnover frequency (TOF) for HER, surpassing Pt/C by 4.6-fold and 1.5-fold in acidic and alkaline electrolytes, respectively. It also demonstrates high stability in alkaline electrolyte at a current density of 220 mA/cm2 for 280 h, highlighting its potential for practical applications under industrial current conditions. PdPt NWs exhibited ultrathin structures with head-to-tail kinks and inherent defects, significantly increasing the density of active sites and precisely tuning the electronic structure, which could accelerate reaction kinetics and boost water-splitting electrocatalytic performance. This study highlights the potential of PdPt NWs as highly efficient catalysts, offering outstanding catalytic performance and stability for practical applications.
Herein, we have developed a straightforward wet-chemical method to synthesize a series of Pd-based alloy nanowires (NWs), including PdPt NWs, PdAu NWs, PdIr NWs, and PdRu NWs, which exhibits high mass activity and turnover frequency (TOF) for HER, surpassing Pt/C by 4.6-fold and 1.5-fold in acidic and alkaline electrolytes, respectively. It also demonstrates high stability in alkaline electrolyte at a current density of 220 mA/cm2 for 280 h, highlighting its potential for practical applications under industrial current conditions. PdPt NWs exhibited ultrathin structures with head-to-tail kinks and inherent defects, significantly increasing the density of active sites and precisely tuning the electronic structure, which could accelerate reaction kinetics and boost water-splitting electrocatalytic performance. This study highlights the potential of PdPt NWs as highly efficient catalysts, offering outstanding catalytic performance and stability for practical applications.
2026, 37(1): 111736
doi: 10.1016/j.cclet.2025.111736
摘要:
Co-assembling chiral molecules with achiral compounds via non-covalent interactions like arene-perfluoroarene (AP) interactions offers an effective approach for fabricating chiral functional materials. Herein, chiral molecules L/D-PF1 and L/D-PF2 with pyrene groups were synthesized and its chiroptical properties upon co-assembly with achiral compound octafluoronaphthalene (OFN) through AP interaction were systemically studied. The co-assembly of L/D-PF1/OFN and L/D-PF2/OFN exhibited distinct chiroptical properties such as circular dichroism (CD) and circularly polarized luminescence (CPL) signals. Chirality transfer from the chirality center of L/D-PF1 and L/D-PF2 to the achiral OFN and chiral amplification were successfully achieved. Besides, no significant CPL signal was observed in the self-assembly of L/D-PF1 or L/D-PF2 while co-assembly with OFN exhibited obvious CPL amplification induced by AP interaction. Notably, a reversal CD signal and CPL signal could be observed in L/D-PF2/OFN when the molar ratio changed from 1:1 to 1:2 while not found in L/D-PF1/OFN, indicating that that minor structural changes of molecules could cause large changes in assembly. In addition, a series of computational calculations were conducted to verify the AP interaction between L-PF1/L-PF2 and OFN. This work demonstrated that arene-perfluoroarene interaction could drive chiral transfer, chiral amplification and chiral inversion and provided a new method for the preparation of chiroptical materials.
Co-assembling chiral molecules with achiral compounds via non-covalent interactions like arene-perfluoroarene (AP) interactions offers an effective approach for fabricating chiral functional materials. Herein, chiral molecules L/D-PF1 and L/D-PF2 with pyrene groups were synthesized and its chiroptical properties upon co-assembly with achiral compound octafluoronaphthalene (OFN) through AP interaction were systemically studied. The co-assembly of L/D-PF1/OFN and L/D-PF2/OFN exhibited distinct chiroptical properties such as circular dichroism (CD) and circularly polarized luminescence (CPL) signals. Chirality transfer from the chirality center of L/D-PF1 and L/D-PF2 to the achiral OFN and chiral amplification were successfully achieved. Besides, no significant CPL signal was observed in the self-assembly of L/D-PF1 or L/D-PF2 while co-assembly with OFN exhibited obvious CPL amplification induced by AP interaction. Notably, a reversal CD signal and CPL signal could be observed in L/D-PF2/OFN when the molar ratio changed from 1:1 to 1:2 while not found in L/D-PF1/OFN, indicating that that minor structural changes of molecules could cause large changes in assembly. In addition, a series of computational calculations were conducted to verify the AP interaction between L-PF1/L-PF2 and OFN. This work demonstrated that arene-perfluoroarene interaction could drive chiral transfer, chiral amplification and chiral inversion and provided a new method for the preparation of chiroptical materials.
2026, 37(1): 111740
doi: 10.1016/j.cclet.2025.111740
摘要:
By means the in situ halogenation of the vinyl C-H bond in o-hydroxyphenyl enaminones, the step efficient synthesis of 3-diphenylphosphinyl chromones has been realized through the challenging construction of C-P(Ⅲ) bond by using diphenyl phosphine as reaction partner. In addition, the tunable synthesis of 2-phosphoryl chromanones has been achieved via hydrophosphorylation by simply modifying reaction conditions without using metal reagent.
By means the in situ halogenation of the vinyl C-H bond in o-hydroxyphenyl enaminones, the step efficient synthesis of 3-diphenylphosphinyl chromones has been realized through the challenging construction of C-P(Ⅲ) bond by using diphenyl phosphine as reaction partner. In addition, the tunable synthesis of 2-phosphoryl chromanones has been achieved via hydrophosphorylation by simply modifying reaction conditions without using metal reagent.
2026, 37(1): 111741
doi: 10.1016/j.cclet.2025.111741
摘要:
The photocatalytic oxidation of methane (CH4) to valuable chemicals like low alcohols (CH3OH and C2H5OH) represents a significant technological advancement with implications for energy conversion and environmental purification. A major challenge in this field is the chemical inertness of methane and the strong oxidizing nature of photogenerated holes, which can lead to over-oxidation and reduced selectivity and efficiency. To address these issues, we have developed a sodium-doped zinc oxide (Na-ZnO) modified with cobalt oxide (CoO) catalyst. This catalyst has demonstrated excellent performance in converting methane to low alcohols, achieving a yield of 130 µmol g−1 h−1 and a selectivity of up to 96 %. The doping of Na in ZnO significantly enhances methane adsorption, while the surface-modified CoO effectively captures photogenerated holes, activates water molecules, and uses hydroxyl radicals to activate methane, thus controlling the dehydrogenation degree of methane and preventing the formation of over-oxidized products. This strategy has successfully improved the efficiency and selectivity of photocatalytic methane oxidation to low alcohols, offering a new perspective for the application of photocatalytic technology in energy and environmental fields.
The photocatalytic oxidation of methane (CH4) to valuable chemicals like low alcohols (CH3OH and C2H5OH) represents a significant technological advancement with implications for energy conversion and environmental purification. A major challenge in this field is the chemical inertness of methane and the strong oxidizing nature of photogenerated holes, which can lead to over-oxidation and reduced selectivity and efficiency. To address these issues, we have developed a sodium-doped zinc oxide (Na-ZnO) modified with cobalt oxide (CoO) catalyst. This catalyst has demonstrated excellent performance in converting methane to low alcohols, achieving a yield of 130 µmol g−1 h−1 and a selectivity of up to 96 %. The doping of Na in ZnO significantly enhances methane adsorption, while the surface-modified CoO effectively captures photogenerated holes, activates water molecules, and uses hydroxyl radicals to activate methane, thus controlling the dehydrogenation degree of methane and preventing the formation of over-oxidized products. This strategy has successfully improved the efficiency and selectivity of photocatalytic methane oxidation to low alcohols, offering a new perspective for the application of photocatalytic technology in energy and environmental fields.
2026, 37(1): 111756
doi: 10.1016/j.cclet.2025.111756
摘要:
The three-dimensional (3D) Pd-based nanoflower structures, assembled from two-dimensional (2D) nanosheets, are characterized by their stable and ordered configurations. These structures have been extensively designed as anode materials for fuel cells. However, the exploration of trimetallic nanoflowers with porous architectures remains limited. In this study, we present a straightforward one-step solvothermal method for the synthesis of trimetallic PdCuNi porous nanoflowers (PNFs). Leveraging several unique advantages, such as an open superstructure, high porosity, and enhanced electronic interactions among the trimetals, the resulting PdCuNi PNFs demonstrate significantly improved electrochemical performance, with mass activities reaching 5.94 and 10.14 A/mg for the ethanol oxidation reaction (EOR) and the ethylene glycol oxidation reaction (EGOR), respectively. Furthermore, the PdCuNi PNFs exhibit optimized d-band centers and the most negative onset oxidation potential, indicating enhanced antitoxicity and stability. This study not only provides a novel perspective on the synthesis of 3D porous nanomaterials but also highlights the potential application value of trimetallic nanoalloys in catalysis.
The three-dimensional (3D) Pd-based nanoflower structures, assembled from two-dimensional (2D) nanosheets, are characterized by their stable and ordered configurations. These structures have been extensively designed as anode materials for fuel cells. However, the exploration of trimetallic nanoflowers with porous architectures remains limited. In this study, we present a straightforward one-step solvothermal method for the synthesis of trimetallic PdCuNi porous nanoflowers (PNFs). Leveraging several unique advantages, such as an open superstructure, high porosity, and enhanced electronic interactions among the trimetals, the resulting PdCuNi PNFs demonstrate significantly improved electrochemical performance, with mass activities reaching 5.94 and 10.14 A/mg for the ethanol oxidation reaction (EOR) and the ethylene glycol oxidation reaction (EGOR), respectively. Furthermore, the PdCuNi PNFs exhibit optimized d-band centers and the most negative onset oxidation potential, indicating enhanced antitoxicity and stability. This study not only provides a novel perspective on the synthesis of 3D porous nanomaterials but also highlights the potential application value of trimetallic nanoalloys in catalysis.
2026, 37(1): 111779
doi: 10.1016/j.cclet.2025.111779
摘要:
α-Chiral amides are common in pharmaceuticals, agrochemicals, natural products, and peptides, prompting the need for new synthetic methods. Here, we introduce a nickel-catalyzed asymmetric reductive amidation method to synthesize α-chiral amides from benzyl ammonium salts and isocyanates. The key to success is using a chiral 2,2′-bipyridine ligand (-)-Ph-SBpy, enabling high yield (up to 95%) and enantiomeric ratio (up to 98:2 er) under mild conditions. Addition of phenol prevents isocyanate polymerization by reversibly forming a carbamate intermediate, enhancing selectivity and efficiency. The synthetic utility is showcased through transformations of the enantioenriched amides, and the mechanism and enantioselectivity are supported by experimental and computational studies.
α-Chiral amides are common in pharmaceuticals, agrochemicals, natural products, and peptides, prompting the need for new synthetic methods. Here, we introduce a nickel-catalyzed asymmetric reductive amidation method to synthesize α-chiral amides from benzyl ammonium salts and isocyanates. The key to success is using a chiral 2,2′-bipyridine ligand (-)-Ph-SBpy, enabling high yield (up to 95%) and enantiomeric ratio (up to 98:2 er) under mild conditions. Addition of phenol prevents isocyanate polymerization by reversibly forming a carbamate intermediate, enhancing selectivity and efficiency. The synthetic utility is showcased through transformations of the enantioenriched amides, and the mechanism and enantioselectivity are supported by experimental and computational studies.
2026, 37(1): 111787
doi: 10.1016/j.cclet.2025.111787
摘要:
In the field of organic solar cells (OSCs), side-chain engineering is a key strategy for developing high-performance non-fullerene small molecule acceptors (SMAs), which could adjust the material solubility and modulate the intermolecular stacking properties, profoundly impacting the film morphology and thus acting on the final power conversion efficiency (PCE) of the materials. In this study, two asymmetric acceptor molecules, Qx-PhBr-BO and Qx-PhBr-X, were synthesized by migrating the branching site of the outer side chain from the β-site to the γ-site. The branching site located at the γ-site could reduce the steric-hindrance effect and enhance the molecular aggregation behavior, giving rise to redshifted absorption and tight π-π stacking. Morphology analysis shows that the Qx-PhBr-X-based devices have smoother surfaces and a phase-separated structure, which is more favorable for charge transport and extraction. The Qx-PhBr-X-based devices exhibit balanced hole-electron mobility, efficient exciton dissociation, and low charge recombination. As a result, Qx-PhBr-X with γ-site branching exhibits superior photovoltaic performance with a PCE of 17.16%, which is significantly higher than that of Qx-PhBr-BO at 16.28%. These results highlight the importance of side-chain modifications for optimizing OSC efficiency and provide an important reference for precise tuning of side-chain structures in future molecular design.
In the field of organic solar cells (OSCs), side-chain engineering is a key strategy for developing high-performance non-fullerene small molecule acceptors (SMAs), which could adjust the material solubility and modulate the intermolecular stacking properties, profoundly impacting the film morphology and thus acting on the final power conversion efficiency (PCE) of the materials. In this study, two asymmetric acceptor molecules, Qx-PhBr-BO and Qx-PhBr-X, were synthesized by migrating the branching site of the outer side chain from the β-site to the γ-site. The branching site located at the γ-site could reduce the steric-hindrance effect and enhance the molecular aggregation behavior, giving rise to redshifted absorption and tight π-π stacking. Morphology analysis shows that the Qx-PhBr-X-based devices have smoother surfaces and a phase-separated structure, which is more favorable for charge transport and extraction. The Qx-PhBr-X-based devices exhibit balanced hole-electron mobility, efficient exciton dissociation, and low charge recombination. As a result, Qx-PhBr-X with γ-site branching exhibits superior photovoltaic performance with a PCE of 17.16%, which is significantly higher than that of Qx-PhBr-BO at 16.28%. These results highlight the importance of side-chain modifications for optimizing OSC efficiency and provide an important reference for precise tuning of side-chain structures in future molecular design.
2026, 37(1): 111804
doi: 10.1016/j.cclet.2025.111804
摘要:
Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction (OER) is crucial for advancing overall water splitting (OWS) systems. In this study, we synthesized the electrode material Ce-NiCo-LDHs@SnO2/NF through a two-step hydrothermal reaction, where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO2 layer. Ce doping adjusts the internal electronic distribution of NiCo-LDHs, while the introduction of the SnO2 layer enhances electron transfer capability. Together, these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism (LOM). Consequently, Ce-NiCo-LDHs@SnO2/NF exhibits high level electrochemical performance in OER, requiring only 234 mV overpotential to achieve a current density of 10 mA/cm2, with a Tafel slope of just 27.39 mV/dec. When paired with Pt/C/NF, an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 mA/cm2. Furthermore, the catalyst demonstrates stability for 100 h during the OWS stability test. This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO2 layer.
Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction (OER) is crucial for advancing overall water splitting (OWS) systems. In this study, we synthesized the electrode material Ce-NiCo-LDHs@SnO2/NF through a two-step hydrothermal reaction, where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO2 layer. Ce doping adjusts the internal electronic distribution of NiCo-LDHs, while the introduction of the SnO2 layer enhances electron transfer capability. Together, these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism (LOM). Consequently, Ce-NiCo-LDHs@SnO2/NF exhibits high level electrochemical performance in OER, requiring only 234 mV overpotential to achieve a current density of 10 mA/cm2, with a Tafel slope of just 27.39 mV/dec. When paired with Pt/C/NF, an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 mA/cm2. Furthermore, the catalyst demonstrates stability for 100 h during the OWS stability test. This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO2 layer.
2026, 37(1): 111806
doi: 10.1016/j.cclet.2025.111806
摘要:
Rational design of nanozymes with enhanced catalytic efficiency remains a central challenge in the development of artificial enzymes. Herein, we report the construction of ultrasmall gold nanocluster-based nanoassemblies (Dp-AuNCs@Fe2+) through the coordination of Fe2+ ions by a dopa-containing peptidomimetic ligand (DpCDp). This nanoarchitecture simultaneously integrates catalytically active gold cores and redox-active Fe2+ centers, bridged by DpCDp to facilitate directional electron transfer. Comprehensive spectroscopic and kinetic analyses reveal that DpCDp promotes efficient charge migration from the Au core to surface-bound Fe2+, significantly enhancing H2O2-mediated peroxidase-like activity. Compared to bare Dp-AuNCs, Dp-AuNCs@Fe2+ display a 4.3-fold improvement in detection sensitivity, a 6.7-fold increase in catalytic efficiency, and markedly stronger hydroxyl radical generation. Mechanistically, this activity stems from a synergistic triad: direct H2O2 oxidation at gold surfaces, radical generation at Fe2+ sites, and DpCDp-facilitated electron shuttling. This work presents a robust strategy for nanozyme enhancement via electronic and structural co-engineering, offering valuable insights for the future design of bioinspired catalytic systems.
Rational design of nanozymes with enhanced catalytic efficiency remains a central challenge in the development of artificial enzymes. Herein, we report the construction of ultrasmall gold nanocluster-based nanoassemblies (Dp-AuNCs@Fe2+) through the coordination of Fe2+ ions by a dopa-containing peptidomimetic ligand (DpCDp). This nanoarchitecture simultaneously integrates catalytically active gold cores and redox-active Fe2+ centers, bridged by DpCDp to facilitate directional electron transfer. Comprehensive spectroscopic and kinetic analyses reveal that DpCDp promotes efficient charge migration from the Au core to surface-bound Fe2+, significantly enhancing H2O2-mediated peroxidase-like activity. Compared to bare Dp-AuNCs, Dp-AuNCs@Fe2+ display a 4.3-fold improvement in detection sensitivity, a 6.7-fold increase in catalytic efficiency, and markedly stronger hydroxyl radical generation. Mechanistically, this activity stems from a synergistic triad: direct H2O2 oxidation at gold surfaces, radical generation at Fe2+ sites, and DpCDp-facilitated electron shuttling. This work presents a robust strategy for nanozyme enhancement via electronic and structural co-engineering, offering valuable insights for the future design of bioinspired catalytic systems.
2026, 37(1): 111826
doi: 10.1016/j.cclet.2025.111826
摘要:
Conversion of ammonia into hydrogen, a crucial pathway for the hydrogen economy, is severely constrained by the intricacy of the required equipment and the low efficiency. Herein, Pd@PtNiCoRuIr core-shell mesoporous bifunctional electrocatalysts were fabricated via a one-step wet-chemical reduction approach. By utilizing the limiting effect of triblock copolymers, gradient distribution control of six metal elements (Pd core and Pt/Ni/Co/Ru/Ir high-entropy alloys shell) was achieved, where the high-entropy alloy shell forms high-density active sites through lattice distortion effect. With the help of lattice distortion and mesoporous-confinement-enabled interfacial coupling effects, Pd@PtNiCoRuIr catalyst exhibited exceptional bifunctional performance in alkaline media: A low hydrogen evolution reaction (HER) overpotential of 30.5 mV at 10 mA/cm2 and a high ammonia oxidation reaction (AOR) peak current density of 19.6 mA/cm2 at 0.7 V vs. RHE, representing a 3.83-fold enhancement over commercial Pt/C. Moreover, a rechargeable Zn-NH3 battery system was constructed and achieved 92.3% Faradaic efficiency (FE) for NH3-to-H2 conversion with outstanding stability at 16 mA/cm2, thereby providing an innovative solution for efficient ammonia decomposition-based hydrogen production.
Conversion of ammonia into hydrogen, a crucial pathway for the hydrogen economy, is severely constrained by the intricacy of the required equipment and the low efficiency. Herein, Pd@PtNiCoRuIr core-shell mesoporous bifunctional electrocatalysts were fabricated via a one-step wet-chemical reduction approach. By utilizing the limiting effect of triblock copolymers, gradient distribution control of six metal elements (Pd core and Pt/Ni/Co/Ru/Ir high-entropy alloys shell) was achieved, where the high-entropy alloy shell forms high-density active sites through lattice distortion effect. With the help of lattice distortion and mesoporous-confinement-enabled interfacial coupling effects, Pd@PtNiCoRuIr catalyst exhibited exceptional bifunctional performance in alkaline media: A low hydrogen evolution reaction (HER) overpotential of 30.5 mV at 10 mA/cm2 and a high ammonia oxidation reaction (AOR) peak current density of 19.6 mA/cm2 at 0.7 V vs. RHE, representing a 3.83-fold enhancement over commercial Pt/C. Moreover, a rechargeable Zn-NH3 battery system was constructed and achieved 92.3% Faradaic efficiency (FE) for NH3-to-H2 conversion with outstanding stability at 16 mA/cm2, thereby providing an innovative solution for efficient ammonia decomposition-based hydrogen production.
2026, 37(1): 111926
doi: 10.1016/j.cclet.2025.111926
摘要:
Developing advanced electrocatalysts to convert CO2 into liquid fuels such as C2H5OH is critical for utilizing intermittent renewable energy. The formation of C2H5OH, however, is generally less favored compared with the other hydrocarbon products from Cu-based electrocatalysts. In this work, an alkanethiol-modified Cu2O nanowire array (OTT-Cu2O) was constructed with asymmetric Cu sites consisting of paired Cu–O and Cu–S motifs to overcome previous limitations of C2H5OH electrosynthesis via CO2RR pathway. This catalyst achieves a high Faradaic efficiency of 45% for CO2-to-C2H5OH conversion at 300 mA/cm2, representing a more than two-fold enhancement over the Cu2O electrode. Mechanistic investigations reveal that the Cu–S site exhibits distinct C-binding capability that stabilizes key intermediates (*OCH2 and *CO), in contrast to the O-affinitive Cu–O site. The asymmetric S–Cu–O configuration promotes thermodynamically favorable asymmetric C–C coupling between *CO and *OCH2, forming the critical CO–OCH2 intermediate and facilitating C2H5OH production, as opposed to symmetric O–Cu–O sites that mainly generate HCOOH. This work offers an effective strategy for designing multi-active-site catalysts toward highly selective CO2 reduction to C2H5OH and provides fundamental insight into the reaction mechanism.
Developing advanced electrocatalysts to convert CO2 into liquid fuels such as C2H5OH is critical for utilizing intermittent renewable energy. The formation of C2H5OH, however, is generally less favored compared with the other hydrocarbon products from Cu-based electrocatalysts. In this work, an alkanethiol-modified Cu2O nanowire array (OTT-Cu2O) was constructed with asymmetric Cu sites consisting of paired Cu–O and Cu–S motifs to overcome previous limitations of C2H5OH electrosynthesis via CO2RR pathway. This catalyst achieves a high Faradaic efficiency of 45% for CO2-to-C2H5OH conversion at 300 mA/cm2, representing a more than two-fold enhancement over the Cu2O electrode. Mechanistic investigations reveal that the Cu–S site exhibits distinct C-binding capability that stabilizes key intermediates (*OCH2 and *CO), in contrast to the O-affinitive Cu–O site. The asymmetric S–Cu–O configuration promotes thermodynamically favorable asymmetric C–C coupling between *CO and *OCH2, forming the critical CO–OCH2 intermediate and facilitating C2H5OH production, as opposed to symmetric O–Cu–O sites that mainly generate HCOOH. This work offers an effective strategy for designing multi-active-site catalysts toward highly selective CO2 reduction to C2H5OH and provides fundamental insight into the reaction mechanism.
2026, 37(1): 111930
doi: 10.1016/j.cclet.2025.111930
摘要:
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science. Multi-nuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mono-nuclear catalysts, but which substantially involve multi-step, tedious, and difficult synthesis. Herein, this study reports an intriguing approach to construct multi-nuclear catalysts for the milestone α-diimine nickel catalysts using an oligomeric strategy. A polymerizable norbornene unit is incorporated into the α-diimine ligand backbone, leading to the formation of the monomeric nickel catalyst Ni1 and its corresponding oligomeric nickel catalysts (Ni3 and Ni5) with varying degrees of polymerization (DP = 3 and 5). Notably, the oligomeric catalyst Ni5 was facilely scaled up (50 g-level), showed enhanced thermal stability, exhibited 4.6 times higher activity, and yielded polyethylene elastomer with a 379% increased molecular weight in ethylene polymerization, compared to the monomeric catalyst Ni1. Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent. The kilogram-scale polyethylene, produced using Ni5 in a 20 L reactor, presented a highly branched all-hydrocarbon structure, which demonstrated typical elastic properties (tensile strength: 4 MPa, elastic recovery: SR = 72%) along with great processability (MFI = 3.0 g/10 min), insulating characteristics (volume resistivity = 2 × 1016 Ω/m), and hydrophobicity (water vapor permeability: 0.03 g/m2/day), suggesting potentially practical applications.
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science. Multi-nuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mono-nuclear catalysts, but which substantially involve multi-step, tedious, and difficult synthesis. Herein, this study reports an intriguing approach to construct multi-nuclear catalysts for the milestone α-diimine nickel catalysts using an oligomeric strategy. A polymerizable norbornene unit is incorporated into the α-diimine ligand backbone, leading to the formation of the monomeric nickel catalyst Ni1 and its corresponding oligomeric nickel catalysts (Ni3 and Ni5) with varying degrees of polymerization (DP = 3 and 5). Notably, the oligomeric catalyst Ni5 was facilely scaled up (50 g-level), showed enhanced thermal stability, exhibited 4.6 times higher activity, and yielded polyethylene elastomer with a 379% increased molecular weight in ethylene polymerization, compared to the monomeric catalyst Ni1. Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent. The kilogram-scale polyethylene, produced using Ni5 in a 20 L reactor, presented a highly branched all-hydrocarbon structure, which demonstrated typical elastic properties (tensile strength: 4 MPa, elastic recovery: SR = 72%) along with great processability (MFI = 3.0 g/10 min), insulating characteristics (volume resistivity = 2 × 1016 Ω/m), and hydrophobicity (water vapor permeability: 0.03 g/m2/day), suggesting potentially practical applications.
2026, 37(1): 110967
doi: 10.1016/j.cclet.2025.110967
摘要:
Detecting biomarkers in body fluids by optical lateral flow immune assay (LFIA) technology provides rapid access to disease information for early diagnosis. LFIA is based on an antigen-antibody reaction and is rapidly becoming the preferred choice of physicians and patients for point-of-care testing due to its simplicity, cost-effectiveness, and rapid detection. Observing the optical signal change from the colloidal gold of the traditional LFIA strip has been widely applied for various biomarkers detection in body fluids. Despite the significant progress, rapid real-time detection of color changes in the colloidal gold by the naked eye still faces many limitations, such as large errors and the inability to quantify and accurately detect. New optical LFIA strip technology has emerged in recent years to extend its application scenarios for achieving quantitative detection such as fluorescence, afterglow, and chemiluminescence. Herein, we summarized the development of optical LFIA technology from single to hyphenated optical signals for biomarkers detection in body fluids from invasive and non-invasive sources. Moreover, the challenge and outlook of optical LFIA strip technology are highlighted to inspire the designing of next-generation diagnostic platforms.
Detecting biomarkers in body fluids by optical lateral flow immune assay (LFIA) technology provides rapid access to disease information for early diagnosis. LFIA is based on an antigen-antibody reaction and is rapidly becoming the preferred choice of physicians and patients for point-of-care testing due to its simplicity, cost-effectiveness, and rapid detection. Observing the optical signal change from the colloidal gold of the traditional LFIA strip has been widely applied for various biomarkers detection in body fluids. Despite the significant progress, rapid real-time detection of color changes in the colloidal gold by the naked eye still faces many limitations, such as large errors and the inability to quantify and accurately detect. New optical LFIA strip technology has emerged in recent years to extend its application scenarios for achieving quantitative detection such as fluorescence, afterglow, and chemiluminescence. Herein, we summarized the development of optical LFIA technology from single to hyphenated optical signals for biomarkers detection in body fluids from invasive and non-invasive sources. Moreover, the challenge and outlook of optical LFIA strip technology are highlighted to inspire the designing of next-generation diagnostic platforms.
2026, 37(1): 111120
doi: 10.1016/j.cclet.2025.111120
摘要:
Groundwater is a key part of the terrestrial ecosystem, but it is vulnerable to pollution in the context of chemical industry development. Treating contaminated groundwater is challenging due to its stable water quality, hidden contamination, and complex treatment requirements. Current research focuses on advanced treatment technologies, among which the advanced oxidation process (AOPs) of peroxomonosulfate (PMS) has great potential. Although there are many reviews of PMS-based AOP, most of them focus on surface water. This review aims to explore the activation reaction of PMS to groundwater by in-situ chemical oxidation (ISCO) technology, further study the reaction mechanism, compare the treatment effect of characteristic pollutants in the groundwater of the chemical industry park, propose new activation methods and catalyst selection, and provide guidance for future groundwater treatment research.
Groundwater is a key part of the terrestrial ecosystem, but it is vulnerable to pollution in the context of chemical industry development. Treating contaminated groundwater is challenging due to its stable water quality, hidden contamination, and complex treatment requirements. Current research focuses on advanced treatment technologies, among which the advanced oxidation process (AOPs) of peroxomonosulfate (PMS) has great potential. Although there are many reviews of PMS-based AOP, most of them focus on surface water. This review aims to explore the activation reaction of PMS to groundwater by in-situ chemical oxidation (ISCO) technology, further study the reaction mechanism, compare the treatment effect of characteristic pollutants in the groundwater of the chemical industry park, propose new activation methods and catalyst selection, and provide guidance for future groundwater treatment research.
2026, 37(1): 111183
doi: 10.1016/j.cclet.2025.111183
摘要:
Antibiotic resistance genes (ARGs) are recognized as a primary threat to the sustainability of environment and human health in the 21st century. Nanomaterials (NMs) have attracted substantial attention due to their unique dimensions and structures. Unfortunately, emerging evidence suggests that NMs may facilitate the transmission of ARGs. It is crucial to elucidate how NMs affect the evolution and dissemination of ARGs. The current review comprehensively examines the role of NMs in the widespread transmission of ARGs in aquatic environments and the underlying mechanisms involved in the process. It aims to clarify the effects and mechanisms of NMs on the horizontal gene transfer processes that are associated with ARGs, including the enhancement of cell membrane permeability, the formation of nanopores on membranes, promotion of mutagenesis, and the generation of reactive oxygen species (ROSs). Furthermore, the trade-off between the removal of ARGs and horizontal transfer has been elucidated. The review aspires to guide future research directions, advance knowledge on the implications of NMs in the field of ARGs' transmission, and provide a theoretical foundation for the development of safer and more effective applications of NMs.
Antibiotic resistance genes (ARGs) are recognized as a primary threat to the sustainability of environment and human health in the 21st century. Nanomaterials (NMs) have attracted substantial attention due to their unique dimensions and structures. Unfortunately, emerging evidence suggests that NMs may facilitate the transmission of ARGs. It is crucial to elucidate how NMs affect the evolution and dissemination of ARGs. The current review comprehensively examines the role of NMs in the widespread transmission of ARGs in aquatic environments and the underlying mechanisms involved in the process. It aims to clarify the effects and mechanisms of NMs on the horizontal gene transfer processes that are associated with ARGs, including the enhancement of cell membrane permeability, the formation of nanopores on membranes, promotion of mutagenesis, and the generation of reactive oxygen species (ROSs). Furthermore, the trade-off between the removal of ARGs and horizontal transfer has been elucidated. The review aspires to guide future research directions, advance knowledge on the implications of NMs in the field of ARGs' transmission, and provide a theoretical foundation for the development of safer and more effective applications of NMs.
2026, 37(1): 111232
doi: 10.1016/j.cclet.2025.111232
摘要:
The development of highly effective therapeutics is a priority in addressing the escalating threat that cancer poses to human health. Cyclodextrins (CDs) with exceptional biocompatibility and devisable structural hierarchy are emerging as versatile building blocks for engineered drug delivery systems, showing a promising prospect in cancer therapy. CDs enable precise synthesis of functionalized polymers with tailored architectures, endowing their excellent stability and large surface area to prolong drug circulation, enhance solubility, and increase targeting efficiency. Recently, CD-based nanotherapeutics has shown transformative potential in chemotherapy, phototherapy, immunotherapy, gene therapy and other co-delivery systems of combination therapy. This review will introduce the types of CD-based nanotherapeutics, systematically summarize their design methods and anticancer application, and further discuss the prospects and challenges, providing a roadmap for advancing CD nanotechnology toward cancer therapeutics.
The development of highly effective therapeutics is a priority in addressing the escalating threat that cancer poses to human health. Cyclodextrins (CDs) with exceptional biocompatibility and devisable structural hierarchy are emerging as versatile building blocks for engineered drug delivery systems, showing a promising prospect in cancer therapy. CDs enable precise synthesis of functionalized polymers with tailored architectures, endowing their excellent stability and large surface area to prolong drug circulation, enhance solubility, and increase targeting efficiency. Recently, CD-based nanotherapeutics has shown transformative potential in chemotherapy, phototherapy, immunotherapy, gene therapy and other co-delivery systems of combination therapy. This review will introduce the types of CD-based nanotherapeutics, systematically summarize their design methods and anticancer application, and further discuss the prospects and challenges, providing a roadmap for advancing CD nanotechnology toward cancer therapeutics.
2026, 37(1): 111249
doi: 10.1016/j.cclet.2025.111249
摘要:
The escalating global issues of water scarcity and pollution emphasize the critical need for the rapid development of efficient and eco-friendly water treatment technologies. Photoelectrocatalytic technology has emerged as a promising solution for effectively degrading refractory organic pollutants in water under light conditions. This review delves into the advancements made in the field, focusing on strategies to enhance the generation of active species by modulating the micro-interface of the photoanode. Strategies, such as morphological control, element doping, introduction of surface oxygen vacancies, and construction of heterostructures, significantly improve the separation efficiency of photogenerated charges and the generation of active species, thereby boosting the efficiency of photoelectrocatalytic performance. Furthermore, the review explores the potential applications of photoelectrocatalytic technology in organic pollutant degradation in solutions. It also outlines the current challenges and future development directions. Despite its remarkable laboratory success, practical implementation of photoelectrocatalytic technology encounters obstacles related to stability, cost-effectiveness, and operational efficiency. Future investigations need to focus on optimizing the performance of photoelectrocatalytic materials and exploring strategies for upscaling their application in real water treatment scenarios.
The escalating global issues of water scarcity and pollution emphasize the critical need for the rapid development of efficient and eco-friendly water treatment technologies. Photoelectrocatalytic technology has emerged as a promising solution for effectively degrading refractory organic pollutants in water under light conditions. This review delves into the advancements made in the field, focusing on strategies to enhance the generation of active species by modulating the micro-interface of the photoanode. Strategies, such as morphological control, element doping, introduction of surface oxygen vacancies, and construction of heterostructures, significantly improve the separation efficiency of photogenerated charges and the generation of active species, thereby boosting the efficiency of photoelectrocatalytic performance. Furthermore, the review explores the potential applications of photoelectrocatalytic technology in organic pollutant degradation in solutions. It also outlines the current challenges and future development directions. Despite its remarkable laboratory success, practical implementation of photoelectrocatalytic technology encounters obstacles related to stability, cost-effectiveness, and operational efficiency. Future investigations need to focus on optimizing the performance of photoelectrocatalytic materials and exploring strategies for upscaling their application in real water treatment scenarios.
2026, 37(1): 111273
doi: 10.1016/j.cclet.2025.111273
摘要:
Chitosan (CS), a natural polymer derived from chitin found in the exoskeletons of crustaceans, has garnered significant interest in the pharmaceutical field due to its unique properties, including biocompatibility and biodegradability. In recent years, various studies have reported that CS can affect drug bioavailability, and interestingly, it works as an oral absorption enhancer and inhibitor. This review offers an in-depth analysis of the mechanisms underlying such a phenomenon and supports its application as a pharmaceutical excipient. CS enhances oral drug absorption through various mechanisms, such as interaction with the intestinal mucosa, tight junction modulation, inhibition of efflux transporters, enzyme inhibition, solubility and stability enhancement, and complexation. On the other side, CS exhibits the ability to inhibit the absorption of certain drugs by adsorbing to lipids and sterols, modulating bile acids and gut microbiota, altering drug-cell interaction at the polar interface, and mucus-mediated entrapment and interference. Future potential pharmaceutical research in this field includes elucidating the underneath absorption relevant mechanisms, rational use in formulations as excipient, exploring functional CS derivatives, and developing CS-based drug delivery systems. This comprehensive review highlights CS’s versatile and significant role in enhancing and inhibiting oral drug absorption, providing insights into the complexities of drug delivery and the potential of CS to improve therapeutic outcomes.
Chitosan (CS), a natural polymer derived from chitin found in the exoskeletons of crustaceans, has garnered significant interest in the pharmaceutical field due to its unique properties, including biocompatibility and biodegradability. In recent years, various studies have reported that CS can affect drug bioavailability, and interestingly, it works as an oral absorption enhancer and inhibitor. This review offers an in-depth analysis of the mechanisms underlying such a phenomenon and supports its application as a pharmaceutical excipient. CS enhances oral drug absorption through various mechanisms, such as interaction with the intestinal mucosa, tight junction modulation, inhibition of efflux transporters, enzyme inhibition, solubility and stability enhancement, and complexation. On the other side, CS exhibits the ability to inhibit the absorption of certain drugs by adsorbing to lipids and sterols, modulating bile acids and gut microbiota, altering drug-cell interaction at the polar interface, and mucus-mediated entrapment and interference. Future potential pharmaceutical research in this field includes elucidating the underneath absorption relevant mechanisms, rational use in formulations as excipient, exploring functional CS derivatives, and developing CS-based drug delivery systems. This comprehensive review highlights CS’s versatile and significant role in enhancing and inhibiting oral drug absorption, providing insights into the complexities of drug delivery and the potential of CS to improve therapeutic outcomes.
2026, 37(1): 111512
doi: 10.1016/j.cclet.2025.111512
摘要:
The diagnostic efficacy of contemporary bioimaging technologies remains constrained by inherent limitations of conventional imaging agents, including suboptimal sensitivity, off-target biodistribution, and inherent cytotoxicity. These limitations have catalyzed the development of intelligent stimuli-responsive block copolymers-based bioimaging agents, which was engineered to dynamically respond to endogenous biochemical cues (e.g., pH gradients, redox potential, enzyme activity, hypoxia environment) or exogenous physical triggers (e.g., photoirradiation, thermal gradients, ultrasound (US)/magnetic stimuli). Through spatiotemporally controlled structural transformations, stimuli-responsive block copolymers enable precise contrast targeting, activatable signal amplification, and theranostic integration, thereby substantially enhancing signal-to-noise ratios of bioimaging and diagnostic specificity. Hence, this mini-review systematically examines molecular engineering principles for designing pH-, redox-, enzyme-, light-, thermo-, and US/magnetic-responsive polymers, with emphasis on structure-property relationships governing imaging performance modulation. Furthermore, we critically analyze emerging strategies for optical imaging, US synergies, and magnetic resonance imaging (MRI). Multimodal bioimaging has also been elaborated, which could overcome the inherent trade-offs between resolution, penetration depth, and functional specificity in single-modal approaches. By elucidating mechanistic insights and translational challenges, this mini-review aims to establish a design framework of stimuli-responsive block copolymers-based for high fidelity bioimaging agents and accelerate their clinical translation in precise diagnosis and therapy.
The diagnostic efficacy of contemporary bioimaging technologies remains constrained by inherent limitations of conventional imaging agents, including suboptimal sensitivity, off-target biodistribution, and inherent cytotoxicity. These limitations have catalyzed the development of intelligent stimuli-responsive block copolymers-based bioimaging agents, which was engineered to dynamically respond to endogenous biochemical cues (e.g., pH gradients, redox potential, enzyme activity, hypoxia environment) or exogenous physical triggers (e.g., photoirradiation, thermal gradients, ultrasound (US)/magnetic stimuli). Through spatiotemporally controlled structural transformations, stimuli-responsive block copolymers enable precise contrast targeting, activatable signal amplification, and theranostic integration, thereby substantially enhancing signal-to-noise ratios of bioimaging and diagnostic specificity. Hence, this mini-review systematically examines molecular engineering principles for designing pH-, redox-, enzyme-, light-, thermo-, and US/magnetic-responsive polymers, with emphasis on structure-property relationships governing imaging performance modulation. Furthermore, we critically analyze emerging strategies for optical imaging, US synergies, and magnetic resonance imaging (MRI). Multimodal bioimaging has also been elaborated, which could overcome the inherent trade-offs between resolution, penetration depth, and functional specificity in single-modal approaches. By elucidating mechanistic insights and translational challenges, this mini-review aims to establish a design framework of stimuli-responsive block copolymers-based for high fidelity bioimaging agents and accelerate their clinical translation in precise diagnosis and therapy.
2026, 37(1): 111513
doi: 10.1016/j.cclet.2025.111513
摘要:
Malignant pleural effusion (MPE) is a serious disease caused by malignant tumors with high morbidity and mortality. Chemotherapy, immunotherapy, and antiangiogenic therapy are common treatments for MPE at present. However, traditional chemotherapeutic drugs have many side effects and can easily lead to drug resistance in patients. The complex tumor microenvironment (TME) of MPE directly reduces the antitumor efficacy of immunotherapy. Fortunately, drug delivery systems (DDSs) based on biomaterials have the ability to overcome some of the drawbacks of conventional treatments by improving drug stability, increasing the accuracy of tumor cell targeting, reducing toxic side effects, and remodeling TME, ultimately improving drug efficacy. Therefore, the purpose of this review is to provide an overview and discussion of the latest progress in biomaterial-based DDSs for the treatment of MPE. We discuss the application of biomaterials in the treatment of MPE from multiple perspectives, including chemotherapy, immunotherapy, combination therapy, and pleurodesis, where microspheres, cell membrane-derived microparticles (MPs), micelles, nanoparticles, and liposomes, are involved. The application of these biomaterials has been proven to have great potential in the treatment of MPE, providing a new idea for follow-up research.
Malignant pleural effusion (MPE) is a serious disease caused by malignant tumors with high morbidity and mortality. Chemotherapy, immunotherapy, and antiangiogenic therapy are common treatments for MPE at present. However, traditional chemotherapeutic drugs have many side effects and can easily lead to drug resistance in patients. The complex tumor microenvironment (TME) of MPE directly reduces the antitumor efficacy of immunotherapy. Fortunately, drug delivery systems (DDSs) based on biomaterials have the ability to overcome some of the drawbacks of conventional treatments by improving drug stability, increasing the accuracy of tumor cell targeting, reducing toxic side effects, and remodeling TME, ultimately improving drug efficacy. Therefore, the purpose of this review is to provide an overview and discussion of the latest progress in biomaterial-based DDSs for the treatment of MPE. We discuss the application of biomaterials in the treatment of MPE from multiple perspectives, including chemotherapy, immunotherapy, combination therapy, and pleurodesis, where microspheres, cell membrane-derived microparticles (MPs), micelles, nanoparticles, and liposomes, are involved. The application of these biomaterials has been proven to have great potential in the treatment of MPE, providing a new idea for follow-up research.
2026, 37(1): 111524
doi: 10.1016/j.cclet.2025.111524
摘要:
In recent years, development of strategies to treat central nervous system (CNS) diseases has attracted extensive attention. A major obstacle in this field is the blood-brain barrier (BBB), which significantly limits the efficient delivery of therapeutic agents to the brain and hinders the treatment of CNS diseases. Overcoming the restrictive nature of the BBB has thus emerged as a key objective in CNS drug development. Nanomaterials have garnered growing interest due to their unique physicochemical properties and potential to traverse the BBB, enabling targeted drug delivery to brain tissue and improving therapeutic efficacy. In this review, we present current insights into the structure and function of the BBB and highlight a range of nanomaterial-based strategies for BBB penetration, including receptor-mediated transport (RMT), adsorptive-mediated transcytosis, reversible BBB disruption, and intranasal administration. Finally, we summarize recent advances in enhancing BBB permeability for CNS therapeutics and discuss persisting challenges, offering perspectives for future research in this field.
In recent years, development of strategies to treat central nervous system (CNS) diseases has attracted extensive attention. A major obstacle in this field is the blood-brain barrier (BBB), which significantly limits the efficient delivery of therapeutic agents to the brain and hinders the treatment of CNS diseases. Overcoming the restrictive nature of the BBB has thus emerged as a key objective in CNS drug development. Nanomaterials have garnered growing interest due to their unique physicochemical properties and potential to traverse the BBB, enabling targeted drug delivery to brain tissue and improving therapeutic efficacy. In this review, we present current insights into the structure and function of the BBB and highlight a range of nanomaterial-based strategies for BBB penetration, including receptor-mediated transport (RMT), adsorptive-mediated transcytosis, reversible BBB disruption, and intranasal administration. Finally, we summarize recent advances in enhancing BBB permeability for CNS therapeutics and discuss persisting challenges, offering perspectives for future research in this field.
2026, 37(1): 111543
doi: 10.1016/j.cclet.2025.111543
摘要:
Plant bacterial diseases cause significant harm to agricultural production because of their frequent, intermittent and regional outbreaks. Currently, chemical control is still a more effective method for bacterial disease. To develop new, efficient and safe antibacterial agrochemicals, we summarize the research progress of compounds with antibacterial activities in the past ten years, classify them according to their active skeletons, and discuss their structure-activity relationships and mechanisms of action. Finally, the development trend of antibacterial agrochemicals was prospected. This review provides valuable information for the development of antibacterial agrochemicals.
Plant bacterial diseases cause significant harm to agricultural production because of their frequent, intermittent and regional outbreaks. Currently, chemical control is still a more effective method for bacterial disease. To develop new, efficient and safe antibacterial agrochemicals, we summarize the research progress of compounds with antibacterial activities in the past ten years, classify them according to their active skeletons, and discuss their structure-activity relationships and mechanisms of action. Finally, the development trend of antibacterial agrochemicals was prospected. This review provides valuable information for the development of antibacterial agrochemicals.
2026, 37(1): 111545
doi: 10.1016/j.cclet.2025.111545
摘要:
Given the broad applicability of carbazole structural moieties in materials science and medicinal chemistry, significant efforts have been devoted to developing efficient synthetic catalytic methodologies to access this valuable scaffold. Catalyzed direct Csp2–H functionalization provides an effective and cost-efficient approach to synthesizing carbazoles from simple and readily available starting materials, ensuring a promising path characterized by excellent atom and step economy. This review highlights the substantial progress made in the last 10 years in advancing catalytic Csp2–H functionalization techniques for synthesizing carbazoles.
Given the broad applicability of carbazole structural moieties in materials science and medicinal chemistry, significant efforts have been devoted to developing efficient synthetic catalytic methodologies to access this valuable scaffold. Catalyzed direct Csp2–H functionalization provides an effective and cost-efficient approach to synthesizing carbazoles from simple and readily available starting materials, ensuring a promising path characterized by excellent atom and step economy. This review highlights the substantial progress made in the last 10 years in advancing catalytic Csp2–H functionalization techniques for synthesizing carbazoles.
2026, 37(1): 111596
doi: 10.1016/j.cclet.2025.111596
摘要:
In recent years, different drugs therapies for treatment pulmonary fibrosis (PF) have gained much attention due to development of drug delivery technology and urgent clinical needs. PF treatment existed a variety of currently clinical problem but PF could be treated with different drugs potentially though drug delivery technology. This review systematically expounds its basic theory, various drug delivery technologies, and future development directions. In the introduction, the relationship between the pathological mechanism of PF and drug delivery, the basic principles of the drug delivery system and the biological barriers faced by pulmonary drug delivery are analyzed. This review details delivery of small molecule drug, macromolecular drug and cells, including chemical synthesis and natural small molecule drug delivery, as well as RNA and cell-based delivery. Finally, the challenges and perspectives of these drugs to treat PF delivery technologies are discussed and key aspects in the development of PF drugs are considered. We hoped that this review can provide comprehensive and in-depth theoretical reference and technical support for the drug treatment of PF.
In recent years, different drugs therapies for treatment pulmonary fibrosis (PF) have gained much attention due to development of drug delivery technology and urgent clinical needs. PF treatment existed a variety of currently clinical problem but PF could be treated with different drugs potentially though drug delivery technology. This review systematically expounds its basic theory, various drug delivery technologies, and future development directions. In the introduction, the relationship between the pathological mechanism of PF and drug delivery, the basic principles of the drug delivery system and the biological barriers faced by pulmonary drug delivery are analyzed. This review details delivery of small molecule drug, macromolecular drug and cells, including chemical synthesis and natural small molecule drug delivery, as well as RNA and cell-based delivery. Finally, the challenges and perspectives of these drugs to treat PF delivery technologies are discussed and key aspects in the development of PF drugs are considered. We hoped that this review can provide comprehensive and in-depth theoretical reference and technical support for the drug treatment of PF.
2026, 37(1): 111604
doi: 10.1016/j.cclet.2025.111604
摘要:
Hydrogen peroxide (H2O2) has been recognized as a green and nonpolluting multifunctional oxidant with extensive applications in environmental protection, metal etching, textile printing and dyeing, chemical synthesis and food processing. However, over 90% of industrial H2O2 is currently produced through the multi-step anthraquinone oxidation process, which suffers from a process with some drawbacks such as complex, high-energy consumption, and toxic byproducts emissions. Compared to the traditional anthraquinone method, artificial photosynthesis of H2O2 using semiconductor photocatalysts has emerged as a sustainable alternative due to its use of water and O2 as the clean reactants and sole energy as the driving force. In recent years, metal-free photocatalysts mainly including covalent organic frameworks (COFs), covalent triazine frameworks (CTFs) and carbon nitrile (g-C3N4) have garnered significant interest due to their superior thermal and chemical stability, diverse synthesis methods, tunable functionality, light weight nature and non-toxicity. These materials also exhibit adjustable band structure and unique photoelectric properties. Sustainable efforts have been made to advance metal-free photocatalysts for artificial photosynthesis of H2O2, however, a comprehensive summary of current research status on metal-free-based photocatalytic overall H2O2 production remain scarce. This review outlines recent process in overall H2O2 photosynthesis based on metal-free photocatalysts. First, we introduced the fundamental concepts of photocatalytic overall H2O2 production. Then, we analyze representative studies on photocatalytic overall H2O2 synthesis using metal-free materials. Finally, we discuss the challenges and future perspectives in this field to guide the design and synthesis of metal-free systems for H2O2 generation.
Hydrogen peroxide (H2O2) has been recognized as a green and nonpolluting multifunctional oxidant with extensive applications in environmental protection, metal etching, textile printing and dyeing, chemical synthesis and food processing. However, over 90% of industrial H2O2 is currently produced through the multi-step anthraquinone oxidation process, which suffers from a process with some drawbacks such as complex, high-energy consumption, and toxic byproducts emissions. Compared to the traditional anthraquinone method, artificial photosynthesis of H2O2 using semiconductor photocatalysts has emerged as a sustainable alternative due to its use of water and O2 as the clean reactants and sole energy as the driving force. In recent years, metal-free photocatalysts mainly including covalent organic frameworks (COFs), covalent triazine frameworks (CTFs) and carbon nitrile (g-C3N4) have garnered significant interest due to their superior thermal and chemical stability, diverse synthesis methods, tunable functionality, light weight nature and non-toxicity. These materials also exhibit adjustable band structure and unique photoelectric properties. Sustainable efforts have been made to advance metal-free photocatalysts for artificial photosynthesis of H2O2, however, a comprehensive summary of current research status on metal-free-based photocatalytic overall H2O2 production remain scarce. This review outlines recent process in overall H2O2 photosynthesis based on metal-free photocatalysts. First, we introduced the fundamental concepts of photocatalytic overall H2O2 production. Then, we analyze representative studies on photocatalytic overall H2O2 synthesis using metal-free materials. Finally, we discuss the challenges and future perspectives in this field to guide the design and synthesis of metal-free systems for H2O2 generation.
2026, 37(1): 111661
doi: 10.1016/j.cclet.2025.111661
摘要:
The catalytic transferred of small molecules into high-value chemical products in green methods are highly perused, and has obtained huge attention. In this field, great progress has been achieved during the past five years. Followed by the roadmap (Chinese Chemical Letters, 2019, 30, 2089–2109) written by us before five years, we think that it should be updated to give more insights in this field. Thus, we write the present roadmap based on the fast changed background. In this roadmap, oxygen and carbon dioxide reduction reactions (including at high temperature), photocatalytic hydrogen generation and carbon dioxide reduction reactions, (photo)electrocatalytic reduction of O2 to H2O2 and NH3 generated from N2 are discussed. The progress and challenges in above catalytic processes are given. We believe this manuscript will give the researchers more suggestions and help them to obtain useful information in this field.
The catalytic transferred of small molecules into high-value chemical products in green methods are highly perused, and has obtained huge attention. In this field, great progress has been achieved during the past five years. Followed by the roadmap (Chinese Chemical Letters, 2019, 30, 2089–2109) written by us before five years, we think that it should be updated to give more insights in this field. Thus, we write the present roadmap based on the fast changed background. In this roadmap, oxygen and carbon dioxide reduction reactions (including at high temperature), photocatalytic hydrogen generation and carbon dioxide reduction reactions, (photo)electrocatalytic reduction of O2 to H2O2 and NH3 generated from N2 are discussed. The progress and challenges in above catalytic processes are given. We believe this manuscript will give the researchers more suggestions and help them to obtain useful information in this field.
2026, 37(1): 111673
doi: 10.1016/j.cclet.2025.111673
摘要:
The combination of electrochemistry and metal catalysts has been a popular research topic in the field of organic synthesis due to the abundance and controllable valence states of transition metals, where electron transfer at the electrode produces catalysts with more valence states. Among these transition metal catalysts, electrochemical conversions catalyzed by inexpensive copper metals have received considerable attention. This article systematically investigated this field and reviewed the electrochemical copper catalytic methods applied in organic synthesis from the different activation modes of substrates, which can be broadly classified into the functionalization of C = C bonds, C−H bond activation, C−C and C−X bond activation, and so on.
The combination of electrochemistry and metal catalysts has been a popular research topic in the field of organic synthesis due to the abundance and controllable valence states of transition metals, where electron transfer at the electrode produces catalysts with more valence states. Among these transition metal catalysts, electrochemical conversions catalyzed by inexpensive copper metals have received considerable attention. This article systematically investigated this field and reviewed the electrochemical copper catalytic methods applied in organic synthesis from the different activation modes of substrates, which can be broadly classified into the functionalization of C = C bonds, C−H bond activation, C−C and C−X bond activation, and so on.
2026, 37(1): 111886
doi: 10.1016/j.cclet.2025.111886
摘要:
Radical cycloaddition reactions (RCRs) are highly effective methods for constructing complex carbo- and heterocycles, which are frequently encountered in natural products that exhibit intriguing biological properties and hold significant potential for applications in medicinal chemistry. Radical-mediated cycloaddition strategies, which recycle radical character, are particularly appealing because they require only a catalytic amount of reagent and promise reactions with theoretically high atom economy. This review focuses on recent developments and synthetic applications in RCRs, with an emphasis on visible light-induced radical photocycloaddition reactions (RPCRs), transition metal-catalyzed approaches, and small molecule-catalyzed methods. By highlighting some outstanding innovations and addressing current challenges, this review aims to identify potential areas for improvement. These advancements will provide more efficient pathways for the synthesis of natural product molecules and offer valuable insights for the development of new synthetic methodologies.
Radical cycloaddition reactions (RCRs) are highly effective methods for constructing complex carbo- and heterocycles, which are frequently encountered in natural products that exhibit intriguing biological properties and hold significant potential for applications in medicinal chemistry. Radical-mediated cycloaddition strategies, which recycle radical character, are particularly appealing because they require only a catalytic amount of reagent and promise reactions with theoretically high atom economy. This review focuses on recent developments and synthetic applications in RCRs, with an emphasis on visible light-induced radical photocycloaddition reactions (RPCRs), transition metal-catalyzed approaches, and small molecule-catalyzed methods. By highlighting some outstanding innovations and addressing current challenges, this review aims to identify potential areas for improvement. These advancements will provide more efficient pathways for the synthesis of natural product molecules and offer valuable insights for the development of new synthetic methodologies.
2026, 37(1): 111894
doi: 10.1016/j.cclet.2025.111894
摘要:
Interlocked covalent organic cages have aesthetic skeletons endowed with structural and topological complexity. Their self-assembly provides a unique possibility to mimic the hierarchical self-assembly of biomacromolecules. In recent years, significant progresses in interlocked covalent organic cages have been witnessed. Different topological structures have been fabricated via various non-template induced methods, and diverse weak interactions are demonstrated to play critical roles in guiding the formation of interlocked structures. Therefore, this article systematically summarizes the recent advances in interlocked covalent organic cages, especially their design, synthesis, and self-assembly properties. Depending on different types of chemical reactions, irreversible and reversible reactions are separately introduced. In each section, proper monomer selection, critical topology design, key driving forces as well as detailed interlocked mechanisms for the formation of interlocked structures, and their self-assembly behaviors in single crystals are discussed detailedly. Finally, the challenge and future development of interlocked covalent organic cages are briefly prospected.
Interlocked covalent organic cages have aesthetic skeletons endowed with structural and topological complexity. Their self-assembly provides a unique possibility to mimic the hierarchical self-assembly of biomacromolecules. In recent years, significant progresses in interlocked covalent organic cages have been witnessed. Different topological structures have been fabricated via various non-template induced methods, and diverse weak interactions are demonstrated to play critical roles in guiding the formation of interlocked structures. Therefore, this article systematically summarizes the recent advances in interlocked covalent organic cages, especially their design, synthesis, and self-assembly properties. Depending on different types of chemical reactions, irreversible and reversible reactions are separately introduced. In each section, proper monomer selection, critical topology design, key driving forces as well as detailed interlocked mechanisms for the formation of interlocked structures, and their self-assembly behaviors in single crystals are discussed detailedly. Finally, the challenge and future development of interlocked covalent organic cages are briefly prospected.
2026, 37(1): 111638
doi: 10.1016/j.cclet.2025.111638
摘要:
2026, 37(1): 111796
doi: 10.1016/j.cclet.2025.111796
摘要:
