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2026 Volume 37 Issue 6
2026, 37(6): 110887
doi: 10.1016/j.cclet.2025.110887
Abstract:
Controlling gas sorption via pore environment regulation is of significance yet challenging in the adsorption and separation process. Herein, we report a pillar modification strategy in the pillar–layered metal–organic frameworks for enhancing C2H2/CO2 separation by controlling host-guest interactions. Altering pillars from aromatic ligand to aliphatic ligand in the prototype MOF (Ni-MOF-1) not only manufactures an aliphatic pore environment conducive to generate multiple van der Waals interactions with C2H2 but also increases adsorption sites for C2H2 verified by theoretical calculations. The pore environment optimized Ni-MOF-2 exhibits 3.5-fold enhanced equimolar C2H2/CO2 selectivity and practical separation performance evidenced by dynamic breakthrough experiments. This work provides an example for the in-depth investigation of delicate pore environment regulation and offers an alternative for the C2H2/CO2 separation.
Controlling gas sorption via pore environment regulation is of significance yet challenging in the adsorption and separation process. Herein, we report a pillar modification strategy in the pillar–layered metal–organic frameworks for enhancing C2H2/CO2 separation by controlling host-guest interactions. Altering pillars from aromatic ligand to aliphatic ligand in the prototype MOF (Ni-MOF-1) not only manufactures an aliphatic pore environment conducive to generate multiple van der Waals interactions with C2H2 but also increases adsorption sites for C2H2 verified by theoretical calculations. The pore environment optimized Ni-MOF-2 exhibits 3.5-fold enhanced equimolar C2H2/CO2 selectivity and practical separation performance evidenced by dynamic breakthrough experiments. This work provides an example for the in-depth investigation of delicate pore environment regulation and offers an alternative for the C2H2/CO2 separation.
2026, 37(6): 110985
doi: 10.1016/j.cclet.2025.110985
Abstract:
Though polyvinylidene fluoride (PVDF) is commonly employed as a binder for lithium-sulfur (Li-S) batteries, it still faces the challenge of serious electrode fracture caused by dramatic volume changes during cycling, and lacks extended functions such as capturing dissolved lithium polysulfides (LIPSs) and promoting Li+ transfer. Herein, a multifunctional water-soluble binder lithium sulfonated cellulose (Cel-SO3Li) is designed and prepared. The Cel-SO3Li binder can capture LIPSs due to nucleophilic substitution reaction between -SO4Li and dissolved LIPSs. Its abundant hydroxyl groups provide excellent electrode mechanical properties, which effectively alleviate sulfur volume changes during cycling. Furthermore, the -SO3Li groups also enhance the diffusion of Li+ in the electrodes. In addition, density functional theory calculations reveal that the Cel-SO3Li exhibits strong affinity and catalytic ability for LIPSs, indicating that it can effectively suppress the shuttle effect and enhance their reaction kinetics. Therefore, the electrode using Cel-SO3Li binder reach a high initial discharge capacity of 1165 mAh/g at 0.5 C, remain 545 mAh/g after 1000 cycles with a low capacity decay rate of 0.053% per cycle. This study proposes the concept of a multifunctional and environmentally friendly binder with the ability of "three birds with one stone" (high adhesion, fast Li+ diffusion, effective capture and even catalysis for LIPSs), which will contribute to accelerating applications of Li-S batteries.
Though polyvinylidene fluoride (PVDF) is commonly employed as a binder for lithium-sulfur (Li-S) batteries, it still faces the challenge of serious electrode fracture caused by dramatic volume changes during cycling, and lacks extended functions such as capturing dissolved lithium polysulfides (LIPSs) and promoting Li+ transfer. Herein, a multifunctional water-soluble binder lithium sulfonated cellulose (Cel-SO3Li) is designed and prepared. The Cel-SO3Li binder can capture LIPSs due to nucleophilic substitution reaction between -SO4Li and dissolved LIPSs. Its abundant hydroxyl groups provide excellent electrode mechanical properties, which effectively alleviate sulfur volume changes during cycling. Furthermore, the -SO3Li groups also enhance the diffusion of Li+ in the electrodes. In addition, density functional theory calculations reveal that the Cel-SO3Li exhibits strong affinity and catalytic ability for LIPSs, indicating that it can effectively suppress the shuttle effect and enhance their reaction kinetics. Therefore, the electrode using Cel-SO3Li binder reach a high initial discharge capacity of 1165 mAh/g at 0.5 C, remain 545 mAh/g after 1000 cycles with a low capacity decay rate of 0.053% per cycle. This study proposes the concept of a multifunctional and environmentally friendly binder with the ability of "three birds with one stone" (high adhesion, fast Li+ diffusion, effective capture and even catalysis for LIPSs), which will contribute to accelerating applications of Li-S batteries.
2026, 37(6): 110999
doi: 10.1016/j.cclet.2025.110999
Abstract:
Exploring multiphase interfaces to modulate the electronic structure of catalysts is critical for energy conversion catalysis processes. Herein, we demonstrated the carbon-constrained heterogeneous NiTe-MoTe2 microsphere catalysts with high performance induced by heterostructure charge redistribution for energy-saving hydrogen generation from urea electrolysis. The hybrid NiTe-MoTe2 generated the optimized Gibbs adsorption-free energy for reducing the reaction energy barrier and enhancing catalytic kinetics. The high-valence Mo created a favorable chemical environment for positively charged Ni species formation by modulating the electronic structure. The NiTe-MoTe2 composites exhibit superior electrocatalytic activity compared to the pure-phase NiTe or MoTe2 catalysts, achieving a current density of 10 mA/cm2 at 1.40 V for urea oxidation, along with rapid catalytic kinetics and robust stability. The NiTe-MoTe2Pt/C electrolyzer achieves a current density of 10 mA/cm2 at a cell potential of 1.49 V and maintains excellent long-term durability over 120 h at 1.60 V for urea electrolysis. The promoted spontaneous dehydrogenation and CO2 desorption ability catalyzed by NiTe-MoTe2 largely improved the reaction kinetics and performance. The current work showed new insights for the development of advanced energy conversion catalytic mate.
Exploring multiphase interfaces to modulate the electronic structure of catalysts is critical for energy conversion catalysis processes. Herein, we demonstrated the carbon-constrained heterogeneous NiTe-MoTe2 microsphere catalysts with high performance induced by heterostructure charge redistribution for energy-saving hydrogen generation from urea electrolysis. The hybrid NiTe-MoTe2 generated the optimized Gibbs adsorption-free energy for reducing the reaction energy barrier and enhancing catalytic kinetics. The high-valence Mo created a favorable chemical environment for positively charged Ni species formation by modulating the electronic structure. The NiTe-MoTe2 composites exhibit superior electrocatalytic activity compared to the pure-phase NiTe or MoTe2 catalysts, achieving a current density of 10 mA/cm2 at 1.40 V for urea oxidation, along with rapid catalytic kinetics and robust stability. The NiTe-MoTe2Pt/C electrolyzer achieves a current density of 10 mA/cm2 at a cell potential of 1.49 V and maintains excellent long-term durability over 120 h at 1.60 V for urea electrolysis. The promoted spontaneous dehydrogenation and CO2 desorption ability catalyzed by NiTe-MoTe2 largely improved the reaction kinetics and performance. The current work showed new insights for the development of advanced energy conversion catalytic mate.
2026, 37(6): 111001
doi: 10.1016/j.cclet.2025.111001
Abstract:
Glycerol oxidation reaction has got lots of attention in an electrocatalytic system of simultaneous hydrogen production and valuable chemicals generation. However, the lack of electrochemical dehydrogenation capability of the active phase is hard to deliver a large current density at a low potential. Furthermore, high selectivity of products is also still far from being completed due to the adsorption-desorption disequilibrium of glycerol and the obtained products, reducing the economic feasibility and limiting the practical application. Here, we propose a strategy to boost the electrocatalytic glycerol oxidation through electron-deficient Ni sites induced by electron transfer of heterojunction interface. Taking Ni3S2/Cu2S as a pre-catalysts, we demonstrate that the electron-deficient Ni site can favor the dehydrogenation of the active phase to facilitate the rapid transformation of Ni2+/Ni3+ in the electrooxidation process of glycerol. Furthermore, electron deficient Ni sites balance competitive adsorption of active species, improving the activity and selectivity of glycerol oxidation. As expected, the electrocatalysts exhibit selectivity of 93.3% for formate at the 1.35 V, and require only 1.45 V to drive an industrial-level current densities of 600 mA/cm2. This work provides valuable insights into constructing highly active and selective electrocatalysts for organic electrosynthesis in hybrid water electrolysis.
Glycerol oxidation reaction has got lots of attention in an electrocatalytic system of simultaneous hydrogen production and valuable chemicals generation. However, the lack of electrochemical dehydrogenation capability of the active phase is hard to deliver a large current density at a low potential. Furthermore, high selectivity of products is also still far from being completed due to the adsorption-desorption disequilibrium of glycerol and the obtained products, reducing the economic feasibility and limiting the practical application. Here, we propose a strategy to boost the electrocatalytic glycerol oxidation through electron-deficient Ni sites induced by electron transfer of heterojunction interface. Taking Ni3S2/Cu2S as a pre-catalysts, we demonstrate that the electron-deficient Ni site can favor the dehydrogenation of the active phase to facilitate the rapid transformation of Ni2+/Ni3+ in the electrooxidation process of glycerol. Furthermore, electron deficient Ni sites balance competitive adsorption of active species, improving the activity and selectivity of glycerol oxidation. As expected, the electrocatalysts exhibit selectivity of 93.3% for formate at the 1.35 V, and require only 1.45 V to drive an industrial-level current densities of 600 mA/cm2. This work provides valuable insights into constructing highly active and selective electrocatalysts for organic electrosynthesis in hybrid water electrolysis.
2026, 37(6): 111002
doi: 10.1016/j.cclet.2025.111002
Abstract:
Developing non-precious electrocatalysts with high-efficiency hydrogen evolution reaction (HER) activity for hydrogen production at all pH values is crucial for the application and promotion of water electrolysis. Herein, a unique structure of nickel-cobalt (Ni–Co) nanoparticles@Ni0.19Co0.26P nanowires core/shell arrays on Ni foam as a pH-universal electrocatalyst for hydrogen evolution is synthesized by a simple hydrothermal process and thermal reduction treatment. The morphological analysis reveals that numerous Ni–Co nanoparticles are densely packed inside the hollow interior of Ni0.19Co0.26P nanowires. This unique structure integrates the advantages of high surface area from the nanowires and enhanced electronic conductivity from the Ni–Co nanoparticles, effectively addressing the conventional issue of slow charge transfer rate in 3D metal-based compounds, which is typically caused by a long transfer distance. The electrocatalysts provide an excellent hydrogen evolution reaction performance in alkaline, neutral, and acidic media with an overpotential of 35, 36, and 23 mV to reach the current density of 10 mA/cm2, respectively. This study highlights the potential of Ni–Co nanoparticles@Ni0.19Co0.26P nanowires as a cost-effective and pH-universal HER electrocatalyst, offering promising prospects for sustainable hydrogen production.
Developing non-precious electrocatalysts with high-efficiency hydrogen evolution reaction (HER) activity for hydrogen production at all pH values is crucial for the application and promotion of water electrolysis. Herein, a unique structure of nickel-cobalt (Ni–Co) nanoparticles@Ni0.19Co0.26P nanowires core/shell arrays on Ni foam as a pH-universal electrocatalyst for hydrogen evolution is synthesized by a simple hydrothermal process and thermal reduction treatment. The morphological analysis reveals that numerous Ni–Co nanoparticles are densely packed inside the hollow interior of Ni0.19Co0.26P nanowires. This unique structure integrates the advantages of high surface area from the nanowires and enhanced electronic conductivity from the Ni–Co nanoparticles, effectively addressing the conventional issue of slow charge transfer rate in 3D metal-based compounds, which is typically caused by a long transfer distance. The electrocatalysts provide an excellent hydrogen evolution reaction performance in alkaline, neutral, and acidic media with an overpotential of 35, 36, and 23 mV to reach the current density of 10 mA/cm2, respectively. This study highlights the potential of Ni–Co nanoparticles@Ni0.19Co0.26P nanowires as a cost-effective and pH-universal HER electrocatalyst, offering promising prospects for sustainable hydrogen production.
2026, 37(6): 111003
doi: 10.1016/j.cclet.2025.111003
Abstract:
Scarce investigations have focused on coinage metal clusters possessing fixed cores but varying binding ligands in the context of catalysis. Here in this work, we successfully employed two types of carboxylic acid-based molecular tweezers to selectively capture two Cu6 clusters (Cu6-a and Cu6-b). Cu6-a and Cu6-b have identical cluster cores but different protected ligands, therefore provide accurate platform for investigating ligand effects in cluster catalysis. Notably, Cu6-b represents a rare example of a two-directional rod framework, marking the first instance of such a structure in coinage metal cluster-based MOFs. The integration of oxygen within OBB significantly enhances local spatial polarization, facilitating the charge separation and ROS generation efficiency of Cu6-b under visible-light irradiation. Consequently, the oxygen-containing Cu6-b exhibits superior photocatalytic performance in the aerobic oxidation of sulfide, achieving both high yield and selectivity. This work provides a valuable approach for precisely control the Cu clusters structures to regulate their properties.
Scarce investigations have focused on coinage metal clusters possessing fixed cores but varying binding ligands in the context of catalysis. Here in this work, we successfully employed two types of carboxylic acid-based molecular tweezers to selectively capture two Cu6 clusters (Cu6-a and Cu6-b). Cu6-a and Cu6-b have identical cluster cores but different protected ligands, therefore provide accurate platform for investigating ligand effects in cluster catalysis. Notably, Cu6-b represents a rare example of a two-directional rod framework, marking the first instance of such a structure in coinage metal cluster-based MOFs. The integration of oxygen within OBB significantly enhances local spatial polarization, facilitating the charge separation and ROS generation efficiency of Cu6-b under visible-light irradiation. Consequently, the oxygen-containing Cu6-b exhibits superior photocatalytic performance in the aerobic oxidation of sulfide, achieving both high yield and selectivity. This work provides a valuable approach for precisely control the Cu clusters structures to regulate their properties.
2026, 37(6): 111011
doi: 10.1016/j.cclet.2025.111011
Abstract:
Ultraviolet (UV) nonlinear optical (NLO) crystals have received substantial interest in advanced laser technology. However, tailoring a UV NLO material with a large second harmonic generation (SHG) response and good UV transparency remains a challenge. Here, inspired by the classic A3-RE2-[BO3]3 parent template, two new rare-earth borate NLO crystals, RbNa2La2(BO3)3 (RNLBO-Ⅰ) and Rb0.681Na2.319La2(BO3)3 (RNLBO-Ⅱ), were extracted by merging larger ionic radius cations Rb+ and La3+ simultaneously using a chemical substitution-oriented strategy. As expected, both compounds achieve significant enhancements in SHG activities, reaching 4.5 × and 4.3 × KDP, respectively, exceeding three times that of the isomorphic Na3Gd2B3O9. Notably, RNLBO-Ⅰ displayed the highest SHG response among alkali metal RE-borate NLO crystals containing isolated [BO3] groups in the short-wave UV region. Moreover, RNLBO-Ⅰ and -Ⅱ demonstrated short UV cutoff edges at 213 and 207 nm, corresponding to wide bandgaps of 5.3 and 5.6 eV, respectively. Additionally, theoretical calculations and dipole moment analysis were conducted to clarify the origin of the enhanced SHG activities of RNLBO-Ⅰ and -Ⅱ. The optimal balance between SHG intensity and UV transparency in RNLBO-Ⅰ and -Ⅱ underscores their potential as UV NLO candidates and offers valuable insights for fabricating new advanced UV NLO materials.
Ultraviolet (UV) nonlinear optical (NLO) crystals have received substantial interest in advanced laser technology. However, tailoring a UV NLO material with a large second harmonic generation (SHG) response and good UV transparency remains a challenge. Here, inspired by the classic A3-RE2-[BO3]3 parent template, two new rare-earth borate NLO crystals, RbNa2La2(BO3)3 (RNLBO-Ⅰ) and Rb0.681Na2.319La2(BO3)3 (RNLBO-Ⅱ), were extracted by merging larger ionic radius cations Rb+ and La3+ simultaneously using a chemical substitution-oriented strategy. As expected, both compounds achieve significant enhancements in SHG activities, reaching 4.5 × and 4.3 × KDP, respectively, exceeding three times that of the isomorphic Na3Gd2B3O9. Notably, RNLBO-Ⅰ displayed the highest SHG response among alkali metal RE-borate NLO crystals containing isolated [BO3] groups in the short-wave UV region. Moreover, RNLBO-Ⅰ and -Ⅱ demonstrated short UV cutoff edges at 213 and 207 nm, corresponding to wide bandgaps of 5.3 and 5.6 eV, respectively. Additionally, theoretical calculations and dipole moment analysis were conducted to clarify the origin of the enhanced SHG activities of RNLBO-Ⅰ and -Ⅱ. The optimal balance between SHG intensity and UV transparency in RNLBO-Ⅰ and -Ⅱ underscores their potential as UV NLO candidates and offers valuable insights for fabricating new advanced UV NLO materials.
2026, 37(6): 111012
doi: 10.1016/j.cclet.2025.111012
Abstract:
Polyoxometalate-based metal-organic complexes (POMOCs) which combine the structural features and performance advantages of MOCs and POMs, have a wide application in the field of catalysis. However, the catalytic capacity of POMOCs commonly cannot be fully utilized due to their imporosity and low surface area of single-crystals. In this work, a new POMOC with a formula of [Cu3O(4-atrz)6(PO3)(PMo12O40)] (POMOC 1, 4-atrz = 4-amino-4H-1,2,4-triazole) was synthesized. And the size regulation of POMOC 1 from single-crystal to nanoscale was achieved by using citric acid as a modulator and adjusting the reaction temperature. Nano-sized POMOC 1 exhibited excellent catalytic performance in the oxidation reaction of phenols owing to the synergistic catalysis of POM and coordinatively unsaturated Cu(Ⅱ), and more surface-accessible catalytic sites of nano-catalyst.
Polyoxometalate-based metal-organic complexes (POMOCs) which combine the structural features and performance advantages of MOCs and POMs, have a wide application in the field of catalysis. However, the catalytic capacity of POMOCs commonly cannot be fully utilized due to their imporosity and low surface area of single-crystals. In this work, a new POMOC with a formula of [Cu3O(4-atrz)6(PO3)(PMo12O40)] (POMOC 1, 4-atrz = 4-amino-4H-1,2,4-triazole) was synthesized. And the size regulation of POMOC 1 from single-crystal to nanoscale was achieved by using citric acid as a modulator and adjusting the reaction temperature. Nano-sized POMOC 1 exhibited excellent catalytic performance in the oxidation reaction of phenols owing to the synergistic catalysis of POM and coordinatively unsaturated Cu(Ⅱ), and more surface-accessible catalytic sites of nano-catalyst.
2026, 37(6): 111015
doi: 10.1016/j.cclet.2025.111015
Abstract:
Oxygen (O) doping is a promising strategy for enhancing the air stability and lithium metal compatibility of sulfide solid electrolytes (SSEs). However, the impact of various O sources on the structure and properties of SSEs remains unclear. In this study, we synthesized a series of O-doped electrolytes, Li5.5PS4.5-xOxCl1.5 (LPSCOx, 0.1 ≤ x ≤ 0.5), using Li2O and P2O5 as O sources, and systematically investigated their differences in structure, air stability, and electrochemical properties. O preferentially substitutes sulfur (S) at the 16e site and begins to replace S at the 4d site once a certain O concentration is reached. Notably, the P2O5-doped electrolytes (P-LPSCOx) exhibit a greater oxygen tolerance content (0.24) at the 16e site, along with better air stability, higher ionic conductivity, and superior lithium metal compatibility. XRD, SEM, and XPS analyses reveal that the P2O5-doped electrolytes exhibit larger cell parameters, higher densification, and fewer side reactions with lithium metal compared to the Li2O-doped counterparts. This study provides valuable insights into the development of high-performance O-doped sulfide electrolytes.
Oxygen (O) doping is a promising strategy for enhancing the air stability and lithium metal compatibility of sulfide solid electrolytes (SSEs). However, the impact of various O sources on the structure and properties of SSEs remains unclear. In this study, we synthesized a series of O-doped electrolytes, Li5.5PS4.5-xOxCl1.5 (LPSCOx, 0.1 ≤ x ≤ 0.5), using Li2O and P2O5 as O sources, and systematically investigated their differences in structure, air stability, and electrochemical properties. O preferentially substitutes sulfur (S) at the 16e site and begins to replace S at the 4d site once a certain O concentration is reached. Notably, the P2O5-doped electrolytes (P-LPSCOx) exhibit a greater oxygen tolerance content (0.24) at the 16e site, along with better air stability, higher ionic conductivity, and superior lithium metal compatibility. XRD, SEM, and XPS analyses reveal that the P2O5-doped electrolytes exhibit larger cell parameters, higher densification, and fewer side reactions with lithium metal compared to the Li2O-doped counterparts. This study provides valuable insights into the development of high-performance O-doped sulfide electrolytes.
2026, 37(6): 111016
doi: 10.1016/j.cclet.2025.111016
Abstract:
Oxygen evolution reaction (OER) is a key reaction in proton exchange membrane water electrolyzers (PEMWEs). Therefore, developing cost-effective acid-stable electrocatalysts to drive efficient OER is crucial. Here, we constructed a RuO2 electrocatalyst (MoB-RuO2) co-doped Mo and B atoms, which exhibits excellent OER performance in acidic media. In 0.5 mol/L H2SO4, MoB-RuO2 exhibited a very low overpotential (166 mV) and could be operated stably for more than 550 h at 10 mA/cm2 current density without significant loss of activity. More than 240 h of stable operation at 200 mA/cm2 current density was achieved when using MoB-RuO2 as a PEMWE anode. Experimental and theoretical results demonstrated that the excellent OER activity and stability of MoB-RuO2 mainly originated from the incorporation of B atoms leading to the coordination unsaturation of the active centre Ru, and the simultaneous doping of Mo and B atoms modulated the electronic structure of Ru, which lowered the covalency of the Ru-O bond, thus making the catalyst exhibit excellent stability.
Oxygen evolution reaction (OER) is a key reaction in proton exchange membrane water electrolyzers (PEMWEs). Therefore, developing cost-effective acid-stable electrocatalysts to drive efficient OER is crucial. Here, we constructed a RuO2 electrocatalyst (MoB-RuO2) co-doped Mo and B atoms, which exhibits excellent OER performance in acidic media. In 0.5 mol/L H2SO4, MoB-RuO2 exhibited a very low overpotential (166 mV) and could be operated stably for more than 550 h at 10 mA/cm2 current density without significant loss of activity. More than 240 h of stable operation at 200 mA/cm2 current density was achieved when using MoB-RuO2 as a PEMWE anode. Experimental and theoretical results demonstrated that the excellent OER activity and stability of MoB-RuO2 mainly originated from the incorporation of B atoms leading to the coordination unsaturation of the active centre Ru, and the simultaneous doping of Mo and B atoms modulated the electronic structure of Ru, which lowered the covalency of the Ru-O bond, thus making the catalyst exhibit excellent stability.
2026, 37(6): 111036
doi: 10.1016/j.cclet.2025.111036
Abstract:
The immense potential of one-dimensional (1D) hybrid lead halide perovskites (HLHPs) in single crystal X-ray detection is hindered by their relatively low charge transport abilities and needle-like morphology. Alloying mixed cations in 1D HLHP is expected to realize superior charge mobility and large single crystals. Herein, we report a 1D HLHP of (ATZ)(EA)4Pb3I11 (1) with thiazol-2-aminium (ATZ)+ and ethanaminium (EA)+ as the mixed cations, demonstrating an exceptional 1D HLHP for high-performance X-ray detector. The H···I hydrogen bonds with a fraction of 69.7% are stronger than those in 1D HLHPs containing solely (ATZ)+ or (EA)+ cations. The single crystal of 1 posesses remarkable semiconducting properties, including a high resistivity (1.94 × 1011 Ω cm) and a large mobility-lifetime product (2.22 × 10−4 cm2/V), which contribute to the outstanding X-ray detection, manifested by a high sensitivity of 1356 µC Gyair−1 cm−2 and an ultra-low dark current drift of 5.01 × 10−8 nA cm−1 s−1 V−1.
The immense potential of one-dimensional (1D) hybrid lead halide perovskites (HLHPs) in single crystal X-ray detection is hindered by their relatively low charge transport abilities and needle-like morphology. Alloying mixed cations in 1D HLHP is expected to realize superior charge mobility and large single crystals. Herein, we report a 1D HLHP of (ATZ)(EA)4Pb3I11 (1) with thiazol-2-aminium (ATZ)+ and ethanaminium (EA)+ as the mixed cations, demonstrating an exceptional 1D HLHP for high-performance X-ray detector. The H···I hydrogen bonds with a fraction of 69.7% are stronger than those in 1D HLHPs containing solely (ATZ)+ or (EA)+ cations. The single crystal of 1 posesses remarkable semiconducting properties, including a high resistivity (1.94 × 1011 Ω cm) and a large mobility-lifetime product (2.22 × 10−4 cm2/V), which contribute to the outstanding X-ray detection, manifested by a high sensitivity of 1356 µC Gyair−1 cm−2 and an ultra-low dark current drift of 5.01 × 10−8 nA cm−1 s−1 V−1.
2026, 37(6): 111038
doi: 10.1016/j.cclet.2025.111038
Abstract:
Reactive oxygen species (ROS)-based endoplasmic reticulum (ER) stress is a prerequisite for the induction of immunogenic cell death (ICD), and the development of metal-based ICD inducers has garnered significant attention. However, the drug-target mechanisms of ICD inducers still require further exploration. Herein, we reported an ER-targeting iron(Ⅱ) complex (Fe-NBM) as an ICD inducer, which was obtained through a solvothermal domino reaction. Accordingly, pyridin-2-ylmethanamine and 1-methyl-2-formylbenzimidazole underwent consecutive covalent transformations to form a novel N-heterocyclic ligand, which subsequently coordinated with ferrous chloride to directly yield the crystalline Fe-NBM in one pot. Confocal laser scanning microscope (CLSM), molecular docking and cellular thermal shift assay (CETSA) showed that Fe-NBM could specifically target the ER by binding to the IRE1α (Inositol requiring kinase enzyme 1 alpha) and induce ICD by generating ROS-based ER stress. In an immunocompetent mouse model, Fe-NBM could significantly inhibit tumor growth and stimulate anti-tumor immunity, and exhibit an enhanced effect when combined with anti-PD1 therapy, leading to near-complete tumor elimination. To gain deeper understanding of how to synthesize such effective ICD inducers at the molecular level, a combination of electrospray ionization mass spectrometry (ESI-MS) and crystallography was employed for thoroughly tracking the step-economy synthetic process. To the best of our knowledge, Fe-NBM is the first iron-based ICD inducer that directly targets ER through binding to IRE1α. We believe that the ICD-related target information presented in this work will enhance our understanding of the molecular mechanisms underlying ICD and facilitate the design of new ICD inducers.
Reactive oxygen species (ROS)-based endoplasmic reticulum (ER) stress is a prerequisite for the induction of immunogenic cell death (ICD), and the development of metal-based ICD inducers has garnered significant attention. However, the drug-target mechanisms of ICD inducers still require further exploration. Herein, we reported an ER-targeting iron(Ⅱ) complex (Fe-NBM) as an ICD inducer, which was obtained through a solvothermal domino reaction. Accordingly, pyridin-2-ylmethanamine and 1-methyl-2-formylbenzimidazole underwent consecutive covalent transformations to form a novel N-heterocyclic ligand, which subsequently coordinated with ferrous chloride to directly yield the crystalline Fe-NBM in one pot. Confocal laser scanning microscope (CLSM), molecular docking and cellular thermal shift assay (CETSA) showed that Fe-NBM could specifically target the ER by binding to the IRE1α (Inositol requiring kinase enzyme 1 alpha) and induce ICD by generating ROS-based ER stress. In an immunocompetent mouse model, Fe-NBM could significantly inhibit tumor growth and stimulate anti-tumor immunity, and exhibit an enhanced effect when combined with anti-PD1 therapy, leading to near-complete tumor elimination. To gain deeper understanding of how to synthesize such effective ICD inducers at the molecular level, a combination of electrospray ionization mass spectrometry (ESI-MS) and crystallography was employed for thoroughly tracking the step-economy synthetic process. To the best of our knowledge, Fe-NBM is the first iron-based ICD inducer that directly targets ER through binding to IRE1α. We believe that the ICD-related target information presented in this work will enhance our understanding of the molecular mechanisms underlying ICD and facilitate the design of new ICD inducers.
2026, 37(6): 111040
doi: 10.1016/j.cclet.2025.111040
Abstract:
Lithium/fluorinated graphite (Li/CFx) primary batteries with great energy density advantages still struggle to realize large-scale applications, due to the sluggish cathode reaction kinetics accompanied by poor rate capability and power density. One key challenge arises from the inert electronic structure of CFx predominated by covalent C–F bond, which results in poor intrinsic electronic conductivity. To address this issue, cathode surface activation engineering is proposed to modify CFx with hybrid transitional metal oxide/carbon layer, which is derived by one-pot pyrolysis of structurally designable metallic ionic liquids (Bmim[MCln], M = Fe, Al, Cu, Zn, etc.). Generally, the presence of metal oxides induces generation of highly conductive semi-ionic C–F species, cooperating with abundant oxygen vacancies and carbon matrix to synergistically improve electronic/ionic conduction and accelerate CFx conversion kinetics, while the Bmim[FeCl4]-derived system is the optimal solution. As expected, the surface activated CFx cathode achieves nearly 4 times the power density (22,581 W/kg at 14 C) of pristine CFx and higher conversion depth. This metallic ionic liquid-derived surface activation design efficiently regulates the intrinsically inert electronic structure of CFx cathode, and widens its chemical design space of metal oxides as composite components, furthermore, providing a universal solution for electrodes faced with electronic conduction challenges.
Lithium/fluorinated graphite (Li/CFx) primary batteries with great energy density advantages still struggle to realize large-scale applications, due to the sluggish cathode reaction kinetics accompanied by poor rate capability and power density. One key challenge arises from the inert electronic structure of CFx predominated by covalent C–F bond, which results in poor intrinsic electronic conductivity. To address this issue, cathode surface activation engineering is proposed to modify CFx with hybrid transitional metal oxide/carbon layer, which is derived by one-pot pyrolysis of structurally designable metallic ionic liquids (Bmim[MCln], M = Fe, Al, Cu, Zn, etc.). Generally, the presence of metal oxides induces generation of highly conductive semi-ionic C–F species, cooperating with abundant oxygen vacancies and carbon matrix to synergistically improve electronic/ionic conduction and accelerate CFx conversion kinetics, while the Bmim[FeCl4]-derived system is the optimal solution. As expected, the surface activated CFx cathode achieves nearly 4 times the power density (22,581 W/kg at 14 C) of pristine CFx and higher conversion depth. This metallic ionic liquid-derived surface activation design efficiently regulates the intrinsically inert electronic structure of CFx cathode, and widens its chemical design space of metal oxides as composite components, furthermore, providing a universal solution for electrodes faced with electronic conduction challenges.
2026, 37(6): 111043
doi: 10.1016/j.cclet.2025.111043
Abstract:
The proton conduction mechanism of imidazole and its homologues within confined spaces has attracted much attention from researchers, which is highly beneficial for the development of novel proton exchange membranes. Traditionally, the hydrogen at the 1-position (H-1) on the nitrogen (N-1) of imidazole is seen as the exclusive source of mobile protons. However, we suggest that the 3-position nitrogen atom (N-3) can also generate mobile protons under hydrous conditions. This is because N-3 can form hydrogen bonds with water, which are particularly robust in confined spaces, thereby enhancing proton ionization from water and facilitating proton transfer. Based on this concept, 1-methylimidazole was introduced into a covalent organic framework (COF), resulting in a remarkable proton conductivity of 2.40 × 10–3 S/cm at 70 ℃ and 100% relative humidity. This performance is on par with that of COFs doped with imidazole, demonstrating the key role of N-3···H2O interactions within the framework in producing mobile protons and facilitating proton diffusion. Furthermore, this challenges the conventional viewpoint that H-1 of imidazole is the sole contributor to proton concentration, offering a new strategy for the preparation of high-performance proton conductors.
The proton conduction mechanism of imidazole and its homologues within confined spaces has attracted much attention from researchers, which is highly beneficial for the development of novel proton exchange membranes. Traditionally, the hydrogen at the 1-position (H-1) on the nitrogen (N-1) of imidazole is seen as the exclusive source of mobile protons. However, we suggest that the 3-position nitrogen atom (N-3) can also generate mobile protons under hydrous conditions. This is because N-3 can form hydrogen bonds with water, which are particularly robust in confined spaces, thereby enhancing proton ionization from water and facilitating proton transfer. Based on this concept, 1-methylimidazole was introduced into a covalent organic framework (COF), resulting in a remarkable proton conductivity of 2.40 × 10–3 S/cm at 70 ℃ and 100% relative humidity. This performance is on par with that of COFs doped with imidazole, demonstrating the key role of N-3···H2O interactions within the framework in producing mobile protons and facilitating proton diffusion. Furthermore, this challenges the conventional viewpoint that H-1 of imidazole is the sole contributor to proton concentration, offering a new strategy for the preparation of high-performance proton conductors.
2026, 37(6): 111044
doi: 10.1016/j.cclet.2025.111044
Abstract:
The limited stability of Pt-based catalysts as a result of irreversible support corrosion and Pt dissolution/aggregation remains a major barrier to the widespread deployment for Proton exchange membrane fuel cells. To overcome the issues, amorphous TaOx with corrosion-resistance was introduced to stabilize Pt nanoparticles in this work. Benefiting from the strong metal-support interaction, Pt oxidation and dissolution is suppressed through efficient electron transfer from the support. Optimized Pt/TaOx-C catalyst shows remarkable stability with voltage loss @0.8 A/cm2 of only 29 mV after 50k cycles accelerated durability test, which is much lower than the goal for DOE 2025 (30 mV after 30k cycles). Besides, the strong anchoring effect of the amorphous TaOx enables well dispersion of Pt with an ultra-small particle size of approximately 1.3 nm, reducing the local mass transfer resistance towards superior fuel cell performance of 2.29 W/cm2, which is higher than the commercial Pt/C of 1.56 W/cm2. This study offers a highly active and durable cathode electrocatalyst for fuel cells.
The limited stability of Pt-based catalysts as a result of irreversible support corrosion and Pt dissolution/aggregation remains a major barrier to the widespread deployment for Proton exchange membrane fuel cells. To overcome the issues, amorphous TaOx with corrosion-resistance was introduced to stabilize Pt nanoparticles in this work. Benefiting from the strong metal-support interaction, Pt oxidation and dissolution is suppressed through efficient electron transfer from the support. Optimized Pt/TaOx-C catalyst shows remarkable stability with voltage loss @0.8 A/cm2 of only 29 mV after 50k cycles accelerated durability test, which is much lower than the goal for DOE 2025 (30 mV after 30k cycles). Besides, the strong anchoring effect of the amorphous TaOx enables well dispersion of Pt with an ultra-small particle size of approximately 1.3 nm, reducing the local mass transfer resistance towards superior fuel cell performance of 2.29 W/cm2, which is higher than the commercial Pt/C of 1.56 W/cm2. This study offers a highly active and durable cathode electrocatalyst for fuel cells.
2026, 37(6): 111045
doi: 10.1016/j.cclet.2025.111045
Abstract:
The electrocatalytic two-electron oxygen reduction reaction (2e– ORR) offers an environmentally friendly method for hydrogen peroxide (H2O2) production, yet the development of efficient and cost-effective electrocatalysts remains a significant challenge. Herein, we have synthesized Ni3N2 clusters anchored on N-doped carbon nanostructures (Ni3N2/NC) through a straightforward biomass-derived modification-pyrolysis method for efficient H2O2 production. Theoretical calculations reveal that the D-band center of Ni sites in Ni3N2/NC shows a downshift and successive state, which is beneficial to the formation of key *OOH intermediates and occurrence of subsequent reactions. Remarkably, Ni3N2/NC achieves a 2e– ORR selectivity of 91.65% and an onset potential of 0.69 V. When tested in a practical flow cell, Ni3N2/NC exhibits a Faradaic efficiency (FE) of 91.42% and attains a maximum H2O2 yield of 3.26 mol gcat−1 h−1 at 100 mA/cm2. Additionally, the FE remains above 85% during a 12 h constant current stability test at 40 mA/cm2, highlighting its potential for sustainable H2O2 production.
The electrocatalytic two-electron oxygen reduction reaction (2e– ORR) offers an environmentally friendly method for hydrogen peroxide (H2O2) production, yet the development of efficient and cost-effective electrocatalysts remains a significant challenge. Herein, we have synthesized Ni3N2 clusters anchored on N-doped carbon nanostructures (Ni3N2/NC) through a straightforward biomass-derived modification-pyrolysis method for efficient H2O2 production. Theoretical calculations reveal that the D-band center of Ni sites in Ni3N2/NC shows a downshift and successive state, which is beneficial to the formation of key *OOH intermediates and occurrence of subsequent reactions. Remarkably, Ni3N2/NC achieves a 2e– ORR selectivity of 91.65% and an onset potential of 0.69 V. When tested in a practical flow cell, Ni3N2/NC exhibits a Faradaic efficiency (FE) of 91.42% and attains a maximum H2O2 yield of 3.26 mol gcat−1 h−1 at 100 mA/cm2. Additionally, the FE remains above 85% during a 12 h constant current stability test at 40 mA/cm2, highlighting its potential for sustainable H2O2 production.
2026, 37(6): 111046
doi: 10.1016/j.cclet.2025.111046
Abstract:
Searching for new oxide-ion conductors is of great significance in energy-related technologies. Here we identified a novel barium tellurate, Ba10.55Te4.45O23.90, by chemical screening for superstructural oxide-ion conductors. Its crystal structure, solved from polycrystalline specimen by the combination of three-dimension electron diffraction, X-ray diffraction, and neutron diffraction, adopts a quadruple (4 × 4 × 4) cubic superstructure (Fm-3m, a = 17.30612(2) Å) and can be regarded as a derivative of ABO3 perovskite like (Ba1.75□0.25)ABaBWB'O5.75□0.25. The ordered A-site metal vacancies and disordered oxygen vacancies are responsible for the enlarged superstructure. The titled compound is indeed an oxide-ion conductor but shows rather low ionic conductivity, owing to the high inter-polyhedral energy barrier of ionic migration. The discoveries unveil a new structural type for oxide-ion conductor exploration, and will evoke performance improvement by chemical modification such as aliovalent substitution.
Searching for new oxide-ion conductors is of great significance in energy-related technologies. Here we identified a novel barium tellurate, Ba10.55Te4.45O23.90, by chemical screening for superstructural oxide-ion conductors. Its crystal structure, solved from polycrystalline specimen by the combination of three-dimension electron diffraction, X-ray diffraction, and neutron diffraction, adopts a quadruple (4 × 4 × 4) cubic superstructure (Fm-3m, a = 17.30612(2) Å) and can be regarded as a derivative of ABO3 perovskite like (Ba1.75□0.25)ABaBWB'O5.75□0.25. The ordered A-site metal vacancies and disordered oxygen vacancies are responsible for the enlarged superstructure. The titled compound is indeed an oxide-ion conductor but shows rather low ionic conductivity, owing to the high inter-polyhedral energy barrier of ionic migration. The discoveries unveil a new structural type for oxide-ion conductor exploration, and will evoke performance improvement by chemical modification such as aliovalent substitution.
2026, 37(6): 111077
doi: 10.1016/j.cclet.2025.111077
Abstract:
This study reveals the unique electrochemical mechanism of violet phosphorus (VP) as an anode material for lithium-ion batteries. Using solid-state nuclear magnetic resonance (NMR) spectroscopy, we detail the alloying reaction mechanism of VP during lithiation. While alloying behavior in black and red phosphorus has been widely studied, intermediate phases remain poorly understood due to complex phase transitions. Our precise NMR assignments link specific signals in VP to distinct atomic sites. The results show that [P8] cage atoms preferentially react with lithium in the early stages, while [P9] cages provide structural support. VP layered structure allows lithium ions to first intercalate between layers, followed by alloying reactions. These findings offer new insights into VP alloying mechanism, advancing the fundamental understanding of its potential in next-generation energy storage systems.
This study reveals the unique electrochemical mechanism of violet phosphorus (VP) as an anode material for lithium-ion batteries. Using solid-state nuclear magnetic resonance (NMR) spectroscopy, we detail the alloying reaction mechanism of VP during lithiation. While alloying behavior in black and red phosphorus has been widely studied, intermediate phases remain poorly understood due to complex phase transitions. Our precise NMR assignments link specific signals in VP to distinct atomic sites. The results show that [P8] cage atoms preferentially react with lithium in the early stages, while [P9] cages provide structural support. VP layered structure allows lithium ions to first intercalate between layers, followed by alloying reactions. These findings offer new insights into VP alloying mechanism, advancing the fundamental understanding of its potential in next-generation energy storage systems.
2026, 37(6): 111078
doi: 10.1016/j.cclet.2025.111078
Abstract:
Hydrogel electrolytes are widely used in zinc-ion batteries (ZIBs) due to their advantages of regulating zinc deposition/stripping process, and limiting dendrite growth. However, their relatively poor ionic conductivity and mechanical properties remain significant obstacles to their practical application in ZIBs. Herein, the multi-component cross-linked polyacrylamide/carboxymethyl cellulose/agarose (PCA) hydrogel polymerized electrolytes are designed via a heat-initiated polymerization approach. The PCA hydrogel electrolytes exhibit high ionic conductivity of 38.78 mS/cm and excellent mechanical strength from 2.9 MPa to 5.6 MPa. Meanwhile, the ample hydroxyl (-OH) functional groups on the PCA hydrogel electrolytes chain can capture and anchor H2O molecules via hydrogen bonding, thus fundamentally regulating the coordination environment of Zn2+ and inhibiting side reactions. The combined effect of carboxyl (-COOH) groups and amino (-NH2) groups in PCA hydrogel electrolytes can induce the uniform deposition of zinc ions. Consequently, The Zn//Zn symmetrical cell assembled with this hydrogel electrolytes demonstrate excellent cycling stability over 2500 h at the current density of 1 mA/cm2. Furthermore, the Zn//MnO2/CNT full cell retains a specific capacity of 127.2 mAh/g after 1000 cycles at 1 A/g, with 97.8% capacity retention.
Hydrogel electrolytes are widely used in zinc-ion batteries (ZIBs) due to their advantages of regulating zinc deposition/stripping process, and limiting dendrite growth. However, their relatively poor ionic conductivity and mechanical properties remain significant obstacles to their practical application in ZIBs. Herein, the multi-component cross-linked polyacrylamide/carboxymethyl cellulose/agarose (PCA) hydrogel polymerized electrolytes are designed via a heat-initiated polymerization approach. The PCA hydrogel electrolytes exhibit high ionic conductivity of 38.78 mS/cm and excellent mechanical strength from 2.9 MPa to 5.6 MPa. Meanwhile, the ample hydroxyl (-OH) functional groups on the PCA hydrogel electrolytes chain can capture and anchor H2O molecules via hydrogen bonding, thus fundamentally regulating the coordination environment of Zn2+ and inhibiting side reactions. The combined effect of carboxyl (-COOH) groups and amino (-NH2) groups in PCA hydrogel electrolytes can induce the uniform deposition of zinc ions. Consequently, The Zn//Zn symmetrical cell assembled with this hydrogel electrolytes demonstrate excellent cycling stability over 2500 h at the current density of 1 mA/cm2. Furthermore, the Zn//MnO2/CNT full cell retains a specific capacity of 127.2 mAh/g after 1000 cycles at 1 A/g, with 97.8% capacity retention.
2026, 37(6): 111386
doi: 10.1016/j.cclet.2025.111386
Abstract:
Tuning molecular chirality through external stimuli stands at the forefront of chemical science. Here, we systematically examine the stereodynamic properties of a series of Cu(Ⅱ)-based perovskite single crystals, CystaH2[CuCl(4-x)Brx] (CystaH2 = protonated cystamine cation, x = 0.74, 0.80, 1.05, 1.11, 1.18), which undergo a polar-to-nonpolar ferroelectric phase transition. In these compounds, the symmetry breaking structural change is governed by an unusually thermally driven P ↔ M helical inversion of the helical CystaH22+ organic cations. The conformational inversion can be substantially modulated by bromide doping. As the bromide content increases, the phase-transition temperature progressively shifts closer to room temperature, decreasing by up to 49 K. Detailed structural analyses reveal that the chiral inversion of CystaH22+ is highly sensitive to local chemical environments, and this doping strategy offers an effective route for precisely governing temperature-mediated chiral transformations, thereby expanding the design space for advanced chiral materials.
Tuning molecular chirality through external stimuli stands at the forefront of chemical science. Here, we systematically examine the stereodynamic properties of a series of Cu(Ⅱ)-based perovskite single crystals, CystaH2[CuCl(4-x)Brx] (CystaH2 = protonated cystamine cation, x = 0.74, 0.80, 1.05, 1.11, 1.18), which undergo a polar-to-nonpolar ferroelectric phase transition. In these compounds, the symmetry breaking structural change is governed by an unusually thermally driven P ↔ M helical inversion of the helical CystaH22+ organic cations. The conformational inversion can be substantially modulated by bromide doping. As the bromide content increases, the phase-transition temperature progressively shifts closer to room temperature, decreasing by up to 49 K. Detailed structural analyses reveal that the chiral inversion of CystaH22+ is highly sensitive to local chemical environments, and this doping strategy offers an effective route for precisely governing temperature-mediated chiral transformations, thereby expanding the design space for advanced chiral materials.
2026, 37(6): 111409
doi: 10.1016/j.cclet.2025.111409
Abstract:
Azido molecules (azidos) have been extensively investigated for their potential as biomedical tools. However, the precise mechanism underlying their intracellular activation remains elusive. In this study, we adopted experimental and computational approaches to demonstrate that this activation mechanism is a photo-bioactivation process, facilitated by intracellular proteins that interact with azidos. Building on these findings, we developed a passive cell-specific fluorescence imaging tool for non-invasive cell tracking within three-dimensional (3D) scaffolds, an active-targeting subcellular organelle imaging system, and a controllable prodrug delivery platform that enables the spatiotemporal regulation of intracellular release and distribution of therapeutic agents. Overall, our study provides the first comprehensive elucidation of the cellular activation mechanism of azidos, which has significant implications for the development of a diverse array of photo-bioactivated tools and prodrugs.
Azido molecules (azidos) have been extensively investigated for their potential as biomedical tools. However, the precise mechanism underlying their intracellular activation remains elusive. In this study, we adopted experimental and computational approaches to demonstrate that this activation mechanism is a photo-bioactivation process, facilitated by intracellular proteins that interact with azidos. Building on these findings, we developed a passive cell-specific fluorescence imaging tool for non-invasive cell tracking within three-dimensional (3D) scaffolds, an active-targeting subcellular organelle imaging system, and a controllable prodrug delivery platform that enables the spatiotemporal regulation of intracellular release and distribution of therapeutic agents. Overall, our study provides the first comprehensive elucidation of the cellular activation mechanism of azidos, which has significant implications for the development of a diverse array of photo-bioactivated tools and prodrugs.
2026, 37(6): 111410
doi: 10.1016/j.cclet.2025.111410
Abstract:
Cancer vaccines have proven to be a powerful tool in anti-tumor immunotherapy, leveraging antigen-specific T-cell responses. The effective activation of the stimulator of the interferon gene (STING) protein signal pathway by natural or synthetic agonists leads to the creation of a pro-immune tumor microenvironment. Here, we report the preparation of ovalbumin (OVA) loaded cancer vaccines based on nanoemulsions, denoted as DMMF59-OVA, for the co-delivery of antigens and a STING agonist (MSA-2). The nanovaccines were obtained via encapsulation of MSA-2 into squalene phase, which was stabilized by surfactants and coated with OVA. Upon intramuscular administration, the engineered nanovaccine facilitates antigen internalization, maturation of antigen-presenting cells (APCs), and efficient activation of the STING pathway. These results in enhanced antigen-specific humoral and cellular immune responses that significantly inhibit tumor growth in an E.G7-OVA mouse model. The studies provide an avenue for the application of nanovaccine in tumor immunotherapy. Given the ease of preparation and tunable physicochemical properties, DMMF59-OVA represents a promising therapeutic nanovaccine for biomedical applications
Cancer vaccines have proven to be a powerful tool in anti-tumor immunotherapy, leveraging antigen-specific T-cell responses. The effective activation of the stimulator of the interferon gene (STING) protein signal pathway by natural or synthetic agonists leads to the creation of a pro-immune tumor microenvironment. Here, we report the preparation of ovalbumin (OVA) loaded cancer vaccines based on nanoemulsions, denoted as DMMF59-OVA, for the co-delivery of antigens and a STING agonist (MSA-2). The nanovaccines were obtained via encapsulation of MSA-2 into squalene phase, which was stabilized by surfactants and coated with OVA. Upon intramuscular administration, the engineered nanovaccine facilitates antigen internalization, maturation of antigen-presenting cells (APCs), and efficient activation of the STING pathway. These results in enhanced antigen-specific humoral and cellular immune responses that significantly inhibit tumor growth in an E.G7-OVA mouse model. The studies provide an avenue for the application of nanovaccine in tumor immunotherapy. Given the ease of preparation and tunable physicochemical properties, DMMF59-OVA represents a promising therapeutic nanovaccine for biomedical applications
2026, 37(6): 111422
doi: 10.1016/j.cclet.2025.111422
Abstract:
Radiation-induced gastrointestinal toxicity during abdominal/pelvic radiotherapy for solid malignancies remains a global clinical challenge, with current radioprotective agents demonstrating suboptimal efficacy and systemic toxicity. This study systematically investigates the radioprotective efficacy and mechanisms of purified spores derived from three clinically approved Bacillus species (B. coagulans, B. subtilis, and B. licheniformis). All the three spores exhibit significantly superior X-ray resistance and colonization efficiency to their parent probiotics. Based on this, it is found that these spores significantly reduce X-ray induced injury in intestine and colon tissues by rescuing radiation-induced crypts/villi damage, preventing apoptosis of intestinal epithelial cells, alleviating inflammation level and enhancing the intestinal barrier functions. Moreover, 16S ribosomal DNA (rDNA) sequencing results demonstrate that Bacillus spores can inhibit harmful bacteria while increase relative abundance of probiotics, especially Lactobacillus. Consequently, oral administration of these spores obviously alleviates bodyweight loss and promotes weight gain of mice received total abdominal X-ray radiation, among which mice in the BCS (spores of B. coagulans) group achieves full bodyweight recovery. This work may provide promising radioprotectants for efficiently attenuating radiation-induced gastrointestinal syndrome.
Radiation-induced gastrointestinal toxicity during abdominal/pelvic radiotherapy for solid malignancies remains a global clinical challenge, with current radioprotective agents demonstrating suboptimal efficacy and systemic toxicity. This study systematically investigates the radioprotective efficacy and mechanisms of purified spores derived from three clinically approved Bacillus species (B. coagulans, B. subtilis, and B. licheniformis). All the three spores exhibit significantly superior X-ray resistance and colonization efficiency to their parent probiotics. Based on this, it is found that these spores significantly reduce X-ray induced injury in intestine and colon tissues by rescuing radiation-induced crypts/villi damage, preventing apoptosis of intestinal epithelial cells, alleviating inflammation level and enhancing the intestinal barrier functions. Moreover, 16S ribosomal DNA (rDNA) sequencing results demonstrate that Bacillus spores can inhibit harmful bacteria while increase relative abundance of probiotics, especially Lactobacillus. Consequently, oral administration of these spores obviously alleviates bodyweight loss and promotes weight gain of mice received total abdominal X-ray radiation, among which mice in the BCS (spores of B. coagulans) group achieves full bodyweight recovery. This work may provide promising radioprotectants for efficiently attenuating radiation-induced gastrointestinal syndrome.
2026, 37(6): 111447
doi: 10.1016/j.cclet.2025.111447
Abstract:
Sensorineural hearing loss (SNHL) is a prevalent global health issue, primarily caused by excessive generation of reactive oxygen species (ROS) due to acoustic trauma, aging, and ototoxic drugs. Natural antioxidant enzymes, such as catalase (CAT), possess remarkable ROS scavenging capabilities and hold significant potential for SNHL treatment. However, their clinical application is hindered by inefficient delivery and limited stability. Here, we introduce a novel peptide-oligosaccharide conjugate, sELP-ON, which forms coacervate microdroplets via liquid–liquid phase separation. These microdroplets efficiently encapsulate and stably carry CAT, releasing it in a glutathione-triggered, redox-responsive manner. The CAT-loaded sELP-ON (sELP-ON@CAT) enhanced cellular uptake through direct cytoplasmic internalization and demonstrates a more robust ROS scavenging activity than naked CAT treatment. Local administration of sELP-ON@CAT in an acoustic injury mouse model effectively rescues hearing loss by reducing cochlear ROS levels, thereby mitigating hair cell loss, ribbon synapse depletion, stria vascularis shrinkage and spiral ganglion neuron degeneration. In summary, our innovative coacervate microdroplet system enables targeted, redox-responsive cytoplasmic delivery of macromolecular antioxidants, offering a novel and effective strategy for treating SNHL.
Sensorineural hearing loss (SNHL) is a prevalent global health issue, primarily caused by excessive generation of reactive oxygen species (ROS) due to acoustic trauma, aging, and ototoxic drugs. Natural antioxidant enzymes, such as catalase (CAT), possess remarkable ROS scavenging capabilities and hold significant potential for SNHL treatment. However, their clinical application is hindered by inefficient delivery and limited stability. Here, we introduce a novel peptide-oligosaccharide conjugate, sELP-ON, which forms coacervate microdroplets via liquid–liquid phase separation. These microdroplets efficiently encapsulate and stably carry CAT, releasing it in a glutathione-triggered, redox-responsive manner. The CAT-loaded sELP-ON (sELP-ON@CAT) enhanced cellular uptake through direct cytoplasmic internalization and demonstrates a more robust ROS scavenging activity than naked CAT treatment. Local administration of sELP-ON@CAT in an acoustic injury mouse model effectively rescues hearing loss by reducing cochlear ROS levels, thereby mitigating hair cell loss, ribbon synapse depletion, stria vascularis shrinkage and spiral ganglion neuron degeneration. In summary, our innovative coacervate microdroplet system enables targeted, redox-responsive cytoplasmic delivery of macromolecular antioxidants, offering a novel and effective strategy for treating SNHL.
2026, 37(6): 111483
doi: 10.1016/j.cclet.2025.111483
Abstract:
Hydrogel bioadhesives, known for their ability to rapidly inhibit bleeding and minimize damage to surrounding tissues, are revolutionizing traditional surgical procedures. The interfacial force between hydrogel bioadhesives and tissue is critical for achieving strong adhesion in wound healing applications. However, preformed hydrogel bioadhesives cannot achieve seamless closure of irregular shape wounds and tend to detach in bleeding environments, limiting their practical applications. In this study, we developed an in-situ photopolymerization hydrogel bioadhesive (IPHB) method to fully seal irregular shape wounds in bleeding conditions within 5 min, eliminating the need for risky artery-blocking procedures. The fluidic hydrogel precursor solution can infiltrate micro- and nanostructured wound, penetrate tissues, and rapidly form an adhesive hydrogel under ultraviolet (UV) irradiation through strong topological entanglement at the interface. The resulting hydrogel demonstrates excellent stretchability, low swelling, and intrinsic antibacterial properties. The IPHB method was successfully employed to seal kidney wounds in a living pig, achieving rapid hemostasis and promoting wound healing without harming healthy tissues. This innovative approach significantly reduces surgical duration and enhances safety. Notably, this study marks the first application of a hydrogel bioadhesive for kidney wound treatment in a living pig, paving the way for safer and more efficient surgical practices.
Hydrogel bioadhesives, known for their ability to rapidly inhibit bleeding and minimize damage to surrounding tissues, are revolutionizing traditional surgical procedures. The interfacial force between hydrogel bioadhesives and tissue is critical for achieving strong adhesion in wound healing applications. However, preformed hydrogel bioadhesives cannot achieve seamless closure of irregular shape wounds and tend to detach in bleeding environments, limiting their practical applications. In this study, we developed an in-situ photopolymerization hydrogel bioadhesive (IPHB) method to fully seal irregular shape wounds in bleeding conditions within 5 min, eliminating the need for risky artery-blocking procedures. The fluidic hydrogel precursor solution can infiltrate micro- and nanostructured wound, penetrate tissues, and rapidly form an adhesive hydrogel under ultraviolet (UV) irradiation through strong topological entanglement at the interface. The resulting hydrogel demonstrates excellent stretchability, low swelling, and intrinsic antibacterial properties. The IPHB method was successfully employed to seal kidney wounds in a living pig, achieving rapid hemostasis and promoting wound healing without harming healthy tissues. This innovative approach significantly reduces surgical duration and enhances safety. Notably, this study marks the first application of a hydrogel bioadhesive for kidney wound treatment in a living pig, paving the way for safer and more efficient surgical practices.
2026, 37(6): 111494
doi: 10.1016/j.cclet.2025.111494
Abstract:
Wound healing remains a significant challenge in medical science due to the complexity of the process. Hydrogels have emerged as promising materials for wound management, yet achieving non-cytotoxicity, biodegradability, and mechanical robustness in a single formulation continues to be a research focus. This study aims to develop polysulfonate-polyvinyl alcohol (PVA)/poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPs) membranes reinforced with ZnO nanoparticles (NPs) and g-C3N4 to meet these requirements. The fabricated membranes were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and atomic force microscopy (AFM), and were subjected to various biological evaluations including swelling ratios, water vapor transmission rates (WVTR), antibacterial activity, cytotoxicity, and in-vivo wound healing in a mouse model. The membranes exhibited mechanical strengths of 42.6 MPa and strains up to 183.35%. XRD and FTIR confirmed the successful incorporation of ZnO NPs and g-C3N4, while SEM and AFM revealed a rough surface morphology conducive to cell adhesion. The membranes achieved moisture retention rates over 90%, WVTR values up to 71.66 h g−1 m−2, and swelling ratios as high as 116.06%. Cytotoxicity tests demonstrated cellular viability exceeding 84.37%, and antibacterial assays showed significant inhibition zones. In vivo studies indicated an 88.26% wound healing rate within 9 days, surpassing traditional dressings and saline treatments. These results suggest that PAMPs/PVA/g-C3N4/ZnO membranes are found to be highly effective for wound dressing applications, combining superior mechanical properties, biocompatibility, and enhanced healing efficacy.
Wound healing remains a significant challenge in medical science due to the complexity of the process. Hydrogels have emerged as promising materials for wound management, yet achieving non-cytotoxicity, biodegradability, and mechanical robustness in a single formulation continues to be a research focus. This study aims to develop polysulfonate-polyvinyl alcohol (PVA)/poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPs) membranes reinforced with ZnO nanoparticles (NPs) and g-C3N4 to meet these requirements. The fabricated membranes were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and atomic force microscopy (AFM), and were subjected to various biological evaluations including swelling ratios, water vapor transmission rates (WVTR), antibacterial activity, cytotoxicity, and in-vivo wound healing in a mouse model. The membranes exhibited mechanical strengths of 42.6 MPa and strains up to 183.35%. XRD and FTIR confirmed the successful incorporation of ZnO NPs and g-C3N4, while SEM and AFM revealed a rough surface morphology conducive to cell adhesion. The membranes achieved moisture retention rates over 90%, WVTR values up to 71.66 h g−1 m−2, and swelling ratios as high as 116.06%. Cytotoxicity tests demonstrated cellular viability exceeding 84.37%, and antibacterial assays showed significant inhibition zones. In vivo studies indicated an 88.26% wound healing rate within 9 days, surpassing traditional dressings and saline treatments. These results suggest that PAMPs/PVA/g-C3N4/ZnO membranes are found to be highly effective for wound dressing applications, combining superior mechanical properties, biocompatibility, and enhanced healing efficacy.
2026, 37(6): 111509
doi: 10.1016/j.cclet.2025.111509
Abstract:
The development of organic dyes with fluorescence in the second near-infrared (NIR-Ⅱ, 1000–1700 nm) biological window is crucial for deep-tissue tumor phototheranostics. Herein, we synthesized a thienothiadiazole-based NIR-Ⅱ fluorescent dye TTDOC with donor-acceptor-donor (D-A-D) molecular architecture for photoacoustic/fluorescence imaging-guided photothermal therapy (PTT). NIR-Ⅱ dye TTDOC, taking electron-deficient thienothiadiazole as an acceptor and triphenylamine as a donor, exhibited a high fluorescence quantum yield of 1.7% in dichloromethane (IR-1061 as standard, 1.7% in dichloromethane). Upon encapsulation in biocompatible polymer F-127, TTDOC nanoparticles (NPs) were formulated with NIR absorption and fluorescence band covering 900–1150 nm, and demonstrated an outstanding photothermal conversion efficiency (η) of 51.6% upon 808 nm photoirradiation. In vivo studies, including fluorescence and photoacoustic imaging, revealed that TTDOC NPs effectively accumulated in tumor tissues, reaching maximal tumor enrichment at 20 h post-injection. In vitro and in vivo results confirmed the ability of TTDOC NPs to enable efficient photoacoustic/fluorescence imaging-guided PTT, offering a promising strategy for deep-tissue tumor treatment.
The development of organic dyes with fluorescence in the second near-infrared (NIR-Ⅱ, 1000–1700 nm) biological window is crucial for deep-tissue tumor phototheranostics. Herein, we synthesized a thienothiadiazole-based NIR-Ⅱ fluorescent dye TTDOC with donor-acceptor-donor (D-A-D) molecular architecture for photoacoustic/fluorescence imaging-guided photothermal therapy (PTT). NIR-Ⅱ dye TTDOC, taking electron-deficient thienothiadiazole as an acceptor and triphenylamine as a donor, exhibited a high fluorescence quantum yield of 1.7% in dichloromethane (IR-1061 as standard, 1.7% in dichloromethane). Upon encapsulation in biocompatible polymer F-127, TTDOC nanoparticles (NPs) were formulated with NIR absorption and fluorescence band covering 900–1150 nm, and demonstrated an outstanding photothermal conversion efficiency (η) of 51.6% upon 808 nm photoirradiation. In vivo studies, including fluorescence and photoacoustic imaging, revealed that TTDOC NPs effectively accumulated in tumor tissues, reaching maximal tumor enrichment at 20 h post-injection. In vitro and in vivo results confirmed the ability of TTDOC NPs to enable efficient photoacoustic/fluorescence imaging-guided PTT, offering a promising strategy for deep-tissue tumor treatment.
2026, 37(6): 111510
doi: 10.1016/j.cclet.2025.111510
Abstract:
Neutrophil extracellular traps (NETs) are a significant unfavorable factor for wound healing in diabetes. Citrullination of histone by peptidyl arginine deiminase 4 (PAD4) is the prerequisite for NETs formation. Therefore, PAD4 inhibitors are a promising NETs-targeting strategy to accelerate diabetic wound healing. Herein, a virtual screening workflow incorporating molecular docking and molecular dynamics was performed on a library of U.S. Food and Drug Administration (FDA)-approved drugs, resulting in the identification of gliquidone as a new PAD4 inhibitor. Gliquidone binds directly to PAD4, inhibits its activity, and interrupts NETs formation in neutrophils, which in turn rescues functional impairment in fibroblasts. Furthermore, in streptozotocin-induced diabetic mice, gliquidone accelerates wound healing. Taken together, gliquidone was successfully identified as a new PAD4 inhibitor through a computer-aided virtual screening pipeline, which might be a therapeutic agent against diabetic foot ulcers.
Neutrophil extracellular traps (NETs) are a significant unfavorable factor for wound healing in diabetes. Citrullination of histone by peptidyl arginine deiminase 4 (PAD4) is the prerequisite for NETs formation. Therefore, PAD4 inhibitors are a promising NETs-targeting strategy to accelerate diabetic wound healing. Herein, a virtual screening workflow incorporating molecular docking and molecular dynamics was performed on a library of U.S. Food and Drug Administration (FDA)-approved drugs, resulting in the identification of gliquidone as a new PAD4 inhibitor. Gliquidone binds directly to PAD4, inhibits its activity, and interrupts NETs formation in neutrophils, which in turn rescues functional impairment in fibroblasts. Furthermore, in streptozotocin-induced diabetic mice, gliquidone accelerates wound healing. Taken together, gliquidone was successfully identified as a new PAD4 inhibitor through a computer-aided virtual screening pipeline, which might be a therapeutic agent against diabetic foot ulcers.
2026, 37(6): 111511
doi: 10.1016/j.cclet.2025.111511
Abstract:
Glutaminyl cyclase (QC), a key enzyme catalyzing the pyroglutamate modification of bioactive peptides, has emerged as a promising pharmacological target in cancer and other human diseases. Inhibition of QC activity represents a potential therapeutic strategy for diseases associated with QC dysregulation, suggesting that QC inhibitors might be as promising therapeutic approach for these diseases. Building upon our previous lead compound 1 (half maximal inhibitory concentration (IC50): Golgi resident QC (gQC), 3.22 µmol/L; secretory QC (sQC), 4.04 µmol/L), we performed systematic structural optimization to develop novel 3,4-disubstituted indole-2-ketone derivatives. Structure-activity relationship (SAR) studies identified highly active gQC and sQC inhibitors (compounds 24, 28, and 29) with significantly enhanced QC inhibitory activity. Among them, 28 exhibited superior inhibitory activity against gQC (IC50 = 0.095 µmol/L) compared to sQC (IC50 = 1.33 µmol/L), and could most significantly improve the thermal stability of gQC protein. Using compound 17 with similar structure but 130 times lower gQC inhibitory activity than 28 as a negative control, the in vitro anti-tumor activity study found that 28 can bind to gQC in MDA-MB-231 breast cancer cells and significantly inhibit the growth and migration, by affecting cell proliferation and inducing G0/G1 phase cell cycle arrest. In nude mice bearing MDA-MB-231 cell xenograft, intratumor injection of 28 (25 mg/kg) produced 40.6% inhibition rates. This work not only provides structural basis and new leads for drug discovery targeting QC, but also presents compelling evidence supporting QC, especially gQC as a potential target for breast cancer therapy.
Glutaminyl cyclase (QC), a key enzyme catalyzing the pyroglutamate modification of bioactive peptides, has emerged as a promising pharmacological target in cancer and other human diseases. Inhibition of QC activity represents a potential therapeutic strategy for diseases associated with QC dysregulation, suggesting that QC inhibitors might be as promising therapeutic approach for these diseases. Building upon our previous lead compound 1 (half maximal inhibitory concentration (IC50): Golgi resident QC (gQC), 3.22 µmol/L; secretory QC (sQC), 4.04 µmol/L), we performed systematic structural optimization to develop novel 3,4-disubstituted indole-2-ketone derivatives. Structure-activity relationship (SAR) studies identified highly active gQC and sQC inhibitors (compounds 24, 28, and 29) with significantly enhanced QC inhibitory activity. Among them, 28 exhibited superior inhibitory activity against gQC (IC50 = 0.095 µmol/L) compared to sQC (IC50 = 1.33 µmol/L), and could most significantly improve the thermal stability of gQC protein. Using compound 17 with similar structure but 130 times lower gQC inhibitory activity than 28 as a negative control, the in vitro anti-tumor activity study found that 28 can bind to gQC in MDA-MB-231 breast cancer cells and significantly inhibit the growth and migration, by affecting cell proliferation and inducing G0/G1 phase cell cycle arrest. In nude mice bearing MDA-MB-231 cell xenograft, intratumor injection of 28 (25 mg/kg) produced 40.6% inhibition rates. This work not only provides structural basis and new leads for drug discovery targeting QC, but also presents compelling evidence supporting QC, especially gQC as a potential target for breast cancer therapy.
2026, 37(6): 111519
doi: 10.1016/j.cclet.2025.111519
Abstract:
Phenanthridine-based luminogens are known for their exceptional opto-electronic properties. They have been used in fluorescent materials as well as in biological fields. However, traditional methods for constructing the phenanthridine scaffold typically require pre-functionalized starting materials, photosensitizers or noble transition metals, which will complicate the synthesis and increase the cost. In this study, we introduce an efficient and metal-free approach to synthesize the phenanthridine derivates from free amines under visible-light irradiation. The phenanthridine ring is formed through a carbon insertion π-extension strategy. Significantly, rational design of the leaving group for the carbon-insertion reactions plays a crucial role. We successfully synthesized phenanthridine-based luminogens (DPA-Phen, MeO-DPA-Phen, and DMA-DPA-Phen). These luminogens display robust aggregation-induced emission (AIE) characteristics. Notably, they selectively localize within the lipid droplets (LDs) of tumor cells, demonstrating the potential of phenanthridine-based frameworks as viable LDs-selective fluorescent probes.
Phenanthridine-based luminogens are known for their exceptional opto-electronic properties. They have been used in fluorescent materials as well as in biological fields. However, traditional methods for constructing the phenanthridine scaffold typically require pre-functionalized starting materials, photosensitizers or noble transition metals, which will complicate the synthesis and increase the cost. In this study, we introduce an efficient and metal-free approach to synthesize the phenanthridine derivates from free amines under visible-light irradiation. The phenanthridine ring is formed through a carbon insertion π-extension strategy. Significantly, rational design of the leaving group for the carbon-insertion reactions plays a crucial role. We successfully synthesized phenanthridine-based luminogens (DPA-Phen, MeO-DPA-Phen, and DMA-DPA-Phen). These luminogens display robust aggregation-induced emission (AIE) characteristics. Notably, they selectively localize within the lipid droplets (LDs) of tumor cells, demonstrating the potential of phenanthridine-based frameworks as viable LDs-selective fluorescent probes.
2026, 37(6): 111523
doi: 10.1016/j.cclet.2025.111523
Abstract:
Near-infrared Ⅱ (NIR-Ⅱ) absorbing dye have garnered significant attention for deep-tissue tumor phototherapy and photoacoustic (PA) imaging. However, NIR-Ⅱ dyes often suffer from poor photostability due to extensive conjugated systems, and J-aggregation type typically exhibit narrow absorption spectra, posing significant challenges in matching laser wavelengths. In this work, we propose a mechanism where charge transfer (CT)-type J aggregation, driven by enhanced intramolecular charge transfer, enables the broad NIR-Ⅱ absorption peak and high photostability. The resulting dyes exhibit strong NIR-Ⅱ absorption, low dark toxicity and high phototoxicity as well as improved biocompatibility. Upon 1064 nm excitation, BDP2-NPs achieve a photothermal conversion efficiency of 34.2% and a maximum temperature of 47 ℃, indicating moderate photothermal performance. In addition, PA imaging was assessed by different laser wavelength. This study underscores the potential of aza-boron-dipyrromethene (aza-BODIPY)-based dyes for developing advanced NIR-Ⅱ agents in photothermal therapy and PA imaging.
Near-infrared Ⅱ (NIR-Ⅱ) absorbing dye have garnered significant attention for deep-tissue tumor phototherapy and photoacoustic (PA) imaging. However, NIR-Ⅱ dyes often suffer from poor photostability due to extensive conjugated systems, and J-aggregation type typically exhibit narrow absorption spectra, posing significant challenges in matching laser wavelengths. In this work, we propose a mechanism where charge transfer (CT)-type J aggregation, driven by enhanced intramolecular charge transfer, enables the broad NIR-Ⅱ absorption peak and high photostability. The resulting dyes exhibit strong NIR-Ⅱ absorption, low dark toxicity and high phototoxicity as well as improved biocompatibility. Upon 1064 nm excitation, BDP2-NPs achieve a photothermal conversion efficiency of 34.2% and a maximum temperature of 47 ℃, indicating moderate photothermal performance. In addition, PA imaging was assessed by different laser wavelength. This study underscores the potential of aza-boron-dipyrromethene (aza-BODIPY)-based dyes for developing advanced NIR-Ⅱ agents in photothermal therapy and PA imaging.
2026, 37(6): 111525
doi: 10.1016/j.cclet.2025.111525
Abstract:
The overuse and improper disposal of tetracyclines raise significant environmental and public health concerns due to their persistent ecotoxicological effects. However, there is still a lack of simple, readily available, and effective method for simultaneously detecting multiple tetracyclines. Herein, we present a simple fluorescent sensor array for the detection and identification of multiple tetracyclines (including tetracycline, oxytetracycline, chlortetracycline, and doxycycline) based on host-guest recognitions between albumin (host) and tetracycline (guest). Upon entering the hydrophobic cavity of albumin, tetracycline exhibits a significant enhancement in its intrinsic fluorescence. The differential binding affinity of two albumins to four tetracyclines resulted in different fluorescent responses, creating distinct fluorescence patterns for each tetracycline. With the assistance of machine learning technique, including linear discriminant analysis (LDA) and hierarchical cluster analysis (HCA), this sensor array demonstrated the significant discrimination and classification capabilities for four common tetracyclines and their mixtures with 100% accuracy. Additionally, the array has been successfully applied to differentiate tetracyclines in real food samples. The spiked antibiotics in water sample were determined with a satisfactory recovery of 96.33%–106.5%. This work offers a simple but promising method for differentiating tetracycline antibiotics and presents a versatile strategy for sensor array design.
The overuse and improper disposal of tetracyclines raise significant environmental and public health concerns due to their persistent ecotoxicological effects. However, there is still a lack of simple, readily available, and effective method for simultaneously detecting multiple tetracyclines. Herein, we present a simple fluorescent sensor array for the detection and identification of multiple tetracyclines (including tetracycline, oxytetracycline, chlortetracycline, and doxycycline) based on host-guest recognitions between albumin (host) and tetracycline (guest). Upon entering the hydrophobic cavity of albumin, tetracycline exhibits a significant enhancement in its intrinsic fluorescence. The differential binding affinity of two albumins to four tetracyclines resulted in different fluorescent responses, creating distinct fluorescence patterns for each tetracycline. With the assistance of machine learning technique, including linear discriminant analysis (LDA) and hierarchical cluster analysis (HCA), this sensor array demonstrated the significant discrimination and classification capabilities for four common tetracyclines and their mixtures with 100% accuracy. Additionally, the array has been successfully applied to differentiate tetracyclines in real food samples. The spiked antibiotics in water sample were determined with a satisfactory recovery of 96.33%–106.5%. This work offers a simple but promising method for differentiating tetracycline antibiotics and presents a versatile strategy for sensor array design.
2026, 37(6): 111539
doi: 10.1016/j.cclet.2025.111539
Abstract:
Osteosarcoma (OS) is the most common primary bone malignancy. However, treatment remains challenging due to multidrug resistance, toxic side effects from high-dose and frequent chemotherapy, and surgery-induced bone defects. Herein, we report a double-sensitizing chemotherapeutic hydrogel for efficient OS treatment and bone regeneration, which is constructed by loading doxorubicin hydrochloride (DOX) and icaritin (ICT) into Pluronic F127 (F127) and Pluronic F68 (F68) hydrogel matrix (DOX/ICT-gel). Both ICT and Pluronics can sensitize cancer cells to DOX treatment and enhance intracellular DOX accumulation, thereby boosting the cytotoxic activity of DOX. The addition of ICT can not only downregulate the required dose of DOX and reduce the toxic side effects of DOX, but also induce osteoblast differentiation, contributing to bone regeneration. In the in-situ anti-OS study, the DOX/ICT-gel was shown to stay locally for 7 days, and effectively inhibits OS tumor growth and metastasis, providing robust anticancer efficacy with low toxicity from a single injection for long-lasting treatment. This research provides a novel dual-sensitive DOX strategy for localized OS therapy, potentially advancing the clinical management of this challenging disease.
Osteosarcoma (OS) is the most common primary bone malignancy. However, treatment remains challenging due to multidrug resistance, toxic side effects from high-dose and frequent chemotherapy, and surgery-induced bone defects. Herein, we report a double-sensitizing chemotherapeutic hydrogel for efficient OS treatment and bone regeneration, which is constructed by loading doxorubicin hydrochloride (DOX) and icaritin (ICT) into Pluronic F127 (F127) and Pluronic F68 (F68) hydrogel matrix (DOX/ICT-gel). Both ICT and Pluronics can sensitize cancer cells to DOX treatment and enhance intracellular DOX accumulation, thereby boosting the cytotoxic activity of DOX. The addition of ICT can not only downregulate the required dose of DOX and reduce the toxic side effects of DOX, but also induce osteoblast differentiation, contributing to bone regeneration. In the in-situ anti-OS study, the DOX/ICT-gel was shown to stay locally for 7 days, and effectively inhibits OS tumor growth and metastasis, providing robust anticancer efficacy with low toxicity from a single injection for long-lasting treatment. This research provides a novel dual-sensitive DOX strategy for localized OS therapy, potentially advancing the clinical management of this challenging disease.
2026, 37(6): 111541
doi: 10.1016/j.cclet.2025.111541
Abstract:
In situ stimuli-responsive nanodevices have gained substantial attention in recent years owing to their remarkable potential to enhance tumor imaging and therapeutic effects. Herein, we formulated a pH-responsive, aptamer-functionalized DNA tetrahedral nanoplatform (ASTD) for improved visualization of survivin mRNA and chemo/gene therapy. ASTD, assembled by four single-stranded DNA, integrates pH-responsive i-motif sequences, survivin mRNA-targeted molecular beacons and AS1411 aptamers. Taking advantage of the tumor-targeting ability of AS1411 aptamer, ASTD monomers self-assemble into a multifunctional DNA polymeric tetrahedron (ASPD) on the tumor cell surface upon exposure to acidic tumor microenvironment. ASPD exhibits enhanced cellular uptake, superior survivin mRNA imaging, and efficient survivin gene silencing. Furthermore, Dox-loaded ASPD shows a significant antitumor effect, resulting in approximately 66% apoptosis of tumor cells. This study develops a dynamic DNA tetrahedral nanoplatform with diagnostic and therapeutic dual-functionalities, offering a promising strategy for advancing precise cancer theranostics.
In situ stimuli-responsive nanodevices have gained substantial attention in recent years owing to their remarkable potential to enhance tumor imaging and therapeutic effects. Herein, we formulated a pH-responsive, aptamer-functionalized DNA tetrahedral nanoplatform (ASTD) for improved visualization of survivin mRNA and chemo/gene therapy. ASTD, assembled by four single-stranded DNA, integrates pH-responsive i-motif sequences, survivin mRNA-targeted molecular beacons and AS1411 aptamers. Taking advantage of the tumor-targeting ability of AS1411 aptamer, ASTD monomers self-assemble into a multifunctional DNA polymeric tetrahedron (ASPD) on the tumor cell surface upon exposure to acidic tumor microenvironment. ASPD exhibits enhanced cellular uptake, superior survivin mRNA imaging, and efficient survivin gene silencing. Furthermore, Dox-loaded ASPD shows a significant antitumor effect, resulting in approximately 66% apoptosis of tumor cells. This study develops a dynamic DNA tetrahedral nanoplatform with diagnostic and therapeutic dual-functionalities, offering a promising strategy for advancing precise cancer theranostics.
2026, 37(6): 111553
doi: 10.1016/j.cclet.2025.111553
Abstract:
Reactive oxygen species (ROS) mediated oxidative stress represents a pivotal mechanism in antimicrobial activity, but most ROS-releasing materials require external stimuli, restricting their efficacy for continuous day-night applications. In this study, we present a novel substitution strategy to synthesize Cu-doped bimetallic organic frameworks with coordinatively unsaturated metal sites (CUMS), aiming to enhance ROS-mediated antimicrobial efficacy by regulating electron transfer between Cu and valence-variable Fe sites through Cu doping. The incorporation of Cu sites effectively modifies the electronic structure of Fe sites and optimizes the energy band structure of Fe-MIL-101, facilitating the effective electron transfer between the metal sites. Furthermore, the thermal treatment promotes the formation of coordinatively unsaturated electron-rich Fe active sites, significantly enhancing the O2 adsorption and activation, which in turn boosts ROS generation. Notably, the 0.5Cu-Fe-MIL-101(CUMS) exhibits remarkable ROS generation capability, demonstrates a 99.99% antibacterial effectiveness against Escherichia coli (E. coli) within 30 min of light exposure, and maintains a 99.99% antimicrobial efficacy after 4 h in darkness, thus achieving robust day-night antimicrobial activity. Density functional theory calculations and X-ray photoelectron spectroscopy (XPS) analyses confirm that the enhanced electron transfer between Cu and Fe sites facilitates the adsorption of O2 and H2O2 on the valence-variable Fe sites, promoting the spontaneous generation of ·O2− and ·OH, which induce oxidative stress and membrane damage in bacterial cells. This study highlights the potential of strategically tailoring the electronic properties surrounding the coordinatively unsaturated metal sites in bimetallic metal organic frameworks (MOFs) for advanced antibacterial applications.
Reactive oxygen species (ROS) mediated oxidative stress represents a pivotal mechanism in antimicrobial activity, but most ROS-releasing materials require external stimuli, restricting their efficacy for continuous day-night applications. In this study, we present a novel substitution strategy to synthesize Cu-doped bimetallic organic frameworks with coordinatively unsaturated metal sites (CUMS), aiming to enhance ROS-mediated antimicrobial efficacy by regulating electron transfer between Cu and valence-variable Fe sites through Cu doping. The incorporation of Cu sites effectively modifies the electronic structure of Fe sites and optimizes the energy band structure of Fe-MIL-101, facilitating the effective electron transfer between the metal sites. Furthermore, the thermal treatment promotes the formation of coordinatively unsaturated electron-rich Fe active sites, significantly enhancing the O2 adsorption and activation, which in turn boosts ROS generation. Notably, the 0.5Cu-Fe-MIL-101(CUMS) exhibits remarkable ROS generation capability, demonstrates a 99.99% antibacterial effectiveness against Escherichia coli (E. coli) within 30 min of light exposure, and maintains a 99.99% antimicrobial efficacy after 4 h in darkness, thus achieving robust day-night antimicrobial activity. Density functional theory calculations and X-ray photoelectron spectroscopy (XPS) analyses confirm that the enhanced electron transfer between Cu and Fe sites facilitates the adsorption of O2 and H2O2 on the valence-variable Fe sites, promoting the spontaneous generation of ·O2− and ·OH, which induce oxidative stress and membrane damage in bacterial cells. This study highlights the potential of strategically tailoring the electronic properties surrounding the coordinatively unsaturated metal sites in bimetallic metal organic frameworks (MOFs) for advanced antibacterial applications.
2026, 37(6): 111580
doi: 10.1016/j.cclet.2025.111580
Abstract:
Hypertaxoids A (Hyp A, 1) and B (Hyp B, 2), two highly modified benzoyl polycyclic polyprenylated acylphloroglucinols (PPAPs) with an unprecedented carbon skeleton, were isolated from the aerial parts of Hypericum elatoides. Compounds 1 and 2 share a bicyclo[5.3.1]hendecane motif fused a 1,1-dimethylcyclohexane unit, with a taxoid-like 6/8/6 tricyclic core, while compound 1 possesses a new 6/8/6/5 tetracyclic ring system. Their structures were elucidated by a combination of nuclear magnetic resonance spectroscopy (NMR) analysis, high resolution electrospray ionization mass spectroscopy (HRESIMS), X-ray crystallography, and electronic circular dichroism (ECD) calculations. A key cation-anion progress in formation mechanism of 1 and 2 was revealed based on density functional theory (DFT) calculations. Among them, hypertaxoid B displayed selective inhibition on cell growth of human cervical cancer lines. The mechanism of action revealed that Hyp B could stabilize tubulin polymerization and disrupt the microtubule network, leading to apoptosis in C-33A cells through the mitochondria signaling pathway. Moreover, Hyp B significantly suppressed the C-33A tumor growth, brain metastasis, and angiogenesis in zebrafish xenograft models. Compound 2 represents the first tubulin polymerization-promoting natural product of PPAPs, which highlights it as a promising lead compound with a new type of skeleton for antineoplastic drug development for cervical cancer treatment.
Hypertaxoids A (Hyp A, 1) and B (Hyp B, 2), two highly modified benzoyl polycyclic polyprenylated acylphloroglucinols (PPAPs) with an unprecedented carbon skeleton, were isolated from the aerial parts of Hypericum elatoides. Compounds 1 and 2 share a bicyclo[5.3.1]hendecane motif fused a 1,1-dimethylcyclohexane unit, with a taxoid-like 6/8/6 tricyclic core, while compound 1 possesses a new 6/8/6/5 tetracyclic ring system. Their structures were elucidated by a combination of nuclear magnetic resonance spectroscopy (NMR) analysis, high resolution electrospray ionization mass spectroscopy (HRESIMS), X-ray crystallography, and electronic circular dichroism (ECD) calculations. A key cation-anion progress in formation mechanism of 1 and 2 was revealed based on density functional theory (DFT) calculations. Among them, hypertaxoid B displayed selective inhibition on cell growth of human cervical cancer lines. The mechanism of action revealed that Hyp B could stabilize tubulin polymerization and disrupt the microtubule network, leading to apoptosis in C-33A cells through the mitochondria signaling pathway. Moreover, Hyp B significantly suppressed the C-33A tumor growth, brain metastasis, and angiogenesis in zebrafish xenograft models. Compound 2 represents the first tubulin polymerization-promoting natural product of PPAPs, which highlights it as a promising lead compound with a new type of skeleton for antineoplastic drug development for cervical cancer treatment.
2026, 37(6): 111633
doi: 10.1016/j.cclet.2025.111633
Abstract:
Multivalent supramolecular assemblies not only can efficiently enhance the photophysical properties of functional molecules, but also are able to intelligently modulate the luminescence behavior. Herein, the photo-controlled reversible multicolor luminescent supramolecular assembly was constructed on agarose substrate by non-covalent interactions, which was composed of multicharged β-cyclodextrin (AMCD) with adamantane-modified spiropyrane derivative (Adam-SP) and tetraphenylethene derivatives (TPE). Firstly, the positively charged AMCD and negatively charged TPE form a binary assembly AMCD@TPE through electrostatic interaction, significantly enhancing the luminescence of TPE at 480 nm with a quantum yield (QY) jump from 0.68% to 31.24%. Moreover, the binary assembly AMCD@TPE and Adam-SP further formed a ternary assembly Adam-MC@AMCD@TPE through strong host-guest interaction, which not only achieved photo-regulated multicolor reversible fluorescence in both aqueous solution and agarose hydrogel under alternating visible light irradiation and dark treatment, but also produced adjustable luminescence changes under thermal stimulation. The ternary assembly Adam-MC@AMCD@TPE was successfully applied to photo-controlled multiple anti-counterfeiting.
Multivalent supramolecular assemblies not only can efficiently enhance the photophysical properties of functional molecules, but also are able to intelligently modulate the luminescence behavior. Herein, the photo-controlled reversible multicolor luminescent supramolecular assembly was constructed on agarose substrate by non-covalent interactions, which was composed of multicharged β-cyclodextrin (AMCD) with adamantane-modified spiropyrane derivative (Adam-SP) and tetraphenylethene derivatives (TPE). Firstly, the positively charged AMCD and negatively charged TPE form a binary assembly AMCD@TPE through electrostatic interaction, significantly enhancing the luminescence of TPE at 480 nm with a quantum yield (QY) jump from 0.68% to 31.24%. Moreover, the binary assembly AMCD@TPE and Adam-SP further formed a ternary assembly Adam-MC@AMCD@TPE through strong host-guest interaction, which not only achieved photo-regulated multicolor reversible fluorescence in both aqueous solution and agarose hydrogel under alternating visible light irradiation and dark treatment, but also produced adjustable luminescence changes under thermal stimulation. The ternary assembly Adam-MC@AMCD@TPE was successfully applied to photo-controlled multiple anti-counterfeiting.
2026, 37(6): 111672
doi: 10.1016/j.cclet.2025.111672
Abstract:
The first synthesis, characterization, and hydride reduction reactions of a series of PNP-pincer ligand supported molybdenum and tungsten carbyne complexes [(PNP)M(≡CAr)X(CO)] [M = Mo, W; PNP = Ph2P(CH2)2N(CH3)(CH2)2PPh2, R2P(CH2)2N(H)(CH2)2PR2, R = Ph, Cy] are reported. Treatment of [(PNP)M(≡CAr)X(CO)] with LiAlH4 led to full reduction of the carbyne carbon, giving PP-bidentate η6-arene molybdenum and tungsten complexes. Alternatively, when NaBH4 was used as a reductant, the carbyne ligand completely dissociated from the molybdenum center to yield toluene and dimolybdenum biscarbonyl complex [(PNP)Mo(CO)]2. These PNP-pincer molybdenum and tungsten carbyne complexes showed unique reactivity with hydride reagents preferably at the carbyne carbons, in contrast to the metal centers of non-pincer molybdenum and tungsten carbyne complexes in previous reports.
The first synthesis, characterization, and hydride reduction reactions of a series of PNP-pincer ligand supported molybdenum and tungsten carbyne complexes [(PNP)M(≡CAr)X(CO)] [M = Mo, W; PNP = Ph2P(CH2)2N(CH3)(CH2)2PPh2, R2P(CH2)2N(H)(CH2)2PR2, R = Ph, Cy] are reported. Treatment of [(PNP)M(≡CAr)X(CO)] with LiAlH4 led to full reduction of the carbyne carbon, giving PP-bidentate η6-arene molybdenum and tungsten complexes. Alternatively, when NaBH4 was used as a reductant, the carbyne ligand completely dissociated from the molybdenum center to yield toluene and dimolybdenum biscarbonyl complex [(PNP)Mo(CO)]2. These PNP-pincer molybdenum and tungsten carbyne complexes showed unique reactivity with hydride reagents preferably at the carbyne carbons, in contrast to the metal centers of non-pincer molybdenum and tungsten carbyne complexes in previous reports.
2026, 37(6): 111709
doi: 10.1016/j.cclet.2025.111709
Abstract:
A neutral Diels-Alder reaction lacking enough electronic bias typically requires forcing conditions to proceed owing to the enlarged energy gap between HOMO and LUMO. We herein report an electrophotocatalytic decarbonylative [4 + 2] cyclization of indenones under mild reaction conditions for facile access toward various benzo[c]fluorenones. Mechanistic investigations revealed that this reaction first underwent photocatalytic decarbonylative [4 + 2] cyclization followed by an electrocatalytic oxidation. Consistent with their photophysical properties and DFT calculations, the obtained benzo[c]fluorenones displayed remarkable photocatalytic activity both in the current electrophotocatalytic decarbonylative [4 + 2] cyclization of indenones and in the oxidation of benzhydrol.
A neutral Diels-Alder reaction lacking enough electronic bias typically requires forcing conditions to proceed owing to the enlarged energy gap between HOMO and LUMO. We herein report an electrophotocatalytic decarbonylative [4 + 2] cyclization of indenones under mild reaction conditions for facile access toward various benzo[c]fluorenones. Mechanistic investigations revealed that this reaction first underwent photocatalytic decarbonylative [4 + 2] cyclization followed by an electrocatalytic oxidation. Consistent with their photophysical properties and DFT calculations, the obtained benzo[c]fluorenones displayed remarkable photocatalytic activity both in the current electrophotocatalytic decarbonylative [4 + 2] cyclization of indenones and in the oxidation of benzhydrol.
2026, 37(6): 111712
doi: 10.1016/j.cclet.2025.111712
Abstract:
Hypoxic-ischemic encephalopathy (HIE) is a major cause of infant mortality and permanent neurological abnormalities, highlighting the importance of early identification and accurate diagnosis. Fluorescence sensing provides various benefits over traditional diagnostic methods, including real-time detection of hypoxia, which is often linked to HIE, and molecular-level insights. Herein, a novel hypoxia-responsive fluorescent probe, BOD, was created to overcome the difficulties associated with blood–brain barrier (BBB) penetration for brain damage imaging using a HIE model. BOD can be cleaved by azoreductase to produce a red fluorescent signal, with excellent sensitivity, selectivity, and biocompatibility. Crucially, BOD effectively monitors neural cells across varying oxygen concentrations, particularly in hypoxic microenvironments, providing vital insights into the impact of oxygen deprivation on neural cell function during HIE. In both cellular and ex vivo mouse brain tissue models, the effectiveness of BOD was confirmed: it outperformed conventional techniques in the reliable identification of hypoxic injury sites, differentiating between mild, moderate, and severe injury. Thanks to its excellent permeability due to its lipophilicity and positive charge, BOD can pass through the BBB, with strong fluorescence in the periventricular white matter (PWM) and cortex strongly correlated with injury severity. This study is novel in its application of a hypoxia-responsive fluorescent probe for brain damage imaging in an HIE model, highlighting the substantial potential of BOD for real-time, in vivo imaging, representing a promising tool for early diagnosis and investigation of HIE.
Hypoxic-ischemic encephalopathy (HIE) is a major cause of infant mortality and permanent neurological abnormalities, highlighting the importance of early identification and accurate diagnosis. Fluorescence sensing provides various benefits over traditional diagnostic methods, including real-time detection of hypoxia, which is often linked to HIE, and molecular-level insights. Herein, a novel hypoxia-responsive fluorescent probe, BOD, was created to overcome the difficulties associated with blood–brain barrier (BBB) penetration for brain damage imaging using a HIE model. BOD can be cleaved by azoreductase to produce a red fluorescent signal, with excellent sensitivity, selectivity, and biocompatibility. Crucially, BOD effectively monitors neural cells across varying oxygen concentrations, particularly in hypoxic microenvironments, providing vital insights into the impact of oxygen deprivation on neural cell function during HIE. In both cellular and ex vivo mouse brain tissue models, the effectiveness of BOD was confirmed: it outperformed conventional techniques in the reliable identification of hypoxic injury sites, differentiating between mild, moderate, and severe injury. Thanks to its excellent permeability due to its lipophilicity and positive charge, BOD can pass through the BBB, with strong fluorescence in the periventricular white matter (PWM) and cortex strongly correlated with injury severity. This study is novel in its application of a hypoxia-responsive fluorescent probe for brain damage imaging in an HIE model, highlighting the substantial potential of BOD for real-time, in vivo imaging, representing a promising tool for early diagnosis and investigation of HIE.
2026, 37(6): 111715
doi: 10.1016/j.cclet.2025.111715
Abstract:
Nitrile oxide is a highly reactive species used for organic synthesis and bioconjugation. Herein, we developed a novel approach for disulfide formation and capping of N-terminal cysteine in peptides mediated by bromo nitrile oxide. 1,1-Dibromoformaldoxime acts as the precursor for bromo nitrile oxide. This transformation proceeds under mild conditions with rapid kinetics, efficiently converting a broad range of thiophenols, thiols, and cysteine-containing native peptides into disulfides, cyclic disulfides, or thiazolidin-2-one oximes. Notably, oxidant-sensitive residues such as methionine, tyrosine, and tryptophan are well tolerated without over-oxidation. The compatibility with aqueous media further highlights its potential for the late-stage modification of native peptides and the derivatization of biologically active molecules.
Nitrile oxide is a highly reactive species used for organic synthesis and bioconjugation. Herein, we developed a novel approach for disulfide formation and capping of N-terminal cysteine in peptides mediated by bromo nitrile oxide. 1,1-Dibromoformaldoxime acts as the precursor for bromo nitrile oxide. This transformation proceeds under mild conditions with rapid kinetics, efficiently converting a broad range of thiophenols, thiols, and cysteine-containing native peptides into disulfides, cyclic disulfides, or thiazolidin-2-one oximes. Notably, oxidant-sensitive residues such as methionine, tyrosine, and tryptophan are well tolerated without over-oxidation. The compatibility with aqueous media further highlights its potential for the late-stage modification of native peptides and the derivatization of biologically active molecules.
2026, 37(6): 111718
doi: 10.1016/j.cclet.2025.111718
Abstract:
Polycyclic heterocycles are prevalent in medicines, functional materials and natural products, making their synthesis a significant focus in modern organic chemistry. Herein, we present a Lewis acid-mediated cascade annulation of 1,6-enynols with o-aminobenzonitriles for the chemoselective synthesis of oxepino[3,4,5-de][1,6]naphthyridine and chromeno[2,3,4-de][1,6]naphthyridine derivatives. This reaction design enables selective control over the carbon-heteroatom and carbon-carbon bond formation in an efficient, atom-economical manner, allowing the one-step synthesis of rare [6-6-7] and [6-6-6] core polycyclic heterocycles containing three heteroatoms. Density functional theory (DFT) calculations and control experiments reveal that the reaction's high selectivity is achieved by modulating the reactivity of electron-rich alkenyl groups in the enynols, which selectively directs the intramolecular dehydroaromatization and cyclization processes.
Polycyclic heterocycles are prevalent in medicines, functional materials and natural products, making their synthesis a significant focus in modern organic chemistry. Herein, we present a Lewis acid-mediated cascade annulation of 1,6-enynols with o-aminobenzonitriles for the chemoselective synthesis of oxepino[3,4,5-de][1,6]naphthyridine and chromeno[2,3,4-de][1,6]naphthyridine derivatives. This reaction design enables selective control over the carbon-heteroatom and carbon-carbon bond formation in an efficient, atom-economical manner, allowing the one-step synthesis of rare [6-6-7] and [6-6-6] core polycyclic heterocycles containing three heteroatoms. Density functional theory (DFT) calculations and control experiments reveal that the reaction's high selectivity is achieved by modulating the reactivity of electron-rich alkenyl groups in the enynols, which selectively directs the intramolecular dehydroaromatization and cyclization processes.
2026, 37(6): 111719
doi: 10.1016/j.cclet.2025.111719
Abstract:
Nanographenes (NGs) incorporating N-doped heptagonal units demonstrate intriguing physicochemical properties, attributed to their negatively curved structure induced by the angular strain of the heptagons and the electronic effects of nitrogen atoms, while their precise synthesis remains a challenging task. Herein, we developed an efficient approach for the construction of azepine-embedded NGs via two-fold SNAr/gold(I)-catalyzed 7-endo-dig annulation from commercially available 4,7-dibromo-5,6-difluorobenzo[2,1,3]thiadiazole. The fusion of two heptagonal rings dramatically increases the intramolecular strain and forces the central skeleton to twist, giving rise to a unique packing mode in the crystal. The incorporation of thiadiazole leads to a pronounced bathochromic shift in the fluorescence emission, which causes the typical product to display NIR-emission. Furthermore, it is found that the backbone core of these NGs with thiadiazole exhibits excellent single-molecule conductivity as well.
Nanographenes (NGs) incorporating N-doped heptagonal units demonstrate intriguing physicochemical properties, attributed to their negatively curved structure induced by the angular strain of the heptagons and the electronic effects of nitrogen atoms, while their precise synthesis remains a challenging task. Herein, we developed an efficient approach for the construction of azepine-embedded NGs via two-fold SNAr/gold(I)-catalyzed 7-endo-dig annulation from commercially available 4,7-dibromo-5,6-difluorobenzo[2,1,3]thiadiazole. The fusion of two heptagonal rings dramatically increases the intramolecular strain and forces the central skeleton to twist, giving rise to a unique packing mode in the crystal. The incorporation of thiadiazole leads to a pronounced bathochromic shift in the fluorescence emission, which causes the typical product to display NIR-emission. Furthermore, it is found that the backbone core of these NGs with thiadiazole exhibits excellent single-molecule conductivity as well.
2026, 37(6): 111737
doi: 10.1016/j.cclet.2025.111737
Abstract:
In this work, a periodically ordered cruciform DNA nanowire (POCDN) guided-localized hybridization chain reaction (LHCR) was designed for the simultaneous and rapid detection and imaging of dual-miRNAs in cancer cells. In the presence of the targets miRNA-21 and miRNA-155 associated with breast cancer, the hairpins on both sides of the DNA nanowire were opened to undergo a LHCR, and the trace amount of the target miRNAs were converted into numerous 5-carboxyfluorescein (FAM) and Cy5 signals, which in turn enabled the simultaneous and sensitive detection and visualization of dual-miRNAs targets in malignant tumor cells. Impressively, folic acid (FA) labelled on the structural backbone of DNA nanowires could be specifically targeted to malignant tumor cells with overexpressing the folate receptor, which greatly improved the efficiency of delivery into the cell and enabled precise imaging of intracellular miRNAs without the liposomal transfection. Compared with conventional hybridization chain reaction (HCR), the POCDN-guided LHCR confined the reactants in a compact space, greatly improving the sensitivity of the assay and the reaction rate, with a 5.3-fold reduction in reaction time to just 5 min and detection limits as low as 0.97 and 0.58 pmol/L for miRNA-21 and miRNA-155, respectively. This strategy provides a programmable platform for simultaneous rapid and sensitive detection and precise visualization of multi-miRNAs with eventual applications in bioanalytical studies and potential for future clinical diagnostics of diseases.
In this work, a periodically ordered cruciform DNA nanowire (POCDN) guided-localized hybridization chain reaction (LHCR) was designed for the simultaneous and rapid detection and imaging of dual-miRNAs in cancer cells. In the presence of the targets miRNA-21 and miRNA-155 associated with breast cancer, the hairpins on both sides of the DNA nanowire were opened to undergo a LHCR, and the trace amount of the target miRNAs were converted into numerous 5-carboxyfluorescein (FAM) and Cy5 signals, which in turn enabled the simultaneous and sensitive detection and visualization of dual-miRNAs targets in malignant tumor cells. Impressively, folic acid (FA) labelled on the structural backbone of DNA nanowires could be specifically targeted to malignant tumor cells with overexpressing the folate receptor, which greatly improved the efficiency of delivery into the cell and enabled precise imaging of intracellular miRNAs without the liposomal transfection. Compared with conventional hybridization chain reaction (HCR), the POCDN-guided LHCR confined the reactants in a compact space, greatly improving the sensitivity of the assay and the reaction rate, with a 5.3-fold reduction in reaction time to just 5 min and detection limits as low as 0.97 and 0.58 pmol/L for miRNA-21 and miRNA-155, respectively. This strategy provides a programmable platform for simultaneous rapid and sensitive detection and precise visualization of multi-miRNAs with eventual applications in bioanalytical studies and potential for future clinical diagnostics of diseases.
2026, 37(6): 111738
doi: 10.1016/j.cclet.2025.111738
Abstract:
Over the past decades, vinyl cations have been developed as versatile synthetic intermediates in organic chemistry, that allow the construction of various C–C and C–X bonds. However, the catalytic enantioselective transformation of vinyl cations remains one of the major challenges in asymmetric catalysis, especially for the organocatalytic enantioselective reaction. Herein, we report a chiral Brønsted acid-catalyzed atroposelective reaction of vinyl cations by combining organocatalytic diyne cyclization with C(sp2)–H functionalization of diphenols. The effective chiral induction model of vinyl cations enables the streamlined synthesis of axially chiral acyclic tetrasubstituted alkenes with the simultaneous control of chemoselectivity, regioselectivity, E/Z selectivity and enantioselectivity. Further derivatizations and applications demonstrate the potential utility of constructed axially chiral skeletons in asymmetric catalysis. Computational mechanistic studies reveal the reaction mechanism and origin of selectivities. Notably, this protocol represents the first organocatalytic asymmetric intermolecular reaction of vinyl cations, as well as the first organocatalytic enantioselective diyne cyclization.
Over the past decades, vinyl cations have been developed as versatile synthetic intermediates in organic chemistry, that allow the construction of various C–C and C–X bonds. However, the catalytic enantioselective transformation of vinyl cations remains one of the major challenges in asymmetric catalysis, especially for the organocatalytic enantioselective reaction. Herein, we report a chiral Brønsted acid-catalyzed atroposelective reaction of vinyl cations by combining organocatalytic diyne cyclization with C(sp2)–H functionalization of diphenols. The effective chiral induction model of vinyl cations enables the streamlined synthesis of axially chiral acyclic tetrasubstituted alkenes with the simultaneous control of chemoselectivity, regioselectivity, E/Z selectivity and enantioselectivity. Further derivatizations and applications demonstrate the potential utility of constructed axially chiral skeletons in asymmetric catalysis. Computational mechanistic studies reveal the reaction mechanism and origin of selectivities. Notably, this protocol represents the first organocatalytic asymmetric intermolecular reaction of vinyl cations, as well as the first organocatalytic enantioselective diyne cyclization.
2026, 37(6): 111777
doi: 10.1016/j.cclet.2025.111777
Abstract:
Heck/Tsuji-Trost reaction and cyclization reactions have been established as efficient and practical strategies for constructing nitrogen-containing heterocyclic compounds. However, it is challenging to achieve a direct cascade of Heck/Tsuji-Trost and 6-endo cyclization reactions in one-pot synthesis, primarily due to the reactivity of intermediates and the regioselectivity control of the reaction. In this work, a palladium-catalyzed, Heck/Tsuji-Trost and 6-endo cyclization tandem reaction of aryl iodides, vinylacetic acid, and aryl amines has been developed, providing an effective approach for one-pot synthesis of substituted quinolines in moderate to good yields. The broad functional group tolerance, high regioselectivity, gram-scale experiments, and successful late-stage modification of natural products and pharmaceuticals proved the versatility and practicality of this method. Additionally, mechanistic experiments demonstrate that the branched amination product serves as a key intermediate in this reaction.
Heck/Tsuji-Trost reaction and cyclization reactions have been established as efficient and practical strategies for constructing nitrogen-containing heterocyclic compounds. However, it is challenging to achieve a direct cascade of Heck/Tsuji-Trost and 6-endo cyclization reactions in one-pot synthesis, primarily due to the reactivity of intermediates and the regioselectivity control of the reaction. In this work, a palladium-catalyzed, Heck/Tsuji-Trost and 6-endo cyclization tandem reaction of aryl iodides, vinylacetic acid, and aryl amines has been developed, providing an effective approach for one-pot synthesis of substituted quinolines in moderate to good yields. The broad functional group tolerance, high regioselectivity, gram-scale experiments, and successful late-stage modification of natural products and pharmaceuticals proved the versatility and practicality of this method. Additionally, mechanistic experiments demonstrate that the branched amination product serves as a key intermediate in this reaction.
2026, 37(6): 111778
doi: 10.1016/j.cclet.2025.111778
Abstract:
A novel thia[8]helicene (BN[8]H) with B, N heteroatoms incorporated in the molecular skeleton was synthesized via Suzuki coupling reaction and intramolecular direct electrophilic C-H borylation. Its helical structure was confirmed by X-ray crystal analysis. Enantiomers BN[8]H showed the interesting responses to fluoride ion stimulation with novel sign inversion of electronic circular dichroism (ECD) and circularly polarized luminescence (CPL). TD-DFT calculations revealed that the fluoride ions significant influence the transition dipole moments and θu,m, resulting in circularly polarized luminescence reversal.
A novel thia[8]helicene (BN[8]H) with B, N heteroatoms incorporated in the molecular skeleton was synthesized via Suzuki coupling reaction and intramolecular direct electrophilic C-H borylation. Its helical structure was confirmed by X-ray crystal analysis. Enantiomers BN[8]H showed the interesting responses to fluoride ion stimulation with novel sign inversion of electronic circular dichroism (ECD) and circularly polarized luminescence (CPL). TD-DFT calculations revealed that the fluoride ions significant influence the transition dipole moments and θu,m, resulting in circularly polarized luminescence reversal.
2026, 37(6): 111782
doi: 10.1016/j.cclet.2025.111782
Abstract:
Conventional aromatic fluorophores in fluorescent probes can easily initiate molecular aggregation via π–π stacking, which drastically quenches fluorescence and hinders cellular permeability. To address this challenge, we developed an ingenious host-guest recognition strategy that converted detrimental π-π stacking into a relaxed molecular aggregation state, enabling the creation of a rhodamine-based supramolecular fluorescent probe called RAO@2CB[8]. This ternary conjugate, assembled by encapsulating adamantyl-modified rhodamine (RAO) with two cucurbit[8]uril (CB[8]), showcased enhanced fluorescence properties for the precise detection of salicylic acid (SA). Intriguingly, in intricate biological systems, RAO@2CB[8] demonstrated exceptional cell permeability, facilitating susceptible detection and imaging of SA in HEK-293 cells, radish roots, and salt-stressed white pea seedlings. This facile supramolecular strategy not only mitigates aggregation-induced quenching, but also provides profound insights for the precise modulation of molecular aggregation behavior.
Conventional aromatic fluorophores in fluorescent probes can easily initiate molecular aggregation via π–π stacking, which drastically quenches fluorescence and hinders cellular permeability. To address this challenge, we developed an ingenious host-guest recognition strategy that converted detrimental π-π stacking into a relaxed molecular aggregation state, enabling the creation of a rhodamine-based supramolecular fluorescent probe called RAO@2CB[8]. This ternary conjugate, assembled by encapsulating adamantyl-modified rhodamine (RAO) with two cucurbit[8]uril (CB[8]), showcased enhanced fluorescence properties for the precise detection of salicylic acid (SA). Intriguingly, in intricate biological systems, RAO@2CB[8] demonstrated exceptional cell permeability, facilitating susceptible detection and imaging of SA in HEK-293 cells, radish roots, and salt-stressed white pea seedlings. This facile supramolecular strategy not only mitigates aggregation-induced quenching, but also provides profound insights for the precise modulation of molecular aggregation behavior.
2026, 37(6): 111792
doi: 10.1016/j.cclet.2025.111792
Abstract:
The efficient design of novel macrocycles with enhanced properties over their parent scaffold represents a major challenge in supramolecular chemistry. Here, we exemplify imination as a purification-free method to develop novel pillar[n]arene-like macrocycles with partial-belt nitrogen functionalization. Compared to similarly sized pillar[n]arene-inspired arenes, the strategy provides an increased scalability and an up to 16-fold improvement in macrocyclization yield. X-ray crystallography and theoretical calculations reveal a similar electron density and cavity size as pillar[5]arene. The altered geometry and enhanced flexibility, however, permit complexing di-, tri- and tetrasubstituted cyanobenzenes, generating guest complementarity to all-carbon pillar[n]arenes. The suitable positioning of hydrogen bond acceptors facilitates binding based on endo-cavity hydrogen bonding, a feature largely unreported in peralkylated pillar[n]arenes. Reduction straightforwardly afforded a polyamine macrocycle of modified geometry.
The efficient design of novel macrocycles with enhanced properties over their parent scaffold represents a major challenge in supramolecular chemistry. Here, we exemplify imination as a purification-free method to develop novel pillar[n]arene-like macrocycles with partial-belt nitrogen functionalization. Compared to similarly sized pillar[n]arene-inspired arenes, the strategy provides an increased scalability and an up to 16-fold improvement in macrocyclization yield. X-ray crystallography and theoretical calculations reveal a similar electron density and cavity size as pillar[5]arene. The altered geometry and enhanced flexibility, however, permit complexing di-, tri- and tetrasubstituted cyanobenzenes, generating guest complementarity to all-carbon pillar[n]arenes. The suitable positioning of hydrogen bond acceptors facilitates binding based on endo-cavity hydrogen bonding, a feature largely unreported in peralkylated pillar[n]arenes. Reduction straightforwardly afforded a polyamine macrocycle of modified geometry.
2026, 37(6): 111829
doi: 10.1016/j.cclet.2025.111829
Abstract:
The oxygen evolution reaction (OER) is crucial for renewable energy systems, such as water splitting and metal air batteries. However, the slow kinetics of OER significantly limits the overall energy conversion efficiency, necessitating effective catalysts. The multielement transition metal oxides offer a promising alternative compared to precious metal oxides, yet their composition optimization remains challenging due to the vastness of the combinatorial space. Traditional trial-and-error approaches are labor-intensive and inefficient. To address this challenge, we develop an innovative automated platform integrating machine learning (ML) with Bayesian optimization for rapid and cost-effective synthesis and evaluation of electrocatalysts. This platform allows the automation of the entire experimental process, from synthesis to evaluation, enabling real-time feedback and guiding subsequent experiments. In a continuous operation of 32 h, the platform conducted 96 experiments to optimize the composition of (Ni-Fe-Co-Mn-Mo)Ox, resulting in an electrocatalyst with an overpotential of 231 mV at 10 mA/cm2. This automated approach significantly reduces manual intervention and enhances efficiency, proving to be a valuable tool for optimizing materials in complex, multidimensional spaces.
The oxygen evolution reaction (OER) is crucial for renewable energy systems, such as water splitting and metal air batteries. However, the slow kinetics of OER significantly limits the overall energy conversion efficiency, necessitating effective catalysts. The multielement transition metal oxides offer a promising alternative compared to precious metal oxides, yet their composition optimization remains challenging due to the vastness of the combinatorial space. Traditional trial-and-error approaches are labor-intensive and inefficient. To address this challenge, we develop an innovative automated platform integrating machine learning (ML) with Bayesian optimization for rapid and cost-effective synthesis and evaluation of electrocatalysts. This platform allows the automation of the entire experimental process, from synthesis to evaluation, enabling real-time feedback and guiding subsequent experiments. In a continuous operation of 32 h, the platform conducted 96 experiments to optimize the composition of (Ni-Fe-Co-Mn-Mo)Ox, resulting in an electrocatalyst with an overpotential of 231 mV at 10 mA/cm2. This automated approach significantly reduces manual intervention and enhances efficiency, proving to be a valuable tool for optimizing materials in complex, multidimensional spaces.
2026, 37(6): 111880
doi: 10.1016/j.cclet.2025.111880
Abstract:
The construction of quasi-solid-state sodium-air batteries (SABs) by replacing traditional liquid electrolytes with gel electrolytes has become one of the future focus areas in the SABs field. However, the currently developed quasi-solid-state SABs inevitably produce insoluble discharge products during the discharge process, which leads to limited rate capability and poor cycling stability. In this study, a hydrogel electrolyte (PANa-NCNT) containing nitrogen-doped carbon nanotubes (NCNT) and sodium polyacrylate (PANa) was designed, and a quasi-solid-state SAB with highly water-soluble NaOH as the main discharge product was constructed. The physical entanglement between NCNT and PANa in the PANa-NCNT hydrogel electrolyte leads to the heterogeneous structure of gel, which effectively enhances the thermodynamic stability of the hydrogel electrolyte. In addition, the aqueous components of electrolyte determine the reaction pathway of battery. During discharge, the oxygen reduction reaction proceeds via 2e- pathway to generate soluble NaOH, while during charging, the oxygen evolution reaction exhibits a mixed 2e-/4e- reaction pathway. Benefiting from the good thermodynamic stability of PANa-NCNT hydrogel electrolyte and the water-soluble discharge products, the fabricated quasi-solid-state SAB demonstrates stable cycling for 330 cycles (187 h) at 0.5 mA/cm2 in ambient air. These findings reveal the influence of the liquid-phase components in the gel electrolyte on the reaction pathways, which is conducive to promoting the application of hydrogels in quasi-solid-state SABs.
The construction of quasi-solid-state sodium-air batteries (SABs) by replacing traditional liquid electrolytes with gel electrolytes has become one of the future focus areas in the SABs field. However, the currently developed quasi-solid-state SABs inevitably produce insoluble discharge products during the discharge process, which leads to limited rate capability and poor cycling stability. In this study, a hydrogel electrolyte (PANa-NCNT) containing nitrogen-doped carbon nanotubes (NCNT) and sodium polyacrylate (PANa) was designed, and a quasi-solid-state SAB with highly water-soluble NaOH as the main discharge product was constructed. The physical entanglement between NCNT and PANa in the PANa-NCNT hydrogel electrolyte leads to the heterogeneous structure of gel, which effectively enhances the thermodynamic stability of the hydrogel electrolyte. In addition, the aqueous components of electrolyte determine the reaction pathway of battery. During discharge, the oxygen reduction reaction proceeds via 2e- pathway to generate soluble NaOH, while during charging, the oxygen evolution reaction exhibits a mixed 2e-/4e- reaction pathway. Benefiting from the good thermodynamic stability of PANa-NCNT hydrogel electrolyte and the water-soluble discharge products, the fabricated quasi-solid-state SAB demonstrates stable cycling for 330 cycles (187 h) at 0.5 mA/cm2 in ambient air. These findings reveal the influence of the liquid-phase components in the gel electrolyte on the reaction pathways, which is conducive to promoting the application of hydrogels in quasi-solid-state SABs.
2026, 37(6): 111918
doi: 10.1016/j.cclet.2025.111918
Abstract:
High-performance bifunctional oxygen electrocatalysts are urgently required for rechargeable zinc-air batteries (ZABs) due to sluggish kinetics of oxygen reduction/evolution reactions (ORR/OER) at the air cathode. In this study, an iron single-atom catalyst (Fe-SAC, FeTCPP@UiO-66–800) is synthesized by direct pyrolysis of a metalloporphyrin-incorporated multivariate MOF. The spatial separation effect of the framework linkers endows Fe-SAC with hierarchical porosity, improved metal utilization efficiency, and enhanced site accessibility by suppressing the metal agglomeration during pyrolysis. Moreover, the possible formation of di- or tri-atomic iron sites facilitates the OER activity via the oxide pathway mechanism (OPM), contributing to the excellent bifunctional ORR/OER performance with a ΔE of 0.59 V. Both liquid and flexible ZAB assembled with FeTCPP@UiO-66–800 demonstrate enhanced activity, long-term durability, and anti-deformation ability (340.5 mW/cm2 peak power density in liquid device). This study presents a novel strategy for preparing MOF-derived SACs with highly accessible single-atom sites, offering a promising route to high-performance energy conversion devices.
High-performance bifunctional oxygen electrocatalysts are urgently required for rechargeable zinc-air batteries (ZABs) due to sluggish kinetics of oxygen reduction/evolution reactions (ORR/OER) at the air cathode. In this study, an iron single-atom catalyst (Fe-SAC, FeTCPP@UiO-66–800) is synthesized by direct pyrolysis of a metalloporphyrin-incorporated multivariate MOF. The spatial separation effect of the framework linkers endows Fe-SAC with hierarchical porosity, improved metal utilization efficiency, and enhanced site accessibility by suppressing the metal agglomeration during pyrolysis. Moreover, the possible formation of di- or tri-atomic iron sites facilitates the OER activity via the oxide pathway mechanism (OPM), contributing to the excellent bifunctional ORR/OER performance with a ΔE of 0.59 V. Both liquid and flexible ZAB assembled with FeTCPP@UiO-66–800 demonstrate enhanced activity, long-term durability, and anti-deformation ability (340.5 mW/cm2 peak power density in liquid device). This study presents a novel strategy for preparing MOF-derived SACs with highly accessible single-atom sites, offering a promising route to high-performance energy conversion devices.
2026, 37(6): 111934
doi: 10.1016/j.cclet.2025.111934
Abstract:
Metal-free carbon materials are effective catalysts for electrochemical H2O2 synthesis. Here, we employ a hydrothermal-ball milling tandem strategy to convert nitrogen-doped carbon quantum dot (N-CQD) into N, B, O-codoped carbon nanosheets via mechanochemical crosslinking. The formation of covalent N–B–O linkages correlate with nanosheet thickness and boosts 2e− ORR performance. The optimized CN-B-3 catalyst achieves 98.4% selectivity at 0.68 V vs. RHE, a low Tafel slope of 73.5 mV/dec, and a high ring current density of 0.46 mA/cm2. It maintains 92.2% and 88.7% of initial ring and disk currents after 18 h, with exceptional long-term stability demonstrated over 50 h in both flow and solid-state electrolyte cells, yielding up to 213 mmol/L H2O2. DFT calculations reveal that covalent bonds formed by dehydration of two -OH groups (BO2HN-, B(OH)2-PyN- and B(OH)-PyN-) are key to nanosheet formation. Linkages between B and nitrogen atoms on the carbon ring favor H2O2 generation more than B–pyridinic-N connections. This study paves an avenue for converting 0D CQD to 2D carbon nanosheets and highlights the catalytic role of N–B–O linkers in sustainable H2O2 electrosynthesis.
Metal-free carbon materials are effective catalysts for electrochemical H2O2 synthesis. Here, we employ a hydrothermal-ball milling tandem strategy to convert nitrogen-doped carbon quantum dot (N-CQD) into N, B, O-codoped carbon nanosheets via mechanochemical crosslinking. The formation of covalent N–B–O linkages correlate with nanosheet thickness and boosts 2e− ORR performance. The optimized CN-B-3 catalyst achieves 98.4% selectivity at 0.68 V vs. RHE, a low Tafel slope of 73.5 mV/dec, and a high ring current density of 0.46 mA/cm2. It maintains 92.2% and 88.7% of initial ring and disk currents after 18 h, with exceptional long-term stability demonstrated over 50 h in both flow and solid-state electrolyte cells, yielding up to 213 mmol/L H2O2. DFT calculations reveal that covalent bonds formed by dehydration of two -OH groups (BO2HN-, B(OH)2-PyN- and B(OH)-PyN-) are key to nanosheet formation. Linkages between B and nitrogen atoms on the carbon ring favor H2O2 generation more than B–pyridinic-N connections. This study paves an avenue for converting 0D CQD to 2D carbon nanosheets and highlights the catalytic role of N–B–O linkers in sustainable H2O2 electrosynthesis.
2026, 37(6): 111968
doi: 10.1016/j.cclet.2025.111968
Abstract:
Nitidine chloride (NC) exhibits potent antitumor activity through ferroptosis induction. However, its clinical application is limited by poor aqueous solubility and non-selective cytotoxicity. To overcome these challenges, we developed a pH-responsive delivery system (HD@NC@MOF), combining a hyaluronic acid (HA)-cloaked and mixed-valence iron-based metal-organic framework (Fe-MOF), enabling strategic targeting of lung squamous cell carcinoma (LUSC) cells via CD44 receptor recognition. Within the acidic intracellular microenvironment, HD@NC@MOF co-releases NC and iron ions, triggering a profound reactive oxygen species (ROS) surge, and ultimately inducing ferroptosis and necroptosis through the solute carrier family 7 member 11 (SLC7A11)/glutathione peroxidase 4 (GPX4) and receptor-interacting serine/threonine-protein kinase 1 (RIPK1)/receptor-interacting serine/threonine-protein kinase 3 (RIPK3)/mixed lineage kinase domain-like protein (MLKL) pathways. In vitro, HD@NC@MOF exhibited significantly enhanced selective cytotoxicity towards LUSC cells compared to free NC (selectivity index improved from 0.54 to 2.58). Mechanistic studies revealed that NC stimulated mitochondrial ROS production, synergizing with Fe-MOF-derived iron to amplify oxidative stress. In vivo, HD@NC@MOF achieved a 69.02% tumor inhibition rate (1.72-fold higher than free NC) with minimal systemic toxicity. This work highlighted the potential of HD@NC@MOF as an efficient and targeted carrier for NC in LUSC chemotherapy.
Nitidine chloride (NC) exhibits potent antitumor activity through ferroptosis induction. However, its clinical application is limited by poor aqueous solubility and non-selective cytotoxicity. To overcome these challenges, we developed a pH-responsive delivery system (HD@NC@MOF), combining a hyaluronic acid (HA)-cloaked and mixed-valence iron-based metal-organic framework (Fe-MOF), enabling strategic targeting of lung squamous cell carcinoma (LUSC) cells via CD44 receptor recognition. Within the acidic intracellular microenvironment, HD@NC@MOF co-releases NC and iron ions, triggering a profound reactive oxygen species (ROS) surge, and ultimately inducing ferroptosis and necroptosis through the solute carrier family 7 member 11 (SLC7A11)/glutathione peroxidase 4 (GPX4) and receptor-interacting serine/threonine-protein kinase 1 (RIPK1)/receptor-interacting serine/threonine-protein kinase 3 (RIPK3)/mixed lineage kinase domain-like protein (MLKL) pathways. In vitro, HD@NC@MOF exhibited significantly enhanced selective cytotoxicity towards LUSC cells compared to free NC (selectivity index improved from 0.54 to 2.58). Mechanistic studies revealed that NC stimulated mitochondrial ROS production, synergizing with Fe-MOF-derived iron to amplify oxidative stress. In vivo, HD@NC@MOF achieved a 69.02% tumor inhibition rate (1.72-fold higher than free NC) with minimal systemic toxicity. This work highlighted the potential of HD@NC@MOF as an efficient and targeted carrier for NC in LUSC chemotherapy.
2026, 37(6): 111979
doi: 10.1016/j.cclet.2025.111979
Abstract:
The strategic engineering of heterointerface architecture is demonstrating its critical pathway for optimizing charge dynamics in metal-organic framework (MOF)-based photo-Fenton systems. This work presents a novel ZIF-8@NH2−MIL-101(Fe) heterostructure with precisely controlled MOF-on-MOF configuration, which exhibits exceptional catalytic performance in the degradation of antibiotics. Experimental results revealed desired catalytic capacity with 91.4% tetracycline hydrochloride (TCH) degradation within a short time and satisfactory stability across pH 3.0–9.0 under visible light irradiation (λ ≥ 420 nm). Ecotoxicological assessment exhibits that the ecological risks of degradation intermediates diminish significantly when compared with those of the parent TCH. Comprehensive mechanistic investigation indicates that TCH decomposition is governed by superoxide radical (•O2−) and hydroxyl radical (•OH) as the primary reactive species. The proposed S-scheme charge transfer mechanism is verified by Mott–Schottky analysis and in X-ray photoelectron spectroscopy. Meanwhile, the enhanced interfacial charge separation efficiency is confirmed by electrochemical impedance spectroscopy. This work not only advances the development of Fe-based MOF heterojunctions for photo-Fenton catalysis but also provides critical insights into the relationship between heterostructure engineering and catalytic efficiency.
The strategic engineering of heterointerface architecture is demonstrating its critical pathway for optimizing charge dynamics in metal-organic framework (MOF)-based photo-Fenton systems. This work presents a novel ZIF-8@NH2−MIL-101(Fe) heterostructure with precisely controlled MOF-on-MOF configuration, which exhibits exceptional catalytic performance in the degradation of antibiotics. Experimental results revealed desired catalytic capacity with 91.4% tetracycline hydrochloride (TCH) degradation within a short time and satisfactory stability across pH 3.0–9.0 under visible light irradiation (λ ≥ 420 nm). Ecotoxicological assessment exhibits that the ecological risks of degradation intermediates diminish significantly when compared with those of the parent TCH. Comprehensive mechanistic investigation indicates that TCH decomposition is governed by superoxide radical (•O2−) and hydroxyl radical (•OH) as the primary reactive species. The proposed S-scheme charge transfer mechanism is verified by Mott–Schottky analysis and in X-ray photoelectron spectroscopy. Meanwhile, the enhanced interfacial charge separation efficiency is confirmed by electrochemical impedance spectroscopy. This work not only advances the development of Fe-based MOF heterojunctions for photo-Fenton catalysis but also provides critical insights into the relationship between heterostructure engineering and catalytic efficiency.
2026, 37(6): 111980
doi: 10.1016/j.cclet.2025.111980
Abstract:
The efficient removal and conversion of nitrate (NO3-) from wastewater is an urgent environmental issue. The catalytic nitrate reduction reaction (NO3RR) process, which involves transferring eight electrons and nine protons, poses significant challenges in improving hydrogen atom transfer (HAT). In this study, we synthesized Bi4O5X2 (BOX, X = Cl, Br, I) nanosheets to enhance HAT efficiency by managing halogen vacancies and optimizing oxidation half-reactions. This approach significantly increased ammonia selectivity. We found that larger halogen radii and higher vacancy concentrations improve water dissociation, boosting HAT efficiency. Additionally, replacing the challenging water oxidation half-reaction with ethylene glycol (EG) oxidation aligned with NO3- reduction further improved HAT efficiency, achieving an NH4+ selectivity of 97.2%. Rapid-scan in situ Fourier transform infrared (FT-IR) spectroscopy showed that iodine-rich vacancy surfaces accelerated the conversion of EG hydroxyl groups into carbonyls, releasing active hydrogen atoms and suppressing NO2- formation. This process efficiently converted nitrate to ammonia, presenting a promising method for photocatalytic NO3RR pollutant resourcing. These findings offer valuable strategies for enhancing the production of reactive hydrogen atoms and effectively managing nitrate-nitrogen pollution.
The efficient removal and conversion of nitrate (NO3-) from wastewater is an urgent environmental issue. The catalytic nitrate reduction reaction (NO3RR) process, which involves transferring eight electrons and nine protons, poses significant challenges in improving hydrogen atom transfer (HAT). In this study, we synthesized Bi4O5X2 (BOX, X = Cl, Br, I) nanosheets to enhance HAT efficiency by managing halogen vacancies and optimizing oxidation half-reactions. This approach significantly increased ammonia selectivity. We found that larger halogen radii and higher vacancy concentrations improve water dissociation, boosting HAT efficiency. Additionally, replacing the challenging water oxidation half-reaction with ethylene glycol (EG) oxidation aligned with NO3- reduction further improved HAT efficiency, achieving an NH4+ selectivity of 97.2%. Rapid-scan in situ Fourier transform infrared (FT-IR) spectroscopy showed that iodine-rich vacancy surfaces accelerated the conversion of EG hydroxyl groups into carbonyls, releasing active hydrogen atoms and suppressing NO2- formation. This process efficiently converted nitrate to ammonia, presenting a promising method for photocatalytic NO3RR pollutant resourcing. These findings offer valuable strategies for enhancing the production of reactive hydrogen atoms and effectively managing nitrate-nitrogen pollution.
2026, 37(6): 111982
doi: 10.1016/j.cclet.2025.111982
Abstract:
Despite the compelling potential of metal-organic framework (MOF) membranes for water remediation, their poor membrane-forming crystallinity, limited solution-processability, and propensity to aggregate have impeded industrial deployment. Through interfacial cooperative assembly, we construct a well-dispersed 2D/3D nanofluidic composite membrane by coupling novel three-dimensional CoBDC-NH2 nanocrystals (one-dimensional channels, 7 Å × 8.6 Å) with two-dimensional graphene oxide (GO). The synergistic interfacial interactions between flexible GO and rigid MOF components create a highly uniform architecture while furnishing rapid electron-transfer pathways and strong electrostatic repulsion; the rigid CoBD-CNH2 imparts angstrom-scale molecular sieving, ultrafast water-transport channels, and catalytically active Co sites. This interfacial synergy delivers an exceptional pure-water flux of 737.5 L m−2 h−1 bar−1 together with 99.8% rejection of bulky anionic dyes, decisively breaking the canonical flux-selectivity trade-off. XDLVO theory analysis confirms pronounced antifouling propensity, and density-functional-theory (DFT) calculations show that interfacial cooperative effects between GO and MOF lower the activation barrier for peroxymonosulfate (PMS) activation, enabling a self-cleaning cycle that restores 90.3% of the initial flux after fouling. By integrating molecular-precision sieving, charge-regulated transport, and in-situ catalytic regeneration within a scalable platform via interfacial cooperative assembly, this work offers a versatile blueprint for next-generation high-performance MOF membranes and signals broad opportunities in sustainable wastewater treatment and beyond.
Despite the compelling potential of metal-organic framework (MOF) membranes for water remediation, their poor membrane-forming crystallinity, limited solution-processability, and propensity to aggregate have impeded industrial deployment. Through interfacial cooperative assembly, we construct a well-dispersed 2D/3D nanofluidic composite membrane by coupling novel three-dimensional CoBDC-NH2 nanocrystals (one-dimensional channels, 7 Å × 8.6 Å) with two-dimensional graphene oxide (GO). The synergistic interfacial interactions between flexible GO and rigid MOF components create a highly uniform architecture while furnishing rapid electron-transfer pathways and strong electrostatic repulsion; the rigid CoBD-CNH2 imparts angstrom-scale molecular sieving, ultrafast water-transport channels, and catalytically active Co sites. This interfacial synergy delivers an exceptional pure-water flux of 737.5 L m−2 h−1 bar−1 together with 99.8% rejection of bulky anionic dyes, decisively breaking the canonical flux-selectivity trade-off. XDLVO theory analysis confirms pronounced antifouling propensity, and density-functional-theory (DFT) calculations show that interfacial cooperative effects between GO and MOF lower the activation barrier for peroxymonosulfate (PMS) activation, enabling a self-cleaning cycle that restores 90.3% of the initial flux after fouling. By integrating molecular-precision sieving, charge-regulated transport, and in-situ catalytic regeneration within a scalable platform via interfacial cooperative assembly, this work offers a versatile blueprint for next-generation high-performance MOF membranes and signals broad opportunities in sustainable wastewater treatment and beyond.
2026, 37(6): 111984
doi: 10.1016/j.cclet.2025.111984
Abstract:
Ultraviolet (UV) disinfection has some disadvantages such as unstable disinfection effect and bacterial revival. The UV/ozone (O3) co-disinfection process can be capable of solving the above-mentioned problems, but the current technology has the disadvantages of high costs and high operational risk. In this study, a new type of simultaneous O3-producing microwave electrodeless UV lamp (O3−MWUVL) was developed. The device can emit 254 nm and 185 nm UV, which can produce O3 while disinfecting. The O3−MWUVL exhibited significant disinfecting effects against Escherichia coli (E. coli) and Bacillus subtilis (B. subtilis). The disinfection effect of MWUV/O3 was better than that of MWUV or O3. The inactivation rate of E. coli disinfected by MWUV/O3 can reach 3.44 log when the UV dose was 16 mJ/cm2, and the inactivation rate of B. subtilis disinfected by MWUV/O3 can reach 4.64 log when the UV dose was 30 mJ/cm2. At the same time, the MWUV/O3 treatment can effectively inhibit the photoreactivation of E. coli. The maximum photoreactivation rate of E. coli treated by MWUV/O3 was only 0.11%. Additionally, the disinfection efficacy of the O3−MWUVL on actual wastewater was investigated, revealing that O3 pretreatment enhanced the UV inactivation capacity significantly. Furthermore, it was found that sequential disinfection using O3−MWUV or MWUV/O3 synergistic approach yielded superior results compared to MWUV-O3 sequential disinfection. Finally, investigation into the disinfection mechanism in the MWUV/O3 disinfection process substantiated the generation of hydroxyl radicals (•OH) within the system, while observations from scanning electron microscopy and laser confocal scanning microscopy also demonstrated that O3 plays an important role in dismantling cellular structures.
Ultraviolet (UV) disinfection has some disadvantages such as unstable disinfection effect and bacterial revival. The UV/ozone (O3) co-disinfection process can be capable of solving the above-mentioned problems, but the current technology has the disadvantages of high costs and high operational risk. In this study, a new type of simultaneous O3-producing microwave electrodeless UV lamp (O3−MWUVL) was developed. The device can emit 254 nm and 185 nm UV, which can produce O3 while disinfecting. The O3−MWUVL exhibited significant disinfecting effects against Escherichia coli (E. coli) and Bacillus subtilis (B. subtilis). The disinfection effect of MWUV/O3 was better than that of MWUV or O3. The inactivation rate of E. coli disinfected by MWUV/O3 can reach 3.44 log when the UV dose was 16 mJ/cm2, and the inactivation rate of B. subtilis disinfected by MWUV/O3 can reach 4.64 log when the UV dose was 30 mJ/cm2. At the same time, the MWUV/O3 treatment can effectively inhibit the photoreactivation of E. coli. The maximum photoreactivation rate of E. coli treated by MWUV/O3 was only 0.11%. Additionally, the disinfection efficacy of the O3−MWUVL on actual wastewater was investigated, revealing that O3 pretreatment enhanced the UV inactivation capacity significantly. Furthermore, it was found that sequential disinfection using O3−MWUV or MWUV/O3 synergistic approach yielded superior results compared to MWUV-O3 sequential disinfection. Finally, investigation into the disinfection mechanism in the MWUV/O3 disinfection process substantiated the generation of hydroxyl radicals (•OH) within the system, while observations from scanning electron microscopy and laser confocal scanning microscopy also demonstrated that O3 plays an important role in dismantling cellular structures.
2026, 37(6): 111986
doi: 10.1016/j.cclet.2025.111986
Abstract:
Herein, we propose a synergistic regulation strategy that combines steric hindrance with the multiple resonance (MR) effect to design and synthesize a thermally activated delayed fluorescent (TADF) emitter, SF-PhDABNA. This is achieved by incorporating spirofluorene units and introducing meta-position phenyl linkages into the DABNA-1 core. As a result, SF-PhDABNA exhibits narrowband pure blue emission centered at 472 nm with a full width at half maximum (FWHM) of 23 nm. The unique steric hindrance structure of the material effectively suppresses π-π interaction, while maintaining a tightly ordered molecular arrangement through C–H···π and C–H···B weak intermolecular interactions. This special packing pattern ensures a high photoluminescence quantum yield (PLQY) of 86% in the doped film. Moreover, the significant directionality of the transition dipole moment (TDM) further enhances the light output coupling efficiency, thereby significantly improving the electroluminescence (EL) performance. The corresponding TADF-sensitized (TSF) OLED based on SF-PhDABNA achieves a maximum external quantum efficiency (EQEmax) of 23.9% with CIE coordinates of (0.121, 0.284).
Herein, we propose a synergistic regulation strategy that combines steric hindrance with the multiple resonance (MR) effect to design and synthesize a thermally activated delayed fluorescent (TADF) emitter, SF-PhDABNA. This is achieved by incorporating spirofluorene units and introducing meta-position phenyl linkages into the DABNA-1 core. As a result, SF-PhDABNA exhibits narrowband pure blue emission centered at 472 nm with a full width at half maximum (FWHM) of 23 nm. The unique steric hindrance structure of the material effectively suppresses π-π interaction, while maintaining a tightly ordered molecular arrangement through C–H···π and C–H···B weak intermolecular interactions. This special packing pattern ensures a high photoluminescence quantum yield (PLQY) of 86% in the doped film. Moreover, the significant directionality of the transition dipole moment (TDM) further enhances the light output coupling efficiency, thereby significantly improving the electroluminescence (EL) performance. The corresponding TADF-sensitized (TSF) OLED based on SF-PhDABNA achieves a maximum external quantum efficiency (EQEmax) of 23.9% with CIE coordinates of (0.121, 0.284).
2026, 37(6): 111987
doi: 10.1016/j.cclet.2025.111987
Abstract:
Azulene derivatives are promising for optoelectronics but suffer from weak fluorescence due to anti-Kasha behavior. This study designed and synthesized four asymmetric 1-azaazulene-based BF2 complexes (Ph-NN, Ph-ON, Ca-NN, Py-NN) to explore their optoelectronic potential. Unlike azulene derivatives, which predominantly exhibit S2→S0 emission, 1-azaazulene constructs demonstrate effective S1-S0 transitions, resulting in enhanced fluorescence. Py-NN, incorporating a pyrrole group, achieved a remarkable photoluminescence quantum yield (PLQY) of 19.3% at 560 nm, attributed to enhanced HOMO-LUMO orbital overlap with an oscillator strength (f) of 0.4973, resulting in a high radiative rate (kr = 9.51 × 107 s−1) and suppressed non-radiative decay (knr = 0.40 × 109 s−1). OLEDs employing Py-NN as an emitter exhibited orange electroluminescence at 565 nm with a maximum external quantum efficiency (EQE) of 3.0%. The results demonstrate that 1-azaazulene can serve as a versatile platform for developing efficient fluorescent materials with applications in optoelectronics.
Azulene derivatives are promising for optoelectronics but suffer from weak fluorescence due to anti-Kasha behavior. This study designed and synthesized four asymmetric 1-azaazulene-based BF2 complexes (Ph-NN, Ph-ON, Ca-NN, Py-NN) to explore their optoelectronic potential. Unlike azulene derivatives, which predominantly exhibit S2→S0 emission, 1-azaazulene constructs demonstrate effective S1-S0 transitions, resulting in enhanced fluorescence. Py-NN, incorporating a pyrrole group, achieved a remarkable photoluminescence quantum yield (PLQY) of 19.3% at 560 nm, attributed to enhanced HOMO-LUMO orbital overlap with an oscillator strength (f) of 0.4973, resulting in a high radiative rate (kr = 9.51 × 107 s−1) and suppressed non-radiative decay (knr = 0.40 × 109 s−1). OLEDs employing Py-NN as an emitter exhibited orange electroluminescence at 565 nm with a maximum external quantum efficiency (EQE) of 3.0%. The results demonstrate that 1-azaazulene can serve as a versatile platform for developing efficient fluorescent materials with applications in optoelectronics.
2026, 37(6): 111988
doi: 10.1016/j.cclet.2025.111988
Abstract:
Utilizing sunlight to directly convert CO2 into value-added chemicals presents a pivotal strategy for sustainable CO2 conversion and mitigating environmental challenges. Herein, a surface-mounted 5,10,15,20-tetra(4-carboxyphenyl)porphyrin copper(Ⅱ) (CuTCPP) anchoring on Bi12O17Br2 nanotubes (CuTCPP/Bi12O17Br2) heterojunction was employed as an operable platform for photocatalytic CO2 reduction. The built-in electric field at the interface facilitates the efficient electron transfer from Bi12O17Br2 to CuTCPP, significantly enhancing photoexcited charge separation and transfer kinetics. Besides, the Cu(Ⅱ) sites in CuTCPP act as supplementary catalytic centers that reduce the adsorption and activation energy barrier of CO2, thus accelerating the formation of *CO intermediates. The CuTCPP/Bi12O17Br2 heterojunction exhibits enhanced photoreduction activity of CO2, achieving a CO evolution rate of 92.2 μmol g-1 h-1, which represents a 4.0-fold enhancement over Bi12O17Br2. This work offers new insights into the development of heterojunctions with synergistically optimized charge transfer and active sites.
Utilizing sunlight to directly convert CO2 into value-added chemicals presents a pivotal strategy for sustainable CO2 conversion and mitigating environmental challenges. Herein, a surface-mounted 5,10,15,20-tetra(4-carboxyphenyl)porphyrin copper(Ⅱ) (CuTCPP) anchoring on Bi12O17Br2 nanotubes (CuTCPP/Bi12O17Br2) heterojunction was employed as an operable platform for photocatalytic CO2 reduction. The built-in electric field at the interface facilitates the efficient electron transfer from Bi12O17Br2 to CuTCPP, significantly enhancing photoexcited charge separation and transfer kinetics. Besides, the Cu(Ⅱ) sites in CuTCPP act as supplementary catalytic centers that reduce the adsorption and activation energy barrier of CO2, thus accelerating the formation of *CO intermediates. The CuTCPP/Bi12O17Br2 heterojunction exhibits enhanced photoreduction activity of CO2, achieving a CO evolution rate of 92.2 μmol g-1 h-1, which represents a 4.0-fold enhancement over Bi12O17Br2. This work offers new insights into the development of heterojunctions with synergistically optimized charge transfer and active sites.
2026, 37(6): 111991
doi: 10.1016/j.cclet.2025.111991
Abstract:
Water-based lubrication systems incorporating nanoparticles as highly promising additives are of great importance for enabling sustainable and environmentally benign tribological solutions. However, persistent limitations encompass pronounced substrate dependence, inadequate dynamic responsiveness under operating conditions, and intrinsically constrained lubrication performance, collectively impeding their transition from laboratory potential to robust industrial deployment. To tackle these challenges, we have developed a substrate-adaptable and dual-responsive lysine-based surfactant (LBS) as a cutting-edge water-based lubrication additive. LBS achieves substrate-independent adsorption through multiple interactions between its head group and substrates of varying properties. LBS maintains consistent lubrication performance with minimal COF variation across substrates with divergent surface charges, confirming its adaptability to diverse tribological substrates. Notably, the engineered surfactant demonstrates outstanding lubricating properties, achieving a coefficient of friction (COF) of ~0.06 under extreme pressure condition (~500 MPa), a 95% reduction in COF compared to pure water and maintaining stable lubrication over 25,000 cycles without significant wear or interfacial degradation. Additionally, by leveraging the pH sensitivity of the molecular structure and the temperature responsiveness of the micellar assembly, the COF can be rapidly modulated over a 10-fold range in response by changes pH and temperature. By synergistically integrating universal substrate adaptability with stimuli-responsive behavior, this work not only ensures stable lubrication in complex substrates, but also opens new avenues for the intelligent design of surfactants, offering significant potential for large-scale applications in intelligent lubrication.
Water-based lubrication systems incorporating nanoparticles as highly promising additives are of great importance for enabling sustainable and environmentally benign tribological solutions. However, persistent limitations encompass pronounced substrate dependence, inadequate dynamic responsiveness under operating conditions, and intrinsically constrained lubrication performance, collectively impeding their transition from laboratory potential to robust industrial deployment. To tackle these challenges, we have developed a substrate-adaptable and dual-responsive lysine-based surfactant (LBS) as a cutting-edge water-based lubrication additive. LBS achieves substrate-independent adsorption through multiple interactions between its head group and substrates of varying properties. LBS maintains consistent lubrication performance with minimal COF variation across substrates with divergent surface charges, confirming its adaptability to diverse tribological substrates. Notably, the engineered surfactant demonstrates outstanding lubricating properties, achieving a coefficient of friction (COF) of ~0.06 under extreme pressure condition (~500 MPa), a 95% reduction in COF compared to pure water and maintaining stable lubrication over 25,000 cycles without significant wear or interfacial degradation. Additionally, by leveraging the pH sensitivity of the molecular structure and the temperature responsiveness of the micellar assembly, the COF can be rapidly modulated over a 10-fold range in response by changes pH and temperature. By synergistically integrating universal substrate adaptability with stimuli-responsive behavior, this work not only ensures stable lubrication in complex substrates, but also opens new avenues for the intelligent design of surfactants, offering significant potential for large-scale applications in intelligent lubrication.
2026, 37(6): 112004
doi: 10.1016/j.cclet.2025.112004
Abstract:
The surface activity and continuous photosynthesis with easy product separation are two main concerns for practical H2O2 photogeneration which calls for integration of efficient photocatalyst with specifically designed reactor. Taking advantage of the intrinsic superior charge separation and electron transfer of the one-dimensional CN, herein, N-vacancy abundant carbon nitride nanorod arrays (CNNRs) were demonstrated as an efficient photocatalyst either in convention photocatalysis or in emerging flow photocatalytic H2O2 production. The N-vacancies multifunctionally enhance light harvesting, elevate conduction band, adsorb and activate O2 molecules. As a result, the N-defective CNNRs delivered 5.2 and 2.1 times higher H2O2 yield in its powder form than common CN nanosheets and defect-free CNNRs, reaching 18.8 mmol g-1 h-1 with AQY of 13.4% at 400 nm in ethanol-containing solution. Moreover, the CNNRs on glass, as a photocatalyst panel, exhibits remarkable fixed-bed and continuous flow photocatalytic H2O2 production performances, with yield up to 23.6 and 14.2 mmol m-2 h-1, respectively. Mechanism investigation discloses the sequential two-step 1e oxygen reduction pathway that accounts for H2O2 photogeneration, with further thermal-dynamical confirmation by DFT calculation. This work introduces a new paradigm by combining photocatalyst design with advanced flow reactors to achieve continuous photosynthesis of H2O2, which may inspire many other photo-to-chemical conversions as well.
The surface activity and continuous photosynthesis with easy product separation are two main concerns for practical H2O2 photogeneration which calls for integration of efficient photocatalyst with specifically designed reactor. Taking advantage of the intrinsic superior charge separation and electron transfer of the one-dimensional CN, herein, N-vacancy abundant carbon nitride nanorod arrays (CNNRs) were demonstrated as an efficient photocatalyst either in convention photocatalysis or in emerging flow photocatalytic H2O2 production. The N-vacancies multifunctionally enhance light harvesting, elevate conduction band, adsorb and activate O2 molecules. As a result, the N-defective CNNRs delivered 5.2 and 2.1 times higher H2O2 yield in its powder form than common CN nanosheets and defect-free CNNRs, reaching 18.8 mmol g-1 h-1 with AQY of 13.4% at 400 nm in ethanol-containing solution. Moreover, the CNNRs on glass, as a photocatalyst panel, exhibits remarkable fixed-bed and continuous flow photocatalytic H2O2 production performances, with yield up to 23.6 and 14.2 mmol m-2 h-1, respectively. Mechanism investigation discloses the sequential two-step 1e oxygen reduction pathway that accounts for H2O2 photogeneration, with further thermal-dynamical confirmation by DFT calculation. This work introduces a new paradigm by combining photocatalyst design with advanced flow reactors to achieve continuous photosynthesis of H2O2, which may inspire many other photo-to-chemical conversions as well.
2026, 37(6): 112025
doi: 10.1016/j.cclet.2025.112025
Abstract:
Two-dimensional (2D) materials exhibit great potential for osmotic power generation due to their high membrane selectivity. However, performance enhancement remains hindered by substantial resistance arising from tortuous ion transport pathways within 2D nanofluidic membranes. MXenes, a novel class of 2D layered materials, have garnered significant attention as promising candidates for reverse electrodialysis (RED) membranes due to their laminated nanochannels and surface-charged functional groups. Although MXene-derived ion-exchange membranes display exceptional ionic discrimination capabilities and enhanced charge transport properties, their implementation in practical systems is limited by structural fragility and compromised performance under hydrated conditions, primarily due to weak interlayer interactions, restricting their RED performance. This study demonstrates an MXene-sodium ligninsulfonate (MSL) lamellar architecture to feature record-low internal resistance, achieving breakthrough osmotic energy conversion efficiency through synergistic interfacial engineering. In addition, the well-aligned MXene framework significantly shortens ion permeation pathways, thus lowering internal resistance. As a result, the MSL membrane delivers a high power density of approximately 22.15 W/m2 when mixing artificial seawater and river water, representing a 6.78-fold improvement over pristine MXene membranes. This interfacial engineering protocol addresses the longstanding trade-off between ion selectivity and membrane durability in nanofluidic systems, paving the way for the practical implementation of MXene-based technologies in marine energy conversion.
Two-dimensional (2D) materials exhibit great potential for osmotic power generation due to their high membrane selectivity. However, performance enhancement remains hindered by substantial resistance arising from tortuous ion transport pathways within 2D nanofluidic membranes. MXenes, a novel class of 2D layered materials, have garnered significant attention as promising candidates for reverse electrodialysis (RED) membranes due to their laminated nanochannels and surface-charged functional groups. Although MXene-derived ion-exchange membranes display exceptional ionic discrimination capabilities and enhanced charge transport properties, their implementation in practical systems is limited by structural fragility and compromised performance under hydrated conditions, primarily due to weak interlayer interactions, restricting their RED performance. This study demonstrates an MXene-sodium ligninsulfonate (MSL) lamellar architecture to feature record-low internal resistance, achieving breakthrough osmotic energy conversion efficiency through synergistic interfacial engineering. In addition, the well-aligned MXene framework significantly shortens ion permeation pathways, thus lowering internal resistance. As a result, the MSL membrane delivers a high power density of approximately 22.15 W/m2 when mixing artificial seawater and river water, representing a 6.78-fold improvement over pristine MXene membranes. This interfacial engineering protocol addresses the longstanding trade-off between ion selectivity and membrane durability in nanofluidic systems, paving the way for the practical implementation of MXene-based technologies in marine energy conversion.
2026, 37(6): 112026
doi: 10.1016/j.cclet.2025.112026
Abstract:
Loading transition metal oxyhydroxides (TMOH) electrocatalyst on semiconductors (SC) improves the photoelectrochemical (PEC) water splitting performance. However, the inevitable interface charge recombination between SC and TMOH hinders the PEC efficiency. Herein, differing from the conventional charge transfer process, a novel charge modulation layer, i.e., Ce-CoOx, like a "hole transporter" has been incorporated into the SC/TMOH system. A series of electrochemical characterizations confirm that the "hole transporter" can directly and rapidly transfer holes from BiVO4 to FeNiOOH, resulting in a highly efficient charge separation. As expected, the BiVO4/Ce-CoOx/FeNiOOH photoanode presents a desirable photocurrent of 6.0 mA/cm2 and good stability. More importantly, the smart approach can also be extended to BiVO4/Ce-NiOx/FeNiOOH system, proving its universality. This work opens up a new avenue for designing efficient photoanode for PEC water splitting.
Loading transition metal oxyhydroxides (TMOH) electrocatalyst on semiconductors (SC) improves the photoelectrochemical (PEC) water splitting performance. However, the inevitable interface charge recombination between SC and TMOH hinders the PEC efficiency. Herein, differing from the conventional charge transfer process, a novel charge modulation layer, i.e., Ce-CoOx, like a "hole transporter" has been incorporated into the SC/TMOH system. A series of electrochemical characterizations confirm that the "hole transporter" can directly and rapidly transfer holes from BiVO4 to FeNiOOH, resulting in a highly efficient charge separation. As expected, the BiVO4/Ce-CoOx/FeNiOOH photoanode presents a desirable photocurrent of 6.0 mA/cm2 and good stability. More importantly, the smart approach can also be extended to BiVO4/Ce-NiOx/FeNiOOH system, proving its universality. This work opens up a new avenue for designing efficient photoanode for PEC water splitting.
2026, 37(6): 112041
doi: 10.1016/j.cclet.2025.112041
Abstract:
Biological systems exploit their sophisticated hierarchical anisotropic architectures to achieve complex shape morphing under external stimuli. However, artificial soft intelligent actuators often suffer from limited response speeds and poor programmability of deformation, primarily due to densely crosslinked network designs and insufficient anisotropic resolution. Here, we report a synergistic method combining directional freezing-induced self-assembly and dynamic metal coordination crosslinked mechanical alignment to fabricate anisotropic hydrogels with fast multiple responsiveness and programmable three-dimensional (3D) deformation. Benefiting from an interconnected lamellar network and open-oriented mass transport channels, the hydrogel exhibits rapid anisotropic stimuli-responsive deformations with a shrinkage along the lamellar direction that is 1.9 times greater than that in the perpendicular direction in 5 s of thermal stimulation, and a complete recovery within 4 s upon cooling. By developing a spatially modulated coordination photodissociation strategy, a gradient crosslinking network is further constructed within the hydrogel, enabling diverse and programmable 3D deformations in response to external stimuli, which facilitate complex actuation behaviors such as object grasping, biomimetic gestures, and light-driven lifting. Thus, the hydrogel with hierarchically anisotropic structure and porous dynamic crosslinked network is potential for intelligent soft robotics requiring flexible controllable deformation.
Biological systems exploit their sophisticated hierarchical anisotropic architectures to achieve complex shape morphing under external stimuli. However, artificial soft intelligent actuators often suffer from limited response speeds and poor programmability of deformation, primarily due to densely crosslinked network designs and insufficient anisotropic resolution. Here, we report a synergistic method combining directional freezing-induced self-assembly and dynamic metal coordination crosslinked mechanical alignment to fabricate anisotropic hydrogels with fast multiple responsiveness and programmable three-dimensional (3D) deformation. Benefiting from an interconnected lamellar network and open-oriented mass transport channels, the hydrogel exhibits rapid anisotropic stimuli-responsive deformations with a shrinkage along the lamellar direction that is 1.9 times greater than that in the perpendicular direction in 5 s of thermal stimulation, and a complete recovery within 4 s upon cooling. By developing a spatially modulated coordination photodissociation strategy, a gradient crosslinking network is further constructed within the hydrogel, enabling diverse and programmable 3D deformations in response to external stimuli, which facilitate complex actuation behaviors such as object grasping, biomimetic gestures, and light-driven lifting. Thus, the hydrogel with hierarchically anisotropic structure and porous dynamic crosslinked network is potential for intelligent soft robotics requiring flexible controllable deformation.
2026, 37(6): 112060
doi: 10.1016/j.cclet.2025.112060
Abstract:
Differentiating structural isomers in mass spectrometry (MS) poses significant challenges due to the difficulties in generating fragment ions by atmospheric pressure ionization and the spectral similarities encountered in tandem MS/MS analysis. The continuous arc plasma enables in-source dissociation fingerprinting analysis of isomers but presents a risk of solvent ignition during sample introduction because of high temperatures, posing safety concerns. To address these challenges, the tunable pulsed arc plasma (TPAP) ionization and dissociation device has been developed. The TPAP device converts continuous arc plasma into a pulsed mode, reduces plasma temperatures, enhances discharge stability and safety, and enables adjustable plasma energy for in-source compound dissociation. Programmable control over the pulsed arc plasma voltage allows the scanning of compounds under varying dissociation energies, facilitates the construction of compound-specific energy-resolved spectra. Validation experiments with disubstituted benzene species, chlorogenic acid derivatives, disaccharide and diacylglycerol have demonstrated the capability of TPAP-MS to effectively differentiate isomers through distinct energy-resolved spectra. The TPAP-MS requires minimal instrumental modifications and provides rapid and precise structural annotations directly from the ion source, offering broad potential applications in the analysis of structural isomers.
Differentiating structural isomers in mass spectrometry (MS) poses significant challenges due to the difficulties in generating fragment ions by atmospheric pressure ionization and the spectral similarities encountered in tandem MS/MS analysis. The continuous arc plasma enables in-source dissociation fingerprinting analysis of isomers but presents a risk of solvent ignition during sample introduction because of high temperatures, posing safety concerns. To address these challenges, the tunable pulsed arc plasma (TPAP) ionization and dissociation device has been developed. The TPAP device converts continuous arc plasma into a pulsed mode, reduces plasma temperatures, enhances discharge stability and safety, and enables adjustable plasma energy for in-source compound dissociation. Programmable control over the pulsed arc plasma voltage allows the scanning of compounds under varying dissociation energies, facilitates the construction of compound-specific energy-resolved spectra. Validation experiments with disubstituted benzene species, chlorogenic acid derivatives, disaccharide and diacylglycerol have demonstrated the capability of TPAP-MS to effectively differentiate isomers through distinct energy-resolved spectra. The TPAP-MS requires minimal instrumental modifications and provides rapid and precise structural annotations directly from the ion source, offering broad potential applications in the analysis of structural isomers.
2026, 37(6): 112061
doi: 10.1016/j.cclet.2025.112061
Abstract:
Ovarian cancer is among the deadliest cancers, with the highest mortality rate among gynecological cancers; thus, highly sensitive early diagnosis is of paramount importance. In this study, we developed an innovative biosensor that integrates DNA-functionalized covalent organic frameworks with CRISPR-Cas12a technology for dual-signal amplification to achieve ultra-sensitive detection of ovarian cancer biomarkers. The COFs were co-functionalized with aptamers specific to target protein biomarkers and a larger number of activators. Upon recognition and binding to target proteins, the activators anchored on the COF surface become accessible in the detection system, converting low-abundance protein signals into amplified nucleic acid signals, which represents the first stage of signal amplification. These activators subsequently trigger the trans-cleavage activity of CRISPR-Cas12a, leading to the cleavage of fluorophore–quencher reporters and resulting in further amplified fluorescence output, constituting the second stage of amplification. This dual-signal amplification strategy, integrated with a microfluidic chip, enabled the sensitive detection of CA125 and HE4, with detection limits as low as 0.001 U/mL and 0.2 pg/mL, respectively, providing a robust, accurate, and scalable platform for ovarian cancer diagnostics and demonstrating potential applications in clinical bioanalysis and diagnosis.
Ovarian cancer is among the deadliest cancers, with the highest mortality rate among gynecological cancers; thus, highly sensitive early diagnosis is of paramount importance. In this study, we developed an innovative biosensor that integrates DNA-functionalized covalent organic frameworks with CRISPR-Cas12a technology for dual-signal amplification to achieve ultra-sensitive detection of ovarian cancer biomarkers. The COFs were co-functionalized with aptamers specific to target protein biomarkers and a larger number of activators. Upon recognition and binding to target proteins, the activators anchored on the COF surface become accessible in the detection system, converting low-abundance protein signals into amplified nucleic acid signals, which represents the first stage of signal amplification. These activators subsequently trigger the trans-cleavage activity of CRISPR-Cas12a, leading to the cleavage of fluorophore–quencher reporters and resulting in further amplified fluorescence output, constituting the second stage of amplification. This dual-signal amplification strategy, integrated with a microfluidic chip, enabled the sensitive detection of CA125 and HE4, with detection limits as low as 0.001 U/mL and 0.2 pg/mL, respectively, providing a robust, accurate, and scalable platform for ovarian cancer diagnostics and demonstrating potential applications in clinical bioanalysis and diagnosis.
2026, 37(6): 112065
doi: 10.1016/j.cclet.2025.112065
Abstract:
In gas separation mixed matrix membranes (MMMs), the interlayer stacking of nanosheet fillers directly leads to tortuous transport pathways that significantly reduce both membrane permeability and selectivity. To solve this issue, this study employs cellulose (MC) to interweave MXene for preparing cellulose-MXene (MC-MX) networks, which are then mixed with Pebax MH 1657 to prepare MMMs for enhancing CO2 separation performance. The MC-MX network mimics the tollgate-highway system within the MMMs. In this system, MX acts as a selective tollgate that preferentially recognizes CO2 through hydrogen bond interactions while improving CO2/CH4 selectivity in MMMs. Meanwhile, the hydroxyl–rich surfaces of MC provide low-resistance transport highway for accelerated CO2 transport within the MMMs. Compared to the pure Pebax membrane, the CO2 permeability of the Pebax/MC-MX-1wt% MMM increases to 580.46 Barrer (97%), and the CO2/CH4 selectivity increased to 41.48 (70%). Furthermore, the separation performance of the Pebax/MC-MX-1wt% MMM approaches the 2019 upper bound. The research results indicate that the tollgate-highway strategy effectively improves CO2/CH4 separation performance in MMMs, offering practical implications for the rational design of high-performance membranes.
In gas separation mixed matrix membranes (MMMs), the interlayer stacking of nanosheet fillers directly leads to tortuous transport pathways that significantly reduce both membrane permeability and selectivity. To solve this issue, this study employs cellulose (MC) to interweave MXene for preparing cellulose-MXene (MC-MX) networks, which are then mixed with Pebax MH 1657 to prepare MMMs for enhancing CO2 separation performance. The MC-MX network mimics the tollgate-highway system within the MMMs. In this system, MX acts as a selective tollgate that preferentially recognizes CO2 through hydrogen bond interactions while improving CO2/CH4 selectivity in MMMs. Meanwhile, the hydroxyl–rich surfaces of MC provide low-resistance transport highway for accelerated CO2 transport within the MMMs. Compared to the pure Pebax membrane, the CO2 permeability of the Pebax/MC-MX-1wt% MMM increases to 580.46 Barrer (97%), and the CO2/CH4 selectivity increased to 41.48 (70%). Furthermore, the separation performance of the Pebax/MC-MX-1wt% MMM approaches the 2019 upper bound. The research results indicate that the tollgate-highway strategy effectively improves CO2/CH4 separation performance in MMMs, offering practical implications for the rational design of high-performance membranes.
2026, 37(6): 112066
doi: 10.1016/j.cclet.2025.112066
Abstract:
The simultaneous removal of antibiotics and heavy metals from wastewater remains a complex and challenging task. A stable α-Fe2O3/Cd0.9Zn0.1S catalyst with rod structure is constructed for simultaneous oxidation of ciprofloxacin and reduction of Cr(Ⅵ) via the in situ growth of α-Fe2O3 nanodots on Cd0.9Zn0.1S nanorod using lattice matching. The unique in situ growth pattern not only strengthens light absorption but also improves electron transfer capacity. The formed iron-sulfur (Fe-S) bonds improved the poor contact at the heterojunction interface, effectively promoted charge separation, and successfully suppressed photocorrosion. Consequently, the S-scheme heterojunction with the synergistic effect of rod structure and chemical bonds significantly enhances photocatalytic performance. Under the coexisting pollutant system, photocatalytic reaction rate constants of α-Fe2O3/Cd0.9Zn0.1S under optimal composite ratio conditions were 1.5-times (ciprofloxacin) and 5.1-times (Cr(Ⅵ)) higher than Cd0.9Zn0.1S. Benefiting from the dual action of active free radicals and the internal electric field stimulating electron transfer and utilization, the photocatalytic membrane technology has demonstrated the possibility of practical wastewater in a photocatalytic system.
The simultaneous removal of antibiotics and heavy metals from wastewater remains a complex and challenging task. A stable α-Fe2O3/Cd0.9Zn0.1S catalyst with rod structure is constructed for simultaneous oxidation of ciprofloxacin and reduction of Cr(Ⅵ) via the in situ growth of α-Fe2O3 nanodots on Cd0.9Zn0.1S nanorod using lattice matching. The unique in situ growth pattern not only strengthens light absorption but also improves electron transfer capacity. The formed iron-sulfur (Fe-S) bonds improved the poor contact at the heterojunction interface, effectively promoted charge separation, and successfully suppressed photocorrosion. Consequently, the S-scheme heterojunction with the synergistic effect of rod structure and chemical bonds significantly enhances photocatalytic performance. Under the coexisting pollutant system, photocatalytic reaction rate constants of α-Fe2O3/Cd0.9Zn0.1S under optimal composite ratio conditions were 1.5-times (ciprofloxacin) and 5.1-times (Cr(Ⅵ)) higher than Cd0.9Zn0.1S. Benefiting from the dual action of active free radicals and the internal electric field stimulating electron transfer and utilization, the photocatalytic membrane technology has demonstrated the possibility of practical wastewater in a photocatalytic system.
2026, 37(6): 112067
doi: 10.1016/j.cclet.2025.112067
Abstract:
Herein, a novel type of flexible network hydrogel was formed by cross-linking of chitosan (CS) and acrylamide (AM) monomer through non-covalent bond, and was named CS/PAM/hydrogel (CPH). Subsequent functional modification of the CPH was then undertaken through the implementation of in-situ green growth technology, and the cobalt organic framework (ZIF-67) was successfully grown on the hydrogel. Ultimately, the composite hydrogel CS/PAM/ZIF-67/hydrogel (CPZH) was prepared. Subsequently, an electrochemical sensor was developed by combining a composite hydrogel with a glassy carbon electrode, and it was demonstrated that this combination exhibited excellent performance, especially in the electrochemical detection of the target molecule 2,4.6-trichlorophenol. Excellent linear ranges (0.01–10 and 10–1000 μmol/L) and low detection limit (0.003 μmol/L) were achieved. The excellent electrochemical performance can be attributed to (ⅰ) 3D network structure of the hydrogel provides an effective mass transfer channel for the electrochemical reactants; (ⅱ) The MOF layer provides a wealth of catalytic active sites, resulting in electrochemical signal amplification of the CPZH composite, (ⅲ) The growth of ZIF-67 in the original location of the hydrogel network successfully solved the problem that traditional ZIF-67 particles are prone to agglomeration and exhibit weak bonding force with the substrate, which significantly improved the stability and electrochemical performance.
Herein, a novel type of flexible network hydrogel was formed by cross-linking of chitosan (CS) and acrylamide (AM) monomer through non-covalent bond, and was named CS/PAM/hydrogel (CPH). Subsequent functional modification of the CPH was then undertaken through the implementation of in-situ green growth technology, and the cobalt organic framework (ZIF-67) was successfully grown on the hydrogel. Ultimately, the composite hydrogel CS/PAM/ZIF-67/hydrogel (CPZH) was prepared. Subsequently, an electrochemical sensor was developed by combining a composite hydrogel with a glassy carbon electrode, and it was demonstrated that this combination exhibited excellent performance, especially in the electrochemical detection of the target molecule 2,4.6-trichlorophenol. Excellent linear ranges (0.01–10 and 10–1000 μmol/L) and low detection limit (0.003 μmol/L) were achieved. The excellent electrochemical performance can be attributed to (ⅰ) 3D network structure of the hydrogel provides an effective mass transfer channel for the electrochemical reactants; (ⅱ) The MOF layer provides a wealth of catalytic active sites, resulting in electrochemical signal amplification of the CPZH composite, (ⅲ) The growth of ZIF-67 in the original location of the hydrogel network successfully solved the problem that traditional ZIF-67 particles are prone to agglomeration and exhibit weak bonding force with the substrate, which significantly improved the stability and electrochemical performance.
2026, 37(6): 112068
doi: 10.1016/j.cclet.2025.112068
Abstract:
Recently, iron-based heterogenous catalysts have attracted widespread attention in the activation of peracetic acid (PAA) for generating reactive oxygen species (ROS) to degrade pollutants. However, in heterogeneous PAA activation systems, the role of coexisting H2O2 in PAA is often overlooked. To clarify the dynamic roles of both PAA and H2O2, herein, iron boride (FeB) was employed as a heterogeneous activator of PAA for carbamazepine (CBZ) degradation. The generation of high valent iron (Fe(Ⅳ)), hydroxyl radicals (•OH) and organic radicals (RO•) in the FeB/PAA system were identified through quenching experiments, electron paramagnetic resonance (EPR) spectroscopy, and semi-quantitative analysis. At the initial stage of the reaction, the active sites of FeB preferentially reacted with PAA, rather than H2O2, primarily generating Fe(Ⅳ) to oxidize CBZ. Subsequently, PAA was gradually depleted, dissolved Fe(Ⅱ) slowly released from FeB reacts with H2O2 in the solution to generate •OH. Besides, density functional theory (DFT) calculations and masking experiments revealed that the surface Fe(Ⅱ) (≡Fe(Ⅱ)) acts as the dominant active center for PAA activation. Moreover, the selective oxidation of various pollutants by these ROS is governed by the differing sensitivities of the contaminants to ROS. The electron-donating B–B bonds in FeB can effectively promote the Fe(Ⅲ)/Fe(Ⅱ) redox cycling, exhibiting exceptional catalytic performance. Additionally, the possible degradation pathways of CBZ were proposed by combining ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS/MS) and DFT calculations. This work provides new insights into the activation mechanism of PAA by FeB, offering a sustainable and efficient approach for the treatment of emerging pollutants.
Recently, iron-based heterogenous catalysts have attracted widespread attention in the activation of peracetic acid (PAA) for generating reactive oxygen species (ROS) to degrade pollutants. However, in heterogeneous PAA activation systems, the role of coexisting H2O2 in PAA is often overlooked. To clarify the dynamic roles of both PAA and H2O2, herein, iron boride (FeB) was employed as a heterogeneous activator of PAA for carbamazepine (CBZ) degradation. The generation of high valent iron (Fe(Ⅳ)), hydroxyl radicals (•OH) and organic radicals (RO•) in the FeB/PAA system were identified through quenching experiments, electron paramagnetic resonance (EPR) spectroscopy, and semi-quantitative analysis. At the initial stage of the reaction, the active sites of FeB preferentially reacted with PAA, rather than H2O2, primarily generating Fe(Ⅳ) to oxidize CBZ. Subsequently, PAA was gradually depleted, dissolved Fe(Ⅱ) slowly released from FeB reacts with H2O2 in the solution to generate •OH. Besides, density functional theory (DFT) calculations and masking experiments revealed that the surface Fe(Ⅱ) (≡Fe(Ⅱ)) acts as the dominant active center for PAA activation. Moreover, the selective oxidation of various pollutants by these ROS is governed by the differing sensitivities of the contaminants to ROS. The electron-donating B–B bonds in FeB can effectively promote the Fe(Ⅲ)/Fe(Ⅱ) redox cycling, exhibiting exceptional catalytic performance. Additionally, the possible degradation pathways of CBZ were proposed by combining ultra-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS/MS) and DFT calculations. This work provides new insights into the activation mechanism of PAA by FeB, offering a sustainable and efficient approach for the treatment of emerging pollutants.
2026, 37(6): 112109
doi: 10.1016/j.cclet.2025.112109
Abstract:
Precise assessment of tacrolimus (TAC) concentrations is critical in clinical diagnostics, and liquid chromatography–mass spectrometry (LC-MS/MS) is the preferred approach due to its high specificity and sensitivity. However, classic LC-MS/MS systems are frequently enormous, costly, and need expert operation, which restricts its applicability in numerous industries. In this paper, a liquid chromatography–miniature mass spectrometry (LC-MiniMS) system was designed and developed. The miniature linear ion trap spectrometer had a footprint of 59 × 38 × 27 cm3, which substantially reduced the instrument size and cost while maintaining quantitative performance. The LC-MiniMS system's circuit boards were integrated and the software automation was optimized, so it was more convenient to use and maintain. Results demonstrated excellent linearity over the range of 0.5–50 ng/mL with R2 > 0.99. The limit of detection and limit of quantification were 0.1 and 0.3 ng/mL, respectively. The accuracy ranged from 99.67% to 106.10%, intraday precision was between 0.70% and 2.61%, and interday precision was between 0.90% and 2.90%, all within acceptable limits, and matrix effects were negligible. The method was successfully applied to quantify TAC in 32 clinical whole-blood samples, and the results strongly agreed with those from a conventional LC-MS/MS system (QTRAP 6500+). The LC-MiniMS system can efficiently quantify TAC in whole blood and provide a tiny, cost-effective, and uncomplicated option for therapeutic drug monitoring in clinical settings, especially in decentralized or resource-limited scenarios.
Precise assessment of tacrolimus (TAC) concentrations is critical in clinical diagnostics, and liquid chromatography–mass spectrometry (LC-MS/MS) is the preferred approach due to its high specificity and sensitivity. However, classic LC-MS/MS systems are frequently enormous, costly, and need expert operation, which restricts its applicability in numerous industries. In this paper, a liquid chromatography–miniature mass spectrometry (LC-MiniMS) system was designed and developed. The miniature linear ion trap spectrometer had a footprint of 59 × 38 × 27 cm3, which substantially reduced the instrument size and cost while maintaining quantitative performance. The LC-MiniMS system's circuit boards were integrated and the software automation was optimized, so it was more convenient to use and maintain. Results demonstrated excellent linearity over the range of 0.5–50 ng/mL with R2 > 0.99. The limit of detection and limit of quantification were 0.1 and 0.3 ng/mL, respectively. The accuracy ranged from 99.67% to 106.10%, intraday precision was between 0.70% and 2.61%, and interday precision was between 0.90% and 2.90%, all within acceptable limits, and matrix effects were negligible. The method was successfully applied to quantify TAC in 32 clinical whole-blood samples, and the results strongly agreed with those from a conventional LC-MS/MS system (QTRAP 6500+). The LC-MiniMS system can efficiently quantify TAC in whole blood and provide a tiny, cost-effective, and uncomplicated option for therapeutic drug monitoring in clinical settings, especially in decentralized or resource-limited scenarios.
2026, 37(6): 112110
doi: 10.1016/j.cclet.2025.112110
Abstract:
Ultralong organic phosphorescence (UOP) materials have attracted increasing attention due to its potential applications in opto-electronics, bioelectronics, and security protection. However, it is still a formidable challenge to develop a material with simultaneous efficiency and lifetime enhancement under ambient conditions. Here, highly efficient UOP is achieved by doping crown ether derivatives into rigid poly(vinyl alcohol) (PVA) matrix. Two crown ether derivatives exhibited weak yellow UOP. Impressively, after doped into PVA films, the resultant PVA films demonstrated bright blue UOP with a long lifetime of 595.9 ms and high phosphorescence efficiency of 13.3%. The sharp enhancement of efficiency and lifetime can be ascribed to abundant hydrogen bonding between the crown ether derivatives and PVA polymer chains. This work provides a new avenue for developing highly efficient UOP materials.
Ultralong organic phosphorescence (UOP) materials have attracted increasing attention due to its potential applications in opto-electronics, bioelectronics, and security protection. However, it is still a formidable challenge to develop a material with simultaneous efficiency and lifetime enhancement under ambient conditions. Here, highly efficient UOP is achieved by doping crown ether derivatives into rigid poly(vinyl alcohol) (PVA) matrix. Two crown ether derivatives exhibited weak yellow UOP. Impressively, after doped into PVA films, the resultant PVA films demonstrated bright blue UOP with a long lifetime of 595.9 ms and high phosphorescence efficiency of 13.3%. The sharp enhancement of efficiency and lifetime can be ascribed to abundant hydrogen bonding between the crown ether derivatives and PVA polymer chains. This work provides a new avenue for developing highly efficient UOP materials.
2026, 37(6): 112112
doi: 10.1016/j.cclet.2025.112112
Abstract:
Oxygen vacancy engineering in heterogeneous catalysts has attracted considerable interest for peroxymonosulfate (PMS) activation. In this study, nano-Co3O4-encapsulated montmorillonite catalysts with tunable oxygen vacancy (OV) concentrations (denoted as Co3O4−Mt-xOV, x = 2, 4, 6) were synthesized for enhanced PMS activation. These OV defects not only modulate the electronic structure of Co3O4 but also strengthen PMS and contaminant adsorption. The optimized Co3O4−Mt-xOV/PMS system exhibited exceptional ofloxacin (OFL) degradation efficiency, achieving 2.74–3.43-fold enhancement over OV-free Co3O4−Mt. Density functional theory calculations and experimental studies revealed that the performance improvement stemmed from OV formation, which synergistically enhanced redox pair cycling, strengthened PMS adsorption, and promoted active species generation during electron transfer. Further studies demonstrated that OV sites selectively drive PMS decomposition to generate high-valent cobalt-oxo species (Co(Ⅳ)=O) and singlet oxygen (1O2) as the dominant reactive species for OFL oxidation. The in-depth investigation into the catalytic mechanism revealed that the Co(Ⅳ)=O species facilitated O2•− generation in surpassing the reaction energy barrier, which subsequently converted to 1O2. This non-radical pathway endowed the system with robust anti-interference capability against complex water matrices. The critical role of OV in PMS activation was mechanistically confirmed through experimental and theoretical analyses. Furthermore, Co3O4−Mt-4OV demonstrated outstanding chemical stability and recyclability, highlighting its practical potential. This work provides fundamental insights into vacancy defect engineering for advanced PMS activation and offers strategic guidance for designing high-performance catalysts.
Oxygen vacancy engineering in heterogeneous catalysts has attracted considerable interest for peroxymonosulfate (PMS) activation. In this study, nano-Co3O4-encapsulated montmorillonite catalysts with tunable oxygen vacancy (OV) concentrations (denoted as Co3O4−Mt-xOV, x = 2, 4, 6) were synthesized for enhanced PMS activation. These OV defects not only modulate the electronic structure of Co3O4 but also strengthen PMS and contaminant adsorption. The optimized Co3O4−Mt-xOV/PMS system exhibited exceptional ofloxacin (OFL) degradation efficiency, achieving 2.74–3.43-fold enhancement over OV-free Co3O4−Mt. Density functional theory calculations and experimental studies revealed that the performance improvement stemmed from OV formation, which synergistically enhanced redox pair cycling, strengthened PMS adsorption, and promoted active species generation during electron transfer. Further studies demonstrated that OV sites selectively drive PMS decomposition to generate high-valent cobalt-oxo species (Co(Ⅳ)=O) and singlet oxygen (1O2) as the dominant reactive species for OFL oxidation. The in-depth investigation into the catalytic mechanism revealed that the Co(Ⅳ)=O species facilitated O2•− generation in surpassing the reaction energy barrier, which subsequently converted to 1O2. This non-radical pathway endowed the system with robust anti-interference capability against complex water matrices. The critical role of OV in PMS activation was mechanistically confirmed through experimental and theoretical analyses. Furthermore, Co3O4−Mt-4OV demonstrated outstanding chemical stability and recyclability, highlighting its practical potential. This work provides fundamental insights into vacancy defect engineering for advanced PMS activation and offers strategic guidance for designing high-performance catalysts.
2026, 37(6): 112124
doi: 10.1016/j.cclet.2025.112124
Abstract:
The correlation between the distinct doping modalities of heteroatoms in metal oxides and the activation pathways of peroxymonosulfate (PMS) remains underappreciated. To address the issue, herein, we synthesized Te-doped Co3O4-α via a simple hydrothermal method and employed it as a heterogeneous catalyst for PMS activation to degrade levofloxacin (LEV). The incorporation of Te via both interstitial and substitutional doping synergistically enhanced the activity of Co3O4 toward PMS activation, resulting in a 66-fold increase in the LEV degradation kinetics. Various characterizations and trial results revealed that the coexistence of these doping configurations unlocked multiple pathways for reactive species generation. Interstitial Te dominates the formation of radicals and singlet oxygen (1O2), and synergistically cooperates with the generated oxygen vacancies to promote the cyclic regeneration of low-valent Co sites. On the other hand, substitutional Te primarily tailors the electron density of Co atoms through Co-O-Te sites, driving the formation of high-valent Co(Ⅳ)=O species. The factors affecting the LEV degradation were investigated, and the potential applications of the Te-Co3O4-α/PMS system were explored. Also, LEV degradation pathways were discussed. This work elucidates the correlation between doping modalities and PMS activation pathways, rendering a novel strategy to develop high performance catalysts for PMS activation.
The correlation between the distinct doping modalities of heteroatoms in metal oxides and the activation pathways of peroxymonosulfate (PMS) remains underappreciated. To address the issue, herein, we synthesized Te-doped Co3O4-α via a simple hydrothermal method and employed it as a heterogeneous catalyst for PMS activation to degrade levofloxacin (LEV). The incorporation of Te via both interstitial and substitutional doping synergistically enhanced the activity of Co3O4 toward PMS activation, resulting in a 66-fold increase in the LEV degradation kinetics. Various characterizations and trial results revealed that the coexistence of these doping configurations unlocked multiple pathways for reactive species generation. Interstitial Te dominates the formation of radicals and singlet oxygen (1O2), and synergistically cooperates with the generated oxygen vacancies to promote the cyclic regeneration of low-valent Co sites. On the other hand, substitutional Te primarily tailors the electron density of Co atoms through Co-O-Te sites, driving the formation of high-valent Co(Ⅳ)=O species. The factors affecting the LEV degradation were investigated, and the potential applications of the Te-Co3O4-α/PMS system were explored. Also, LEV degradation pathways were discussed. This work elucidates the correlation between doping modalities and PMS activation pathways, rendering a novel strategy to develop high performance catalysts for PMS activation.
2026, 37(6): 112143
doi: 10.1016/j.cclet.2025.112143
Abstract:
Covalent organic frameworks (COFs) with structural designability and functional predictability display great potential as emerging metal-free semiconductor catalysts in the field of photocatalytic degradation for antibiotics. However, the disadvantages of COFs, such as weak interfacial contact with antibiotics, light response limitation, charge-carrier recombination, and low oxygen activation efficiency, limit their practical application in the photocatalytic degradation of antibiotics. On this basis, PyTTA-COF-OH via good crystallinity and hydrophilicity was constructed through the synergistic strategy combining hydroxylation modulation of the surface microenvironment and expansion of the π-conjugated structure. Simultaneously, Surface hydroxyl functionalization of PyTTA-COF-OH not only reduced the band gap width but also enhanced the light absorption in the visible band. Significantly, theoretical calculations indicated that the introduction of hydroxyl groups widened the electrostatic potential difference within the molecular structure, further promoting exciton dissociation and charge separation. PyTTA-COF-OH removed sulfadiazine (SDZ) up to 99% in 10 mg/L SDZ solution. Besides, the results of the interference experiments and the cycling experiments proved that PyTTA-COF-OH had better anti-interference and stability. Based on the mechanistic analysis, the surface hydroxyl–functionalized PyTTA-COF-OH effectively promoted the adsorption of oxygen and the transfer of electrons to the adsorbed oxygen, thus increasing the efficiency of the O2•- generation, aiming at the efficient degradation of antibiotics under the visible light conditions.
Covalent organic frameworks (COFs) with structural designability and functional predictability display great potential as emerging metal-free semiconductor catalysts in the field of photocatalytic degradation for antibiotics. However, the disadvantages of COFs, such as weak interfacial contact with antibiotics, light response limitation, charge-carrier recombination, and low oxygen activation efficiency, limit their practical application in the photocatalytic degradation of antibiotics. On this basis, PyTTA-COF-OH via good crystallinity and hydrophilicity was constructed through the synergistic strategy combining hydroxylation modulation of the surface microenvironment and expansion of the π-conjugated structure. Simultaneously, Surface hydroxyl functionalization of PyTTA-COF-OH not only reduced the band gap width but also enhanced the light absorption in the visible band. Significantly, theoretical calculations indicated that the introduction of hydroxyl groups widened the electrostatic potential difference within the molecular structure, further promoting exciton dissociation and charge separation. PyTTA-COF-OH removed sulfadiazine (SDZ) up to 99% in 10 mg/L SDZ solution. Besides, the results of the interference experiments and the cycling experiments proved that PyTTA-COF-OH had better anti-interference and stability. Based on the mechanistic analysis, the surface hydroxyl–functionalized PyTTA-COF-OH effectively promoted the adsorption of oxygen and the transfer of electrons to the adsorbed oxygen, thus increasing the efficiency of the O2•- generation, aiming at the efficient degradation of antibiotics under the visible light conditions.
2026, 37(6): 112171
doi: 10.1016/j.cclet.2025.112171
Abstract:
This study reports the discovery of three shortened streptovaricin analogues, prestreptovaricins A–C (2–4), from Streptomyces spectabilis NA07477. Through comprehensive NMR and HRMS analysis, we elucidated their structures as a linear C13-polyketide (2), a 15-membered (3), and a 17-membered macrolactam (4), representing the first divergence from the character-istic C23 ansa chain in this antibiotic family. Gene inactivation experiments demonstrated that these truncated metabolites result from premature chain release at modules 5–7 of the polyketide synthase, rather than module skipping. Notably, the cyclized products 3 and 4 persisted upon knockout of the dedicated amide synthase stvF, implying catalysis by promiscuous cyclases. Our findings uncover premature termination as a previously unrecognized pathway for structural diversification in ansamycin biosynthesis.
This study reports the discovery of three shortened streptovaricin analogues, prestreptovaricins A–C (2–4), from Streptomyces spectabilis NA07477. Through comprehensive NMR and HRMS analysis, we elucidated their structures as a linear C13-polyketide (2), a 15-membered (3), and a 17-membered macrolactam (4), representing the first divergence from the character-istic C23 ansa chain in this antibiotic family. Gene inactivation experiments demonstrated that these truncated metabolites result from premature chain release at modules 5–7 of the polyketide synthase, rather than module skipping. Notably, the cyclized products 3 and 4 persisted upon knockout of the dedicated amide synthase stvF, implying catalysis by promiscuous cyclases. Our findings uncover premature termination as a previously unrecognized pathway for structural diversification in ansamycin biosynthesis.
2026, 37(6): 112344
doi: 10.1016/j.cclet.2025.112344
Abstract:
Phenolic compounds are highly toxic environmental pollutants, posing significant risks to ecosystems and human health. Designing multifunctional catalysts capable of detecting, discriminating, and transforming these hazardous phenolics into valuable products represents a promising "waste-to-treasure" strategy. In this work, a novel Anderson-type polyoxometalate-based hybrid [Ag(AlMo6(OH)6O18)]·H2L·2H2O (1) (L = N,N'-bis(3-menthylpyridin-yl)naphthalene-2,6-dicarboxamide), was synthesized under solvothermal conditions. The assembly of AlMo6(OH)6O183− (AlMo6) anion with Ag+ ions formed a unique anionic inorganic [Ag-AlMo6] nanosheet, further extended into a three-dimensional (3D) supramolecular by protonated H2L2+ cations in an "S"-shaped arrangement. Compound 1 exhibits excellent peroxidase-like activity, enabling highly sensitive colorimetric detection of phenolic compounds with LODs ranging from 9.5 nmol/L to 63 nmol/L. Taking 2,3,6-TMP as a model analyte, smartphone-assisted visual detection was established with an LOD of 370 nmol/L. Moreover, a colorimetric sensor array combined with principal component analysis (PCA), successfully discriminated five structure similar phenolic compounds (2,3,6-trimethylphenol, 3,5-dimethylphenol, 2,3-dimethylphenol, o-chlorophenol, and o-bromophenol), demonstrating its potential for environmental monitoring. Beyond detection, compound 1 serves as an efficient heterogeneous catalyst for the selective oxidation of phenols to their corresponding quinones, achieving high conversion rates and selectivity. The catalytic mechanism and stability were systematically investigated using PXRD, the X-ray photoelectron spectroscopy (XPS), free radical trapping experiment, electron paramagnetic resonance (EPR) and Raman spectroscopy (RS). This work not only provides a robust platform for phenolic pollutant detection and discrimination but also advances the sustainable transformation of harmful waste into valuable chemical feed-stocks.
Phenolic compounds are highly toxic environmental pollutants, posing significant risks to ecosystems and human health. Designing multifunctional catalysts capable of detecting, discriminating, and transforming these hazardous phenolics into valuable products represents a promising "waste-to-treasure" strategy. In this work, a novel Anderson-type polyoxometalate-based hybrid [Ag(AlMo6(OH)6O18)]·H2L·2H2O (1) (L = N,N'-bis(3-menthylpyridin-yl)naphthalene-2,6-dicarboxamide), was synthesized under solvothermal conditions. The assembly of AlMo6(OH)6O183− (AlMo6) anion with Ag+ ions formed a unique anionic inorganic [Ag-AlMo6] nanosheet, further extended into a three-dimensional (3D) supramolecular by protonated H2L2+ cations in an "S"-shaped arrangement. Compound 1 exhibits excellent peroxidase-like activity, enabling highly sensitive colorimetric detection of phenolic compounds with LODs ranging from 9.5 nmol/L to 63 nmol/L. Taking 2,3,6-TMP as a model analyte, smartphone-assisted visual detection was established with an LOD of 370 nmol/L. Moreover, a colorimetric sensor array combined with principal component analysis (PCA), successfully discriminated five structure similar phenolic compounds (2,3,6-trimethylphenol, 3,5-dimethylphenol, 2,3-dimethylphenol, o-chlorophenol, and o-bromophenol), demonstrating its potential for environmental monitoring. Beyond detection, compound 1 serves as an efficient heterogeneous catalyst for the selective oxidation of phenols to their corresponding quinones, achieving high conversion rates and selectivity. The catalytic mechanism and stability were systematically investigated using PXRD, the X-ray photoelectron spectroscopy (XPS), free radical trapping experiment, electron paramagnetic resonance (EPR) and Raman spectroscopy (RS). This work not only provides a robust platform for phenolic pollutant detection and discrimination but also advances the sustainable transformation of harmful waste into valuable chemical feed-stocks.
2026, 37(6): 112355
doi: 10.1016/j.cclet.2025.112355
Abstract:
We demonstrate here a macrocyclic host capable of simultaneously binding two Co2+-porphyrin complexes in its adaptive giant cavity. Such a geometrically confined porphyrin dimer promotes highly efficient transport of anions across the lipid membrane by virtue of dynamic metal-anion bonding interactions, which is in sharp contrast to the most studied class of anionphores that mediates anion transport through intermolecular H-bonds. The transport activity increases in the order of Br−, Cl−, ClO4− and NO3−, with the corresponding EC50 values of 0.57, 0.69, 0.74 and 1.30 µmol/L, and transport rate enhancements by up to ~35 folds over the monomeric Co2+-porphyrin complex. The determined binding constants suggest 1-mediated cooperative binding toward G3 molecules might account for the unique behavior by Co2+ with respect to other metal ions.
We demonstrate here a macrocyclic host capable of simultaneously binding two Co2+-porphyrin complexes in its adaptive giant cavity. Such a geometrically confined porphyrin dimer promotes highly efficient transport of anions across the lipid membrane by virtue of dynamic metal-anion bonding interactions, which is in sharp contrast to the most studied class of anionphores that mediates anion transport through intermolecular H-bonds. The transport activity increases in the order of Br−, Cl−, ClO4− and NO3−, with the corresponding EC50 values of 0.57, 0.69, 0.74 and 1.30 µmol/L, and transport rate enhancements by up to ~35 folds over the monomeric Co2+-porphyrin complex. The determined binding constants suggest 1-mediated cooperative binding toward G3 molecules might account for the unique behavior by Co2+ with respect to other metal ions.
2026, 37(6): 112368
doi: 10.1016/j.cclet.2026.112368
Abstract:
Achieving highly selective recognition of structurally similar substrates in water has been, and still remains, challenging. Herein, we report highly selective recognition of adenosine (A) and its analogs by using a hybridtube (HT) with endo-functionalized cavity. Fluorescence titration data and density-functional theory calculations reveal that the macrocycle's hydrophobic cavity and its internal hydrogen-bonding sites are crucial for attaining this high binding selectivity to A and its analogs. Decreasing the number of hydrophilic hydroxyl groups on the ribose ring while increasing the number of hydrophobic methyl groups on the purine ring can significantly enhance the hydrophobic effect between host and guest, thereby strengthening the binding affinity. Furthermore, different hydrogen bond acceptors on the guest can greatly affect host-guest binding, leading to a substantial enhancement in binding selectivity (A/dA up to 61.7-fold). Based on the high binding selectivity of HT, a substrate-selective fluorescent supramolecular tandem assay was developed for real-time and continuous monitoring of the enzyme activity of adenosine deaminase (ADA). Finally, we demonstrated the potential of this tandem assay for inhibitor screening, which holds significant implications for drug design and medical diagnostics.
Achieving highly selective recognition of structurally similar substrates in water has been, and still remains, challenging. Herein, we report highly selective recognition of adenosine (A) and its analogs by using a hybridtube (HT) with endo-functionalized cavity. Fluorescence titration data and density-functional theory calculations reveal that the macrocycle's hydrophobic cavity and its internal hydrogen-bonding sites are crucial for attaining this high binding selectivity to A and its analogs. Decreasing the number of hydrophilic hydroxyl groups on the ribose ring while increasing the number of hydrophobic methyl groups on the purine ring can significantly enhance the hydrophobic effect between host and guest, thereby strengthening the binding affinity. Furthermore, different hydrogen bond acceptors on the guest can greatly affect host-guest binding, leading to a substantial enhancement in binding selectivity (A/dA up to 61.7-fold). Based on the high binding selectivity of HT, a substrate-selective fluorescent supramolecular tandem assay was developed for real-time and continuous monitoring of the enzyme activity of adenosine deaminase (ADA). Finally, we demonstrated the potential of this tandem assay for inhibitor screening, which holds significant implications for drug design and medical diagnostics.
2026, 37(6): 110998
doi: 10.1016/j.cclet.2025.110998
Abstract:
Single-atom catalysts (SACs) with their maximized atomic efficiency, unique atomic structure and electronic properties, have attracted widespread research interest. The systematic understanding of reaction mechanism for single atom catalysis is an important frontier in catalysis research. The bonding energy and electron transfer between a single metal atom and its neighboring coordinating atoms can determine the charge density and distribution of the central metal sites, thereby affecting the overall catalytic performance of SACs. This review describes recent progress on understanding the electronic micro-environment for single atom sites, the bonding energy and electron transfers among the single atoms/supports/reactants during chemical/electrochemical reactions. We firstly introduce the theoretical insights in single atom catalysis, and then three characterization methods for characterizing the electronic structure and coordination environments of SACs are demonstrated. The detailed information about the bonding energy and electron transfer in SACs are emphasis described in three parts: (1) Bonding energy between SACs and substrates; (2) bonding energy between neighboring metal atoms; (3) bonding energy between SACs and reactants during reactions. The systematic summary of the microelectronic structure change of single atoms could provide a deep understanding of the catalytic mechanism during single atom catalysis.
Single-atom catalysts (SACs) with their maximized atomic efficiency, unique atomic structure and electronic properties, have attracted widespread research interest. The systematic understanding of reaction mechanism for single atom catalysis is an important frontier in catalysis research. The bonding energy and electron transfer between a single metal atom and its neighboring coordinating atoms can determine the charge density and distribution of the central metal sites, thereby affecting the overall catalytic performance of SACs. This review describes recent progress on understanding the electronic micro-environment for single atom sites, the bonding energy and electron transfers among the single atoms/supports/reactants during chemical/electrochemical reactions. We firstly introduce the theoretical insights in single atom catalysis, and then three characterization methods for characterizing the electronic structure and coordination environments of SACs are demonstrated. The detailed information about the bonding energy and electron transfer in SACs are emphasis described in three parts: (1) Bonding energy between SACs and substrates; (2) bonding energy between neighboring metal atoms; (3) bonding energy between SACs and reactants during reactions. The systematic summary of the microelectronic structure change of single atoms could provide a deep understanding of the catalytic mechanism during single atom catalysis.
2026, 37(6): 111000
doi: 10.1016/j.cclet.2025.111000
Abstract:
The zinc-air battery (ZAB)-hydrogen peroxide (H2O2) generation system produces H2O2 through a 2-electron oxygen reduction reaction (ORR) at the ZAB air cathode while simultaneously providing external electrical power. This system offers a promising, eco-friendly solution for both energy storage and chemical production. Despite its promise, a comprehensive review of this topic is still scarce. To fill this void, this review discusses the background and mechanisms of the ZAB-H2O2 generation system and covers approaches to achieving efficient and stable operation through 2e− ORR catalyst design and optimization, the regulation of the electrolyte, cathode configuration design, and electrochemical operating conditions. From the perspective of the cathode, anode, electrolyte, and their integration with energy systems, this review systematically analyzes the key challenges and optimization strategies. In addition, this review summarizes the main technical bottlenecks this system faces and proposes potential solutions and development suggestions for future research and practical applications.
The zinc-air battery (ZAB)-hydrogen peroxide (H2O2) generation system produces H2O2 through a 2-electron oxygen reduction reaction (ORR) at the ZAB air cathode while simultaneously providing external electrical power. This system offers a promising, eco-friendly solution for both energy storage and chemical production. Despite its promise, a comprehensive review of this topic is still scarce. To fill this void, this review discusses the background and mechanisms of the ZAB-H2O2 generation system and covers approaches to achieving efficient and stable operation through 2e− ORR catalyst design and optimization, the regulation of the electrolyte, cathode configuration design, and electrochemical operating conditions. From the perspective of the cathode, anode, electrolyte, and their integration with energy systems, this review systematically analyzes the key challenges and optimization strategies. In addition, this review summarizes the main technical bottlenecks this system faces and proposes potential solutions and development suggestions for future research and practical applications.
2026, 37(6): 111448
doi: 10.1016/j.cclet.2025.111448
Abstract:
Nanotechnological advancements have established stimuli-responsive nanomaterials as a pivotal strategy for spatiotemporally controlled drug delivery in precision biomedicine. Metal-organic frameworks (MOFs), crystalline porous materials constructed from metal ions/clusters and organic ligands through coordination bonds, exhibit exceptional drug delivery potential owing to their high surface area, tunable pore size, and facile functionalization. This review systematically analyzes recent advances in MOF-based drug delivery, with a focus on synthesis strategies, stimulus-responsive mechanisms, and biomedical applications. A key contribution of this review is the systematic classification of stimuli-responsive mechanisms, covering triggers such as pH, temperature, magnetic fields, humidity, and biological stimuli (e.g., redox factors, enzymes, adenosine triphosphate (ATP), ions, and hydrogen sulfide (H2S)). This framework provides a blueprint for designing targeted drug delivery platforms. By synthesizing cutting-edge research and emerging trends, this review offers actionable insights to advance stimuli-responsive MOF drug delivery systems (DDS).
Nanotechnological advancements have established stimuli-responsive nanomaterials as a pivotal strategy for spatiotemporally controlled drug delivery in precision biomedicine. Metal-organic frameworks (MOFs), crystalline porous materials constructed from metal ions/clusters and organic ligands through coordination bonds, exhibit exceptional drug delivery potential owing to their high surface area, tunable pore size, and facile functionalization. This review systematically analyzes recent advances in MOF-based drug delivery, with a focus on synthesis strategies, stimulus-responsive mechanisms, and biomedical applications. A key contribution of this review is the systematic classification of stimuli-responsive mechanisms, covering triggers such as pH, temperature, magnetic fields, humidity, and biological stimuli (e.g., redox factors, enzymes, adenosine triphosphate (ATP), ions, and hydrogen sulfide (H2S)). This framework provides a blueprint for designing targeted drug delivery platforms. By synthesizing cutting-edge research and emerging trends, this review offers actionable insights to advance stimuli-responsive MOF drug delivery systems (DDS).
2026, 37(6): 111482
doi: 10.1016/j.cclet.2025.111482
Abstract:
Marine ecosystems represent one of the most valuable yet underexplored sources of diverse bioactive compounds with significant potential for economic, healthcare, and environmental applications. Marine-derived bioactive compounds have emerged as promising active ingredients, exhibiting antibacterial, antiviral, anticancer, anti-inflammatory, and antioxidant properties, among others, with growing use in cosmetics and food supplements. Ongoing research in this area is aligned with the United Nations Sustainable Development Goals, particularly Goal 12, which relates to responsible production and consumption. The environmentally friendly extraction of these bioactive compounds from marine sources offers a path toward greener industrial practices and a more sustainable global economy. This review provides a comprehensive overview of the current state of the art on the main classes of marine bioactive compounds, their natural sources, green extraction methods, and their applications in health-related fields, including cosmetics and food supplements. Despite their potential, the use of marine bioactive compounds remains limited. Current research is largely based on in vitro studies using compound mixtures, with limited data on regulatory frameworks and human safety. To unlock their full therapeutic potential, future research should focus on: the standardization of clinical trial protocols, the isolation and characterization of individual compounds, and the expansion of in vivo studies in both animals and humans.
Marine ecosystems represent one of the most valuable yet underexplored sources of diverse bioactive compounds with significant potential for economic, healthcare, and environmental applications. Marine-derived bioactive compounds have emerged as promising active ingredients, exhibiting antibacterial, antiviral, anticancer, anti-inflammatory, and antioxidant properties, among others, with growing use in cosmetics and food supplements. Ongoing research in this area is aligned with the United Nations Sustainable Development Goals, particularly Goal 12, which relates to responsible production and consumption. The environmentally friendly extraction of these bioactive compounds from marine sources offers a path toward greener industrial practices and a more sustainable global economy. This review provides a comprehensive overview of the current state of the art on the main classes of marine bioactive compounds, their natural sources, green extraction methods, and their applications in health-related fields, including cosmetics and food supplements. Despite their potential, the use of marine bioactive compounds remains limited. Current research is largely based on in vitro studies using compound mixtures, with limited data on regulatory frameworks and human safety. To unlock their full therapeutic potential, future research should focus on: the standardization of clinical trial protocols, the isolation and characterization of individual compounds, and the expansion of in vivo studies in both animals and humans.
2026, 37(6): 111493
doi: 10.1016/j.cclet.2025.111493
Abstract:
Diabetic foot ulcers (DFUs) pose substantial clinical challenges due to their high prevalence, intricate pathophysiology, and recalcitrance to conventional therapeutic interventions. Traditional treatment paradigms frequently overlook the multidimensional aspects of DFUs, resulting in protracted healing trajectories and escalated risks of adverse sequelae. To address this critical diabetes-related complication, this comprehensive review delves into the pioneering application of biomaterials as microenvironmental modulators, underscoring their transformative potential in accelerating wound repair. By synthesizing in vivo, in vitro, and clinical evidence, we elucidate the mechanistic underpinnings and translational promise of these advanced materials. Our objective is to engage scholarly readers with state-of-the-art advancements in biomaterial engineering, emphasizing their pivotal contribution to paradigm shifts in DFU management strategies.
Diabetic foot ulcers (DFUs) pose substantial clinical challenges due to their high prevalence, intricate pathophysiology, and recalcitrance to conventional therapeutic interventions. Traditional treatment paradigms frequently overlook the multidimensional aspects of DFUs, resulting in protracted healing trajectories and escalated risks of adverse sequelae. To address this critical diabetes-related complication, this comprehensive review delves into the pioneering application of biomaterials as microenvironmental modulators, underscoring their transformative potential in accelerating wound repair. By synthesizing in vivo, in vitro, and clinical evidence, we elucidate the mechanistic underpinnings and translational promise of these advanced materials. Our objective is to engage scholarly readers with state-of-the-art advancements in biomaterial engineering, emphasizing their pivotal contribution to paradigm shifts in DFU management strategies.
2026, 37(6): 111517
doi: 10.1016/j.cclet.2025.111517
Abstract:
Nuclear medicine imaging plays a critical role in early diagnosis, treatment planning, and monitoring by enabling real-time, non-invasive visualization of molecular processes. Conventional radiotracers, such as [18F]F-FDG, often suffer from limited specificity and unfavorable pharmacokinetics. Nanobodies, with their small size, high affinity, deep tissue penetration, and low immunogenicity, have emerged as valuable tools for molecular imaging. Nanobody-based radiotracers have shown promise across oncology, neurology, and immune-related diseases, supporting precision diagnostics and individualized treatment monitoring. However, challenges such as renal retention and short plasma half-life still hinder clinical translation. In this review, we present the structural and functional advantages of nanobodies and summarize the key advances, challenges, and future prospects of nanobody-based radiopharmaceuticals in nuclear medicine imaging.
Nuclear medicine imaging plays a critical role in early diagnosis, treatment planning, and monitoring by enabling real-time, non-invasive visualization of molecular processes. Conventional radiotracers, such as [18F]F-FDG, often suffer from limited specificity and unfavorable pharmacokinetics. Nanobodies, with their small size, high affinity, deep tissue penetration, and low immunogenicity, have emerged as valuable tools for molecular imaging. Nanobody-based radiotracers have shown promise across oncology, neurology, and immune-related diseases, supporting precision diagnostics and individualized treatment monitoring. However, challenges such as renal retention and short plasma half-life still hinder clinical translation. In this review, we present the structural and functional advantages of nanobodies and summarize the key advances, challenges, and future prospects of nanobody-based radiopharmaceuticals in nuclear medicine imaging.
2026, 37(6): 111552
doi: 10.1016/j.cclet.2025.111552
Abstract:
As a technique with high sensitivity and resolution, fluorescence imaging is widely used in biomedical research, disease diagnosis and environmental monitoring, etc. Traditional fluorescence imaging mostly relies on photoexcitation paradigms, but with the deepening of multidisciplinary cross research, fluorescence excitation strategies based on multiple energy sources have gradually become an emerging frontier. These innovative strategies achieve diversified excitation of fluorescent probes by using multiple external stimuli, such as electric energy, magnetic energy, chemical energy, electromagnetic radiation, optical energy and mechanical energy, providing more flexible choices for different application scenarios, which not only broaden the application scope of fluorescence technology but also provide a new way of thinking for the design of highly efficient and tunable fluorescence systems. To track the latest advancements in fluorescence excitation techniques, this review systematically summarizes the recent multiple energy sources, focusing on their mechanisms, design principles, application prospects and challenges. By synthesizing recent research progress, this work aims to highlight emerging excitation strategies and offer valuable insights for developing next-generation fluorescent probes and broadening the technological applications of fluorescence-based systems.
As a technique with high sensitivity and resolution, fluorescence imaging is widely used in biomedical research, disease diagnosis and environmental monitoring, etc. Traditional fluorescence imaging mostly relies on photoexcitation paradigms, but with the deepening of multidisciplinary cross research, fluorescence excitation strategies based on multiple energy sources have gradually become an emerging frontier. These innovative strategies achieve diversified excitation of fluorescent probes by using multiple external stimuli, such as electric energy, magnetic energy, chemical energy, electromagnetic radiation, optical energy and mechanical energy, providing more flexible choices for different application scenarios, which not only broaden the application scope of fluorescence technology but also provide a new way of thinking for the design of highly efficient and tunable fluorescence systems. To track the latest advancements in fluorescence excitation techniques, this review systematically summarizes the recent multiple energy sources, focusing on their mechanisms, design principles, application prospects and challenges. By synthesizing recent research progress, this work aims to highlight emerging excitation strategies and offer valuable insights for developing next-generation fluorescent probes and broadening the technological applications of fluorescence-based systems.
2026, 37(6): 111932
doi: 10.1016/j.cclet.2025.111932
Abstract:
Mass spectrometry imaging (MSI) is a rapidly advancing field in omics research, offering spatially resolved localization of biomolecules such as metabolites, lipids, and proteins within tissue sections. Recent advancements in high-resolution MSI instrumentation have significantly enhanced the visualization of cellular structures, enabling molecular mapping at the single-cell level. Current single-cell MSI techniques can be broadly categorized into label-free approaches and multiplexed antibody-based strategies, both of which are continuously evolving to support comprehensive molecular profiling with subcellular precision. These technologies have become particularly valuable in cancer and neurodegenerative disease research, where they facilitate the characterization of cellular heterogeneity, metabolic reprogramming, and microenvironmental changes associated with disease progression. To meet the increasing demands of high-content spatial biology, multiple single-cell MSI platforms have been employed to detect low-abundance molecules, distinguish phenotypically distinct cell populations, and uncover region-specific molecular alterations in complex tissues. Moreover, emerging capabilities such as three-dimensional MSI are further extending the potential of this technology to reconstruct tissue biochemical architecture and capture spatially resolved molecular dynamics. In this review, we highlight pioneering advancements in single-cell MSI techniques and their applications in cancer and neurodegenerative disease research, with a particular emphasis on their role in elucidating disease mechanisms at the cellular level. We also discuss current challenges and future perspectives for expanding the utility of single-cell MSI in subcellular imaging and deeper biological discoveries.
Mass spectrometry imaging (MSI) is a rapidly advancing field in omics research, offering spatially resolved localization of biomolecules such as metabolites, lipids, and proteins within tissue sections. Recent advancements in high-resolution MSI instrumentation have significantly enhanced the visualization of cellular structures, enabling molecular mapping at the single-cell level. Current single-cell MSI techniques can be broadly categorized into label-free approaches and multiplexed antibody-based strategies, both of which are continuously evolving to support comprehensive molecular profiling with subcellular precision. These technologies have become particularly valuable in cancer and neurodegenerative disease research, where they facilitate the characterization of cellular heterogeneity, metabolic reprogramming, and microenvironmental changes associated with disease progression. To meet the increasing demands of high-content spatial biology, multiple single-cell MSI platforms have been employed to detect low-abundance molecules, distinguish phenotypically distinct cell populations, and uncover region-specific molecular alterations in complex tissues. Moreover, emerging capabilities such as three-dimensional MSI are further extending the potential of this technology to reconstruct tissue biochemical architecture and capture spatially resolved molecular dynamics. In this review, we highlight pioneering advancements in single-cell MSI techniques and their applications in cancer and neurodegenerative disease research, with a particular emphasis on their role in elucidating disease mechanisms at the cellular level. We also discuss current challenges and future perspectives for expanding the utility of single-cell MSI in subcellular imaging and deeper biological discoveries.
2026, 37(6): 111971
doi: 10.1016/j.cclet.2025.111971
Abstract:
Photochromic materials have drawn considerable interest in chemical and material sciences, owing to their unique photo-responsive properties and transformative potential in smart material applications. Among these, ESIPT-triggered photochromic systems stand out as a particularly promising subclass because of their exceptional photochromic property. However, existing reviews have primarily concentrated on Schiff base derivatives within this category, largely overlooking critical advancements in three key dimensions: (1) The discovery of novel ESIPT-triggered structural frameworks beyond traditional systems, (2) innovative synthetic methodologies enabling precise control of photochromic behaviors in both solid and solution states, and (3) the emergence of unprecedented functional properties driving cutting-edge applications. These oversights have created a significant knowledge gap in comprehensively understanding the rapid evolution of ESIPT-triggered photochromic materials. Therefore, this review systematically summarizes recent breakthroughs through three analytical lenses: First, we establish a structural taxonomy of ESIPT photochromophores, elucidating design principles that govern their performance. Second, we summarize advanced construction strategies that can synthesize tailored ESIPT photochromophores in different phase states. Third, we summarize the expanding application landscape of ESIPT photochromic materials in various functional domains. By integrating fundamental understanding with application-oriented perspectives, this work is expected to inspire the development of smart materials and photoresponsive systems.
Photochromic materials have drawn considerable interest in chemical and material sciences, owing to their unique photo-responsive properties and transformative potential in smart material applications. Among these, ESIPT-triggered photochromic systems stand out as a particularly promising subclass because of their exceptional photochromic property. However, existing reviews have primarily concentrated on Schiff base derivatives within this category, largely overlooking critical advancements in three key dimensions: (1) The discovery of novel ESIPT-triggered structural frameworks beyond traditional systems, (2) innovative synthetic methodologies enabling precise control of photochromic behaviors in both solid and solution states, and (3) the emergence of unprecedented functional properties driving cutting-edge applications. These oversights have created a significant knowledge gap in comprehensively understanding the rapid evolution of ESIPT-triggered photochromic materials. Therefore, this review systematically summarizes recent breakthroughs through three analytical lenses: First, we establish a structural taxonomy of ESIPT photochromophores, elucidating design principles that govern their performance. Second, we summarize advanced construction strategies that can synthesize tailored ESIPT photochromophores in different phase states. Third, we summarize the expanding application landscape of ESIPT photochromic materials in various functional domains. By integrating fundamental understanding with application-oriented perspectives, this work is expected to inspire the development of smart materials and photoresponsive systems.
2026, 37(6): 112020
doi: 10.1016/j.cclet.2025.112020
Abstract:
The utilization of solid electrolytes as substitutes for flammable liquid electrolytes represents a crucial strategy for enhancing both the safety and energy density of lithium metal batteries. However, the poor solid-solid contact between electrodes/electrolytes and the inherent difficulties of Li dendrite growth have seriously hindered their practical applications. Among the various types of solid electrolytes, polymer electrolytes are highly regarded for their potential high ionic conductivity, good deformability, and wide electrochemical window. In-situ curing technology has been demonstrated to be an effective solution to these problems and shows great application prospects in polymer electrolyte all-solid-state lithium-metal batteries. This paper will provide a comprehensive review of the three primary types of polymerization methods: free radical polymerization, ring-opening metathesis polymerization, and ionic polymerization. The technical principles, research progress, and performance optimization of in-situ polymerized solid state electrolytes will be reviewed, and the review will look forward to the future development of in-situ curing. The emerging challenges faced by the field and the potential opportunities in practical applications will be pointed out. As research progresses and technology advances, in-situ curing technology is poised to reinvigorate the development of all-solid-state batteries, propelling them towards enhanced safety, efficiency, and reliability.
The utilization of solid electrolytes as substitutes for flammable liquid electrolytes represents a crucial strategy for enhancing both the safety and energy density of lithium metal batteries. However, the poor solid-solid contact between electrodes/electrolytes and the inherent difficulties of Li dendrite growth have seriously hindered their practical applications. Among the various types of solid electrolytes, polymer electrolytes are highly regarded for their potential high ionic conductivity, good deformability, and wide electrochemical window. In-situ curing technology has been demonstrated to be an effective solution to these problems and shows great application prospects in polymer electrolyte all-solid-state lithium-metal batteries. This paper will provide a comprehensive review of the three primary types of polymerization methods: free radical polymerization, ring-opening metathesis polymerization, and ionic polymerization. The technical principles, research progress, and performance optimization of in-situ polymerized solid state electrolytes will be reviewed, and the review will look forward to the future development of in-situ curing. The emerging challenges faced by the field and the potential opportunities in practical applications will be pointed out. As research progresses and technology advances, in-situ curing technology is poised to reinvigorate the development of all-solid-state batteries, propelling them towards enhanced safety, efficiency, and reliability.
2026, 37(6): 112024
doi: 10.1016/j.cclet.2025.112024
Abstract:
Hydrogen peroxide (H2O2), as a green and mild oxidant, exhibits unique application advantages in several fields, including catalytic systems for organic synthesis and environmental pollutant degradation. In recent years, semiconductor-based photocatalytic strategies for H2O2 production have attracted extensive attention due to their sustainable characteristics, which utilize H2O/O2 as primary reactants to achieve solar-driven chemical energy conversion. Covalent organic frameworks (COFs), with their stable crystalline porous structures, highly ordered π-conjugated systems, modular designability, and ultra-large specific surface areas, provide an ideal platform for photocatalytic H2O2 synthesis. Hybridizing COFs with other functional materials has emerged as an effective strategy to address challenges commonly faced by single-component COFs systems, such as low light utilization efficiency, insufficient redox capability, and rapid recombination of photogenerated charge carriers. This review summarizes research progress in COFs-based heterojunctions for photocatalytic H2O2 synthesis, beginning with a concise introduction to the photosynthesis mechanism of H2O2 and fundamental principles of common heterojunctions in the field, followed by a focused review of reported COFs-based heterojunctions. In addition, the various in-situ applications of H2O2 in the context of photosynthesis by COFs-based heterojunctions were discussed, including sterilization, organic pollutants degradation, biomedical applications and organic synthesis. Then concluding with an overview of current challenges and future prospects in this emerging research area. This work aims to promote practical applications of COFs in green energy sectors while providing insights for developing efficient photocatalysts to advance photocatalytic H2O2 production.
Hydrogen peroxide (H2O2), as a green and mild oxidant, exhibits unique application advantages in several fields, including catalytic systems for organic synthesis and environmental pollutant degradation. In recent years, semiconductor-based photocatalytic strategies for H2O2 production have attracted extensive attention due to their sustainable characteristics, which utilize H2O/O2 as primary reactants to achieve solar-driven chemical energy conversion. Covalent organic frameworks (COFs), with their stable crystalline porous structures, highly ordered π-conjugated systems, modular designability, and ultra-large specific surface areas, provide an ideal platform for photocatalytic H2O2 synthesis. Hybridizing COFs with other functional materials has emerged as an effective strategy to address challenges commonly faced by single-component COFs systems, such as low light utilization efficiency, insufficient redox capability, and rapid recombination of photogenerated charge carriers. This review summarizes research progress in COFs-based heterojunctions for photocatalytic H2O2 synthesis, beginning with a concise introduction to the photosynthesis mechanism of H2O2 and fundamental principles of common heterojunctions in the field, followed by a focused review of reported COFs-based heterojunctions. In addition, the various in-situ applications of H2O2 in the context of photosynthesis by COFs-based heterojunctions were discussed, including sterilization, organic pollutants degradation, biomedical applications and organic synthesis. Then concluding with an overview of current challenges and future prospects in this emerging research area. This work aims to promote practical applications of COFs in green energy sectors while providing insights for developing efficient photocatalysts to advance photocatalytic H2O2 production.
2026, 37(6): 112032
doi: 10.1016/j.cclet.2025.112032
Abstract:
Hydrogen peroxide (H2O2) is a vital oxidant and a promising liquid fuel, serving as one of the 100 most essential chemicals. Covalent organic frameworks (COFs) have emerged as ideal candidates for pure H2O2 photosynthesis due to their fully designable structures and well-defined active sites. The microenvironment engineering of COFs presents exciting opportunities to optimize both selectivity and efficiency in H2O2 photosynthesis, while their precisely identifiable active sites enable rational design of next-generation high-performance COFs. Although significant progress has been made in regulating COFs’ active sites for H2O2 photosynthesis, a comprehensive review systematically analyzing this specific and significant area remains absent. Here, we provide a thorough overview of the recent advances and persistent challenges in the microenvironment engineering of COFs for H2O2 photosynthesis. To begin with, the basic principles of O2-to-H2O2 photocatalytic conversion and outline general strategies for microenvironment engineering of COFs are presented. Subsequently, we critically examine the current research progress in this field. The urgent challenges and the future development of the microenvironment engineering of COFs in H2O2 photosynthesis are finally proposed. This review will provide valuable theoretical guidance for developing the next generation of COF photocatalysts that promote H2O2 photosynthesis.
Hydrogen peroxide (H2O2) is a vital oxidant and a promising liquid fuel, serving as one of the 100 most essential chemicals. Covalent organic frameworks (COFs) have emerged as ideal candidates for pure H2O2 photosynthesis due to their fully designable structures and well-defined active sites. The microenvironment engineering of COFs presents exciting opportunities to optimize both selectivity and efficiency in H2O2 photosynthesis, while their precisely identifiable active sites enable rational design of next-generation high-performance COFs. Although significant progress has been made in regulating COFs’ active sites for H2O2 photosynthesis, a comprehensive review systematically analyzing this specific and significant area remains absent. Here, we provide a thorough overview of the recent advances and persistent challenges in the microenvironment engineering of COFs for H2O2 photosynthesis. To begin with, the basic principles of O2-to-H2O2 photocatalytic conversion and outline general strategies for microenvironment engineering of COFs are presented. Subsequently, we critically examine the current research progress in this field. The urgent challenges and the future development of the microenvironment engineering of COFs in H2O2 photosynthesis are finally proposed. This review will provide valuable theoretical guidance for developing the next generation of COF photocatalysts that promote H2O2 photosynthesis.
2026, 37(6): 112038
doi: 10.1016/j.cclet.2025.112038
Abstract:
Antidepressants (ATDs) have negative impacts on the ecosystem and have been detected globally in concentrations ranging from approximately 0.17 ng/L to 4237 ng/L in municipal wastewater treatment plant influent. However, the removal of ATDs by biological methods is still unsatisfactory at present, due to the extremely complex removal pathway and various removal processes for different ATDs. Therefore, there is an urgent need for a systematic compendium to help people understand the biodegradation process of ATDs. This work provides an overview of the classification, physicochemical properties, and environmental sources of ATDs; systematically reviews the adsorption behaviors and transformation processes of various ATDs during biological treatment; examines the removal efficiency, degradation mechanisms, and critical operating conditions of bioreactors; and discusses the mechanism of ATD adsorption and removal by extracellular polymers secreted by microbial cells during the biological treatment of municipal wastewater. This work clarifies the evolution of different types of ATDs during municipal wastewater biological treatment and proposes future research avenues for the more efficient removal of ATDs.
Antidepressants (ATDs) have negative impacts on the ecosystem and have been detected globally in concentrations ranging from approximately 0.17 ng/L to 4237 ng/L in municipal wastewater treatment plant influent. However, the removal of ATDs by biological methods is still unsatisfactory at present, due to the extremely complex removal pathway and various removal processes for different ATDs. Therefore, there is an urgent need for a systematic compendium to help people understand the biodegradation process of ATDs. This work provides an overview of the classification, physicochemical properties, and environmental sources of ATDs; systematically reviews the adsorption behaviors and transformation processes of various ATDs during biological treatment; examines the removal efficiency, degradation mechanisms, and critical operating conditions of bioreactors; and discusses the mechanism of ATD adsorption and removal by extracellular polymers secreted by microbial cells during the biological treatment of municipal wastewater. This work clarifies the evolution of different types of ATDs during municipal wastewater biological treatment and proposes future research avenues for the more efficient removal of ATDs.
2026, 37(6): 112086
doi: 10.1016/j.cclet.2025.112086
Abstract:
Carbon-chain rubbers have been widely used in many fields including transportation, medicine, construction, and everyday life, owing to their excellent flexibility. Now, waste rubbers have caused serious environmental pollution and resource waste. Chemical recovery is expected to provide a solution to solve these problems fundamentally. Here, the recent progress in selective chain scissions of the waste sulfur-vulcanized carbon-chain rubbers for reuse was reviewed. Based on the different devulcanization approaches, the polysulfide crosslinking chains or carbon chains were broken and the linear or branched degraded products could be obtained as structural prepolymers for new rubber products. After a comprehensive literature review on the effect of the molecular composition and topology of the devulcanized and degraded products on the new rubbers, the future perspectives were proposed.
Carbon-chain rubbers have been widely used in many fields including transportation, medicine, construction, and everyday life, owing to their excellent flexibility. Now, waste rubbers have caused serious environmental pollution and resource waste. Chemical recovery is expected to provide a solution to solve these problems fundamentally. Here, the recent progress in selective chain scissions of the waste sulfur-vulcanized carbon-chain rubbers for reuse was reviewed. Based on the different devulcanization approaches, the polysulfide crosslinking chains or carbon chains were broken and the linear or branched degraded products could be obtained as structural prepolymers for new rubber products. After a comprehensive literature review on the effect of the molecular composition and topology of the devulcanized and degraded products on the new rubbers, the future perspectives were proposed.
2026, 37(6): 112101
doi: 10.1016/j.cclet.2025.112101
Abstract:
Metal-organic frameworks (MOFs) and their derivatives have emerged as promising platforms for constructing heterojunctions in photocatalytic CO2 reduction (PCR). This review systematically summarizes the latest research progress in MOFs and their derivative heterostructures for PCR, focusing on material design, underlying mechanisms, and diverse applications. Besides, this review, by introducing various synthesis methods, emphasizes the significance of controllable synthesis strategies. Furthermore, the in-situ characterization techniques and theoretical calculations in photocatalysis are introduced and summarized, including the study of the morphology and chemical structure of photocatalysts, the transfer of photogenerated charges, spatial distribution, and surface reaction pathways. Systematic reviews of the advantages and disadvantages, features, and applications of various types of MOFs and their derivative heterostructures are conducted in accordance with the band arrangement characteristics. In addition, the discussion scope is expanded to related catalytic systems, including electrocatalysis, photoelectrocatalysis, and photothermal catalysis, fully demonstrating the multifunctionality of MOFs and their derivative heterostructures. Finally, future research directions are proposed from aspects such as material design and synthesis, performance optimization and mechanism research, correlation with practical applications, as well as the interdisciplinary collaboration. We hope it can provide valuable references for the rational design of high-performance MOFs and their derivative heterostructures materials with the wide range of applications.
Metal-organic frameworks (MOFs) and their derivatives have emerged as promising platforms for constructing heterojunctions in photocatalytic CO2 reduction (PCR). This review systematically summarizes the latest research progress in MOFs and their derivative heterostructures for PCR, focusing on material design, underlying mechanisms, and diverse applications. Besides, this review, by introducing various synthesis methods, emphasizes the significance of controllable synthesis strategies. Furthermore, the in-situ characterization techniques and theoretical calculations in photocatalysis are introduced and summarized, including the study of the morphology and chemical structure of photocatalysts, the transfer of photogenerated charges, spatial distribution, and surface reaction pathways. Systematic reviews of the advantages and disadvantages, features, and applications of various types of MOFs and their derivative heterostructures are conducted in accordance with the band arrangement characteristics. In addition, the discussion scope is expanded to related catalytic systems, including electrocatalysis, photoelectrocatalysis, and photothermal catalysis, fully demonstrating the multifunctionality of MOFs and their derivative heterostructures. Finally, future research directions are proposed from aspects such as material design and synthesis, performance optimization and mechanism research, correlation with practical applications, as well as the interdisciplinary collaboration. We hope it can provide valuable references for the rational design of high-performance MOFs and their derivative heterostructures materials with the wide range of applications.
2026, 37(6): 112108
doi: 10.1016/j.cclet.2025.112108
Abstract:
Emerging pollutants—including PFAS, microplastics, antibiotics, and endocrine-disrupting chemicals (EDCs)—pose escalating ecological and health risks while embodying untapped elemental value. Traditional remediation strategies focus on destruction, often overlooking opportunities for resource recovery. In contrast, catalytic upcycling leverages advances in photocatalysis, electrocatalysis, mechanochemistry, and hybrid bio-abiotic systems to selectively convert pollutants into value-added products, aligning with circular economy goals. This review synthesizes overarching catalytic principles—such as C–F and C–C bond activation, ROS selectivity, and redox synergies—that are applicable across pollutant classes. We also contrast pollutant-specific challenges: the chemical inertness of PFAS, the heterogeneity of microplastics, the toxicity and complexity of antibiotic intermediates, and the trace-level persistence of EDCs. Despite these differences, recent breakthroughs demonstrate promising upcycling pathways: PFAS into fluorochemicals, microplastics into olefins and graphitic materials, antibiotics into hydrogen and organic acids, and EDCs into polymeric and pharmaceutical precursors. We further highlight emerging techno-economic and life-cycle assessments, showing that upcycling can reduce CO2 emissions by up to 80% and generate substantial economic returns. By reframing pollutants as chemical feedstocks, this review outlines a transformative strategy for pollution control, resource recovery, and sustainable chemical production.
Emerging pollutants—including PFAS, microplastics, antibiotics, and endocrine-disrupting chemicals (EDCs)—pose escalating ecological and health risks while embodying untapped elemental value. Traditional remediation strategies focus on destruction, often overlooking opportunities for resource recovery. In contrast, catalytic upcycling leverages advances in photocatalysis, electrocatalysis, mechanochemistry, and hybrid bio-abiotic systems to selectively convert pollutants into value-added products, aligning with circular economy goals. This review synthesizes overarching catalytic principles—such as C–F and C–C bond activation, ROS selectivity, and redox synergies—that are applicable across pollutant classes. We also contrast pollutant-specific challenges: the chemical inertness of PFAS, the heterogeneity of microplastics, the toxicity and complexity of antibiotic intermediates, and the trace-level persistence of EDCs. Despite these differences, recent breakthroughs demonstrate promising upcycling pathways: PFAS into fluorochemicals, microplastics into olefins and graphitic materials, antibiotics into hydrogen and organic acids, and EDCs into polymeric and pharmaceutical precursors. We further highlight emerging techno-economic and life-cycle assessments, showing that upcycling can reduce CO2 emissions by up to 80% and generate substantial economic returns. By reframing pollutants as chemical feedstocks, this review outlines a transformative strategy for pollution control, resource recovery, and sustainable chemical production.
2026, 37(6): 112113
doi: 10.1016/j.cclet.2025.112113
Abstract:
Core-shell structured materials exhibit superior stability and catalytic performance in catalytic applications. The unique microenvironment of the core-shell catalyst facilitates efficient enrichment and adsorption of low-concentration, high-mobility atmospheric pollutants. Furthermore, these catalysts have found widespread application in the control of atmospheric contaminants attributed to the synergistic interplay between core-shell components and the protective barrier function of the shell architecture. This paper comprehensively reviews the preparation method of core-shell catalysts and their application in the control of air pollutants. This paper focuses on the advantages of core-shell catalysts and the main types of core-shell catalysts employed in deNOx processes. Recognition of the relationship between the structural composition of core-shell catalysts and their catalytic performance, as well as exploring the synergistic effects, heat and mass transfer, and underlying catalytic mechanism. This review offers critical guidance for the design and development of application-oriented core-shell catalysts to abate atmospheric pollutants.
Core-shell structured materials exhibit superior stability and catalytic performance in catalytic applications. The unique microenvironment of the core-shell catalyst facilitates efficient enrichment and adsorption of low-concentration, high-mobility atmospheric pollutants. Furthermore, these catalysts have found widespread application in the control of atmospheric contaminants attributed to the synergistic interplay between core-shell components and the protective barrier function of the shell architecture. This paper comprehensively reviews the preparation method of core-shell catalysts and their application in the control of air pollutants. This paper focuses on the advantages of core-shell catalysts and the main types of core-shell catalysts employed in deNOx processes. Recognition of the relationship between the structural composition of core-shell catalysts and their catalytic performance, as well as exploring the synergistic effects, heat and mass transfer, and underlying catalytic mechanism. This review offers critical guidance for the design and development of application-oriented core-shell catalysts to abate atmospheric pollutants.
2026, 37(6): 112127
doi: 10.1016/j.cclet.2025.112127
Abstract:
Micro/nanomotors (MNMs) are miniature devices capable of autonomous movement and execution of specific tasks at the micro/nano scale. Compared with traditional drugs, nanomedicines can achieve precise drug delivery through targeting, thereby reducing toxic and side effects on normal tissues. MNMs can utilize inherent fuels in biological systems or absorb external energy and convert it into kinetic energy, which enables them to address the issue that nanomedicines fail to act on the core of lesions due to insufficient tissue penetration. Therefore, they are regarded as excellent candidates for constructing efficient targeted delivery and diagnosis-treatment systems. This review introduces the design and driving strategies of different types of MNMs. Through functionalization of materials and optimization of driving modes, the dual designed objectives of reducing toxic side effects and improving therapeutic efficiency are achieved. In terms of applications, this review mainly introduces the research progress of MNMs in the biomedical field (such as cancer, cardiovascular diseases, wound healing, antibacterial and disease diagnosis-treatment). Finally, the challenges and limitations faced by the practical application of MNMs are discussed, and the future development directions of MNMs are prospected.
Micro/nanomotors (MNMs) are miniature devices capable of autonomous movement and execution of specific tasks at the micro/nano scale. Compared with traditional drugs, nanomedicines can achieve precise drug delivery through targeting, thereby reducing toxic and side effects on normal tissues. MNMs can utilize inherent fuels in biological systems or absorb external energy and convert it into kinetic energy, which enables them to address the issue that nanomedicines fail to act on the core of lesions due to insufficient tissue penetration. Therefore, they are regarded as excellent candidates for constructing efficient targeted delivery and diagnosis-treatment systems. This review introduces the design and driving strategies of different types of MNMs. Through functionalization of materials and optimization of driving modes, the dual designed objectives of reducing toxic side effects and improving therapeutic efficiency are achieved. In terms of applications, this review mainly introduces the research progress of MNMs in the biomedical field (such as cancer, cardiovascular diseases, wound healing, antibacterial and disease diagnosis-treatment). Finally, the challenges and limitations faced by the practical application of MNMs are discussed, and the future development directions of MNMs are prospected.
2026, 37(6): 112151
doi: 10.1016/j.cclet.2025.112151
Abstract:
Colorectal related diseases are generally benign and malignant diseases that occur within the colon, causing psychological disorders, nutrient absorption disorders, anemia, and life threatening conditions. The current treatment strategies for colorectal related diseases have been seriously hampered by unpredictable behaviors, safety risks and limited efficacy. Recent advances in the fields of synthetic biology and materials fabrication have enabled the development of engineered organisms with great controllability, targeted delivery capabilities, and high safety and efficacy for their therapy. In this review, we first analyze the mechanisms underlying the occurrence and development of colorectal related disease. Subsequently, we delved into the latest developments in the application of engineered organisms in the treatment of colorectal diseases, covering the potential regulatory mechanisms, and the exploration of clinical feasibility. Finally, we discuss the key challenges and future perspectives of this biotherapeutic approach, with a focus on achieving precise targeted therapy through the engineering design of organisms. This review aims to provide the valuable insights into the development of precision therapies for colorectal related diseases, and lay the foundation for their clinical management.
Colorectal related diseases are generally benign and malignant diseases that occur within the colon, causing psychological disorders, nutrient absorption disorders, anemia, and life threatening conditions. The current treatment strategies for colorectal related diseases have been seriously hampered by unpredictable behaviors, safety risks and limited efficacy. Recent advances in the fields of synthetic biology and materials fabrication have enabled the development of engineered organisms with great controllability, targeted delivery capabilities, and high safety and efficacy for their therapy. In this review, we first analyze the mechanisms underlying the occurrence and development of colorectal related disease. Subsequently, we delved into the latest developments in the application of engineered organisms in the treatment of colorectal diseases, covering the potential regulatory mechanisms, and the exploration of clinical feasibility. Finally, we discuss the key challenges and future perspectives of this biotherapeutic approach, with a focus on achieving precise targeted therapy through the engineering design of organisms. This review aims to provide the valuable insights into the development of precision therapies for colorectal related diseases, and lay the foundation for their clinical management.
2026, 37(6): 112155
doi: 10.1016/j.cclet.2025.112155
Abstract:
9,9′-Spirobifluorene (SBF) derivatives, as a unique class of conjugated frameworks, have been extensively investigated in the field of organic electronics. The introduction of diverse substituents to various positions on SBF can modulate the photoelectric properties of SBF derivatives. Multisite substitution endows SBF derivatives with structural diversity, thus providing more opportunities for adjusting the photoelectric properties of materials. However, the synthesis of multi-substituted SBFs is more difficult, and their structure-activity relationships are also more unpredictable. This review focuses on multi-substituted SBFs, detailing their synthesis methods, photoelectric properties, thermal stabilities, and applications in organic light-emitting diodes (OLEDs). Multi-substituted SBFs are typically synthesized using multi-halogenated or multi-boronate ester-substituted SBF precursors. In addition, transition metal-catalyzed C–H arylation reactions represent an exceptionally efficient approach for preparing multi-substituted SBFs. The effects of the type, number, and position of substituents on the thermal stability, photophysical and electrochemical properties, and carrier mobility of these SBF derivatives are systematically reviewed. Their roles as emitters, hosts, electron-transport materials, and hole-transport materials in OLED devices are summarized and discussed.
9,9′-Spirobifluorene (SBF) derivatives, as a unique class of conjugated frameworks, have been extensively investigated in the field of organic electronics. The introduction of diverse substituents to various positions on SBF can modulate the photoelectric properties of SBF derivatives. Multisite substitution endows SBF derivatives with structural diversity, thus providing more opportunities for adjusting the photoelectric properties of materials. However, the synthesis of multi-substituted SBFs is more difficult, and their structure-activity relationships are also more unpredictable. This review focuses on multi-substituted SBFs, detailing their synthesis methods, photoelectric properties, thermal stabilities, and applications in organic light-emitting diodes (OLEDs). Multi-substituted SBFs are typically synthesized using multi-halogenated or multi-boronate ester-substituted SBF precursors. In addition, transition metal-catalyzed C–H arylation reactions represent an exceptionally efficient approach for preparing multi-substituted SBFs. The effects of the type, number, and position of substituents on the thermal stability, photophysical and electrochemical properties, and carrier mobility of these SBF derivatives are systematically reviewed. Their roles as emitters, hosts, electron-transport materials, and hole-transport materials in OLED devices are summarized and discussed.
2026, 37(6): 112197
doi: 10.1016/j.cclet.2025.112197
Abstract:
Low-valence-selenium-substituted glucose, a novel organoselenium compound, has emerged as a promising candidate with significant biological application potential. This review highlights its role as an efficient and low-toxicity selenium source in agriculture, livestock farming, and medicine. In agriculture, it enhances selenium uptake in crops, improves plant stress resistance, and reduces heavy metal toxicity. In animal feed, it boosts selenium levels and antioxidant capacity in livestock, thereby improving their health and productivity. Additionally, its medical applications include the development of selenium catalysts for pharmaceutical synthesis and selenium-enriched materials with antibacterial and anticancer properties. This article provides a comprehensive review of its synthesis, biological efficacy, and future prospects.
Low-valence-selenium-substituted glucose, a novel organoselenium compound, has emerged as a promising candidate with significant biological application potential. This review highlights its role as an efficient and low-toxicity selenium source in agriculture, livestock farming, and medicine. In agriculture, it enhances selenium uptake in crops, improves plant stress resistance, and reduces heavy metal toxicity. In animal feed, it boosts selenium levels and antioxidant capacity in livestock, thereby improving their health and productivity. Additionally, its medical applications include the development of selenium catalysts for pharmaceutical synthesis and selenium-enriched materials with antibacterial and anticancer properties. This article provides a comprehensive review of its synthesis, biological efficacy, and future prospects.
2026, 37(6): 112223
doi: 10.1016/j.cclet.2025.112223
Abstract:
In recent years, heterogeneous manganese catalysis has emerged as a significant area of research in catalytic chemistry, leveraging manganese-based materials to facilitate a wide range of chemical transformations. This review explores the fundamental principles, recent advances, applications, and prospects of heterogeneous manganese catalysis in organic synthesis. These catalysts are widely employed in C–C bond formation, C–N bond formation, C–O bond formation, oxidation. Despite this, manganese catalysts have not received as much attention as other metals, such as iron and cobalt, often resulting in their excellent catalytic activity being overlooked. This review focuses on the mechanisms and capabilities of heterogeneous manganese catalysts in various aspects of organic synthesis, highlighting the latest research advancements.
In recent years, heterogeneous manganese catalysis has emerged as a significant area of research in catalytic chemistry, leveraging manganese-based materials to facilitate a wide range of chemical transformations. This review explores the fundamental principles, recent advances, applications, and prospects of heterogeneous manganese catalysis in organic synthesis. These catalysts are widely employed in C–C bond formation, C–N bond formation, C–O bond formation, oxidation. Despite this, manganese catalysts have not received as much attention as other metals, such as iron and cobalt, often resulting in their excellent catalytic activity being overlooked. This review focuses on the mechanisms and capabilities of heterogeneous manganese catalysts in various aspects of organic synthesis, highlighting the latest research advancements.
2026, 37(6): 112318
doi: 10.1016/j.cclet.2025.112318
Abstract:
Antibiotic contamination in aquatic environments poses a serious threat to ecological safety and public health. However, traditional advanced oxidation processes (AOPs) face critical bottlenecks due to unclear microscopic reaction mechanisms, including ambiguous reactive species generation pathways and a lack of theoretical guidance for catalyst design. This review systematically elucidates the pivotal role of density functional theory (DFT) in antibiotic degradation via AOPs: (1) By accurately simulating catalyst electronic structures, adsorption energies, and reaction energy barriers, DFT reveals the evolution rules of active sites (e.g., multi-element doping reduces the O–O bond cleavage energy barrier by 36%), thereby optimizing reaction pathways across photocatalysis, electrochemical oxidation, and persulfate activation systems; (2) Combined with Fukui index and molecular orbital analyses, DFT enables precise identification of vulnerable sites in antibiotic molecules (e.g., C8/C13 of ofloxacin and O23/N15 of ciprofloxacin), and predicts the thermodynamics and kinetics of reactive species (e.g., 1O2, SO4•‒) formation; (3) Under a closed-loop "computational guidance — experimental validation" framework, DFT drives catalyst structure optimization and reaction pathway regulation, significantly enhancing AOP mineralization efficiency (e.g., 2.5-fold increase in tetracycline removal rate). Future directions should focus on integrating non-adiabatic molecular dynamics, machine learning-assisted screening, and toxicity prediction of degradation products to promote the intelligent design and green engineering of AOPs, thereby building an efficient and precise antibiotic pollution control system.
Antibiotic contamination in aquatic environments poses a serious threat to ecological safety and public health. However, traditional advanced oxidation processes (AOPs) face critical bottlenecks due to unclear microscopic reaction mechanisms, including ambiguous reactive species generation pathways and a lack of theoretical guidance for catalyst design. This review systematically elucidates the pivotal role of density functional theory (DFT) in antibiotic degradation via AOPs: (1) By accurately simulating catalyst electronic structures, adsorption energies, and reaction energy barriers, DFT reveals the evolution rules of active sites (e.g., multi-element doping reduces the O–O bond cleavage energy barrier by 36%), thereby optimizing reaction pathways across photocatalysis, electrochemical oxidation, and persulfate activation systems; (2) Combined with Fukui index and molecular orbital analyses, DFT enables precise identification of vulnerable sites in antibiotic molecules (e.g., C8/C13 of ofloxacin and O23/N15 of ciprofloxacin), and predicts the thermodynamics and kinetics of reactive species (e.g., 1O2, SO4•‒) formation; (3) Under a closed-loop "computational guidance — experimental validation" framework, DFT drives catalyst structure optimization and reaction pathway regulation, significantly enhancing AOP mineralization efficiency (e.g., 2.5-fold increase in tetracycline removal rate). Future directions should focus on integrating non-adiabatic molecular dynamics, machine learning-assisted screening, and toxicity prediction of degradation products to promote the intelligent design and green engineering of AOPs, thereby building an efficient and precise antibiotic pollution control system.
2026, 37(6): 112572
doi: 10.1016/j.cclet.2026.112572
Abstract:
The photocatalytic production of hydrogen peroxide (H2O2) utilizing graphitic carbon nitride (g-C3N4) offers a sustainable alternative to the conventional, energy-intensive anthraquinone method. Nevertheless, the practical deployment of pristine g-C3N4 is constrained by its limited absorption of visible light, rapid recombination of photogenerated charge carriers, and low surface catalytic activity. This review critically examines various modification strategies aimed at enhancing the H2O2 generation efficiency of g-C3N4-based photocatalysts. Prominent approaches encompass elemental doping, defect modification, and the junction engineering. These modifications synergistically enhance light absorption, facilitate charge separation, and accelerate oxygen reduction reaction kinetics. Consequently, such engineered photocatalysts have achieved H2O2 production rates reaching millimolar concentrations per hour under visible-light irradiation, alongside marked improvements in selectivity and apparent quantum efficiency. Despite these significant advancements, challenges persist in realizing broad-spectrum solar energy utilization, ensuring long-term operational stability, and developing scalable synthesis methods for catalyst fabrication. This review delineates prospective research directions aimed at advancing efficient and practical photocatalytic systems for sustainable hydrogen peroxide synthesis.
The photocatalytic production of hydrogen peroxide (H2O2) utilizing graphitic carbon nitride (g-C3N4) offers a sustainable alternative to the conventional, energy-intensive anthraquinone method. Nevertheless, the practical deployment of pristine g-C3N4 is constrained by its limited absorption of visible light, rapid recombination of photogenerated charge carriers, and low surface catalytic activity. This review critically examines various modification strategies aimed at enhancing the H2O2 generation efficiency of g-C3N4-based photocatalysts. Prominent approaches encompass elemental doping, defect modification, and the junction engineering. These modifications synergistically enhance light absorption, facilitate charge separation, and accelerate oxygen reduction reaction kinetics. Consequently, such engineered photocatalysts have achieved H2O2 production rates reaching millimolar concentrations per hour under visible-light irradiation, alongside marked improvements in selectivity and apparent quantum efficiency. Despite these significant advancements, challenges persist in realizing broad-spectrum solar energy utilization, ensuring long-term operational stability, and developing scalable synthesis methods for catalyst fabrication. This review delineates prospective research directions aimed at advancing efficient and practical photocatalytic systems for sustainable hydrogen peroxide synthesis.
2026, 37(6): 112019
doi: 10.1016/j.cclet.2025.112019
Abstract:
2026, 37(6): 112053
doi: 10.1016/j.cclet.2025.112053
Abstract:
2026, 37(6): 112070
doi: 10.1016/j.cclet.2025.112070
Abstract:
Light-fueled multicolor luminescent supramolecular driver enabled by cucurbituril-mediated allostery
2026, 37(6): 112486
doi: 10.1016/j.cclet.2026.112486
Abstract:
