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2026 Volume 37 Issue 1
2026, 37(1): 110064
doi: 10.1016/j.cclet.2024.110064
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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): 111796
doi: 10.1016/j.cclet.2025.111796
Abstract:
