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2025 Volume 36 Issue 3
2025, 36(3): 109531
doi: 10.1016/j.cclet.2024.109531
Abstract:
Aqueous zinc-ion batteries are highly favored for their enhanced safety and reduced cost. However, there exist challenges including zinc dendrite, hydrogen evolution, and surface corrosion to be solved. Using electrolyte additives is a highly convenient approach to solving zinc anode-related issues. Inspired by industrial corrosion protection, a trace amount of the corrosion inhibitor urotropine (URT) is used as an electrolyte additive to protect the zinc anode. Theoretical calculation and experimental analysis confirm the adsorption of URT molecules onto the surface of Zn, which inhibits hydrogen evolution. This adsorption further leads to the formation of an inorganic-organic bilayer solid electrolyte interface (SEI) on the surface of the zinc anode, effectively protecting the Zn anode from corrosion, hydrogen evolution and zinc dendrites. The presence of SEI enables symmetrical Zn//Zn cells to exhibit a long cycling performance of 1750 h at 1 mA/cm2 and an average coulombic efficiency of 99.0% at 1 mA/cm2 in Zn//Cu cells. After being coupled with polyaniline (PANI), the Zn//PANI full battery displays excellent cycle stability and specific capacity.
Aqueous zinc-ion batteries are highly favored for their enhanced safety and reduced cost. However, there exist challenges including zinc dendrite, hydrogen evolution, and surface corrosion to be solved. Using electrolyte additives is a highly convenient approach to solving zinc anode-related issues. Inspired by industrial corrosion protection, a trace amount of the corrosion inhibitor urotropine (URT) is used as an electrolyte additive to protect the zinc anode. Theoretical calculation and experimental analysis confirm the adsorption of URT molecules onto the surface of Zn, which inhibits hydrogen evolution. This adsorption further leads to the formation of an inorganic-organic bilayer solid electrolyte interface (SEI) on the surface of the zinc anode, effectively protecting the Zn anode from corrosion, hydrogen evolution and zinc dendrites. The presence of SEI enables symmetrical Zn//Zn cells to exhibit a long cycling performance of 1750 h at 1 mA/cm2 and an average coulombic efficiency of 99.0% at 1 mA/cm2 in Zn//Cu cells. After being coupled with polyaniline (PANI), the Zn//PANI full battery displays excellent cycle stability and specific capacity.
2025, 36(3): 109671
doi: 10.1016/j.cclet.2024.109671
Abstract:
Density functional theory (DFT) was performed to systematically study the adsorption and dissociation of N2 on Ir(100) and Ir(110) surfaces. By analyzing the properties, including adsorption energies, reaction barriers, and optimal adsorption sites, the hollow (H) sites were finally identified as favorable dissociation sites for N2. The dissociation barriers of N2 are 0.87 eV on Ir(100) and 1.12 eV on Ir(110), which can be overcome at around 348 and 448 K, respectively. Therefore, Ir(100) is screened as a promising catalyst for N2 dissociation compared to Ir(110). This can be attributed to the significantly higher adsorption energy of N2 on the H site of Ir(100) (−0.48 eV) compared to that on Ir(110) (−0.22 eV), leading to different dissociation mechanisms on Ir(100) and Ir(110). Ir(100) can dissociate N2 directly on H site and Ir(110) should firstly capture N2 via bridge site and further transfer the adsorbed N2 to the H site, which will dramatically deteriorate the reactivity of N2 dissociation. In addition, the following protonation processes of dissociated *N atoms are all exothermal at 348 K on Ir(100), indicating that the ammonia synthesis can occur spontaneously as the temperature higher than 348 K. These results have provided a reasonable materials design scheme for subsequent ammonia synthesis.
Density functional theory (DFT) was performed to systematically study the adsorption and dissociation of N2 on Ir(100) and Ir(110) surfaces. By analyzing the properties, including adsorption energies, reaction barriers, and optimal adsorption sites, the hollow (H) sites were finally identified as favorable dissociation sites for N2. The dissociation barriers of N2 are 0.87 eV on Ir(100) and 1.12 eV on Ir(110), which can be overcome at around 348 and 448 K, respectively. Therefore, Ir(100) is screened as a promising catalyst for N2 dissociation compared to Ir(110). This can be attributed to the significantly higher adsorption energy of N2 on the H site of Ir(100) (−0.48 eV) compared to that on Ir(110) (−0.22 eV), leading to different dissociation mechanisms on Ir(100) and Ir(110). Ir(100) can dissociate N2 directly on H site and Ir(110) should firstly capture N2 via bridge site and further transfer the adsorbed N2 to the H site, which will dramatically deteriorate the reactivity of N2 dissociation. In addition, the following protonation processes of dissociated *N atoms are all exothermal at 348 K on Ir(100), indicating that the ammonia synthesis can occur spontaneously as the temperature higher than 348 K. These results have provided a reasonable materials design scheme for subsequent ammonia synthesis.
2025, 36(3): 109672
doi: 10.1016/j.cclet.2024.109672
Abstract:
Achieving efficient adsorption and separation of C2H2/CO2 mixtures is a goal that people have always pursued to improve the situation of high energy consumption brought by traditional separation technologies in industry today. High-nuclearity metal cluster-based MOFs with different functionalities are promising for this separation, but it is a complicated and difficult task to precisely control their structures. The strategy of pore-space partition (PSP) is a powerful way to construct this type MOFs, which has the characteristic of isostructural relationship, and can be resulted in a similar performance for them. Therefore, it is an interesting work to explore the effect of MOFs property by adjusting the size of PSP dividers. Herein, three tetranuclear Cu(Ⅱ) cluster-based MOFs (FJU-112/113/114) with dual functionalities has been successfully obtained by PSP strategy with various lengths of divider units. With the highest microporosity and unique functional site, FJU-114 realized a good improvement in the adsorption and separation performance of C2H2/CO2. The gas adsorption and lab-scale C2H2/CO2 breakthrough experiments demonstrated that FJU-114 exhibits the highest adsorption uptake of 77 cm3/g for C2H2, and shows the best separation factor of 4.2 among three MOFs. The GCMC simulation reveals that a stronger adsorption binding site of C2H2 in FJU-114a located in the cage Ⅱ near the unchanged tetranuclear copper node, combined with its high microporosity to achieve the effect of dual functionalities for the improvement performance of C2H2 adsorption and separation.
Achieving efficient adsorption and separation of C2H2/CO2 mixtures is a goal that people have always pursued to improve the situation of high energy consumption brought by traditional separation technologies in industry today. High-nuclearity metal cluster-based MOFs with different functionalities are promising for this separation, but it is a complicated and difficult task to precisely control their structures. The strategy of pore-space partition (PSP) is a powerful way to construct this type MOFs, which has the characteristic of isostructural relationship, and can be resulted in a similar performance for them. Therefore, it is an interesting work to explore the effect of MOFs property by adjusting the size of PSP dividers. Herein, three tetranuclear Cu(Ⅱ) cluster-based MOFs (FJU-112/113/114) with dual functionalities has been successfully obtained by PSP strategy with various lengths of divider units. With the highest microporosity and unique functional site, FJU-114 realized a good improvement in the adsorption and separation performance of C2H2/CO2. The gas adsorption and lab-scale C2H2/CO2 breakthrough experiments demonstrated that FJU-114 exhibits the highest adsorption uptake of 77 cm3/g for C2H2, and shows the best separation factor of 4.2 among three MOFs. The GCMC simulation reveals that a stronger adsorption binding site of C2H2 in FJU-114a located in the cage Ⅱ near the unchanged tetranuclear copper node, combined with its high microporosity to achieve the effect of dual functionalities for the improvement performance of C2H2 adsorption and separation.
2025, 36(3): 109687
doi: 10.1016/j.cclet.2024.109687
Abstract:
Van der Waals (vdW) ferroelectric-semiconductor heterojunction provides reconfigurable band alignment based on optical/electrical-assisted polarization switching, which shows great potential to construct artificial visual neural systems. However, the mechanical exfoliation fabrication scheme for proof-of-concept demonstrations and fundamental studies is cumbersome and not scalable for practical application. Here, we present a synthetic strategy for the large-scale and high crystallinity growth of planar/vertical α-In2Se3/MoS2 heterojunctions by dynamically tuning the growth temperature. Furthermore, based on the α-In2Se3/MoS2 heterostructures, photo-synapse devices are designed and fabricated to simulate visual neural systems functions, including multistate storage, optical logic operation, potentiation and depression, paired-pulse facilitation (PPF), short-term memory (STM), long-term memory (LTM), and Learning-Forgetting-Relearning. By coupling the spatiotemporally relevant optical and electric information, the device can mimic the superior biological visual system's light adaptation and Pavlovian conditioning. This work provides a strategy for dynamically tuning the orientation of ferroelectric-semiconductor heterojunction stacks and will give impetus to applying all-in-one sensing and memory-computing artificial vision systems.
Van der Waals (vdW) ferroelectric-semiconductor heterojunction provides reconfigurable band alignment based on optical/electrical-assisted polarization switching, which shows great potential to construct artificial visual neural systems. However, the mechanical exfoliation fabrication scheme for proof-of-concept demonstrations and fundamental studies is cumbersome and not scalable for practical application. Here, we present a synthetic strategy for the large-scale and high crystallinity growth of planar/vertical α-In2Se3/MoS2 heterojunctions by dynamically tuning the growth temperature. Furthermore, based on the α-In2Se3/MoS2 heterostructures, photo-synapse devices are designed and fabricated to simulate visual neural systems functions, including multistate storage, optical logic operation, potentiation and depression, paired-pulse facilitation (PPF), short-term memory (STM), long-term memory (LTM), and Learning-Forgetting-Relearning. By coupling the spatiotemporally relevant optical and electric information, the device can mimic the superior biological visual system's light adaptation and Pavlovian conditioning. This work provides a strategy for dynamically tuning the orientation of ferroelectric-semiconductor heterojunction stacks and will give impetus to applying all-in-one sensing and memory-computing artificial vision systems.
2025, 36(3): 109690
doi: 10.1016/j.cclet.2024.109690
Abstract:
The performance optimization of materials is an eternal theme and challenge in scientific research, which is reflected in ferroelectric filed to two hot topics of enhancing Curie temperature (TC) and functional versatility. The former one vitally determines ferroelectric operational temperature range while the latter would open up new application possibilities. Effective chemical modification or doping strategies on A-site and X-site components have been successfully developed in hybrid organic-inorganic perovskite (HOIP) ferroelectrics, however, the important role of adjusting B-site ions has long been overlooked. Here, we have implemented regulation on the ion radius of the B-site component to successfully obtain two new HOIP ferroelectrics (3-pyrrolinium)BBr3 (B = Mn and Ni). Compared to parent (3-pyrrolinium)CdBr3, the TC (ΔT = 99 K) was significantly optimized by replacing the Cd2+ with smaller Mn2+ or Ni2+ ions. More strikingly, the introduction of Mn2+ and Ni2+ ions with octahedral coordination bring out intriguing red emission and magnetism respectively, making the multifunctional integration in a single material for multiple uses. This work provides a feasible strategy for performance optimizing of HOIP ferroelectrics, and would shed light for constructing multifunctional ferroelectrics.
The performance optimization of materials is an eternal theme and challenge in scientific research, which is reflected in ferroelectric filed to two hot topics of enhancing Curie temperature (TC) and functional versatility. The former one vitally determines ferroelectric operational temperature range while the latter would open up new application possibilities. Effective chemical modification or doping strategies on A-site and X-site components have been successfully developed in hybrid organic-inorganic perovskite (HOIP) ferroelectrics, however, the important role of adjusting B-site ions has long been overlooked. Here, we have implemented regulation on the ion radius of the B-site component to successfully obtain two new HOIP ferroelectrics (3-pyrrolinium)BBr3 (B = Mn and Ni). Compared to parent (3-pyrrolinium)CdBr3, the TC (ΔT = 99 K) was significantly optimized by replacing the Cd2+ with smaller Mn2+ or Ni2+ ions. More strikingly, the introduction of Mn2+ and Ni2+ ions with octahedral coordination bring out intriguing red emission and magnetism respectively, making the multifunctional integration in a single material for multiple uses. This work provides a feasible strategy for performance optimizing of HOIP ferroelectrics, and would shed light for constructing multifunctional ferroelectrics.
2025, 36(3): 109691
doi: 10.1016/j.cclet.2024.109691
Abstract:
Lithium-sulfur batteries are considered to be a new generation of high energy density batteries due to their non-toxicity, low cost and high theoretical specific capacity. However, the development of practical lithium-sulfur batteries is seriously impeded by the sluggish multi-electron redox reaction of sulfur species and obstinate shuttle effect of polysulfides. In this study, a porous lanthanum oxychloride (LaOCl) nanofiber is designed as adsorbent and electrocatalyst of polysulfides to regulate the redox kinetics and suppress shuttling of sulfur species. Benefiting from the porous architecture and luxuriant active site of LaOCl nanofibers, the meliorative polarization effect and sulfur expansion can be accomplished. The LaOCl/S electrode exhibits an initial discharge specific capacity of 1112.3 mAh/g at 0.1 C and maintains a superior cycling performance with a slight decay of 0.02% per cycle over 1000 cycles at 1.0 C. Furthermore, even under a high sulfur loading of 4.6 mg/cm2, the S cathode with LaOCl nanofibers still retains a high reversible areal capacity of 4.2 mAh/cm2 at 0.2 C and a stable cycling performance. Such a porous host expands the application of rare earth based catalysts in lithium-sulfur batteries and provides an alternative approach to facilitate the polysulfides conversion kinetics.
Lithium-sulfur batteries are considered to be a new generation of high energy density batteries due to their non-toxicity, low cost and high theoretical specific capacity. However, the development of practical lithium-sulfur batteries is seriously impeded by the sluggish multi-electron redox reaction of sulfur species and obstinate shuttle effect of polysulfides. In this study, a porous lanthanum oxychloride (LaOCl) nanofiber is designed as adsorbent and electrocatalyst of polysulfides to regulate the redox kinetics and suppress shuttling of sulfur species. Benefiting from the porous architecture and luxuriant active site of LaOCl nanofibers, the meliorative polarization effect and sulfur expansion can be accomplished. The LaOCl/S electrode exhibits an initial discharge specific capacity of 1112.3 mAh/g at 0.1 C and maintains a superior cycling performance with a slight decay of 0.02% per cycle over 1000 cycles at 1.0 C. Furthermore, even under a high sulfur loading of 4.6 mg/cm2, the S cathode with LaOCl nanofibers still retains a high reversible areal capacity of 4.2 mAh/cm2 at 0.2 C and a stable cycling performance. Such a porous host expands the application of rare earth based catalysts in lithium-sulfur batteries and provides an alternative approach to facilitate the polysulfides conversion kinetics.
2025, 36(3): 109695
doi: 10.1016/j.cclet.2024.109695
Abstract:
The large current density of electrochemical CO2 reduction towards industrial application is challenging. Herein, without strong acid and reductant, the synthesized BiVO4 with abundant oxygen vacancies (Ovs) exhibited a high formate Faradaic efficiency (FE) of 97.45% (-0.9 V) and a large partial current density of -45.82 mA/cm2 (-1.2 V). The good performance benefits from the reconstruction of BiVO4 to generate active metal Bi sites, which results in the electron redistribution to boost the OCHO* formation. In flow cells, near industrial current density of 183.94 mA/cm2 was achieved, with the FE of formate above 95% from 20 mA/cm2 to 180 mA/cm2. Our work provides a facily synthesized BiVO4 precatalyst for CO2 electroreduction.
The large current density of electrochemical CO2 reduction towards industrial application is challenging. Herein, without strong acid and reductant, the synthesized BiVO4 with abundant oxygen vacancies (Ovs) exhibited a high formate Faradaic efficiency (FE) of 97.45% (-0.9 V) and a large partial current density of -45.82 mA/cm2 (-1.2 V). The good performance benefits from the reconstruction of BiVO4 to generate active metal Bi sites, which results in the electron redistribution to boost the OCHO* formation. In flow cells, near industrial current density of 183.94 mA/cm2 was achieved, with the FE of formate above 95% from 20 mA/cm2 to 180 mA/cm2. Our work provides a facily synthesized BiVO4 precatalyst for CO2 electroreduction.
2025, 36(3): 109712
doi: 10.1016/j.cclet.2024.109712
Abstract:
Anode active materials involving transition metal oxides and sulfides are of great significance for high energy density lithium-ion batteries (LIBs), but the huge volume expansion and inferior electronic conductivity upon cycling critically constrain their further application. Herein, from a new perspective, a highly conductive and stable 3D flexible composite current collector is rationally designed by facilely electrodepositing metallic Ni thin layer onto the carbon cloth (CC/Ni), which endows the supported active materials with exceptional electronic conductivity and structural stability. In addition, the homogeneously distributed metallic Ni protrusions external CC can strongly bond with the active components, ensuring the structural integrity of electrodes upon cycling. More importantly, the 3D network structure with large specific surface area provides abundant space to alleviate the volume expansion and more active sites for electrochemical reactions. Therefore, taking Ni3S2 nanosheet (Ni3S2 NS) anode as an example, the prepared Ni3S2 NS@CC/Ni electrode shows a high specific capacity of 2.32 mAh/cm2 at 1 mA/cm2 and high capacity retention of 1.68 mAh/cm2 at a high rate of 8 mA/cm2. This study provides a universal approach to obtain highly conductive and stable 3D flexible current collectors towards high performance metal-ion batteries beyond LIBs.
Anode active materials involving transition metal oxides and sulfides are of great significance for high energy density lithium-ion batteries (LIBs), but the huge volume expansion and inferior electronic conductivity upon cycling critically constrain their further application. Herein, from a new perspective, a highly conductive and stable 3D flexible composite current collector is rationally designed by facilely electrodepositing metallic Ni thin layer onto the carbon cloth (CC/Ni), which endows the supported active materials with exceptional electronic conductivity and structural stability. In addition, the homogeneously distributed metallic Ni protrusions external CC can strongly bond with the active components, ensuring the structural integrity of electrodes upon cycling. More importantly, the 3D network structure with large specific surface area provides abundant space to alleviate the volume expansion and more active sites for electrochemical reactions. Therefore, taking Ni3S2 nanosheet (Ni3S2 NS) anode as an example, the prepared Ni3S2 NS@CC/Ni electrode shows a high specific capacity of 2.32 mAh/cm2 at 1 mA/cm2 and high capacity retention of 1.68 mAh/cm2 at a high rate of 8 mA/cm2. This study provides a universal approach to obtain highly conductive and stable 3D flexible current collectors towards high performance metal-ion batteries beyond LIBs.
2025, 36(3): 109715
doi: 10.1016/j.cclet.2024.109715
Abstract:
Aqueous iron-ion batteries are regarded as one of the most promising candidates for grid applications owing to their low cost, high theoretical capacity, and excellent stability of iron in aqueous electrolytes. However, the slow Fe (de)insertion caused by the high polarity of Fe2+ makes it difficult to match suitable cathode materials. Herein, defect-rich MoS2 with abundant 1T phase is synthesized and successfully applied in aqueous iron-ion batteries. Benefit from abundant active sites generated by the heteroatom incorporation and S vacancy, as well as the highly conductive 1T phase, it can deliver a specific capacity of 123 mAh/g at a current density of 100 mA/g, and demonstrates an impressive capacity retention of 88% after 600 cycles at 200 mA/g. This work presents a novel pathway for the advancement of cathode materials for aqueous iron-ion batteries.
Aqueous iron-ion batteries are regarded as one of the most promising candidates for grid applications owing to their low cost, high theoretical capacity, and excellent stability of iron in aqueous electrolytes. However, the slow Fe (de)insertion caused by the high polarity of Fe2+ makes it difficult to match suitable cathode materials. Herein, defect-rich MoS2 with abundant 1T phase is synthesized and successfully applied in aqueous iron-ion batteries. Benefit from abundant active sites generated by the heteroatom incorporation and S vacancy, as well as the highly conductive 1T phase, it can deliver a specific capacity of 123 mAh/g at a current density of 100 mA/g, and demonstrates an impressive capacity retention of 88% after 600 cycles at 200 mA/g. This work presents a novel pathway for the advancement of cathode materials for aqueous iron-ion batteries.
2025, 36(3): 109717
doi: 10.1016/j.cclet.2024.109717
Abstract:
By introduction of hydrogen peroxide into the reaction system of ZrOCl2·8H2O and K14[As2W19O67(H2O)], a novel polyoxometalate K8Na19.5H0.5[Zr2(O2)2(β-AsVW10O38)]4·68H2O (1) has been successfully obtained via one-pot method and systematically characterized by IR, XPS, solid UV spectra, PXRD pattern, and TGA analysis. The analysis of X-ray crystallography exhibits that compound 1 crystallizes in the triclinic space group P-1 and presents a novel square-shaped Zr-substituted tetrameric polyoxometalate. The catalytic oxidation of sulfides by 1 are carried out, which demonstrate that 1 exhibits a good performance for the catalytic oxidation of sulfides to sulfones with high conversion (100%) and high selectivity (100%).
By introduction of hydrogen peroxide into the reaction system of ZrOCl2·8H2O and K14[As2W19O67(H2O)], a novel polyoxometalate K8Na19.5H0.5[Zr2(O2)2(β-AsVW10O38)]4·68H2O (1) has been successfully obtained via one-pot method and systematically characterized by IR, XPS, solid UV spectra, PXRD pattern, and TGA analysis. The analysis of X-ray crystallography exhibits that compound 1 crystallizes in the triclinic space group P-1 and presents a novel square-shaped Zr-substituted tetrameric polyoxometalate. The catalytic oxidation of sulfides by 1 are carried out, which demonstrate that 1 exhibits a good performance for the catalytic oxidation of sulfides to sulfones with high conversion (100%) and high selectivity (100%).
2025, 36(3): 109719
doi: 10.1016/j.cclet.2024.109719
Abstract:
In the field of Raman spectroscopy detection, the quest for a non–noble metal, recyclable, and highly sensitive detection substrate is of utmost importance. In this work, a new crystalline and noble metal–free substrate of [Bi(DMF)8][PMo12O40] (Bi–PMo12) is designed, which is composed of [PMo12O40]3− and solvated [Bi(DMF)8]3+ cations. Mechanistic studies have revealed that Raman scattering quenching phenomenon arises from two main factors. Firstly, it arises from the absorption of the scattered light due to the transition of a single electron in the reduced state of MoV between 4d orbitals. Secondly, after the interaction between the substrate and hydrazine, the surface undergoes varying degrees of roughening, leading to an impact on the scattered light intensity. These two effects collectively contribute to the detection of low concentrations of N2H4. As a result, Bi–PMo12 opens up a novel Raman scattering quenching mechanism to realize the detection of reduced N2H4 small molecules. A remarkably low detection limit of 4.5 × 10−9 ppm for N2H4 is achieved on the Bi–PMo12 substrate. This detection has a lower concentration than the currently known SERS detection of N2H4. Moreover, Bi–PMo12 can be recovered and reused through recrystallization, achieving a recovery rate of up to ca. 51%. This study reveals the underlying potential of crystalline polyoxometalate materials in the field of Raman detection, thus opening up new avenues for highly sensitive analysis using Raman techniques.
In the field of Raman spectroscopy detection, the quest for a non–noble metal, recyclable, and highly sensitive detection substrate is of utmost importance. In this work, a new crystalline and noble metal–free substrate of [Bi(DMF)8][PMo12O40] (Bi–PMo12) is designed, which is composed of [PMo12O40]3− and solvated [Bi(DMF)8]3+ cations. Mechanistic studies have revealed that Raman scattering quenching phenomenon arises from two main factors. Firstly, it arises from the absorption of the scattered light due to the transition of a single electron in the reduced state of MoV between 4d orbitals. Secondly, after the interaction between the substrate and hydrazine, the surface undergoes varying degrees of roughening, leading to an impact on the scattered light intensity. These two effects collectively contribute to the detection of low concentrations of N2H4. As a result, Bi–PMo12 opens up a novel Raman scattering quenching mechanism to realize the detection of reduced N2H4 small molecules. A remarkably low detection limit of 4.5 × 10−9 ppm for N2H4 is achieved on the Bi–PMo12 substrate. This detection has a lower concentration than the currently known SERS detection of N2H4. Moreover, Bi–PMo12 can be recovered and reused through recrystallization, achieving a recovery rate of up to ca. 51%. This study reveals the underlying potential of crystalline polyoxometalate materials in the field of Raman detection, thus opening up new avenues for highly sensitive analysis using Raman techniques.
2025, 36(3): 109728
doi: 10.1016/j.cclet.2024.109728
Abstract:
Ultrafast reaction kinetics is essential for rapid detection, synthesis, and process monitoring, but the intrinsic energy barrier as a basic material property is challenging to tailor. With the involvement of nanointerfacial chemistry, we propose a carbonization-based strategy for achieving ultrafast chemical reaction. In a case study, ultrafast Griess reaction within 1 min through the carbonization of N-(1-naphthalene)ethylenediamine (NETH) was realized. The carbonization-mediated ultrafast reaction is attributed to the synergic action of reduced electrostatic repulsion, enriched reactant concentration, and boosted NETH nucleophilicity. The enhanced reaction kinetics in o-phenylenediamine-Cu2+ and o-phenylenediamine-ascorbic acid systems validate the universality of carbonization-engineered ultrafast chemical reaction strategy. The finding of this work offers a novel and simple tactic for the fabrication of multifunctional nanoparticles as ultrafast and effective nanoreactants and/or reporters in analytical, biological, and material aspects.
Ultrafast reaction kinetics is essential for rapid detection, synthesis, and process monitoring, but the intrinsic energy barrier as a basic material property is challenging to tailor. With the involvement of nanointerfacial chemistry, we propose a carbonization-based strategy for achieving ultrafast chemical reaction. In a case study, ultrafast Griess reaction within 1 min through the carbonization of N-(1-naphthalene)ethylenediamine (NETH) was realized. The carbonization-mediated ultrafast reaction is attributed to the synergic action of reduced electrostatic repulsion, enriched reactant concentration, and boosted NETH nucleophilicity. The enhanced reaction kinetics in o-phenylenediamine-Cu2+ and o-phenylenediamine-ascorbic acid systems validate the universality of carbonization-engineered ultrafast chemical reaction strategy. The finding of this work offers a novel and simple tactic for the fabrication of multifunctional nanoparticles as ultrafast and effective nanoreactants and/or reporters in analytical, biological, and material aspects.
2025, 36(3): 109729
doi: 10.1016/j.cclet.2024.109729
Abstract:
The utilization of ethane-selective materials for adsorption-based separation technology presents an energy-efficient alternative to cryogenic distillation for ethylene (C2H4) purification from ethane (C2H6). To study the relations between separation performance and pore environments, we carried out the isoreticular chemistry rule to introduce the -NH2 groups into a C2H6-selective MOF [Cu1.5(BTC)(DPU)1.5(H2O)1.5], and successfully improved the adsorption capacity and selectivity for C2H6 over C2H4. The NH2-functionalized MOF [Cu1.5(NH2-BTC)(DPU)1.5(H2O)1.5] with a relatively narrow pore not only forms appropriate pore restriction but also provides additional binding sites to enhance the adsorption capacity of C2H6 relative to C2H4. Both gas adsorption and dynamic breakthrough results indicated that the -NH2 functionalization significantly enhanced the separation performance of materials for C2H6/C2H4 mixtures, allowing the production of C2H4 with a purity of over 99.99% and a productivity of up to 30.02 L/kg in one step. Theoretical calculations revealed that the synergistic effect of appropriate pore confinement and NH2-modified functional surfaces imposed stronger interactions on C2H6 than C2H4.
The utilization of ethane-selective materials for adsorption-based separation technology presents an energy-efficient alternative to cryogenic distillation for ethylene (C2H4) purification from ethane (C2H6). To study the relations between separation performance and pore environments, we carried out the isoreticular chemistry rule to introduce the -NH2 groups into a C2H6-selective MOF [Cu1.5(BTC)(DPU)1.5(H2O)1.5], and successfully improved the adsorption capacity and selectivity for C2H6 over C2H4. The NH2-functionalized MOF [Cu1.5(NH2-BTC)(DPU)1.5(H2O)1.5] with a relatively narrow pore not only forms appropriate pore restriction but also provides additional binding sites to enhance the adsorption capacity of C2H6 relative to C2H4. Both gas adsorption and dynamic breakthrough results indicated that the -NH2 functionalization significantly enhanced the separation performance of materials for C2H6/C2H4 mixtures, allowing the production of C2H4 with a purity of over 99.99% and a productivity of up to 30.02 L/kg in one step. Theoretical calculations revealed that the synergistic effect of appropriate pore confinement and NH2-modified functional surfaces imposed stronger interactions on C2H6 than C2H4.
2025, 36(3): 109814
doi: 10.1016/j.cclet.2024.109814
Abstract:
Glial fibrillary acidic protein (GFAP) is one of the discriminative biomarkers for diagnosing traumatic brain injury (TBI), and accurate determination of GFAP is clinically significant. In this study, a novel fluorescence immunoassay system was designed. We encapsulated carbon dots with a high fluorescence quantum yield (QY = 92.5%) inside silicon nanocapsules to serve as fluorescent markers. These markers were then integrated with the streptavidin (SA)-biotin biomagnification system and immunomagnetic separation technology for the sensitive detection of GFAP. Based on the signal cascade amplification effect of the silicon nanocapsules and SA-biotin, the fluorescence signal of the SA-biotin-modified immunofluorescence nanocapsules increased 3.6-fold compared to the carbon dot-based immunoprobe. The fluorescence immunoassay system was constructed for GFAP using SA-biotin-modified immunocapsules as the sensing probe and immunomagnetic nanoparticles as the immunorecognition probe. The fluorescence immunoassay system can specifically and ultra-sensitively quantify GFAP in blood samples, with a detection range of 10 pg/mL–10 ng/mL and detection limits of 3.2 pg/mL (serum) and 3.6 pg/mL (plasma). Moreover, the fluorescence immunoassay system exhibited prominent recoveries of 99.4%–100.4% (phosphate buffered saline), 96%–102.6% (serum), and 93.2%–110.2% (plasma), with favorable specificity and excellent stabilization. The novel fluorescence immunoassay system provides a new approach to the clinical analysis of GFAP and may serve as a potential tool for screening and diagnosing TBI.
Glial fibrillary acidic protein (GFAP) is one of the discriminative biomarkers for diagnosing traumatic brain injury (TBI), and accurate determination of GFAP is clinically significant. In this study, a novel fluorescence immunoassay system was designed. We encapsulated carbon dots with a high fluorescence quantum yield (QY = 92.5%) inside silicon nanocapsules to serve as fluorescent markers. These markers were then integrated with the streptavidin (SA)-biotin biomagnification system and immunomagnetic separation technology for the sensitive detection of GFAP. Based on the signal cascade amplification effect of the silicon nanocapsules and SA-biotin, the fluorescence signal of the SA-biotin-modified immunofluorescence nanocapsules increased 3.6-fold compared to the carbon dot-based immunoprobe. The fluorescence immunoassay system was constructed for GFAP using SA-biotin-modified immunocapsules as the sensing probe and immunomagnetic nanoparticles as the immunorecognition probe. The fluorescence immunoassay system can specifically and ultra-sensitively quantify GFAP in blood samples, with a detection range of 10 pg/mL–10 ng/mL and detection limits of 3.2 pg/mL (serum) and 3.6 pg/mL (plasma). Moreover, the fluorescence immunoassay system exhibited prominent recoveries of 99.4%–100.4% (phosphate buffered saline), 96%–102.6% (serum), and 93.2%–110.2% (plasma), with favorable specificity and excellent stabilization. The novel fluorescence immunoassay system provides a new approach to the clinical analysis of GFAP and may serve as a potential tool for screening and diagnosing TBI.
2025, 36(3): 109820
doi: 10.1016/j.cclet.2024.109820
Abstract:
Biocompatible amphiphilic nanoparticles (NPs) with tunable particle morphology and surface property are important for their applications as functional materials. However, previously developed methods to prepare amphiphilic NPs generally involve several steps, especially an additional step for surface modification, greatly hindering their largescale production and widespread applications. Here, a versatile one-step strategy is developed to prepare biocompatible amphiphilic dimer NPs with tunable particle morphology and surface property. The amphiphilic dimer NPs, which consist of a hydrophobic shellac bulb and a hydrophilic poly(lactic acid) (PLA) bulb with PLA-poly(ethylene glycol) (PEG) on the bulb surface, are prepared in a single step by controlled co-precipitation and self-assembly. Amphiphilic PLA-PEG/shellac dimer NPs demonstrate excellent tunability in particle morphology, thus showing good performances in controlling the interfacial curvature and emulsion type. In addition, temperature-responsive PLA-poly(N-isopropyl acrylamide) (PNIPAM)/shellac dimer NPs are prepared following the same method and emulsions stabilized by them show temperature-triggered response. The applications of PLA-PEG-folic acid (FA)/shellac dimer NPs for drug delivery have also been demonstrated, which show a very good performance. The strategy of preparing the dimer NPs is green, scalable, facile and versatile, which provides a good platform for the design of dimer NPs with tunable particle morphology and surface property for diverse applications.
Biocompatible amphiphilic nanoparticles (NPs) with tunable particle morphology and surface property are important for their applications as functional materials. However, previously developed methods to prepare amphiphilic NPs generally involve several steps, especially an additional step for surface modification, greatly hindering their largescale production and widespread applications. Here, a versatile one-step strategy is developed to prepare biocompatible amphiphilic dimer NPs with tunable particle morphology and surface property. The amphiphilic dimer NPs, which consist of a hydrophobic shellac bulb and a hydrophilic poly(lactic acid) (PLA) bulb with PLA-poly(ethylene glycol) (PEG) on the bulb surface, are prepared in a single step by controlled co-precipitation and self-assembly. Amphiphilic PLA-PEG/shellac dimer NPs demonstrate excellent tunability in particle morphology, thus showing good performances in controlling the interfacial curvature and emulsion type. In addition, temperature-responsive PLA-poly(N-isopropyl acrylamide) (PNIPAM)/shellac dimer NPs are prepared following the same method and emulsions stabilized by them show temperature-triggered response. The applications of PLA-PEG-folic acid (FA)/shellac dimer NPs for drug delivery have also been demonstrated, which show a very good performance. The strategy of preparing the dimer NPs is green, scalable, facile and versatile, which provides a good platform for the design of dimer NPs with tunable particle morphology and surface property for diverse applications.
2025, 36(3): 109846
doi: 10.1016/j.cclet.2024.109846
Abstract:
Deprivation of glucose and lactate provides an effective pathway to terminate the nutrients supplement for tumor growth. In this work, biomimetic nanozymes called m@BGLC are constructed for catalytic tumor inhibition through nutrients deprivation and oxidative damage induction. Concretely, the catalytic enzymes of glucose oxidase (GOx), lactate oxidase (LOx) and chloroperoxidase (CPO) are precrosslinked with bovine serum albumin (BSA) to construct nanozymes, which are then biomimetic functionalized with cancer cell membrane to prepare m@BGLC. Benefiting from the biomimetic camouflage with homologous cell membrane, m@BGLC inherit homotypic binding and immune escape abilities, facilitating the tumor targeting accumulation and preferable cell internalization for improved drug delivery efficiency. Subsequently, under the cascade catalysis of nanozymes, m@BGLC consume glucose and lactate for tumor starvation therapy through nutrients deprivation, and meanwhile, the resulting hyprochloric acid (HClO) causes an oxidative damage of cells to synergistically inhibit tumor growth. In vitro and in vivo findings demonstrate a robust tumor eradication effect of m@BGLC without obvious adverse reactions via the targeted combination therapy. Such cascade catalytic nanomedicine may inspire the development of sophisticated strategies for tumor combination therapy under unfavorable tumor microenvironments.
Deprivation of glucose and lactate provides an effective pathway to terminate the nutrients supplement for tumor growth. In this work, biomimetic nanozymes called m@BGLC are constructed for catalytic tumor inhibition through nutrients deprivation and oxidative damage induction. Concretely, the catalytic enzymes of glucose oxidase (GOx), lactate oxidase (LOx) and chloroperoxidase (CPO) are precrosslinked with bovine serum albumin (BSA) to construct nanozymes, which are then biomimetic functionalized with cancer cell membrane to prepare m@BGLC. Benefiting from the biomimetic camouflage with homologous cell membrane, m@BGLC inherit homotypic binding and immune escape abilities, facilitating the tumor targeting accumulation and preferable cell internalization for improved drug delivery efficiency. Subsequently, under the cascade catalysis of nanozymes, m@BGLC consume glucose and lactate for tumor starvation therapy through nutrients deprivation, and meanwhile, the resulting hyprochloric acid (HClO) causes an oxidative damage of cells to synergistically inhibit tumor growth. In vitro and in vivo findings demonstrate a robust tumor eradication effect of m@BGLC without obvious adverse reactions via the targeted combination therapy. Such cascade catalytic nanomedicine may inspire the development of sophisticated strategies for tumor combination therapy under unfavorable tumor microenvironments.
2025, 36(3): 109856
doi: 10.1016/j.cclet.2024.109856
Abstract:
The cyclic guanosine monophosphate-adenosine monophosphate synthase and the stimulator of interferon genes (cGAS-STING) has emerged as a promising target for cancer immunotherapy. However, the development of natural STING agonists is impeded by several challenges, including limited biostability, poor pharmacokinetics, and inefficient cytosolic delivery. Herein, we meticulously designed a double-layer polyethylenimine (PEI) modified nanoscale covalent organic polymer (CPGP) for efficient delivery of 2′3′ cyclic guanosine monophosphate-adenosine monophosphate (cGAMP), a natural STING agonist. The double-layer PEI structured CPGP enhanced both the loading capacity and stability of cGAMP. Furthermore, CPGP improved the intracellular delivery efficiency and amplified the activation of STING pathway for the secretion of type-Ⅰ interferon and pro-inflammatory cytokines. In contrast, single-layered nanoparticles failed to permit stable loading and intracellular delivery of cGAMP for immune response. The nano-STING agonist also mitigated the immunosuppressive tumor microenvironment (TME) by reducing regulatory T cells and polarizing M2 macrophages to the M1 phenotype, thereby creating an immune-supportive TME to enhance adaptive immune responses. The combination of CPGP and immune checkpoint blockers showed synergistic effect, further enhancing the inhibition effect on tumor growth. This double-layer PEI modified CPGP may offer a generalizable platform for other natural dinucleotide STING agonists to overcome the cascade delivery barriers, augmenting immune activation for tumor immunotherapy.
The cyclic guanosine monophosphate-adenosine monophosphate synthase and the stimulator of interferon genes (cGAS-STING) has emerged as a promising target for cancer immunotherapy. However, the development of natural STING agonists is impeded by several challenges, including limited biostability, poor pharmacokinetics, and inefficient cytosolic delivery. Herein, we meticulously designed a double-layer polyethylenimine (PEI) modified nanoscale covalent organic polymer (CPGP) for efficient delivery of 2′3′ cyclic guanosine monophosphate-adenosine monophosphate (cGAMP), a natural STING agonist. The double-layer PEI structured CPGP enhanced both the loading capacity and stability of cGAMP. Furthermore, CPGP improved the intracellular delivery efficiency and amplified the activation of STING pathway for the secretion of type-Ⅰ interferon and pro-inflammatory cytokines. In contrast, single-layered nanoparticles failed to permit stable loading and intracellular delivery of cGAMP for immune response. The nano-STING agonist also mitigated the immunosuppressive tumor microenvironment (TME) by reducing regulatory T cells and polarizing M2 macrophages to the M1 phenotype, thereby creating an immune-supportive TME to enhance adaptive immune responses. The combination of CPGP and immune checkpoint blockers showed synergistic effect, further enhancing the inhibition effect on tumor growth. This double-layer PEI modified CPGP may offer a generalizable platform for other natural dinucleotide STING agonists to overcome the cascade delivery barriers, augmenting immune activation for tumor immunotherapy.
2025, 36(3): 109868
doi: 10.1016/j.cclet.2024.109868
Abstract:
Neuropathic pain (NP) is one of the most common pathological pain types and is associated with limited treatment options; moreover, it affects patients’ quality of life and causes a heavy social burden. Despite the emphasis on inhibiting neuronal apoptosis to relieve NP, the crucial role of a neuroinflammation is often overlooked. Therefore, refocusing on the regulation of microglia polarization to create a more conducive environment for neuron holds great potential in NP treatment. In recent years, small interfering RNAs (siRNAs) had become an attractive therapeutic option. However, an efficient loading and delivery system for siRNA is still in lack. In our study, a nanostructured tetrahedral framework nucleic acid loaded with the small interfering RNA C–C chemokine receptor 2 (T-siCCR2) was successfully designed and synthesized for use in NP rat model in vivo and in a lipopolysaccharide (LPS)-induced inflammatory environment in vitro. This nanoscale complex is endowed with structural stability and satisfactory delivery efficiency while assuring the silencing effect of siRNA-CCR2. In vivo, T-siCCR2 treatment exhibited favorable effects on pain relief and functional improvement in the NP animal model by directly targeting microglia. In vitro, T-siCCR2 counteracts LPS-induced inflammation by inhibiting the differentiation of microglia toward the M1 phenotype, thus playing a neuroprotective role. RNA sequencing was subsequently performed to elucidate the underlying mechanism involved. These results indicate that T-siCCR2 may serve as a potential treatment option for NP in the future.
Neuropathic pain (NP) is one of the most common pathological pain types and is associated with limited treatment options; moreover, it affects patients’ quality of life and causes a heavy social burden. Despite the emphasis on inhibiting neuronal apoptosis to relieve NP, the crucial role of a neuroinflammation is often overlooked. Therefore, refocusing on the regulation of microglia polarization to create a more conducive environment for neuron holds great potential in NP treatment. In recent years, small interfering RNAs (siRNAs) had become an attractive therapeutic option. However, an efficient loading and delivery system for siRNA is still in lack. In our study, a nanostructured tetrahedral framework nucleic acid loaded with the small interfering RNA C–C chemokine receptor 2 (T-siCCR2) was successfully designed and synthesized for use in NP rat model in vivo and in a lipopolysaccharide (LPS)-induced inflammatory environment in vitro. This nanoscale complex is endowed with structural stability and satisfactory delivery efficiency while assuring the silencing effect of siRNA-CCR2. In vivo, T-siCCR2 treatment exhibited favorable effects on pain relief and functional improvement in the NP animal model by directly targeting microglia. In vitro, T-siCCR2 counteracts LPS-induced inflammation by inhibiting the differentiation of microglia toward the M1 phenotype, thus playing a neuroprotective role. RNA sequencing was subsequently performed to elucidate the underlying mechanism involved. These results indicate that T-siCCR2 may serve as a potential treatment option for NP in the future.
2025, 36(3): 109872
doi: 10.1016/j.cclet.2024.109872
Abstract:
Oxygen evolution reaction (OER) is one of the most important half-reactions related to metal-air batteries, fuel cells, and water-splitting. Due to the sluggish kinetic and multi-electron transfer, catalysts appear to be particularly important for the OER. Knowing the reaction mechanism is fundamental to developing new catalysts and improving OER efficiency. In this work, phase transition and atomic reconstruction on CoO (111) plane were revealed through ex-situ diffraction methods and X-ray absorption spectroscopy. At the same time, the electronic state evolution of Co(Ⅱ)/Co(Ⅲ) during the OER process has also been concluded by analyzing the magnetic properties. This work shows that during the OER process, Co(Ⅲ) experiences surface electron rearrangement from IS (intermediate-spin state) to LS (low-spin state) and then returns to IS/HS (high-spin state) under high voltage region. This work provides a new view to reveal the reaction mechanism through the magnetic property and it can be extended to more magnetic 3d transition metals for future catalyst design.
Oxygen evolution reaction (OER) is one of the most important half-reactions related to metal-air batteries, fuel cells, and water-splitting. Due to the sluggish kinetic and multi-electron transfer, catalysts appear to be particularly important for the OER. Knowing the reaction mechanism is fundamental to developing new catalysts and improving OER efficiency. In this work, phase transition and atomic reconstruction on CoO (111) plane were revealed through ex-situ diffraction methods and X-ray absorption spectroscopy. At the same time, the electronic state evolution of Co(Ⅱ)/Co(Ⅲ) during the OER process has also been concluded by analyzing the magnetic properties. This work shows that during the OER process, Co(Ⅲ) experiences surface electron rearrangement from IS (intermediate-spin state) to LS (low-spin state) and then returns to IS/HS (high-spin state) under high voltage region. This work provides a new view to reveal the reaction mechanism through the magnetic property and it can be extended to more magnetic 3d transition metals for future catalyst design.
2025, 36(3): 109874
doi: 10.1016/j.cclet.2024.109874
Abstract:
The complexity of cancer therapy has led to the emergence of combination therapy as a promising approach to enhance treatment efficacy and safety. The integration of glutathione (GSH)-activatable two-photon photodynamic therapy (TP-PDT) and chemodynamic therapy (CDT) offers the possibility to advance precision and efficacy in anti-cancer treatments. In this study, a GSH-activatable photosensitizer (PS), namely copper-elsinochrome (CuEC), is synthesized and utilized for combination second near-infrared (NIR-Ⅱ) TP-PDT/CDT. The Cu2+ acts as a “lock”, suppressing the fluorescence and 1O2 generation ability of EC in a normal physiological environment (“OFF” state). However, the overexpressed GSH in the tumor microenvironment acts as the “key”, resulting in the release of EC (“ON” state) and Cu+ (reduced by GSH). The released EC can be utilized for fluorescence imaging and TP-PDT under NIR-Ⅱ (λ = 1000 nm) two-photon excitation, while Cu+ can generate highly toxic hydroxyl radicals (•OH) via Fenton-like reaction for CDT. Additionally, this process consumes GSH and diminishes the tumor’s antioxidant capacity, thereby augmenting the efficacy of combination therapy. The CuEC achieves significant tumor cell ablation in both 2D monolayer cells and 3D multicellular tumor spheres through the combination of NIR-Ⅱ TP-PDT and CDT.
The complexity of cancer therapy has led to the emergence of combination therapy as a promising approach to enhance treatment efficacy and safety. The integration of glutathione (GSH)-activatable two-photon photodynamic therapy (TP-PDT) and chemodynamic therapy (CDT) offers the possibility to advance precision and efficacy in anti-cancer treatments. In this study, a GSH-activatable photosensitizer (PS), namely copper-elsinochrome (CuEC), is synthesized and utilized for combination second near-infrared (NIR-Ⅱ) TP-PDT/CDT. The Cu2+ acts as a “lock”, suppressing the fluorescence and 1O2 generation ability of EC in a normal physiological environment (“OFF” state). However, the overexpressed GSH in the tumor microenvironment acts as the “key”, resulting in the release of EC (“ON” state) and Cu+ (reduced by GSH). The released EC can be utilized for fluorescence imaging and TP-PDT under NIR-Ⅱ (λ = 1000 nm) two-photon excitation, while Cu+ can generate highly toxic hydroxyl radicals (•OH) via Fenton-like reaction for CDT. Additionally, this process consumes GSH and diminishes the tumor’s antioxidant capacity, thereby augmenting the efficacy of combination therapy. The CuEC achieves significant tumor cell ablation in both 2D monolayer cells and 3D multicellular tumor spheres through the combination of NIR-Ⅱ TP-PDT and CDT.
2025, 36(3): 109903
doi: 10.1016/j.cclet.2024.109903
Abstract:
Controllable construction of organic heterostructures is key to developing supramolecular materials with sophisticated functions. Herein, block heterostructures with controllable shape and dimension have been successfully constructed from one molecular pair of Ir(Ⅲ) complexes 1 and 2 in H2O/CH3CN. Different volume ratios of H2O/CH3CN led to controllable morphologies of assemblies 1 from nanofibers (1NF) to nanosheets (1NS). Through reasonable experimental design, both 1NF and 1NS could be used as seeds to trigger the heterogeneous nucleation-elongation of 2. Finally, unprecedented dual control on the length and width of supramolecular block copolymers from the same monomer pair was realized smoothly. The corresponding heterogeneous nucleation-elongation process was confirmed by time-dependent UV–vis absorption spectra and emission spectra. The components of each segment of the fibrous and sheet-like block copolymers were identified by TEM, SEM, and CLSM. The results reveal that the previously unappreciated solvation effect can serve as a powerful tool to control the morphologies of heterostructures.
Controllable construction of organic heterostructures is key to developing supramolecular materials with sophisticated functions. Herein, block heterostructures with controllable shape and dimension have been successfully constructed from one molecular pair of Ir(Ⅲ) complexes 1 and 2 in H2O/CH3CN. Different volume ratios of H2O/CH3CN led to controllable morphologies of assemblies 1 from nanofibers (1NF) to nanosheets (1NS). Through reasonable experimental design, both 1NF and 1NS could be used as seeds to trigger the heterogeneous nucleation-elongation of 2. Finally, unprecedented dual control on the length and width of supramolecular block copolymers from the same monomer pair was realized smoothly. The corresponding heterogeneous nucleation-elongation process was confirmed by time-dependent UV–vis absorption spectra and emission spectra. The components of each segment of the fibrous and sheet-like block copolymers were identified by TEM, SEM, and CLSM. The results reveal that the previously unappreciated solvation effect can serve as a powerful tool to control the morphologies of heterostructures.
2025, 36(3): 109904
doi: 10.1016/j.cclet.2024.109904
Abstract:
Diabetic liver injury is a widespread complication of diabetes and carries a high risk to liver function. Therefore, early diagnosis of diabetic liver injury is of great significance for providing quality of life for diabetic patients. Most of the activated dual-modal probes are usually activated by single factor stimulation, which greatly reduces the diagnostic accuracy of liver injury. Here, a novel cysteine (Cys)/homocysteine (Hcy) and viscosity-enhanced dual-modal probe DAL was developed for the first time to monitor diabetic liver injury and its repair process. In the presence of Cys/Hcy, the near-infrared fluorescence (NIRF) and photoacoustic (PA) signals of the probe DAL were activated, with further signal enhancement in high viscosity environments. This Cys/Hcy and viscosity cascade probe exhibits heightened sensitivity and enhanced anti-interference capabilities, contributing to the advancement of liver injury diagnosis accuracy. In addition, the probe DAL shows exceptional mitochondrial targeting ability, enabling sensitive monitoring of Cys/Hcy and viscosity alterations within mitochondria. Based on NIRF/PA dual-modal imaging technology, the probe was successfully used for the first time in a mouse diabetic liver injury model to evaluate the extent of liver damage and the repair process by tracking the levels of Cys/Hcy and viscosity. Therefore, the two-factor activated dual-modal probe developed in this study provides a powerful instrument for accurate diagnosis and efficacy evaluation of complications related to diabetes.
Diabetic liver injury is a widespread complication of diabetes and carries a high risk to liver function. Therefore, early diagnosis of diabetic liver injury is of great significance for providing quality of life for diabetic patients. Most of the activated dual-modal probes are usually activated by single factor stimulation, which greatly reduces the diagnostic accuracy of liver injury. Here, a novel cysteine (Cys)/homocysteine (Hcy) and viscosity-enhanced dual-modal probe DAL was developed for the first time to monitor diabetic liver injury and its repair process. In the presence of Cys/Hcy, the near-infrared fluorescence (NIRF) and photoacoustic (PA) signals of the probe DAL were activated, with further signal enhancement in high viscosity environments. This Cys/Hcy and viscosity cascade probe exhibits heightened sensitivity and enhanced anti-interference capabilities, contributing to the advancement of liver injury diagnosis accuracy. In addition, the probe DAL shows exceptional mitochondrial targeting ability, enabling sensitive monitoring of Cys/Hcy and viscosity alterations within mitochondria. Based on NIRF/PA dual-modal imaging technology, the probe was successfully used for the first time in a mouse diabetic liver injury model to evaluate the extent of liver damage and the repair process by tracking the levels of Cys/Hcy and viscosity. Therefore, the two-factor activated dual-modal probe developed in this study provides a powerful instrument for accurate diagnosis and efficacy evaluation of complications related to diabetes.
2025, 36(3): 109907
doi: 10.1016/j.cclet.2024.109907
Abstract:
Mn-rich layered oxides are appealing cathodes for potassium ion batteries (PIBs) in view of their comprehensive virtues such as low cost, high energy density and mature craftsmanship. However, the insufficient covalency between transition metal (TM) and O usually induces irreversible structural evolution and cation migration during repeated insertion and extraction of K+, resulting in capacity loss, voltage fading and sluggish kinetics. Herein, an anion substitution strategy is proposed for a stable operation of layered oxide cathode by adjusting the valence electron layer structure between TM and O. The resultant strong TM−O skeleton can inhibit the occurrence of side effects derive from Ni4+ during the deep depotassium process, so as to achieve a gentle structural transition. Consequently, stable cycling performance of K0.39Mn0.77Ni0.23O1.9F0.1 (KMNOF) cathode is achieved with 77% capacity retention over 350 cycles at 100 mA/g, yielding high discharge capacity 93.5 mAh/g at 20 mA/g and significantly improved rate capability of 50.1 mAh/g at 500 mA/g, whereas irreversible structural evolution and rapid capacity fade with KMNO cathode. Finally, in situ/ex situ characterizations and theoretical computations sheds light on the charge transfer and structure evolution mechanisms of KMNOF.
Mn-rich layered oxides are appealing cathodes for potassium ion batteries (PIBs) in view of their comprehensive virtues such as low cost, high energy density and mature craftsmanship. However, the insufficient covalency between transition metal (TM) and O usually induces irreversible structural evolution and cation migration during repeated insertion and extraction of K+, resulting in capacity loss, voltage fading and sluggish kinetics. Herein, an anion substitution strategy is proposed for a stable operation of layered oxide cathode by adjusting the valence electron layer structure between TM and O. The resultant strong TM−O skeleton can inhibit the occurrence of side effects derive from Ni4+ during the deep depotassium process, so as to achieve a gentle structural transition. Consequently, stable cycling performance of K0.39Mn0.77Ni0.23O1.9F0.1 (KMNOF) cathode is achieved with 77% capacity retention over 350 cycles at 100 mA/g, yielding high discharge capacity 93.5 mAh/g at 20 mA/g and significantly improved rate capability of 50.1 mAh/g at 500 mA/g, whereas irreversible structural evolution and rapid capacity fade with KMNO cathode. Finally, in situ/ex situ characterizations and theoretical computations sheds light on the charge transfer and structure evolution mechanisms of KMNOF.
2025, 36(3): 109915
doi: 10.1016/j.cclet.2024.109915
Abstract:
The first total synthesis of marine sesquiterpene (hydro)quinone meroterpenoids dysideanones A and E–G (1 and 4–6) has been accomplished in an enantioselective and divergent way. The sesquiterpene fragment and the aromatic moiety were efficiently connected via a site-selective and diastereoselective intermolecular alkylation of Wieland–Miescher ketone derivative 9 and benzyl bromide 10. The core 6/6/6/6-fused backbone of dysideanones was efficiently constructed through an intramolecular radical cyclization reaction. Dysideanone G (6) was easily prepared on a gram-scale and dysideanones A, E, and F (1, 4, and 5) were divergently transformed from dysideanone G (6) in one or two steps
The first total synthesis of marine sesquiterpene (hydro)quinone meroterpenoids dysideanones A and E–G (1 and 4–6) has been accomplished in an enantioselective and divergent way. The sesquiterpene fragment and the aromatic moiety were efficiently connected via a site-selective and diastereoselective intermolecular alkylation of Wieland–Miescher ketone derivative 9 and benzyl bromide 10. The core 6/6/6/6-fused backbone of dysideanones was efficiently constructed through an intramolecular radical cyclization reaction. Dysideanone G (6) was easily prepared on a gram-scale and dysideanones A, E, and F (1, 4, and 5) were divergently transformed from dysideanone G (6) in one or two steps
2025, 36(3): 109926
doi: 10.1016/j.cclet.2024.109926
Abstract:
A photoredox-catalyzed synthesis of α,α-difluoromethyl sulfones from sulfur dioxide with readily available gem–difluoroalkenes is reported. This protocol features mild reaction conditions, broad substrate scope and good functional group compatibility, giving rise to the target α,α-difluoromethyl sulfones in moderate to excellent yields. Mechanistic studies indicate that this reaction is initiated by an aryl radical with the insertion of sulfur dioxide.
A photoredox-catalyzed synthesis of α,α-difluoromethyl sulfones from sulfur dioxide with readily available gem–difluoroalkenes is reported. This protocol features mild reaction conditions, broad substrate scope and good functional group compatibility, giving rise to the target α,α-difluoromethyl sulfones in moderate to excellent yields. Mechanistic studies indicate that this reaction is initiated by an aryl radical with the insertion of sulfur dioxide.
2025, 36(3): 109941
doi: 10.1016/j.cclet.2024.109941
Abstract:
Microplastics (MPs) are an emerging environmental pollutant and have penetrated the most remote and primitive areas. MPs degradation has received widespread attention. Manganese (Mn) is a highly reactive metal element in the environment, yet its contribution to MPs degradation remains unclear. Herein, we simulated the aging of polyethylene MPs with Mn(Ⅱ) under aqueous conditions at pH 5 and 8 for 720 days. Mn greatly promoted the MPs degradation, and the average particle sizes of polyethylene MPs were reduced from 9.2 µm to 5.9 µm after aging at pH 5 under light irradiation for 720 days. Plenty of oxygen-containing groups were generated on the MPs surfaces, and the carbonyl index remarkably increased, reaching four times that of the control without adding Mn. Mechanistically, the adsorbed Mn(Ⅱ) on the MPs surfaces were primarily oxidized to high-valence Mn(Ⅲ/Ⅳ) profited from the photoproduced radicals, followed by the MPs oxidation via Mn(Ⅲ/Ⅳ), which were reduced to regenerate Mn(Ⅱ), initiating a new redox cycling. During the degradation, dissolved organic matter was continuously released, mainly including bisphenol A and phthalic acid esters. Mn acts as a catalyst to accelerate the MPs degradation by redox cycling. Our results provide a new insight into the mechanisms of abiotic degradation of MPs in aqueous environments.
Microplastics (MPs) are an emerging environmental pollutant and have penetrated the most remote and primitive areas. MPs degradation has received widespread attention. Manganese (Mn) is a highly reactive metal element in the environment, yet its contribution to MPs degradation remains unclear. Herein, we simulated the aging of polyethylene MPs with Mn(Ⅱ) under aqueous conditions at pH 5 and 8 for 720 days. Mn greatly promoted the MPs degradation, and the average particle sizes of polyethylene MPs were reduced from 9.2 µm to 5.9 µm after aging at pH 5 under light irradiation for 720 days. Plenty of oxygen-containing groups were generated on the MPs surfaces, and the carbonyl index remarkably increased, reaching four times that of the control without adding Mn. Mechanistically, the adsorbed Mn(Ⅱ) on the MPs surfaces were primarily oxidized to high-valence Mn(Ⅲ/Ⅳ) profited from the photoproduced radicals, followed by the MPs oxidation via Mn(Ⅲ/Ⅳ), which were reduced to regenerate Mn(Ⅱ), initiating a new redox cycling. During the degradation, dissolved organic matter was continuously released, mainly including bisphenol A and phthalic acid esters. Mn acts as a catalyst to accelerate the MPs degradation by redox cycling. Our results provide a new insight into the mechanisms of abiotic degradation of MPs in aqueous environments.
2025, 36(3): 109954
doi: 10.1016/j.cclet.2024.109954
Abstract:
Herein, we describe a nickel-catalyzed reductive decarboxylative difluoromethylation reaction of alkenes using inexpensive and easy-to-handle difluoroacetic anhydride (DFAA)/pyridine N-oxide reagent system. A variety of C(sp3)-CF2H containing compounds were prepared through a hydrodifluoromethylation process. Besides, various gem–difluoroalkenes bearing CF2H group were synthesized via defluorinative reductive cross-coupling process from trifluoromethyl-substituted alkenes using this new reaction system. Difluoroacetic anhydride has been then extended to other common alkyl anhydrides, and the corresponding hydroalkylation and defluoroalkylation processes have been successfully achieved. This method features broad substrate scope, good functional group tolerance as well as high efficiency.
Herein, we describe a nickel-catalyzed reductive decarboxylative difluoromethylation reaction of alkenes using inexpensive and easy-to-handle difluoroacetic anhydride (DFAA)/pyridine N-oxide reagent system. A variety of C(sp3)-CF2H containing compounds were prepared through a hydrodifluoromethylation process. Besides, various gem–difluoroalkenes bearing CF2H group were synthesized via defluorinative reductive cross-coupling process from trifluoromethyl-substituted alkenes using this new reaction system. Difluoroacetic anhydride has been then extended to other common alkyl anhydrides, and the corresponding hydroalkylation and defluoroalkylation processes have been successfully achieved. This method features broad substrate scope, good functional group tolerance as well as high efficiency.
2025, 36(3): 109967
doi: 10.1016/j.cclet.2024.109967
Abstract:
The cross-photodimerization often comes with the formation of undesired and competitive homo-photodimer as side products. Herein, we report a series of highly selective [4 + 4] cross-photodimerization between anthracene and 4a-azoniaanthracene derivatives within a cucurbit[10]uril (CB[10]) host in water. Heteroternary inclusion complexes were formed through encapsulation of donor (D1-D2, anthracene derivative) and acceptor (A1-A3, 4a-azoniaanthracene derivatives) pairs in CB[10]. In the presence of CB[10] (1.0 equiv.), the [4 + 4] cross-photodimerization between D1 and A1/A2/A3 efficiently gave a single racemic cross-photodimer. Furthermore, the cross-photodimerization between 9-substituted anthracene D2 and A1/A3 was catalyzed by CB[10] (0.1 equiv.) to quantitatively yield a cross-photodimer with high regioselectivity. Efficient formation of selective cross-photodimers could be attributed to the exclusive encapsulation of D-A hetero-guest pairs in CB[10] and the confinement effect of the CB[10] host cavity. Our study further proves host–guest complexation as a powerful strategy for cross-cycloaddition reactions with high efficiency.
The cross-photodimerization often comes with the formation of undesired and competitive homo-photodimer as side products. Herein, we report a series of highly selective [4 + 4] cross-photodimerization between anthracene and 4a-azoniaanthracene derivatives within a cucurbit[10]uril (CB[10]) host in water. Heteroternary inclusion complexes were formed through encapsulation of donor (D1-D2, anthracene derivative) and acceptor (A1-A3, 4a-azoniaanthracene derivatives) pairs in CB[10]. In the presence of CB[10] (1.0 equiv.), the [4 + 4] cross-photodimerization between D1 and A1/A2/A3 efficiently gave a single racemic cross-photodimer. Furthermore, the cross-photodimerization between 9-substituted anthracene D2 and A1/A3 was catalyzed by CB[10] (0.1 equiv.) to quantitatively yield a cross-photodimer with high regioselectivity. Efficient formation of selective cross-photodimers could be attributed to the exclusive encapsulation of D-A hetero-guest pairs in CB[10] and the confinement effect of the CB[10] host cavity. Our study further proves host–guest complexation as a powerful strategy for cross-cycloaddition reactions with high efficiency.
2025, 36(3): 109968
doi: 10.1016/j.cclet.2024.109968
Abstract:
Rational tuning of chiral nanostructures of supramolecular assemblies as catalysts and investigating their chiral morphology-enantioselectivity dependence is rarely reported. Herein, we report a series of supramolecular M/P-helical nanoribbons (HNs) assembled from the chiral L/D-glutamate-based amphiphiles (L/D-GluC16) and Cu(Ⅱ) ions, with their helical screw pitches adjusted from 217 nm to 104 nm through the facile regulation of their water/organic solvent assembly environment. They were then used as ideal models to reveal the chiral morphology-enantioselectivity relationship by catalyzing the asymmetric Diels-Alder reaction. Better enantioselectivity was achieved with more twist morphology. Experimental evidences of stronger chiral transfer effect from the supramolecular HNs with more twist to the aza-chalcone as reactant were obtained to understand such dependence. Our study demonstrates a new perspective for designing supramolecular catalysts with higher enantioselectivity.
Rational tuning of chiral nanostructures of supramolecular assemblies as catalysts and investigating their chiral morphology-enantioselectivity dependence is rarely reported. Herein, we report a series of supramolecular M/P-helical nanoribbons (HNs) assembled from the chiral L/D-glutamate-based amphiphiles (L/D-GluC16) and Cu(Ⅱ) ions, with their helical screw pitches adjusted from 217 nm to 104 nm through the facile regulation of their water/organic solvent assembly environment. They were then used as ideal models to reveal the chiral morphology-enantioselectivity relationship by catalyzing the asymmetric Diels-Alder reaction. Better enantioselectivity was achieved with more twist morphology. Experimental evidences of stronger chiral transfer effect from the supramolecular HNs with more twist to the aza-chalcone as reactant were obtained to understand such dependence. Our study demonstrates a new perspective for designing supramolecular catalysts with higher enantioselectivity.
2025, 36(3): 109971
doi: 10.1016/j.cclet.2024.109971
Abstract:
Aryl ketones as photolabile protecting group (PPG) to modify purine imines is a novel nucleic acid protection strategy. Especially, photoprotection of N7-guanosine is the first reported photoprotected nucleoside that can affect the Hoogsteen recognition site of guanosine. However, the mechanism, which is pivotal to high efficiency of photorelease and applications of PPGs in biological and medical systems, is unclear. Here, a detailed deprotection mechanism of benzophenone protected guanosine (BP-Guo) at N7 position is reported. Upon irradiation, BP-Guo populates to singlet state, which generates 3[BP]-Guo via intersystem crossing process. Thereafter, triplet energy transfer competes with hydrogen atom transfer forming BP-3[Guo] and ketyl-Guo, respectively. Both species break CN bond to release guanosine. These results provide deeper insights into exploiting improved strategies for photo-protecting nucleic acids. In particular, the TTET pathway could trigger well-known cyclization reactions that brings about DNA mutagenic adducts. The latter should be avoided in developing improved strategies for photoprotecting nucleic acids.
Aryl ketones as photolabile protecting group (PPG) to modify purine imines is a novel nucleic acid protection strategy. Especially, photoprotection of N7-guanosine is the first reported photoprotected nucleoside that can affect the Hoogsteen recognition site of guanosine. However, the mechanism, which is pivotal to high efficiency of photorelease and applications of PPGs in biological and medical systems, is unclear. Here, a detailed deprotection mechanism of benzophenone protected guanosine (BP-Guo) at N7 position is reported. Upon irradiation, BP-Guo populates to singlet state, which generates 3[BP]-Guo via intersystem crossing process. Thereafter, triplet energy transfer competes with hydrogen atom transfer forming BP-3[Guo] and ketyl-Guo, respectively. Both species break CN bond to release guanosine. These results provide deeper insights into exploiting improved strategies for photo-protecting nucleic acids. In particular, the TTET pathway could trigger well-known cyclization reactions that brings about DNA mutagenic adducts. The latter should be avoided in developing improved strategies for photoprotecting nucleic acids.
2025, 36(3): 109972
doi: 10.1016/j.cclet.2024.109972
Abstract:
3-Deoxy-D-manno-oct-2-ulosonic acid (Kdo) is widely distributed in bacteria, and the synthesis of Kdo-containing oligosaccharides is important for the development of novel antibiotics and immunological agents. We have recently developed a strategy to achieve α-stereocontrolled glycosylation using a C3-p-tolylthio-substituted Kdo phosphite donor. The wide substrate scope and high reactivity of the donors enabled the efficient synthesis of a series of Kdo-containing glycosides with complete α-stereoselectivity and without the formation of 2,3-ene byproducts. In this study, we improved the method by replacing the leaving group diethyl phosphite with fluoride, which enhanced the stability of the donor and led to cleaner reaction. Furthermore, the substrate range was expanded by synthesizing a series of Kdo O/C/S/N-glycosides, which also opened up a new avenue for the synthesis of CMP-Kdo synthase inhibitors.
3-Deoxy-D-manno-oct-2-ulosonic acid (Kdo) is widely distributed in bacteria, and the synthesis of Kdo-containing oligosaccharides is important for the development of novel antibiotics and immunological agents. We have recently developed a strategy to achieve α-stereocontrolled glycosylation using a C3-p-tolylthio-substituted Kdo phosphite donor. The wide substrate scope and high reactivity of the donors enabled the efficient synthesis of a series of Kdo-containing glycosides with complete α-stereoselectivity and without the formation of 2,3-ene byproducts. In this study, we improved the method by replacing the leaving group diethyl phosphite with fluoride, which enhanced the stability of the donor and led to cleaner reaction. Furthermore, the substrate range was expanded by synthesizing a series of Kdo O/C/S/N-glycosides, which also opened up a new avenue for the synthesis of CMP-Kdo synthase inhibitors.
2025, 36(3): 109991
doi: 10.1016/j.cclet.2024.109991
Abstract:
Herein, we developed the first example of copper-catalyzed silicon radical-initiated 1,4-silylcyanation of unactivated 1,3-enynes, which provided an efficient method to access CN-bearing tri- and tetra-substituted homoallenylsilane derivatives in high yields with excellent regioselectivities. This protocol featured good functional group compatibility and broad substrate scopes, enabling the formation of C-Si bond under cheap copper catalyst with a low loading. Furthermore, this means showed potential application value in the late-stage functionalization of natural products.
Herein, we developed the first example of copper-catalyzed silicon radical-initiated 1,4-silylcyanation of unactivated 1,3-enynes, which provided an efficient method to access CN-bearing tri- and tetra-substituted homoallenylsilane derivatives in high yields with excellent regioselectivities. This protocol featured good functional group compatibility and broad substrate scopes, enabling the formation of C-Si bond under cheap copper catalyst with a low loading. Furthermore, this means showed potential application value in the late-stage functionalization of natural products.
2025, 36(3): 109999
doi: 10.1016/j.cclet.2024.109999
Abstract:
Supramolecular prodrug vesicles (H-4⊃B-2@MB) with selective antibacterial activity have been successfully constructed. Specifically, a natural antibiotic prodrug (B-2) with glutathione (GSH)-responsiveness was synthesized. The hydrophobic interaction between B-2 and a novel water-soluble cavitand with deep cavity (H-4) resulted in the formation of a host-guest complex, which further self-assembled into supramolecular vesicles. The formed vesicles could effectively encapsulate the photosensitizer methylene blue (MB), enabling co-delivery of antibiotics and photosensitizers in the presence of GSH. Moreover, upon excitation at 630 nm, the photosensitizers generate reactive oxygen species (ROS), effectively eradicating E. coli through combined chemo-photodynamic therapy. Considering that GSH is predominantly present in Gram-negative bacteria such as E. coli, this strategy exhibits substantial potential for selectively inhibiting bacteria characterized by high GSH levels to regulate bacterial colony equilibrium.
Supramolecular prodrug vesicles (H-4⊃B-2@MB) with selective antibacterial activity have been successfully constructed. Specifically, a natural antibiotic prodrug (B-2) with glutathione (GSH)-responsiveness was synthesized. The hydrophobic interaction between B-2 and a novel water-soluble cavitand with deep cavity (H-4) resulted in the formation of a host-guest complex, which further self-assembled into supramolecular vesicles. The formed vesicles could effectively encapsulate the photosensitizer methylene blue (MB), enabling co-delivery of antibiotics and photosensitizers in the presence of GSH. Moreover, upon excitation at 630 nm, the photosensitizers generate reactive oxygen species (ROS), effectively eradicating E. coli through combined chemo-photodynamic therapy. Considering that GSH is predominantly present in Gram-negative bacteria such as E. coli, this strategy exhibits substantial potential for selectively inhibiting bacteria characterized by high GSH levels to regulate bacterial colony equilibrium.
2025, 36(3): 110000
doi: 10.1016/j.cclet.2024.110000
Abstract:
Solar interfacial evaporation (SIE), is currently one of the most potential water supply technologies in the remote, insular, and disaster-stricken areas. However, the existence of volatile organic compounds (VOCs) in water deteriorates the distillate quality, threatening human health. Herein, we constructed a carbon-based bimetallic (C/FeCo) photothermal membrane by electrospinning technique. Results illustrated that the membrane can catalytically degrade VOCs during SIE with persulfate (PDS) mediation. PDS, as well as phenol, was mainly reacted on the interface of the photothermal membrane instead of in the bulk solution. The interception efficiency of phenol achieved nearly 100% using the C/FeCo membrane during SIE. Hydroxyl radical (•OH), sulfate radical (SO4•−), superoxide radical (O2•−), and singlet oxygen (1O2) were identified as the main active substances to degrade VOCs. We also conducted SIE experiments using actual river water to evaluate the practical performance of the C/FeCo membrane. This work holds the promise of VOCs interception during SIE and enlarges the application of solar distillation in water/wastewater treatment.
Solar interfacial evaporation (SIE), is currently one of the most potential water supply technologies in the remote, insular, and disaster-stricken areas. However, the existence of volatile organic compounds (VOCs) in water deteriorates the distillate quality, threatening human health. Herein, we constructed a carbon-based bimetallic (C/FeCo) photothermal membrane by electrospinning technique. Results illustrated that the membrane can catalytically degrade VOCs during SIE with persulfate (PDS) mediation. PDS, as well as phenol, was mainly reacted on the interface of the photothermal membrane instead of in the bulk solution. The interception efficiency of phenol achieved nearly 100% using the C/FeCo membrane during SIE. Hydroxyl radical (•OH), sulfate radical (SO4•−), superoxide radical (O2•−), and singlet oxygen (1O2) were identified as the main active substances to degrade VOCs. We also conducted SIE experiments using actual river water to evaluate the practical performance of the C/FeCo membrane. This work holds the promise of VOCs interception during SIE and enlarges the application of solar distillation in water/wastewater treatment.
2025, 36(3): 110001
doi: 10.1016/j.cclet.2024.110001
Abstract:
Heterogeneous metal-catalyzed chemical conversions with a recyclable catalyst are very ideal and challenging for sustainable organic synthesis. A new bipyridyl-Mo(Ⅳ)-carbon nitride (CN-K/Mo-Bpy) was prepared by supporting molybdenum complex on C3N4-K and characterized by FT-IR, XRD, SEM, XPS and ICP-OES. Heterogeneous CN–Mo-Bpy catalyst can be applied to the direct amination of nitroarenes and arylboronic acid, thus constructing various valuable diarylamines in high to excellent yields with a wide substrate scope and good functional group tolerance. It is worth noting that this heterogeneous catalyst has high chemical stability and can be recycled for at least five times without reducing its activity.
Heterogeneous metal-catalyzed chemical conversions with a recyclable catalyst are very ideal and challenging for sustainable organic synthesis. A new bipyridyl-Mo(Ⅳ)-carbon nitride (CN-K/Mo-Bpy) was prepared by supporting molybdenum complex on C3N4-K and characterized by FT-IR, XRD, SEM, XPS and ICP-OES. Heterogeneous CN–Mo-Bpy catalyst can be applied to the direct amination of nitroarenes and arylboronic acid, thus constructing various valuable diarylamines in high to excellent yields with a wide substrate scope and good functional group tolerance. It is worth noting that this heterogeneous catalyst has high chemical stability and can be recycled for at least five times without reducing its activity.
2025, 36(3): 110010
doi: 10.1016/j.cclet.2024.110010
Abstract:
Conversion-type anode materials are highly desirable for Na-ion batteries (NIBs) due to their high theoretical capacity. Nevertheless, the active materials undergo severe expansion and pulverization during the sodiation, resulting in inferior cycling stability. Herein, a self-supporting three-dimensional (3D) graphene sponge decorated with Fe2O3 nanocubes (rGO@Fe2O3) is constructed. Specifically, the 3D graphene sponge with resilience and high porosity benefits to accommodate the volume expansion of the Fe2O3 nanocubes and facilitates the rapid electrons/ions transport, enabling spatial confinement to achieve outstanding results. Besides, the free-standing rGO@Fe2O3 can be directly used as an electrode without additional binders and conductive additives, which helps to obtain a higher energy density. Based on the total mass of the rGO@Fe2O3 material, the rGO@Fe2O3 anode presents a specific capacity of 859 mAh/g at 0.1 A/g. It also delivers an impressive cycling performance (327 mAh/g after 2000 cycles at 1 A/g) and a superior rate capacity (162 mAh/g at 20 A/g). The coin-type Na3V2(PO4)3@C//rGO@Fe2O3 NIB exhibits an energy density of 265.3 Wh/kg. This unique 3D ionic/electronic conductive network may provide new strategies to design advanced conversion-type anode materials for high-performance NIBs.
Conversion-type anode materials are highly desirable for Na-ion batteries (NIBs) due to their high theoretical capacity. Nevertheless, the active materials undergo severe expansion and pulverization during the sodiation, resulting in inferior cycling stability. Herein, a self-supporting three-dimensional (3D) graphene sponge decorated with Fe2O3 nanocubes (rGO@Fe2O3) is constructed. Specifically, the 3D graphene sponge with resilience and high porosity benefits to accommodate the volume expansion of the Fe2O3 nanocubes and facilitates the rapid electrons/ions transport, enabling spatial confinement to achieve outstanding results. Besides, the free-standing rGO@Fe2O3 can be directly used as an electrode without additional binders and conductive additives, which helps to obtain a higher energy density. Based on the total mass of the rGO@Fe2O3 material, the rGO@Fe2O3 anode presents a specific capacity of 859 mAh/g at 0.1 A/g. It also delivers an impressive cycling performance (327 mAh/g after 2000 cycles at 1 A/g) and a superior rate capacity (162 mAh/g at 20 A/g). The coin-type Na3V2(PO4)3@C//rGO@Fe2O3 NIB exhibits an energy density of 265.3 Wh/kg. This unique 3D ionic/electronic conductive network may provide new strategies to design advanced conversion-type anode materials for high-performance NIBs.
2025, 36(3): 110017
doi: 10.1016/j.cclet.2024.110017
Abstract:
Wastewater contains various high-risk trace organic pollutants, such as antibiotics and endocrine disruptors, which seriously restrict wastewater reuse. Cyclodextrin-based functional materials show great potential in the removal of trace pollutants because of their adsorption catalytic synergy. Clarifying the synergistic mechanism of cyclodextrin in oxidation is the key issue in confined catalytic oxidation process design. In this work, we fabricated a BiOIO3@BiOBr/β-CD heterojunction photocatalyst to study the synergistic mechanism of cyclodextrin in the photocatalytic oxidation process. The synergistic mechanism of cyclodextrin was investigated by combining radical chemistry, electrochemistry, spectroscopy, and time-dependent density functional theory. Results showed that the excited intermediate free radicals played an important role in promoting the photocatalytic degradation process. The heterojunction photocatalyst loaded with β-cyclodextrin (β-CD) at the electronic end (C[Cat.] = 0.2 mg/mL) removed about 97% of bisphenol A (BPA) within 30 min, and the first-order kinetic constant (kCDBIB = 0.112 min−1) was about twice that of the unloaded β-CD (kBIB = 0.057 min−1). Cyclodextrin loading improved the photocatalytic performance of the heterojunction and stimulated the intermediate to increase the free radical yield and regulate the reaction path.
Wastewater contains various high-risk trace organic pollutants, such as antibiotics and endocrine disruptors, which seriously restrict wastewater reuse. Cyclodextrin-based functional materials show great potential in the removal of trace pollutants because of their adsorption catalytic synergy. Clarifying the synergistic mechanism of cyclodextrin in oxidation is the key issue in confined catalytic oxidation process design. In this work, we fabricated a BiOIO3@BiOBr/β-CD heterojunction photocatalyst to study the synergistic mechanism of cyclodextrin in the photocatalytic oxidation process. The synergistic mechanism of cyclodextrin was investigated by combining radical chemistry, electrochemistry, spectroscopy, and time-dependent density functional theory. Results showed that the excited intermediate free radicals played an important role in promoting the photocatalytic degradation process. The heterojunction photocatalyst loaded with β-cyclodextrin (β-CD) at the electronic end (C[Cat.] = 0.2 mg/mL) removed about 97% of bisphenol A (BPA) within 30 min, and the first-order kinetic constant (kCDBIB = 0.112 min−1) was about twice that of the unloaded β-CD (kBIB = 0.057 min−1). Cyclodextrin loading improved the photocatalytic performance of the heterojunction and stimulated the intermediate to increase the free radical yield and regulate the reaction path.
2025, 36(3): 110019
doi: 10.1016/j.cclet.2024.110019
Abstract:
Hydrocarbons (HCs), as major poisoning substances, have a crucial influence on NH3-SCR catalysts. In this work, the effects of C3H6 on fresh and hydrothermally aged Cu-SSZ-39 catalysts with different copper contents were investigated. All catalysts suffered a deactivation above 250 ℃, especially between 300-400 ℃, which was mainly related to the reaction between NH3 and C3H6. However, the hydrothermally aged and the high-copper-loaded Cu-SSZ-39 catalysts could achieve a recovery of NH3-SCR performance at high temperatures. Such activity recovery was attributed to the oxidation of C3H6 by CuxOy species, which therefore inhibited the reaction between NH3 and C3H6. As a result, more NH3 could be available for the NH3-SCR reaction and the Cu-SSZ-39 catalysts could maintain a good catalytic activity. Based on these findings, we proposed that high loaded Cu-SSZ-39 catalysts with a little CuOx formed are preferred for application.
Hydrocarbons (HCs), as major poisoning substances, have a crucial influence on NH3-SCR catalysts. In this work, the effects of C3H6 on fresh and hydrothermally aged Cu-SSZ-39 catalysts with different copper contents were investigated. All catalysts suffered a deactivation above 250 ℃, especially between 300-400 ℃, which was mainly related to the reaction between NH3 and C3H6. However, the hydrothermally aged and the high-copper-loaded Cu-SSZ-39 catalysts could achieve a recovery of NH3-SCR performance at high temperatures. Such activity recovery was attributed to the oxidation of C3H6 by CuxOy species, which therefore inhibited the reaction between NH3 and C3H6. As a result, more NH3 could be available for the NH3-SCR reaction and the Cu-SSZ-39 catalysts could maintain a good catalytic activity. Based on these findings, we proposed that high loaded Cu-SSZ-39 catalysts with a little CuOx formed are preferred for application.
2025, 36(3): 110023
doi: 10.1016/j.cclet.2024.110023
Abstract:
Improper abuse of roxarsone (ROX) in industrial production leads to harmful effects on water, soil, food, and living creatures. It is significant to detect its concentration in the environment and biosystem. Herein, two aggregation-induced emission (AIE)-active fluorescence probes, TPE-TPE and TPE-TPE-CN, are successfully synthesized via a sulfur(Ⅵ) fluoride exchange (SuFEx) click reaction and first employed to detect ROX in the environment and living 3T3 cells. These two probes can selectively detect ROX in water due to the synergistic effect of photoinduced electron transfer (PET) and fluorescence resonance energy transfer (FRET) between the probes and ROX. The detection limit of TPE-TPE and TPE-TPE-CN is 0.154 and 0.385 µmol/L, respectively, much lower than the safety concentration stipulated by the World Health Organization (WHO). In addition, with the aid of a color discrimination application in a smartphone, these two probes can also detect ROX in real samples (such as water, soil, and cabbage), demonstrating their excellent potential for monitoring ROX in a practical environment.
Improper abuse of roxarsone (ROX) in industrial production leads to harmful effects on water, soil, food, and living creatures. It is significant to detect its concentration in the environment and biosystem. Herein, two aggregation-induced emission (AIE)-active fluorescence probes, TPE-TPE and TPE-TPE-CN, are successfully synthesized via a sulfur(Ⅵ) fluoride exchange (SuFEx) click reaction and first employed to detect ROX in the environment and living 3T3 cells. These two probes can selectively detect ROX in water due to the synergistic effect of photoinduced electron transfer (PET) and fluorescence resonance energy transfer (FRET) between the probes and ROX. The detection limit of TPE-TPE and TPE-TPE-CN is 0.154 and 0.385 µmol/L, respectively, much lower than the safety concentration stipulated by the World Health Organization (WHO). In addition, with the aid of a color discrimination application in a smartphone, these two probes can also detect ROX in real samples (such as water, soil, and cabbage), demonstrating their excellent potential for monitoring ROX in a practical environment.
2025, 36(3): 110036
doi: 10.1016/j.cclet.2024.110036
Abstract:
The synergistic effect of Se with Fe can enhance the catalytic activities of the system for oxidation reactions. Based on this principle, a series of Se/Fe materials have been invented to develop the heterogeneous catalysts with industrial application potential. However, the present methods suffer from the tedious procedures, the high reaction temperature, and the low synthetic efficiency. In this paper, we report the synthesis of Se/Fe materials just by precipitating Fe(NO3)3 with the in situ prepared aqueous NaSe/NaSeO3 under mild conditions. The concise method may resolve the issues hindering the large-scale applications of Se/Fe materials.
The synergistic effect of Se with Fe can enhance the catalytic activities of the system for oxidation reactions. Based on this principle, a series of Se/Fe materials have been invented to develop the heterogeneous catalysts with industrial application potential. However, the present methods suffer from the tedious procedures, the high reaction temperature, and the low synthetic efficiency. In this paper, we report the synthesis of Se/Fe materials just by precipitating Fe(NO3)3 with the in situ prepared aqueous NaSe/NaSeO3 under mild conditions. The concise method may resolve the issues hindering the large-scale applications of Se/Fe materials.
2025, 36(3): 110037
doi: 10.1016/j.cclet.2024.110037
Abstract:
The dynamic kinetic resolution (DKR) process remains a highly efficacious approach for constructing chiral amino alcohols via the catalytic asymmetric hydrogenation of α-amino ketones. We report herein a highly efficient and enantioselective anti-selective dynamic kinetic asymmetric hydrogenation of α-amino ketones catalyzed by Ir-(S)-f-phamidol system, providing various chiral amino alcohols and chiral oxazolidin-2-ones divergently with high diastereo- and enantioselectivity (up to 99% yield, up to 99% ee and up to 99:1 dr). In addition, the reaction could be performed on the gram-scale, and the resulting chiral amino alcohols are key intermediates of norephedrine and metaraminol.
The dynamic kinetic resolution (DKR) process remains a highly efficacious approach for constructing chiral amino alcohols via the catalytic asymmetric hydrogenation of α-amino ketones. We report herein a highly efficient and enantioselective anti-selective dynamic kinetic asymmetric hydrogenation of α-amino ketones catalyzed by Ir-(S)-f-phamidol system, providing various chiral amino alcohols and chiral oxazolidin-2-ones divergently with high diastereo- and enantioselectivity (up to 99% yield, up to 99% ee and up to 99:1 dr). In addition, the reaction could be performed on the gram-scale, and the resulting chiral amino alcohols are key intermediates of norephedrine and metaraminol.
2025, 36(3): 110046
doi: 10.1016/j.cclet.2024.110046
Abstract:
Although lots of efforts have been devoted on new less hygroscopic dopants to address problems in hole transport materials (HTM), the long-time post-oxidation and the volatilization of 4-tert-butylpyridine (tBP) are still issues. A new doping mechanism for spiro-OMeTAD by disulfiram (TETD) is revealed in this work. Owing to its disulfide bond, TETD can be activated easily to produce reactive sulfur for the rapid oxidation of spiro-OMeTAD in the absence of oxygen with formation of [spiro-OMeTAD•]+[SC(S)N(C2H5)2]-. Thus, in this situation, the Li+ ion has the opportunity to coordinate tBP and fix each other in HTM film. DFT calculations suggest that the resulting favorable energy (with a ΔE of −1.29 eV) must come from the mutual interactions among Li+, TFSI−, and tBP, which is different from the well-known doping process that tBP would not participate in the doping reaction. As a result, the introduction of a new radical into the HTM greatly reduce device performance fluctuations due to the environmental dependence and inhibit tBP volatilizing for enhanced long-term stability.
Although lots of efforts have been devoted on new less hygroscopic dopants to address problems in hole transport materials (HTM), the long-time post-oxidation and the volatilization of 4-tert-butylpyridine (tBP) are still issues. A new doping mechanism for spiro-OMeTAD by disulfiram (TETD) is revealed in this work. Owing to its disulfide bond, TETD can be activated easily to produce reactive sulfur for the rapid oxidation of spiro-OMeTAD in the absence of oxygen with formation of [spiro-OMeTAD•]+[SC(S)N(C2H5)2]-. Thus, in this situation, the Li+ ion has the opportunity to coordinate tBP and fix each other in HTM film. DFT calculations suggest that the resulting favorable energy (with a ΔE of −1.29 eV) must come from the mutual interactions among Li+, TFSI−, and tBP, which is different from the well-known doping process that tBP would not participate in the doping reaction. As a result, the introduction of a new radical into the HTM greatly reduce device performance fluctuations due to the environmental dependence and inhibit tBP volatilizing for enhanced long-term stability.
2025, 36(3): 110054
doi: 10.1016/j.cclet.2024.110054
Abstract:
Butyrylcholinesterase (BChE) is a key enzyme in the metabolism of cholinergic compounds. It has been recognized as a key biomarker for many diseases, including liver diseases and Alzheimer’s disease. However, classical methods for detecting BChE activity suffer from low sensitivity, cumbersome pre-treatment, and poor stability. Chemiluminescence is a promising new method for detecting and imaging the activity of BChE. It has several advantages over traditional methods, including low background interference, high sensitivity, and the absence of external illumination. In this study, we developed a novel BChE-activatable chemiluminescent probe (CL-BChE). It exhibited a significant chemiluminescence enhancement at 525 nm upon incubation with BChE. It had a low limit of detection (6.25 × 10−3 U/mL) and was highly selective for BChE. CL-BChE was used to image BChE activity in living cells and tumor-bearing animal models. It was also successfully applied to detect pesticide residue, even under the interference of representative phytochromes and real vegetable samples. Given its high sensitivity, selectivity, and versatility, we believe that CL-BChE will be a promising tool for investigating BChE’s activity in biomedical research as well as other BChE-related scenarios.
Butyrylcholinesterase (BChE) is a key enzyme in the metabolism of cholinergic compounds. It has been recognized as a key biomarker for many diseases, including liver diseases and Alzheimer’s disease. However, classical methods for detecting BChE activity suffer from low sensitivity, cumbersome pre-treatment, and poor stability. Chemiluminescence is a promising new method for detecting and imaging the activity of BChE. It has several advantages over traditional methods, including low background interference, high sensitivity, and the absence of external illumination. In this study, we developed a novel BChE-activatable chemiluminescent probe (CL-BChE). It exhibited a significant chemiluminescence enhancement at 525 nm upon incubation with BChE. It had a low limit of detection (6.25 × 10−3 U/mL) and was highly selective for BChE. CL-BChE was used to image BChE activity in living cells and tumor-bearing animal models. It was also successfully applied to detect pesticide residue, even under the interference of representative phytochromes and real vegetable samples. Given its high sensitivity, selectivity, and versatility, we believe that CL-BChE will be a promising tool for investigating BChE’s activity in biomedical research as well as other BChE-related scenarios.
2025, 36(3): 110058
doi: 10.1016/j.cclet.2024.110058
Abstract:
In order to protect the environment and economize energy, a nitrogen-fixing photocatalyst, VMCeact, is investigated in this work. This catalyst is prepared from a natural mineral, vermiculite, and modified by Ce-based metal-organic framework, Ce-UiO-66. Vermiculite was treated with formic acid; thus, Ce-UiO-66 particles grew in-situ on vermiculite; then, Ce-UiO-66 particles were activated by ultraviolet irradiation. The vermiculite absorbed visible light with a narrow band gap, and transferred photogenerated electrons to the active sites on Ce-UiO-66. Moreover, the lamella structure of vermiculite protected Ce-UiO-66 during photocatalytic process. Therefore, with only 45.92 wt% of Ce-UiO-66, the nitrogen fixation performance of VMCeact was 2.29 times that of pure activated Ce-UiO-66 particles under 455 nm light irradiation (apparent quantum efficiency of 4.49%), and retained at least 96.05% performance after 7 × 24 h of photocatalytic reaction. This cost-reduced, efficient and stable photocatalyst has the opportunity to facilitate environmentally friendly ammonia production.
In order to protect the environment and economize energy, a nitrogen-fixing photocatalyst, VMCeact, is investigated in this work. This catalyst is prepared from a natural mineral, vermiculite, and modified by Ce-based metal-organic framework, Ce-UiO-66. Vermiculite was treated with formic acid; thus, Ce-UiO-66 particles grew in-situ on vermiculite; then, Ce-UiO-66 particles were activated by ultraviolet irradiation. The vermiculite absorbed visible light with a narrow band gap, and transferred photogenerated electrons to the active sites on Ce-UiO-66. Moreover, the lamella structure of vermiculite protected Ce-UiO-66 during photocatalytic process. Therefore, with only 45.92 wt% of Ce-UiO-66, the nitrogen fixation performance of VMCeact was 2.29 times that of pure activated Ce-UiO-66 particles under 455 nm light irradiation (apparent quantum efficiency of 4.49%), and retained at least 96.05% performance after 7 × 24 h of photocatalytic reaction. This cost-reduced, efficient and stable photocatalyst has the opportunity to facilitate environmentally friendly ammonia production.
2025, 36(3): 110078
doi: 10.1016/j.cclet.2024.110078
Abstract:
Wide bandgap semiconductors are typically activated under ultraviolet (UV) light irradiation for volatile organic compounds (VOCs) degradation. However, our previous study discovered that certain VOCs can interact with some wide bandgap semiconductors, formatting an intermediate bandgap between the VOCs and the conduction band of wide bandgap semiconductor, thus inducing visible light activation of the system, and photo-generated electrons are excited by visible light and transferred from the VOCs to the conduction band of semiconductor. In this work, BaTiO3, traditionally is not active under visible light irradiation, however showed degradation rates of 100% and 20% for styrene and toluene under visible light, respectively. Density functional theory (DFT) calculations indicate that the adsorption of styrene or toluene on the BaTiO3 surface reduces its bandgap from 2.93 eV to 1.36 eV and 2.26 eV, respectively. The intermediate bandgap in this system is primarily formed by the valence band of BaTiO3 and the VOCs, and indicating that photo-generated electrons directly transfer from BaTiO3 to the VOCs under visible light, inducing degradation reactions of VOCs, i.e., this work discovered a new transfer pathway of photo-electrons direct from the valence band of BaTiO3 to VOCs, while photo-electrons are from VOCs to the conductive band of wide-bandgap semiconductors in our previous work.
Wide bandgap semiconductors are typically activated under ultraviolet (UV) light irradiation for volatile organic compounds (VOCs) degradation. However, our previous study discovered that certain VOCs can interact with some wide bandgap semiconductors, formatting an intermediate bandgap between the VOCs and the conduction band of wide bandgap semiconductor, thus inducing visible light activation of the system, and photo-generated electrons are excited by visible light and transferred from the VOCs to the conduction band of semiconductor. In this work, BaTiO3, traditionally is not active under visible light irradiation, however showed degradation rates of 100% and 20% for styrene and toluene under visible light, respectively. Density functional theory (DFT) calculations indicate that the adsorption of styrene or toluene on the BaTiO3 surface reduces its bandgap from 2.93 eV to 1.36 eV and 2.26 eV, respectively. The intermediate bandgap in this system is primarily formed by the valence band of BaTiO3 and the VOCs, and indicating that photo-generated electrons directly transfer from BaTiO3 to the VOCs under visible light, inducing degradation reactions of VOCs, i.e., this work discovered a new transfer pathway of photo-electrons direct from the valence band of BaTiO3 to VOCs, while photo-electrons are from VOCs to the conductive band of wide-bandgap semiconductors in our previous work.
2025, 36(3): 110079
doi: 10.1016/j.cclet.2024.110079
Abstract:
RNA modifications play vital regulatory roles in biological systems. Dysregulated RNA modifications themselves or their regulators are associated with various diseases, including cancers and immune related diseases. However, to the best of our knowledge, RNA modifications in peripheral white blood cells (immune cells) have not been systematically investigated before. Here we utilized hydrophilic interaction liquid chromatography-tandem mass spectrometry (HILIC-MS/MS) for the quantification of 19 chemical modifications in total RNA and 17 chemical modifications in small RNA in peripheral white blood cells from breast cancer patients and healthy controls. We found out 13 RNA modifications were up-regulated in total RNA samples of breast cancer patients. For small RNA samples, only N6-methyladenosine (m6A) was down-regulated in breast cancer patients (P < 0.0001). Receiver operating characteristic (ROC) curves analysis showed that N4-acetylcytidine (ac4C) in total RNA had an area under curve (AUC) value of 0.833, and m6A in small RNA had an AUC value of 0.994. Our results further illustrated that RNA modifications may play vital roles in immune cell biology of breast cancer, and may act as novel biomarkers for the diagnosis of breast cancer.
RNA modifications play vital regulatory roles in biological systems. Dysregulated RNA modifications themselves or their regulators are associated with various diseases, including cancers and immune related diseases. However, to the best of our knowledge, RNA modifications in peripheral white blood cells (immune cells) have not been systematically investigated before. Here we utilized hydrophilic interaction liquid chromatography-tandem mass spectrometry (HILIC-MS/MS) for the quantification of 19 chemical modifications in total RNA and 17 chemical modifications in small RNA in peripheral white blood cells from breast cancer patients and healthy controls. We found out 13 RNA modifications were up-regulated in total RNA samples of breast cancer patients. For small RNA samples, only N6-methyladenosine (m6A) was down-regulated in breast cancer patients (P < 0.0001). Receiver operating characteristic (ROC) curves analysis showed that N4-acetylcytidine (ac4C) in total RNA had an area under curve (AUC) value of 0.833, and m6A in small RNA had an AUC value of 0.994. Our results further illustrated that RNA modifications may play vital roles in immune cell biology of breast cancer, and may act as novel biomarkers for the diagnosis of breast cancer.
2025, 36(3): 110080
doi: 10.1016/j.cclet.2024.110080
Abstract:
Iron-porphyrin metal-organic frameworks (MOFs) have emerged as a remarkable class of semiconductors with adjustable photoelectrical properties and peroxidase-mimicking activities, yet their full potential remains largely unexplored. The organic photoelectrochemical transistor (OPECT) has been proven to be a prominent platform for diverse applications. Herein, iron-porphyrin MOFs, as bifunctional photo-gating module and horseradish peroxidase-mimicking nanozyme, is explored for novel OPECT bioanalysis. Exemplified by alpha-fetoprotein (AFP)-dependent sandwich immunorecognition and therein glucose oxidase (GOx)-generated H2O2 to etch CdS quantum dots on the surface of iron-porphyrin MOFs, this OPECT bioanalysis achieved high-performance AFP detection with a low detection limit of 24 fg/mL. This work featured a bifunctional iron-porphyrin MOFs gated OPECT, which is envisioned to inspire more interest in developing the diverse MOFs-nanozymes toward novel optoelectronics and beyond.
Iron-porphyrin metal-organic frameworks (MOFs) have emerged as a remarkable class of semiconductors with adjustable photoelectrical properties and peroxidase-mimicking activities, yet their full potential remains largely unexplored. The organic photoelectrochemical transistor (OPECT) has been proven to be a prominent platform for diverse applications. Herein, iron-porphyrin MOFs, as bifunctional photo-gating module and horseradish peroxidase-mimicking nanozyme, is explored for novel OPECT bioanalysis. Exemplified by alpha-fetoprotein (AFP)-dependent sandwich immunorecognition and therein glucose oxidase (GOx)-generated H2O2 to etch CdS quantum dots on the surface of iron-porphyrin MOFs, this OPECT bioanalysis achieved high-performance AFP detection with a low detection limit of 24 fg/mL. This work featured a bifunctional iron-porphyrin MOFs gated OPECT, which is envisioned to inspire more interest in developing the diverse MOFs-nanozymes toward novel optoelectronics and beyond.
2025, 36(3): 110085
doi: 10.1016/j.cclet.2024.110085
Abstract:
Fuel cell electric vehicles hold great promise for a diverse range of applications in reducing greenhouse gas emissions. In power fuel cell systems, hydrogen fuel serves as an energy vector. To ensure its suitability, it is necessary for the quality of hydrogen to adhere to the standards set by ISO 14687:2019, which sets maximum limits for 14 impurities in hydrogen, aiming to prevent any degradation of fuel cell performance. Ammonia (NH3) is a prominent pollutant in fuel cells, and accurate measurements of its concentration are crucial for hydrogen fuel cell quantity. In this study, a novel detection platform was developed for determining NH3 in real hydrogen samples. The online analysis platform integrates a self-developed online dilution module with a Fourier transform infrared spectrometer (ODM-FTIR). The ODM-FTIR can be operated fully automatically with remote operation. Under the optimum conditions, this method achieved a wide linear range between (50~1000) nmol/mol. The limit of detection (LOD) was as low as 2 nmol/mol with a relative standard deviation (RSD, n = 7) of 3.6% at a content of 50 nmol/mol. To ensure that the quality of the hydrogen products meets the requirement of proton exchange membrane fuel cell vehicles (PEMFCV), the developed ODM-FTIR system was applied to monitor the NH3 content in Chengdu Hydrogen Energy Co., Ltd. for 21 days during Chengdu 2021 FISU World University Games. The proposed method retains several unique advantages, including a low detection limit, excellent repeatability, high accuracy, high speed, good stability, and calibration flexibility. It is an effective analytical method for accurately quantifying NH3 in hydrogen, especially suitable for online analysis. It also provides a new idea for the analysis of other impurity components in hydrogen.
Fuel cell electric vehicles hold great promise for a diverse range of applications in reducing greenhouse gas emissions. In power fuel cell systems, hydrogen fuel serves as an energy vector. To ensure its suitability, it is necessary for the quality of hydrogen to adhere to the standards set by ISO 14687:2019, which sets maximum limits for 14 impurities in hydrogen, aiming to prevent any degradation of fuel cell performance. Ammonia (NH3) is a prominent pollutant in fuel cells, and accurate measurements of its concentration are crucial for hydrogen fuel cell quantity. In this study, a novel detection platform was developed for determining NH3 in real hydrogen samples. The online analysis platform integrates a self-developed online dilution module with a Fourier transform infrared spectrometer (ODM-FTIR). The ODM-FTIR can be operated fully automatically with remote operation. Under the optimum conditions, this method achieved a wide linear range between (50~1000) nmol/mol. The limit of detection (LOD) was as low as 2 nmol/mol with a relative standard deviation (RSD, n = 7) of 3.6% at a content of 50 nmol/mol. To ensure that the quality of the hydrogen products meets the requirement of proton exchange membrane fuel cell vehicles (PEMFCV), the developed ODM-FTIR system was applied to monitor the NH3 content in Chengdu Hydrogen Energy Co., Ltd. for 21 days during Chengdu 2021 FISU World University Games. The proposed method retains several unique advantages, including a low detection limit, excellent repeatability, high accuracy, high speed, good stability, and calibration flexibility. It is an effective analytical method for accurately quantifying NH3 in hydrogen, especially suitable for online analysis. It also provides a new idea for the analysis of other impurity components in hydrogen.
2025, 36(3): 110086
doi: 10.1016/j.cclet.2024.110086
Abstract:
Photocatalytic NO removal is regarded as an attractive strategy to reduce NO pollution in the air, but the lack of efficient and stable catalysts impedes its applications. Herein, we report on developing Ti3C2 supported on N-defective g-C3N5 nanosheets (CNX/TC) as an efficient photocatalyst toward NO removal. It is noteworthy that TC changed from crystal structure to amorphous structure during the photocatalytic process. Due to the existence of N vacancies and amorphous structure, the designed CNX/TC composites possess abundant unsaturated sites for adsorption and activation of O2 and NO, thus facilitating the removal of NO and inhibiting the generation of NO2. The as-prepared CNX/TC-2% shows the best activity for NO removal and inhibits toxic NO2 generation. The removal rate of NO is up to 48%, which is about 2 and 4 times higher than those of pure CNX and CN, respectively. In addition, the in situ diffused reflection Fourier transform infrared spectroscopy was used to investigate the NO transfer pathway during the photocatalytic process. This work might provide new insights into the catalytic role of N-defect and amorphous, inspiring the rational design of catalysts in the field of photocatalytic NO removal.
Photocatalytic NO removal is regarded as an attractive strategy to reduce NO pollution in the air, but the lack of efficient and stable catalysts impedes its applications. Herein, we report on developing Ti3C2 supported on N-defective g-C3N5 nanosheets (CNX/TC) as an efficient photocatalyst toward NO removal. It is noteworthy that TC changed from crystal structure to amorphous structure during the photocatalytic process. Due to the existence of N vacancies and amorphous structure, the designed CNX/TC composites possess abundant unsaturated sites for adsorption and activation of O2 and NO, thus facilitating the removal of NO and inhibiting the generation of NO2. The as-prepared CNX/TC-2% shows the best activity for NO removal and inhibits toxic NO2 generation. The removal rate of NO is up to 48%, which is about 2 and 4 times higher than those of pure CNX and CN, respectively. In addition, the in situ diffused reflection Fourier transform infrared spectroscopy was used to investigate the NO transfer pathway during the photocatalytic process. This work might provide new insights into the catalytic role of N-defect and amorphous, inspiring the rational design of catalysts in the field of photocatalytic NO removal.
2025, 36(3): 110087
doi: 10.1016/j.cclet.2024.110087
Abstract:
It has been challenging for Fe(Ⅲ) regeneration in Fe-based photocatalysts for continuous peroxydisulfate (PDS) activation due to the lower ability to reduce Fe(Ⅲ). In this work, Fe-doped ultrathin VO2 (Fe-VO2) nanobelts were synthesized for purifying metronidazole (MNZ) via PDS activation. As an efficient Fenton-like catalyst for PDS activation, 2 wt% Fe-doped VO2 can remove 98% of MNZ within 40 min and exhibits impressive recyclability. The synergistic effect of Fe-VO2 and Fe(Ⅲ) activated PDS boosted the photocatalytic performance. Moreover, SO4•−, h+, O2•−, 1O2, and •OH were the main reactive radicals. The effects of initial MNZ concentration, Fe-VO2, PDS dosage, and various anions/cations on MNZ removal by the Fe-VO2/PDS/Vis system were studied. The intermediates of MNZ degradation and possible pathways were determined by density function theory (DFT) calculations and HPLC-MS. This study provided a sustainable technology using Fe-doped ultrathin VO2 nanobelts for photocatalytic PDS activation and decontamination of pharmaceutical wastewater.
It has been challenging for Fe(Ⅲ) regeneration in Fe-based photocatalysts for continuous peroxydisulfate (PDS) activation due to the lower ability to reduce Fe(Ⅲ). In this work, Fe-doped ultrathin VO2 (Fe-VO2) nanobelts were synthesized for purifying metronidazole (MNZ) via PDS activation. As an efficient Fenton-like catalyst for PDS activation, 2 wt% Fe-doped VO2 can remove 98% of MNZ within 40 min and exhibits impressive recyclability. The synergistic effect of Fe-VO2 and Fe(Ⅲ) activated PDS boosted the photocatalytic performance. Moreover, SO4•−, h+, O2•−, 1O2, and •OH were the main reactive radicals. The effects of initial MNZ concentration, Fe-VO2, PDS dosage, and various anions/cations on MNZ removal by the Fe-VO2/PDS/Vis system were studied. The intermediates of MNZ degradation and possible pathways were determined by density function theory (DFT) calculations and HPLC-MS. This study provided a sustainable technology using Fe-doped ultrathin VO2 nanobelts for photocatalytic PDS activation and decontamination of pharmaceutical wastewater.
2025, 36(3): 110107
doi: 10.1016/j.cclet.2024.110107
Abstract:
In contrast to research on active sites in nanomaterials, lithium tantalate single crystals, known for their exceptional optical properties and long-range ordered lattice structure, present a promising avenue for in-depth exploration of photocatalytic reaction systems with fewer constraints imposed by surface chemistry. Typically, the isotropy of a specific facet provides a perfect support for studying heteroatom doping. Herein, this work delves into the intrinsic catalytic sites for photocatalytic nitrogen fixation in iron-doped lithium tantalate single crystals. The presence of iron not only modifies the electronic structure of lithium tantalate, improving its light absorption capacity, but also functions as an active site for the nitrogen adsorption and activation. The photocatalytic ammonia production rate of the iron-doped lithium tantalate in pure water is maximum 26.95 µg cm−2 h−1, which is three times higher than that of undoped lithium tantalate. The combination of first-principles simulations with in situ characterizations confirms that iron doping promotes the rate-determining step and changes the pathway of hydrogenation to associative alternating. This study provides a new perspective on in-depth investigation of intrinsic catalytic active sites in photocatalysis and other catalytic processes.
In contrast to research on active sites in nanomaterials, lithium tantalate single crystals, known for their exceptional optical properties and long-range ordered lattice structure, present a promising avenue for in-depth exploration of photocatalytic reaction systems with fewer constraints imposed by surface chemistry. Typically, the isotropy of a specific facet provides a perfect support for studying heteroatom doping. Herein, this work delves into the intrinsic catalytic sites for photocatalytic nitrogen fixation in iron-doped lithium tantalate single crystals. The presence of iron not only modifies the electronic structure of lithium tantalate, improving its light absorption capacity, but also functions as an active site for the nitrogen adsorption and activation. The photocatalytic ammonia production rate of the iron-doped lithium tantalate in pure water is maximum 26.95 µg cm−2 h−1, which is three times higher than that of undoped lithium tantalate. The combination of first-principles simulations with in situ characterizations confirms that iron doping promotes the rate-determining step and changes the pathway of hydrogenation to associative alternating. This study provides a new perspective on in-depth investigation of intrinsic catalytic active sites in photocatalysis and other catalytic processes.
2025, 36(3): 110170
doi: 10.1016/j.cclet.2024.110170
Abstract:
The imbalance of nitric oxide (NO) homeostasis in the brain is closely related to the occurrence of Parkinson’s disease (PD). Therefore, revealing the fluctuation of NO in brain is crucial for understanding the pathophysiological processes. However, currently developed NO probes are unsuitable for this purpose due to their poor blood-brain barrier permeability. Herein, a fluorescent probe (PO-NH) with blood-brain barrier crossing capability and high selectivity for NO was developed. Under the NO mediation, the photo-induced electron transfer (PET) process of the probe was blocked, giving an intensive fluorescence enhancement (F/F0 = 15). Moreover, PO-NH can be used to effectively monitor changes in intracellular NO levels. Significantly, due to excellent blood-brain barrier crossing ability and near-infrared (NIR) emission, PO-NH is suitable for in vivo imaging of NO in the brain and illustrating with the deterioration of PD, the level of NO gradually increased in the brain of PD mice. We believe that PO-NH may provide a beneficial tool for understanding the biological function of NO in the brain and revealing the complex connection between NO and PD.
The imbalance of nitric oxide (NO) homeostasis in the brain is closely related to the occurrence of Parkinson’s disease (PD). Therefore, revealing the fluctuation of NO in brain is crucial for understanding the pathophysiological processes. However, currently developed NO probes are unsuitable for this purpose due to their poor blood-brain barrier permeability. Herein, a fluorescent probe (PO-NH) with blood-brain barrier crossing capability and high selectivity for NO was developed. Under the NO mediation, the photo-induced electron transfer (PET) process of the probe was blocked, giving an intensive fluorescence enhancement (F/F0 = 15). Moreover, PO-NH can be used to effectively monitor changes in intracellular NO levels. Significantly, due to excellent blood-brain barrier crossing ability and near-infrared (NIR) emission, PO-NH is suitable for in vivo imaging of NO in the brain and illustrating with the deterioration of PD, the level of NO gradually increased in the brain of PD mice. We believe that PO-NH may provide a beneficial tool for understanding the biological function of NO in the brain and revealing the complex connection between NO and PD.
2025, 36(3): 110199
doi: 10.1016/j.cclet.2024.110199
Abstract:
The alkaline hydrogen evolution reaction (HER) is a crucial process for sustainable hydrogen production, yet it requires efficient and stable electrocatalysts to overcome the high activation energy barrier. The article discusses a novel strategy for enhancing the performance of Ni-Fe layered double hydroxide (Ni-Fe LDH) in the alkaline HER by modifying it with a frustrated Lewis acid-base pair (FLP) constructed through vacancy engineering. The study found that the modified Ni-Fe LDH exhibited improved alkaline HER performance. Density functional theory (DFT) calculations demonstrate that the introduction of FLP can activate water and protons more efficiently than monometallic sites, thus reducing the alkaline HER energy barrier and overpotential. In HER under alkaline conditions, the Volmer step involves an additional hydrolysis dissociation compared to acidic conditions, which is one of the factors contributing to the slow reaction kinetics. This paper demonstrates that FLPs can alter the rate-determining step in alkaline HER from the Volmer step to a step with a lower energy barrier, more suitable for hydrogen desorption. The work provides new insights into the role of FLPs in regulating the mechanism and kinetics of HER and opens a new direction for the design and optimization of LDH-based and other electrocatalysts.
The alkaline hydrogen evolution reaction (HER) is a crucial process for sustainable hydrogen production, yet it requires efficient and stable electrocatalysts to overcome the high activation energy barrier. The article discusses a novel strategy for enhancing the performance of Ni-Fe layered double hydroxide (Ni-Fe LDH) in the alkaline HER by modifying it with a frustrated Lewis acid-base pair (FLP) constructed through vacancy engineering. The study found that the modified Ni-Fe LDH exhibited improved alkaline HER performance. Density functional theory (DFT) calculations demonstrate that the introduction of FLP can activate water and protons more efficiently than monometallic sites, thus reducing the alkaline HER energy barrier and overpotential. In HER under alkaline conditions, the Volmer step involves an additional hydrolysis dissociation compared to acidic conditions, which is one of the factors contributing to the slow reaction kinetics. This paper demonstrates that FLPs can alter the rate-determining step in alkaline HER from the Volmer step to a step with a lower energy barrier, more suitable for hydrogen desorption. The work provides new insights into the role of FLPs in regulating the mechanism and kinetics of HER and opens a new direction for the design and optimization of LDH-based and other electrocatalysts.
2025, 36(3): 110318
doi: 10.1016/j.cclet.2024.110318
Abstract:
Introducing ligand into the surface of gold (Au)-based catalyst has been recognized as an efficient strategy to enhance the performance of catalyst in acetylene hydrochlorination reaction. However, due to the multifactorial deactivation, the usage of single type of ligand has limitations on the performance improvement. In this work, two types of ligands including a molecular 2-methylimidazole and an ionic cetrimonium are selected to protect Aun+ species. After kinetics analysis, advanced characterization, and density functional theory simulation, we demonstrate the optimal interaction model between two ligands and Au species: Two 2-methylimidazole molecules are coordinated with high-valent Au species while cetrimonium is interacted via electrostatic interaction. Except the synergistic effect in the decrease of Au species reduction and agglomeration, the existence of molecular ligand greatly increases the adsorption of hydrogen chloride while the ionic ligand significantly inhibits the deposition of coke. Due to the positive effect of dual-ligands, we achieved 97.1% of acetylene conversion and 0.29 h−1 of deactivation rate under high gas hourly space velocity of acetylene. This work establishes a foundation to explore the property-activity relationships in Au-based catalyst via ligand engineering.
Introducing ligand into the surface of gold (Au)-based catalyst has been recognized as an efficient strategy to enhance the performance of catalyst in acetylene hydrochlorination reaction. However, due to the multifactorial deactivation, the usage of single type of ligand has limitations on the performance improvement. In this work, two types of ligands including a molecular 2-methylimidazole and an ionic cetrimonium are selected to protect Aun+ species. After kinetics analysis, advanced characterization, and density functional theory simulation, we demonstrate the optimal interaction model between two ligands and Au species: Two 2-methylimidazole molecules are coordinated with high-valent Au species while cetrimonium is interacted via electrostatic interaction. Except the synergistic effect in the decrease of Au species reduction and agglomeration, the existence of molecular ligand greatly increases the adsorption of hydrogen chloride while the ionic ligand significantly inhibits the deposition of coke. Due to the positive effect of dual-ligands, we achieved 97.1% of acetylene conversion and 0.29 h−1 of deactivation rate under high gas hourly space velocity of acetylene. This work establishes a foundation to explore the property-activity relationships in Au-based catalyst via ligand engineering.
2025, 36(3): 110379
doi: 10.1016/j.cclet.2024.110379
Abstract:
Engineering of sulfur vacancies on the basal plane of molybdenum disulfide (MoS2) may provide effective way to promote the catalytic activity. Although the sulfur vacancy density has previously been correlated with catalytic activity, direct evidence that vacancies create surfaces with enhanced electrocatalytic activity is still lacking. Here, we used a combination of scanning electrochemical cell microscopy (SECCM) with submicrometer resolution and photoluminescence imaging to show that sulfur vacancies in monolayer MoS2 microflakes lead to significant spatial heterogeneity in the electrochemical hydrogen evolution reaction (HER) activity. Specifically, colocated multi-microscopy unveils that regions with superior HER activity are associated with sulfur vacancy defects. As the vacancy density increases, the triangular flakes display significantly enhanced and spatially uniformly distributed electrocatalytic activity. Our multi-microscopic imaging approach using SECCM convincingly highlights the spatial heterogeneity of electrocatalytic activity across monolayer MoS2 by sulfur vacancy engineering.
Engineering of sulfur vacancies on the basal plane of molybdenum disulfide (MoS2) may provide effective way to promote the catalytic activity. Although the sulfur vacancy density has previously been correlated with catalytic activity, direct evidence that vacancies create surfaces with enhanced electrocatalytic activity is still lacking. Here, we used a combination of scanning electrochemical cell microscopy (SECCM) with submicrometer resolution and photoluminescence imaging to show that sulfur vacancies in monolayer MoS2 microflakes lead to significant spatial heterogeneity in the electrochemical hydrogen evolution reaction (HER) activity. Specifically, colocated multi-microscopy unveils that regions with superior HER activity are associated with sulfur vacancy defects. As the vacancy density increases, the triangular flakes display significantly enhanced and spatially uniformly distributed electrocatalytic activity. Our multi-microscopic imaging approach using SECCM convincingly highlights the spatial heterogeneity of electrocatalytic activity across monolayer MoS2 by sulfur vacancy engineering.
2025, 36(3): 110394
doi: 10.1016/j.cclet.2024.110394
Abstract:
Surface-confined metal-organic frameworks have emerged as versatile structures with a broad spectrum of applications such as nanoelectronics, catalysis, sensing, and molecular storage, owing to their unique structural and electronic properties. However, the exploration and optimization of molecular networks typically involve resource-intensive trial-and-error experiments. The complexity comes from factors like metal nodes, organic ligands, substrates, and the preparation conditions. To address this challenge, high-throughput methodologies have been used in materials exploration. In this work, we explored a high-throughput method for preparing sub-monolayer metals with continuous coverage spread on metal surfaces. By employing a physical mask during metal deposition under ultra-high vacuum conditions, we achieved sample libraries with copper (Cu) and silver (Ag) adatoms on the metal substrates, and constructed surface-supported metal-organic frameworks with varying metal-to-molecule stoichiometric ratios. This approach facilitates the exploration of surface-confined metal-organic frameworks, particularly in terms of varying metal-to-ligand stoichiometric ratios, offering an efficient pathway to unlock the potential of these intricate two-dimensional networks.
Surface-confined metal-organic frameworks have emerged as versatile structures with a broad spectrum of applications such as nanoelectronics, catalysis, sensing, and molecular storage, owing to their unique structural and electronic properties. However, the exploration and optimization of molecular networks typically involve resource-intensive trial-and-error experiments. The complexity comes from factors like metal nodes, organic ligands, substrates, and the preparation conditions. To address this challenge, high-throughput methodologies have been used in materials exploration. In this work, we explored a high-throughput method for preparing sub-monolayer metals with continuous coverage spread on metal surfaces. By employing a physical mask during metal deposition under ultra-high vacuum conditions, we achieved sample libraries with copper (Cu) and silver (Ag) adatoms on the metal substrates, and constructed surface-supported metal-organic frameworks with varying metal-to-molecule stoichiometric ratios. This approach facilitates the exploration of surface-confined metal-organic frameworks, particularly in terms of varying metal-to-ligand stoichiometric ratios, offering an efficient pathway to unlock the potential of these intricate two-dimensional networks.
2025, 36(3): 110395
doi: 10.1016/j.cclet.2024.110395
Abstract:
Utilizing superwettability micro/nanostructures to enhance the condensation heat transfer (CHT) performance of engineering materials has attracted great interest due to its values in basic research and technological innovations. Currently, exploring facile micro/nanofabrication approaches to create high-efficiency CHT surfaces has been one of research hotspots. In this work, we propose and demonstrate a type of new superwettability hybrid surface for high-efficiency CHT, which consists of superhydrophobic nanoneedle arrays and triangularly-patterned superhydrophilic microdots (SMDs). Such hybrid surface can be fabricated by the facile growth of densely-packed ZnO nanoneedles on the Zn-electroplated copper surface followed by fluorosilane modification and mask-assisted photodegradation. Through regulating the diameters and interspaces of SMDs, we obtain the optimized triangularly-patterned hybrid surface, which shows 42.7% higher CHT coefficient than the squarely-patterned hybrid surface and 58.5% higher CHT coefficient than the superhydrophobic surface. The key of such hybrid surface design is to considerably increase CHT coefficient brought about by SMD-triggered drop sweeping at the cost of slightly reducing heat transfer area of superhydrophobic functional zone for drop jumping. Such new strategy helps develop advanced CHT surfaces for high-efficiency electronic cooling and energy utilization.
Utilizing superwettability micro/nanostructures to enhance the condensation heat transfer (CHT) performance of engineering materials has attracted great interest due to its values in basic research and technological innovations. Currently, exploring facile micro/nanofabrication approaches to create high-efficiency CHT surfaces has been one of research hotspots. In this work, we propose and demonstrate a type of new superwettability hybrid surface for high-efficiency CHT, which consists of superhydrophobic nanoneedle arrays and triangularly-patterned superhydrophilic microdots (SMDs). Such hybrid surface can be fabricated by the facile growth of densely-packed ZnO nanoneedles on the Zn-electroplated copper surface followed by fluorosilane modification and mask-assisted photodegradation. Through regulating the diameters and interspaces of SMDs, we obtain the optimized triangularly-patterned hybrid surface, which shows 42.7% higher CHT coefficient than the squarely-patterned hybrid surface and 58.5% higher CHT coefficient than the superhydrophobic surface. The key of such hybrid surface design is to considerably increase CHT coefficient brought about by SMD-triggered drop sweeping at the cost of slightly reducing heat transfer area of superhydrophobic functional zone for drop jumping. Such new strategy helps develop advanced CHT surfaces for high-efficiency electronic cooling and energy utilization.
2025, 36(3): 110397
doi: 10.1016/j.cclet.2024.110397
Abstract:
The development of stable and efficient non-noble metal cocatalysts has arisen as a promising yet challenging endeavor in the context of photocatalytic overall water splitting. In this study, NiCo alloy cocatalysts were synthesized with nickel/cobalt metal organic framework (NiCo-MOF) as source of nickel and cobalt. Systematic characterization results demonstrate the successful deposition of alloy cocatalysts onto the surface of SrTiO3. The prepared SrTiO3 loaded NiCo-alloy can generate hydrogen and oxygen in a stoichiometric ratio for photocatalytic overall water splitting, achieving an apparent quantum yield of 11.9% at 350 ± 10 nm. Theoretical calculations indicate that the introduction of cobalt has a beneficial regulatory effect on the hydrogen evolution sites of Ni, reducing the free energy of H adsorption. The synergistic catalytic effect of bimetallic catalysts contributes to enhancing photocatalytic activity and stability. This study offers constructive insights for the development of high-efficiency and cost-effective cocatalyst systems.
The development of stable and efficient non-noble metal cocatalysts has arisen as a promising yet challenging endeavor in the context of photocatalytic overall water splitting. In this study, NiCo alloy cocatalysts were synthesized with nickel/cobalt metal organic framework (NiCo-MOF) as source of nickel and cobalt. Systematic characterization results demonstrate the successful deposition of alloy cocatalysts onto the surface of SrTiO3. The prepared SrTiO3 loaded NiCo-alloy can generate hydrogen and oxygen in a stoichiometric ratio for photocatalytic overall water splitting, achieving an apparent quantum yield of 11.9% at 350 ± 10 nm. Theoretical calculations indicate that the introduction of cobalt has a beneficial regulatory effect on the hydrogen evolution sites of Ni, reducing the free energy of H adsorption. The synergistic catalytic effect of bimetallic catalysts contributes to enhancing photocatalytic activity and stability. This study offers constructive insights for the development of high-efficiency and cost-effective cocatalyst systems.
2025, 36(3): 110425
doi: 10.1016/j.cclet.2024.110425
Abstract:
The tert-butyl nitrite as a bifunctional reagent mediated radical alkene difunctionalization has emerged as a powerful strategy for synthesis of structurally diverse oxime-containing compounds. However, the phosphorus-centered radical initiated transformations remain largely elusive. Herein, a visible-light-induced radical phosphinoyloximation of alkenes with secondary phosphine oxides and tert-butyl nitrite has been developed under photocatalyst- and metal-free conditions. This protocol features mild conditions, broad substrate scope, good functional tolerance, and operational simplicity, yielding a diverse array of α-phosphinoyl oximes in moderate to good yields with high stereoselectivities. The photomediated homolytic cleavage of ONO bond of tert-butyl nitrite generates the reactive tert-butoxyl radical and persistent NO radical to act as both HAT reagent and the source of oximes.
The tert-butyl nitrite as a bifunctional reagent mediated radical alkene difunctionalization has emerged as a powerful strategy for synthesis of structurally diverse oxime-containing compounds. However, the phosphorus-centered radical initiated transformations remain largely elusive. Herein, a visible-light-induced radical phosphinoyloximation of alkenes with secondary phosphine oxides and tert-butyl nitrite has been developed under photocatalyst- and metal-free conditions. This protocol features mild conditions, broad substrate scope, good functional tolerance, and operational simplicity, yielding a diverse array of α-phosphinoyl oximes in moderate to good yields with high stereoselectivities. The photomediated homolytic cleavage of ONO bond of tert-butyl nitrite generates the reactive tert-butoxyl radical and persistent NO radical to act as both HAT reagent and the source of oximes.
2025, 36(3): 110427
doi: 10.1016/j.cclet.2024.110427
Abstract:
As one of the most essential components in photocuring system, photoinitiators (PIs) exert a crucial influence on the properties of the cured product. However, commercially available PIs encounter challenges in simultaneously achieving efficient photoinitiation performance and excellent light absorption properties, significantly limiting their applications in various fields. Here, two bis-chalcones and four corresponding oxime esters (OXEs) were designed and synthesized as highly efficient PIs. Featuring a structure comprising bis-chalcone and two diphenyl sulfides, the conjugated systems in these compounds enhance their light-absorption properties in near-ultraviolet and visible region, effectively. Both the frontier molecular orbital simulations and excited state calculations suggest the contribution of sulfur atoms to electron delocalization and the formation of conjugated structure. Due to the high reactivity of the NO bond in OXE moiety, the four OXEs exhibit exceptional free radical photoinitiating ability in commercial acrylic monomers/oligomers with LED@365 nm as light source. Notably, one of them demonstrates superior performance in the photoinitiation of multifunctional crosslinker, achieving more than 70% conversion within 3 s, coupled with outstanding absorption at 365 nm. These chalcone-based OXEs are considered to exert significant potential in the realm of free radical photocuring.
As one of the most essential components in photocuring system, photoinitiators (PIs) exert a crucial influence on the properties of the cured product. However, commercially available PIs encounter challenges in simultaneously achieving efficient photoinitiation performance and excellent light absorption properties, significantly limiting their applications in various fields. Here, two bis-chalcones and four corresponding oxime esters (OXEs) were designed and synthesized as highly efficient PIs. Featuring a structure comprising bis-chalcone and two diphenyl sulfides, the conjugated systems in these compounds enhance their light-absorption properties in near-ultraviolet and visible region, effectively. Both the frontier molecular orbital simulations and excited state calculations suggest the contribution of sulfur atoms to electron delocalization and the formation of conjugated structure. Due to the high reactivity of the NO bond in OXE moiety, the four OXEs exhibit exceptional free radical photoinitiating ability in commercial acrylic monomers/oligomers with LED@365 nm as light source. Notably, one of them demonstrates superior performance in the photoinitiation of multifunctional crosslinker, achieving more than 70% conversion within 3 s, coupled with outstanding absorption at 365 nm. These chalcone-based OXEs are considered to exert significant potential in the realm of free radical photocuring.
2025, 36(3): 110429
doi: 10.1016/j.cclet.2024.110429
Abstract:
Developing high performance electrocatalysts for the cathodic oxygen reduction reaction (ORR) is essential for the widespread application of fuel cells. Herein, a promising Pt2NiCo atomic ordered ternary intermetallic compound with N-doped carbon layer coating (o-Pt2NiCo@NC) has been synthesized via a facile method and applied in acidic ORR. The confinement effect provided by the carbon layer not only inhibits the agglomeration and sintering of intermetallic nanoparticles during high temperature process but also provides adequate protection for the nanoparticles, mitigating the aggregation, detachment and poisoning of nanoparticles during the electrochemical process. As a result, the o-Pt2NiCo@NC demonstrates a mass activity (MA) and specific activity (SA) of 0.65 A/mgPt and 1.41 mA/cmPt2 in 0.1 mol/L HClO4, respectively. In addition, after 30,000 potential cycles from 0.6 V to 1.0 V, the MA of o-Pt2NiCo@NC shows much lower decrease than the disordered Pt2NiCo alloy and Pt/C. Even cycling at high potential cycles of 1.5 V for 10,000 cycles, the MA still retains ~70%, demonstrating superior long-term durability. Furthermore, the o-Pt2NiCo@NC also exhibits strong tolerance to CO, SOx, and POx molecules in toxicity tolerance tests. The strategy in this work provides a novel insight for the development of ORR catalysts with high catalytic activity, durability and toxicity tolerance.
Developing high performance electrocatalysts for the cathodic oxygen reduction reaction (ORR) is essential for the widespread application of fuel cells. Herein, a promising Pt2NiCo atomic ordered ternary intermetallic compound with N-doped carbon layer coating (o-Pt2NiCo@NC) has been synthesized via a facile method and applied in acidic ORR. The confinement effect provided by the carbon layer not only inhibits the agglomeration and sintering of intermetallic nanoparticles during high temperature process but also provides adequate protection for the nanoparticles, mitigating the aggregation, detachment and poisoning of nanoparticles during the electrochemical process. As a result, the o-Pt2NiCo@NC demonstrates a mass activity (MA) and specific activity (SA) of 0.65 A/mgPt and 1.41 mA/cmPt2 in 0.1 mol/L HClO4, respectively. In addition, after 30,000 potential cycles from 0.6 V to 1.0 V, the MA of o-Pt2NiCo@NC shows much lower decrease than the disordered Pt2NiCo alloy and Pt/C. Even cycling at high potential cycles of 1.5 V for 10,000 cycles, the MA still retains ~70%, demonstrating superior long-term durability. Furthermore, the o-Pt2NiCo@NC also exhibits strong tolerance to CO, SOx, and POx molecules in toxicity tolerance tests. The strategy in this work provides a novel insight for the development of ORR catalysts with high catalytic activity, durability and toxicity tolerance.
2025, 36(3): 110445
doi: 10.1016/j.cclet.2024.110445
Abstract:
Achieving seamless tiling through the self-assembly of organic species has long fascinated scientists for its potential applications across various fields. However, constructing periodic nanostructures with high-order tessellation remains challenging, particularly in achieving precise control at the supramolecular level. In this study, we present the successful creation of multiple seamless 2D tessellations on Au (111) surface using versatile hexagonal tiles derived from a singular molecular unit, namely 2,6,10-tribromotricycloquinazoline. Through scanning tunneling microscopy imaging, seven distinct 2D tessellations, ranging from regular to semiregular to k-uniform tilings, are unveiled at the molecular level. Density functional theory calculations provide a theoretical basis for the formation of these complex 2D tessellation, highlighting the important role of the variability of Br···Br/H contacts in facilitating complex seamless 2D tessellations on surface. This work opens avenues for exploring possibilities in constructing intricate tiling patterns with diverse applications.
Achieving seamless tiling through the self-assembly of organic species has long fascinated scientists for its potential applications across various fields. However, constructing periodic nanostructures with high-order tessellation remains challenging, particularly in achieving precise control at the supramolecular level. In this study, we present the successful creation of multiple seamless 2D tessellations on Au (111) surface using versatile hexagonal tiles derived from a singular molecular unit, namely 2,6,10-tribromotricycloquinazoline. Through scanning tunneling microscopy imaging, seven distinct 2D tessellations, ranging from regular to semiregular to k-uniform tilings, are unveiled at the molecular level. Density functional theory calculations provide a theoretical basis for the formation of these complex 2D tessellation, highlighting the important role of the variability of Br···Br/H contacts in facilitating complex seamless 2D tessellations on surface. This work opens avenues for exploring possibilities in constructing intricate tiling patterns with diverse applications.
2025, 36(3): 110476
doi: 10.1016/j.cclet.2024.110476
Abstract:
Charge-neutral method (CNM) is extensively used in investigating the performance of catalysts and the mechanism of N2 electrochemical reduction (NRR). However, disparities remain between the predicted potentials required for NRR by the CNM methods and those observed experimentally, as the CNM method neglects the charge effect from the electrode potential. To address this issue, we employed the constant electrode potential (CEP) method to screen atomic transition metal-N-graphene (M1/N-graphene) as NRR electrocatalysts and systematically investigated the underlying catalytic mechanism. Among eight types of M1/N-graphene (M1 = Mo, W, Fe, Re, Ni, Co, V, Cr), W1/N-graphene emerges as the most promising NRR electrocatalyst with a limiting potential as low as −0.13 V. Additionally, the W1/N-graphene system consistently maintains a positive charge during the reaction due to its Fermi level being higher than that of the electrode. These results better match with the actual circumstances compared to those calculated by conventional CNM method. Thus, our work not only develops a promising electrocatalyst for NRR but also deepens the understanding of the intrinsic electrocatalytic mechanism.
Charge-neutral method (CNM) is extensively used in investigating the performance of catalysts and the mechanism of N2 electrochemical reduction (NRR). However, disparities remain between the predicted potentials required for NRR by the CNM methods and those observed experimentally, as the CNM method neglects the charge effect from the electrode potential. To address this issue, we employed the constant electrode potential (CEP) method to screen atomic transition metal-N-graphene (M1/N-graphene) as NRR electrocatalysts and systematically investigated the underlying catalytic mechanism. Among eight types of M1/N-graphene (M1 = Mo, W, Fe, Re, Ni, Co, V, Cr), W1/N-graphene emerges as the most promising NRR electrocatalyst with a limiting potential as low as −0.13 V. Additionally, the W1/N-graphene system consistently maintains a positive charge during the reaction due to its Fermi level being higher than that of the electrode. These results better match with the actual circumstances compared to those calculated by conventional CNM method. Thus, our work not only develops a promising electrocatalyst for NRR but also deepens the understanding of the intrinsic electrocatalytic mechanism.
2025, 36(3): 110496
doi: 10.1016/j.cclet.2024.110496
Abstract:
Histopathological analysis of chronic wounds is crucial for clinicians to accurately assess wound healing progress and detect potential malignancy. However, traditional pathological tissue sections require specific staining procedures involving carcinogenic chemicals. This study proposes an interdisciplinary approach merging materials science, medicine, and artificial intelligence (AI) to develop a virtual staining technique and intelligent evaluation model based on deep learning for chronic wound tissue pathology. This innovation aims to enhance clinical diagnosis and treatment by offering personalized AI-driven therapeutic strategies. By establishing a mouse model of chronic wounds and using a series of hydrogel wound dressings, tissue pathology sections were periodically collected for manual staining and healing assessment. We focused on leveraging the pix2pix image translation framework within deep learning networks. Through CNN models implemented in Python using PyTorch, our study involves learning and feature extraction for region segmentation of pathological slides. Comparative analysis between virtual staining and manual staining results, along with healing diagnosis conclusions, aims to optimize AI models. Ultimately, this approach integrates new metrics such as image recognition, quantitative analysis, and digital diagnostics to formulate an intelligent wound assessment model, facilitating smart monitoring and personalized treatment of wounds. In blind evaluation by pathologists, minimal disparities were found between virtual and conventional histologically stained images of murine wound tissue. The evaluation used pathologists' average scores on real stained images as a benchmark. The scores for virtual stained images were 71.1% for cellular features, 75.4% for tissue structures, and 77.8% for overall assessment. Metrics such as PSNR (20.265) and SSIM (0.634) demonstrated our algorithms' superior performance over existing networks. Eight pathological features such as epidermis, hair follicles, and granulation tissue can be accurately identified, and the images were found to be more faithful to the actual tissue feature distribution when compared to manually annotated data.
Histopathological analysis of chronic wounds is crucial for clinicians to accurately assess wound healing progress and detect potential malignancy. However, traditional pathological tissue sections require specific staining procedures involving carcinogenic chemicals. This study proposes an interdisciplinary approach merging materials science, medicine, and artificial intelligence (AI) to develop a virtual staining technique and intelligent evaluation model based on deep learning for chronic wound tissue pathology. This innovation aims to enhance clinical diagnosis and treatment by offering personalized AI-driven therapeutic strategies. By establishing a mouse model of chronic wounds and using a series of hydrogel wound dressings, tissue pathology sections were periodically collected for manual staining and healing assessment. We focused on leveraging the pix2pix image translation framework within deep learning networks. Through CNN models implemented in Python using PyTorch, our study involves learning and feature extraction for region segmentation of pathological slides. Comparative analysis between virtual staining and manual staining results, along with healing diagnosis conclusions, aims to optimize AI models. Ultimately, this approach integrates new metrics such as image recognition, quantitative analysis, and digital diagnostics to formulate an intelligent wound assessment model, facilitating smart monitoring and personalized treatment of wounds. In blind evaluation by pathologists, minimal disparities were found between virtual and conventional histologically stained images of murine wound tissue. The evaluation used pathologists' average scores on real stained images as a benchmark. The scores for virtual stained images were 71.1% for cellular features, 75.4% for tissue structures, and 77.8% for overall assessment. Metrics such as PSNR (20.265) and SSIM (0.634) demonstrated our algorithms' superior performance over existing networks. Eight pathological features such as epidermis, hair follicles, and granulation tissue can be accurately identified, and the images were found to be more faithful to the actual tissue feature distribution when compared to manually annotated data.
2025, 36(3): 110520
doi: 10.1016/j.cclet.2024.110520
Abstract:
Thermally activated delayed fluorescence (TADF) materials driven by a through-space charge transfer (TSCT) mechanism have garnered wide interest. However, access of TSCT-TADF molecules with long-wavelength emission remains a formidable challenge. In this study, we introduce a novel V-type D-A-D-A' emitter, Trz-mCzCbCz, by using a carborane scaffold. This design strategically incorporates carbazole (Cz) and 2,4,6-triphenyl-1,3,5-triazine (Trz) as donor and acceptor moieties, respectively. Theoretical calculations alongside experimental validations affirm the typical TSCT-TADF characteristics of this luminogen. Owing to the unique structural and electronic attributes of carboranes, Trz-mCzCbCz exhibits an orange-red emission, markedly diverging from the traditional blue-to-green emissions observed in classical Cz and Trz-based TADF molecules. Moreover, bright emission in aggregates was observed for Trz-mCzCbCz with absolute photoluminescence quantum yield (PLQY) of up to 88.8%. As such, we have successfully fabricated five organic light-emitting diodes (OLEDs) by utilizing Trz-mCzCbCz as the emitting layer. It is important to note that both the reverse intersystem crossing process and the TADF properties are profoundly influenced by host materials. The fabricated OLED devices reached a maximum external quantum efficiency (EQE) of 12.7%, with an emission peak at 592 nm. This represents the highest recorded efficiency for TSCT-TADF OLEDs employing carborane derivatives as emitting layers.
Thermally activated delayed fluorescence (TADF) materials driven by a through-space charge transfer (TSCT) mechanism have garnered wide interest. However, access of TSCT-TADF molecules with long-wavelength emission remains a formidable challenge. In this study, we introduce a novel V-type D-A-D-A' emitter, Trz-mCzCbCz, by using a carborane scaffold. This design strategically incorporates carbazole (Cz) and 2,4,6-triphenyl-1,3,5-triazine (Trz) as donor and acceptor moieties, respectively. Theoretical calculations alongside experimental validations affirm the typical TSCT-TADF characteristics of this luminogen. Owing to the unique structural and electronic attributes of carboranes, Trz-mCzCbCz exhibits an orange-red emission, markedly diverging from the traditional blue-to-green emissions observed in classical Cz and Trz-based TADF molecules. Moreover, bright emission in aggregates was observed for Trz-mCzCbCz with absolute photoluminescence quantum yield (PLQY) of up to 88.8%. As such, we have successfully fabricated five organic light-emitting diodes (OLEDs) by utilizing Trz-mCzCbCz as the emitting layer. It is important to note that both the reverse intersystem crossing process and the TADF properties are profoundly influenced by host materials. The fabricated OLED devices reached a maximum external quantum efficiency (EQE) of 12.7%, with an emission peak at 592 nm. This represents the highest recorded efficiency for TSCT-TADF OLEDs employing carborane derivatives as emitting layers.
2025, 36(3): 110575
doi: 10.1016/j.cclet.2024.110575
Abstract:
The development of high-performance carbon-based composite hosts plays decisive roles in the electrochemistry of lithium sulfur batteries. Herein, a novel metal-ion induced gelation self-assembly technology is reported to construct sodium alginate carbon (SAC) based polar hierarchical carbon composites with cross-linked network architecture and in-situ co-grown cross-linked polar nanoparticles. Interestingly, it shows high versatility to an extensive array of materials including metals, alloys, and metallic oxides. As a representative, NiCo alloy nanoparticles are chosen to obtain the SAC/NiCo composite host for sulfur in LSBs, which possess superior physical/chemical adsorption capabilities and catalytic conversion kinetics to polysulfide in virtue of synergistic interaction between the hierarchical pore structures and NiCo catalyst. The designed SAC/NiCo-S cathode shows superior electrochemical performance with excellent rate capacity (2 C: 693.5 mAh/g) and enhanced cycling stability (764.3 mAh/g at 0.1 C after 240 cycles). This work provides a straightforward approach for fabricating multifunctional carbon composites with adjustable component for advanced energy storage system.
The development of high-performance carbon-based composite hosts plays decisive roles in the electrochemistry of lithium sulfur batteries. Herein, a novel metal-ion induced gelation self-assembly technology is reported to construct sodium alginate carbon (SAC) based polar hierarchical carbon composites with cross-linked network architecture and in-situ co-grown cross-linked polar nanoparticles. Interestingly, it shows high versatility to an extensive array of materials including metals, alloys, and metallic oxides. As a representative, NiCo alloy nanoparticles are chosen to obtain the SAC/NiCo composite host for sulfur in LSBs, which possess superior physical/chemical adsorption capabilities and catalytic conversion kinetics to polysulfide in virtue of synergistic interaction between the hierarchical pore structures and NiCo catalyst. The designed SAC/NiCo-S cathode shows superior electrochemical performance with excellent rate capacity (2 C: 693.5 mAh/g) and enhanced cycling stability (764.3 mAh/g at 0.1 C after 240 cycles). This work provides a straightforward approach for fabricating multifunctional carbon composites with adjustable component for advanced energy storage system.
2025, 36(3): 110580
doi: 10.1016/j.cclet.2024.110580
Abstract:
The bicarbonate-formate (HCO3− – HCO2−) interconversion provides a promising cycle for a conveniently accessible hydrogen storage system via reversible dehydrogenation and hydrogenation processes. Existing catalytic systems often use organic solvents, tedious optimization as well as manipulation of pH values, solvent, pressure and various additives. Herein, we present an operational, robust, safe and cost-effective catalytic system for hydrogen storage and liberation. We have established a unique catalytic system with two different solid organometallic assemblies (NHC-Ru and NHC-Ir) that facilitate the reversible transformation between sodium formate and bicarbonate in aqueous solutions collaboratively and efficiently. Notably, the NHC-Ru catalyst is privileged for the hydrogenation of sodium bicarbonate, whereas the NHC-Ir component enables the dehydrogenation of sodium formate, all in a single reaction vessel. What sets this system apart is its simplicity. The H2 discharging and recharging is simply regulated by heating the mixture with or without H2. Remarkably, this process requires no extra additives or supplementary treatments. Moreover, the reversible hydrogen storage system is durable and can be reused for over 30 cycles without a discernible decline in activity and selectivity. The strategic paradigm in this study shows significant practical potential in hydrogen fuel cell applications.
The bicarbonate-formate (HCO3− – HCO2−) interconversion provides a promising cycle for a conveniently accessible hydrogen storage system via reversible dehydrogenation and hydrogenation processes. Existing catalytic systems often use organic solvents, tedious optimization as well as manipulation of pH values, solvent, pressure and various additives. Herein, we present an operational, robust, safe and cost-effective catalytic system for hydrogen storage and liberation. We have established a unique catalytic system with two different solid organometallic assemblies (NHC-Ru and NHC-Ir) that facilitate the reversible transformation between sodium formate and bicarbonate in aqueous solutions collaboratively and efficiently. Notably, the NHC-Ru catalyst is privileged for the hydrogenation of sodium bicarbonate, whereas the NHC-Ir component enables the dehydrogenation of sodium formate, all in a single reaction vessel. What sets this system apart is its simplicity. The H2 discharging and recharging is simply regulated by heating the mixture with or without H2. Remarkably, this process requires no extra additives or supplementary treatments. Moreover, the reversible hydrogen storage system is durable and can be reused for over 30 cycles without a discernible decline in activity and selectivity. The strategic paradigm in this study shows significant practical potential in hydrogen fuel cell applications.
2025, 36(3): 110612
doi: 10.1016/j.cclet.2024.110612
Abstract:
Efficient and stable electrocatalyst for oxygen evolution reaction (OER) in acidic environment is vital for polymer electrolyte membrane water electrolysis (PEMWE). In this work, we have devised the formation of heterostructured RuO2/MnO2 with nanoflower structure for acidic OER catalysis. Compared to commercial RuO2, the overpotential at 50 mA/cm2 is decreased by 36 mV, corresponding to a 3.7-fold better mass activity. The boosted acidic OER performance is attributed to the heterostructure inducing more electrons are filled in eg orbital of Ru atom triggering a better deprotonation of bridge oxygen atom in Ru-Obri-Mn structure evidenced by pH-independent cyclic voltammetry test. Moreover, RuO2/MnO2 sustains its acidic OER activity within 20 h, longer than commercial RuO2. The membrane electrode assembly (MEA) test suggests than only 2.18 V is required to achieve a current density of 5 A/cm2. The theoretical calculation reveals that the eg filling of Ru atom is increased from 2.18 to 2.39 after MnO2 incorporation, reducing the energy for the formation of *OOH moiety.
Efficient and stable electrocatalyst for oxygen evolution reaction (OER) in acidic environment is vital for polymer electrolyte membrane water electrolysis (PEMWE). In this work, we have devised the formation of heterostructured RuO2/MnO2 with nanoflower structure for acidic OER catalysis. Compared to commercial RuO2, the overpotential at 50 mA/cm2 is decreased by 36 mV, corresponding to a 3.7-fold better mass activity. The boosted acidic OER performance is attributed to the heterostructure inducing more electrons are filled in eg orbital of Ru atom triggering a better deprotonation of bridge oxygen atom in Ru-Obri-Mn structure evidenced by pH-independent cyclic voltammetry test. Moreover, RuO2/MnO2 sustains its acidic OER activity within 20 h, longer than commercial RuO2. The membrane electrode assembly (MEA) test suggests than only 2.18 V is required to achieve a current density of 5 A/cm2. The theoretical calculation reveals that the eg filling of Ru atom is increased from 2.18 to 2.39 after MnO2 incorporation, reducing the energy for the formation of *OOH moiety.
2025, 36(3): 110701
doi: 10.1016/j.cclet.2024.110701
Abstract:
Manganese dioxide (MnO2) electrode material possesses the advantages of high energy density, structural diversity and high modification potential. This allows it become one of the important cathodes for aqueous zinc ion battery. However, the applications are limited by the poor electrical conductivity, narrow layer spacing and the ease of dissolution. Herein, we prepare MnO2-PVP@0.03GO composites by the co-modification of polyvinylpyrrolidone (PVP) pre-insertion layer and graphene oxide (GO) self-assembly layer. The Zn//MnO2-PVP@0.03GO cells deliver a discharge specific capacity of 442 mAh/g at a current density of 0.2 A/g. It also maintains 100% capacity for 1000 times cycling at 1 A/g. The assembled soft package batteries demonstrate superior flexibility and adaptability under different bending conditions.
Manganese dioxide (MnO2) electrode material possesses the advantages of high energy density, structural diversity and high modification potential. This allows it become one of the important cathodes for aqueous zinc ion battery. However, the applications are limited by the poor electrical conductivity, narrow layer spacing and the ease of dissolution. Herein, we prepare MnO2-PVP@0.03GO composites by the co-modification of polyvinylpyrrolidone (PVP) pre-insertion layer and graphene oxide (GO) self-assembly layer. The Zn//MnO2-PVP@0.03GO cells deliver a discharge specific capacity of 442 mAh/g at a current density of 0.2 A/g. It also maintains 100% capacity for 1000 times cycling at 1 A/g. The assembled soft package batteries demonstrate superior flexibility and adaptability under different bending conditions.
2025, 36(3): 110731
doi: 10.1016/j.cclet.2024.110731
Abstract:
Sluggish conversion reaction kinetics and spontaneous shuttle effect of lithium polysulfides (LiPSs) are deemed as the two big mountains that hinder the practical application of lithium-sulfur batteries (LSBs). Herein, dual-defect engineering strategy is implemented by introducing boron-doping and phosphorus-vacancy sites with MoP@NC composite as the precursor. Based on the experimental characterizations and theoretical calculations, B-MoP1-x@NC-based electrode presents low oxidation potential, high lithium diffusivity, small Tafel slope and strong adsorption capability for polysulfides, which is beneficial to enhance the adsorption capability for LiPSs, reduce the lithium diffusion energy barriers and Gibbs free energy for the conversion reactions of LiPSs. As demonstrated, the corresponding Li-S/B-MoP1-x@NC batteries can remain high reversible capacity of 753 mAh/g at 0.5 C after 300 cycles, and keep a stable capacity of 520 mAh/g at 0.5 C after 100 cycles even at the high-loading content of 5.1 mg/cm2. According to the results of in-situ UV–vis spectra, the satisfactory battery performance majorly originates from the existence of dual-defect characteristics in B-MoP1-x@NC catalyst, which effectively promotes the conversion reaction kinetics of LiPSs, and restrains the shuttle behavior of LiPSs. The key ideas of this work will enlighten the development of catalytic cathode materials for sulfur-based secondary batteries.
Sluggish conversion reaction kinetics and spontaneous shuttle effect of lithium polysulfides (LiPSs) are deemed as the two big mountains that hinder the practical application of lithium-sulfur batteries (LSBs). Herein, dual-defect engineering strategy is implemented by introducing boron-doping and phosphorus-vacancy sites with MoP@NC composite as the precursor. Based on the experimental characterizations and theoretical calculations, B-MoP1-x@NC-based electrode presents low oxidation potential, high lithium diffusivity, small Tafel slope and strong adsorption capability for polysulfides, which is beneficial to enhance the adsorption capability for LiPSs, reduce the lithium diffusion energy barriers and Gibbs free energy for the conversion reactions of LiPSs. As demonstrated, the corresponding Li-S/B-MoP1-x@NC batteries can remain high reversible capacity of 753 mAh/g at 0.5 C after 300 cycles, and keep a stable capacity of 520 mAh/g at 0.5 C after 100 cycles even at the high-loading content of 5.1 mg/cm2. According to the results of in-situ UV–vis spectra, the satisfactory battery performance majorly originates from the existence of dual-defect characteristics in B-MoP1-x@NC catalyst, which effectively promotes the conversion reaction kinetics of LiPSs, and restrains the shuttle behavior of LiPSs. The key ideas of this work will enlighten the development of catalytic cathode materials for sulfur-based secondary batteries.
2025, 36(3): 109676
doi: 10.1016/j.cclet.2024.109676
Abstract:
Large-scale deployment of carbon dioxide (CO2) removal technology is an essential step to cope with global warming and achieve carbon neutrality. Direct air capture (DAC) has recently received increasing attention given the high flexibility to remove CO2 from discrete sources. Porous materials with adjustable pore characteristics are promising sorbents with low or no latent heat of vaporization. This review article has summarized the recent development of porous sorbents for DAC, with a focus of pore engineering strategy and adsorption mechanism. Physisorbents such as zeolites, porous carbons, metal-organic frameworks (MOFs), and amine-modified chemisorbents have been discussed and their challenges in practical application have been analyzed. At last, future directions have been proposed, and it is expected to inspire collaborations from chemistry, environment, material science and engineering communities.
Large-scale deployment of carbon dioxide (CO2) removal technology is an essential step to cope with global warming and achieve carbon neutrality. Direct air capture (DAC) has recently received increasing attention given the high flexibility to remove CO2 from discrete sources. Porous materials with adjustable pore characteristics are promising sorbents with low or no latent heat of vaporization. This review article has summarized the recent development of porous sorbents for DAC, with a focus of pore engineering strategy and adsorption mechanism. Physisorbents such as zeolites, porous carbons, metal-organic frameworks (MOFs), and amine-modified chemisorbents have been discussed and their challenges in practical application have been analyzed. At last, future directions have been proposed, and it is expected to inspire collaborations from chemistry, environment, material science and engineering communities.
2025, 36(3): 109686
doi: 10.1016/j.cclet.2024.109686
Abstract:
As hydrogen energy technologies gain momentum, the role of renewable energy in facilitating sustainable hydrogen production is becoming increasingly critical. As a hydrogen production method, water electrolysis has attracted much attention from researchers due to its operational simplicity, the high purity of the hydrogen generated, and its potential for achieving zero carbon emissions throughout the process. Numerous studies has been manipulated on platinum (Pt)-based catalysts, which exhibit superior performance in hydrogen evolution reactions. Within this category, Pt nanoclusters stand out due to their unique attributes, such as quantum size effects and unique coordination environments. These features enable them to outperform both Pt metal atoms and nanoparticles in hydrogen evolution reactions regarding activity and stability. Here, we primarily delve into the reaction mechanisms underlying Pt nanocluster-based hydrogen catalysts, with particular emphasis on the interactions between the metal catalysts and their associated support materials. We provide an exhaustive summary of the strategies employed in the synthesis, the structural analyses conducted, and the performance metrics observed for Pt nanocluster catalysts when paired with various supporting materials. In closing, we explore the future potential and challenges facing Pt nanocluster-based catalysts in the context of industrial water electrolysis, along with emerging avenues for their design and optimization.
As hydrogen energy technologies gain momentum, the role of renewable energy in facilitating sustainable hydrogen production is becoming increasingly critical. As a hydrogen production method, water electrolysis has attracted much attention from researchers due to its operational simplicity, the high purity of the hydrogen generated, and its potential for achieving zero carbon emissions throughout the process. Numerous studies has been manipulated on platinum (Pt)-based catalysts, which exhibit superior performance in hydrogen evolution reactions. Within this category, Pt nanoclusters stand out due to their unique attributes, such as quantum size effects and unique coordination environments. These features enable them to outperform both Pt metal atoms and nanoparticles in hydrogen evolution reactions regarding activity and stability. Here, we primarily delve into the reaction mechanisms underlying Pt nanocluster-based hydrogen catalysts, with particular emphasis on the interactions between the metal catalysts and their associated support materials. We provide an exhaustive summary of the strategies employed in the synthesis, the structural analyses conducted, and the performance metrics observed for Pt nanocluster catalysts when paired with various supporting materials. In closing, we explore the future potential and challenges facing Pt nanocluster-based catalysts in the context of industrial water electrolysis, along with emerging avenues for their design and optimization.
2025, 36(3): 109875
doi: 10.1016/j.cclet.2024.109875
Abstract:
Metabolism is a general term for a series of ordered chemical reactions in an organism used to maintain life, mainly divided into anabolic and catabolic metabolism. Nucleic acid therapy can not only precisely up-regulate and down-regulate the expression of target genes but also correct mutated disease-causing genes, which demonstrates irreplaceable and outstanding advantages in the treatment of metabolism-related diseases and has been applied to the clinical treatment of metabolism-related diseases. In this review, we introduce the structures of several major nucleic acid drugs and the mechanism of nucleic acid therapy. Subsequently, we describe the mechanisms of various biomolecular and tissue metabolisms and the etiology of metabolic disorders, classified according to metabolic substrates. We analyze the signal pathways and potential targets affecting the metabolism of each substrate and describe the nucleic acid drugs applied to these targets and their delivery technologies. This review aims to provide new ideas and targets for treating these diseases by investigating the role played by metabolism in developing diseases and providing guidance for the selection and design of nucleic acid drugs.
Metabolism is a general term for a series of ordered chemical reactions in an organism used to maintain life, mainly divided into anabolic and catabolic metabolism. Nucleic acid therapy can not only precisely up-regulate and down-regulate the expression of target genes but also correct mutated disease-causing genes, which demonstrates irreplaceable and outstanding advantages in the treatment of metabolism-related diseases and has been applied to the clinical treatment of metabolism-related diseases. In this review, we introduce the structures of several major nucleic acid drugs and the mechanism of nucleic acid therapy. Subsequently, we describe the mechanisms of various biomolecular and tissue metabolisms and the etiology of metabolic disorders, classified according to metabolic substrates. We analyze the signal pathways and potential targets affecting the metabolism of each substrate and describe the nucleic acid drugs applied to these targets and their delivery technologies. This review aims to provide new ideas and targets for treating these diseases by investigating the role played by metabolism in developing diseases and providing guidance for the selection and design of nucleic acid drugs.
2025, 36(3): 109925
doi: 10.1016/j.cclet.2024.109925
Abstract:
The utilization of solar-driven interfacial evaporation technology is highly important in addressing the energy crisis and water scarcity, primarily because of its affordability and minimal energy usage. Enhancing the performance of solar energy evaporation and minimizing material degradation during application can be achieved through the design of novel photothermal materials. In solar interfacial evaporation, photothermal materials exhibit a wide range of additional characteristics, but a systematic overview is lacking. This paper encompasses an examination of various categories and principles pertaining to photothermal materials, as well as the structural design considerations for salt-resistant materials. Additionally, we discuss the versatile uses of this appealing technology in different sectors related to energy and the environment. Furthermore, potential solutions to enhance the durability of photothermal materials are also highlighted, such as the rational design of micro/nano-structures, the use of adhesives, the addition of anti-corrosion coatings, and the preparation of self-healing surfaces. The objective of this review is to offer a viable resolution for the logical creation of high-performance photothermal substances, presenting a guide for the forthcoming advancement of solar evaporation technology.
The utilization of solar-driven interfacial evaporation technology is highly important in addressing the energy crisis and water scarcity, primarily because of its affordability and minimal energy usage. Enhancing the performance of solar energy evaporation and minimizing material degradation during application can be achieved through the design of novel photothermal materials. In solar interfacial evaporation, photothermal materials exhibit a wide range of additional characteristics, but a systematic overview is lacking. This paper encompasses an examination of various categories and principles pertaining to photothermal materials, as well as the structural design considerations for salt-resistant materials. Additionally, we discuss the versatile uses of this appealing technology in different sectors related to energy and the environment. Furthermore, potential solutions to enhance the durability of photothermal materials are also highlighted, such as the rational design of micro/nano-structures, the use of adhesives, the addition of anti-corrosion coatings, and the preparation of self-healing surfaces. The objective of this review is to offer a viable resolution for the logical creation of high-performance photothermal substances, presenting a guide for the forthcoming advancement of solar evaporation technology.
2025, 36(3): 109993
doi: 10.1016/j.cclet.2024.109993
Abstract:
In recent years, the development of wafer-level GaN nanowires photocatalyst loaded onto silicon substrates has progressed rapidly depending on its simplicity of instrumentation, collection and separation from the water. Accordingly, the wafer-level GaN-based nanowires (GaN NWs) photocatalyst can be a fabulous candidate for the application in the field of photocatalytic hydrogen evolution reaction (PHER) and provides a novel route to address the environmental and energy crisis. Herein, a range of innovative strategies to improve the performance of GaN NWs photocatalyst are systematically summarized. Then, the solar-to-hydrogen conversion efficiency, the characteristics of GaN NWs system, the cost of the origin material required, as well as the stability, activity and the corrosion resistance to seawater are discussed in detail as some of the essential conditions for advancing its large-scale industry-friendly application. Last but not least, we provide the potential application of this system for splitting seawater to produce hydrogen and point out the direction for overcoming the barriers to future industrial-scale implementation.
In recent years, the development of wafer-level GaN nanowires photocatalyst loaded onto silicon substrates has progressed rapidly depending on its simplicity of instrumentation, collection and separation from the water. Accordingly, the wafer-level GaN-based nanowires (GaN NWs) photocatalyst can be a fabulous candidate for the application in the field of photocatalytic hydrogen evolution reaction (PHER) and provides a novel route to address the environmental and energy crisis. Herein, a range of innovative strategies to improve the performance of GaN NWs photocatalyst are systematically summarized. Then, the solar-to-hydrogen conversion efficiency, the characteristics of GaN NWs system, the cost of the origin material required, as well as the stability, activity and the corrosion resistance to seawater are discussed in detail as some of the essential conditions for advancing its large-scale industry-friendly application. Last but not least, we provide the potential application of this system for splitting seawater to produce hydrogen and point out the direction for overcoming the barriers to future industrial-scale implementation.
2025, 36(3): 110028
doi: 10.1016/j.cclet.2024.110028
Abstract:
Bacterial infections have always been a major threat to human health. Skin wounds are frequently exposed to the external environment, and they may become contaminated by bacteria derived from the surrounding skin, the local environment, and the patient's own endogenous sources. Contaminated wounds may enter a state of chronic inflammation that impedes healing. Urgent development of antibacterial wound dressings capable of effectively combating bacteria and overcoming resistance is necessary. Nanotechnology and nanomaterials present promising potential as innovative strategies for antimicrobial wound dressings, owing to their robust antibacterial characteristics and the inherent advantage of avoiding antibiotic resistance. Therefore, this review provides a concise overview of the antimicrobial mechanisms exhibited by low-dimensional nanomaterials. It further categorizes common low-dimensional antimicrobial nanomaterials into zero-dimensional (0D), one-dimensional (1D) and two-dimensional (2D) nanomaterials based on their structural characteristics, and gives a detailed compendium of the latest research advances and applications of different low-dimensional antimicrobial nanomaterials in wound healing, which could be helpful for the development of more effective wound dressings.
Bacterial infections have always been a major threat to human health. Skin wounds are frequently exposed to the external environment, and they may become contaminated by bacteria derived from the surrounding skin, the local environment, and the patient's own endogenous sources. Contaminated wounds may enter a state of chronic inflammation that impedes healing. Urgent development of antibacterial wound dressings capable of effectively combating bacteria and overcoming resistance is necessary. Nanotechnology and nanomaterials present promising potential as innovative strategies for antimicrobial wound dressings, owing to their robust antibacterial characteristics and the inherent advantage of avoiding antibiotic resistance. Therefore, this review provides a concise overview of the antimicrobial mechanisms exhibited by low-dimensional nanomaterials. It further categorizes common low-dimensional antimicrobial nanomaterials into zero-dimensional (0D), one-dimensional (1D) and two-dimensional (2D) nanomaterials based on their structural characteristics, and gives a detailed compendium of the latest research advances and applications of different low-dimensional antimicrobial nanomaterials in wound healing, which could be helpful for the development of more effective wound dressings.
2025, 36(3): 110094
doi: 10.1016/j.cclet.2024.110094
Abstract:
Pyrrole is a heterocycle with four carbon atoms and a nitrogen atom, which is extensively used in the pesticide and pharmaceutical industries. In addition, it has a series of analogs such as pyrrolidine, pyrroline, and pyrrolidone. Pesticides containing pyrrole and its analogs have been formally marketed as fungicides, including fenpiclonil, fludioxonil, the insecticide chlorfenapyr, and the herbicide fluorochloridone. In this paper, we analyze the structure-activity relationships (SARs) of pesticides containing these structures. We summarize the characteristics possessed by the most highly active pyrrole and its analogs and provide an overview of research on pyrrole compounds with insecticidal, antimicrobial, herbicidal, and antiviral properties in the past 20 years. It is hoped to provide ideas for the development and design of this type compounds in pesticides and to assist researchers in this area.
Pyrrole is a heterocycle with four carbon atoms and a nitrogen atom, which is extensively used in the pesticide and pharmaceutical industries. In addition, it has a series of analogs such as pyrrolidine, pyrroline, and pyrrolidone. Pesticides containing pyrrole and its analogs have been formally marketed as fungicides, including fenpiclonil, fludioxonil, the insecticide chlorfenapyr, and the herbicide fluorochloridone. In this paper, we analyze the structure-activity relationships (SARs) of pesticides containing these structures. We summarize the characteristics possessed by the most highly active pyrrole and its analogs and provide an overview of research on pyrrole compounds with insecticidal, antimicrobial, herbicidal, and antiviral properties in the past 20 years. It is hoped to provide ideas for the development and design of this type compounds in pesticides and to assist researchers in this area.
2025, 36(3): 110245
doi: 10.1016/j.cclet.2024.110245
Abstract:
Aqueous zinc-based energy storage devices (ZESDs) have garnered considerable interest because of their high specific capacity, abundant zinc reserves, excellent safety, and environmental friendliness. In recent years, various types of boron, nitrogen co-doped carbon (BNC) materials have been developed to improve electrochemical performance of ZESDs. To promote the advancement of these technologies, we herein give a comprehensive review of the progress in BNC materials for ZESDs. The different synthetic methods employed in the preparation of BNC materials, including direct carbonization, template method, chemical vapor deposition, hydrothermal method, etc., are summarized. These methods play a vital role in tailoring the structure, composition, and properties of BNC materials to optimize their performance in energy storage applications. Furthermore, some key achievements of BNC materials in zinc-air batteries and zinc-ion hybrid supercapacitors are elaborated. Lastly, future challenges and development directions of BNC materials in ZESDs are prospected. This comprehensive review could serve as a valuable resource in the energy storage field, providing insights into the potential of BNC materials in zinc-based energy storage technologies.
Aqueous zinc-based energy storage devices (ZESDs) have garnered considerable interest because of their high specific capacity, abundant zinc reserves, excellent safety, and environmental friendliness. In recent years, various types of boron, nitrogen co-doped carbon (BNC) materials have been developed to improve electrochemical performance of ZESDs. To promote the advancement of these technologies, we herein give a comprehensive review of the progress in BNC materials for ZESDs. The different synthetic methods employed in the preparation of BNC materials, including direct carbonization, template method, chemical vapor deposition, hydrothermal method, etc., are summarized. These methods play a vital role in tailoring the structure, composition, and properties of BNC materials to optimize their performance in energy storage applications. Furthermore, some key achievements of BNC materials in zinc-air batteries and zinc-ion hybrid supercapacitors are elaborated. Lastly, future challenges and development directions of BNC materials in ZESDs are prospected. This comprehensive review could serve as a valuable resource in the energy storage field, providing insights into the potential of BNC materials in zinc-based energy storage technologies.
2025, 36(3): 110336
doi: 10.1016/j.cclet.2024.110336
Abstract:
Plants play a crucial role in maintaining ecological balance and biodiversity. However, plant health is easily affected by environmental stresses. Hence, the rapid and precise monitoring of plant health is crucial for global food security and ecological balance. Currently, traditional detection strategies for monitoring plant health mainly rely on expensive equipment and complex operational procedures, which limit their widespread application. Fortunately, near-infrared (NIR) fluorescence and surface-enhanced Raman scattering (SERS) techniques have been recently highlighted in plants. NIR fluorescence imaging holds the advantages of being non-invasive, high-resolution and real-time, which is suitable for rapid screening in large-scale scenarios. While SERS enables highly sensitive and specific detection of trace chemical substances within plant tissues. Therefore, the complementarity of NIR fluorescence and SERS modalities can provide more comprehensive and accurate information for plant disease diagnosis and growth status monitoring. This article summarizes these two modalities in plant applications, and discusses the advantages of multimodal NIR fluorescence/SERS for a better understanding of a plant's response to stress, thereby improving the accuracy and sensitivity of detection.
Plants play a crucial role in maintaining ecological balance and biodiversity. However, plant health is easily affected by environmental stresses. Hence, the rapid and precise monitoring of plant health is crucial for global food security and ecological balance. Currently, traditional detection strategies for monitoring plant health mainly rely on expensive equipment and complex operational procedures, which limit their widespread application. Fortunately, near-infrared (NIR) fluorescence and surface-enhanced Raman scattering (SERS) techniques have been recently highlighted in plants. NIR fluorescence imaging holds the advantages of being non-invasive, high-resolution and real-time, which is suitable for rapid screening in large-scale scenarios. While SERS enables highly sensitive and specific detection of trace chemical substances within plant tissues. Therefore, the complementarity of NIR fluorescence and SERS modalities can provide more comprehensive and accurate information for plant disease diagnosis and growth status monitoring. This article summarizes these two modalities in plant applications, and discusses the advantages of multimodal NIR fluorescence/SERS for a better understanding of a plant's response to stress, thereby improving the accuracy and sensitivity of detection.
2025, 36(3): 110438
doi: 10.1016/j.cclet.2024.110438
Abstract:
Efficient and innovative nano-catalytic oxidation technologies offer a breakthrough in removing emerging contaminants (ECs) from water, surpassing the limitations of traditional methods. Environmental functional materials (EFMs), particularly high-end oxidation systems using eco-friendly nanomaterials, show promise for absorbing and degrading ECs. This literature review presents a comprehensive analysis of diverse traditional restoration techniques-biological, physical, and chemical-assessing their respective applications and limitations in pesticide-contaminated water purification. Through meticulous comparison, we unequivocally advocate for the imperative integration of environmentally benign nanomaterials, notably titanium-based variants, in forthcoming methodologies. Our in-depth exploration scrutinizes the catalytic efficacy, underlying mechanisms, and adaptability of pioneering titanium-based nanomaterials across a spectrum of environmental contexts. Additionally, strategic recommendations are furnished to surmount challenges and propel the frontiers of implementing eco-friendly nanomaterials in practical water treatment scenarios.
Efficient and innovative nano-catalytic oxidation technologies offer a breakthrough in removing emerging contaminants (ECs) from water, surpassing the limitations of traditional methods. Environmental functional materials (EFMs), particularly high-end oxidation systems using eco-friendly nanomaterials, show promise for absorbing and degrading ECs. This literature review presents a comprehensive analysis of diverse traditional restoration techniques-biological, physical, and chemical-assessing their respective applications and limitations in pesticide-contaminated water purification. Through meticulous comparison, we unequivocally advocate for the imperative integration of environmentally benign nanomaterials, notably titanium-based variants, in forthcoming methodologies. Our in-depth exploration scrutinizes the catalytic efficacy, underlying mechanisms, and adaptability of pioneering titanium-based nanomaterials across a spectrum of environmental contexts. Additionally, strategic recommendations are furnished to surmount challenges and propel the frontiers of implementing eco-friendly nanomaterials in practical water treatment scenarios.
2025, 36(3): 110456
doi: 10.1016/j.cclet.2024.110456
Abstract:
In the realm of drug discovery, recent advancements have paved the way for innovative approaches and methodologies. This comprehensive review encapsulates six distinct yet interrelated mini-reviews, each shedding light on novel strategies in drug development. (a) The resurgence of covalent drugs is highlighted, focusing on the targeted covalent inhibitors (TCIs) and their role in enhancing selectivity and affinity. (b) The potential of the quantum mechanics-based computational aid drug design (CADD) tool, Cov_DOX, is introduced for predicting protein-covalent ligand binding structures and affinities. (c) The scaffolding function of proteins is proposed as a new avenue for drug design, with a focus on modulating protein-protein interactions through small molecules and proteolysis targeting chimeras (PROTACs). (d) The concept of pro-PROTACs is explored as a promising strategy for cancer therapy, combining the principles of prodrugs and PROTACs to enhance specificity and reduce toxicity. (e) The design of prodrugs through carbon-carbon bond cleavage is discussed, offering a new perspective for the activation of drugs with limited modifiable functional groups. (f) The targeting of programmed cell death pathways in cancer therapies with small molecules is reviewed, emphasizing the induction of autophagy-dependent cell death, ferroptosis, and cuproptosis. These insights collectively contribute to a deeper understanding of the dynamic landscape of drug discovery.
In the realm of drug discovery, recent advancements have paved the way for innovative approaches and methodologies. This comprehensive review encapsulates six distinct yet interrelated mini-reviews, each shedding light on novel strategies in drug development. (a) The resurgence of covalent drugs is highlighted, focusing on the targeted covalent inhibitors (TCIs) and their role in enhancing selectivity and affinity. (b) The potential of the quantum mechanics-based computational aid drug design (CADD) tool, Cov_DOX, is introduced for predicting protein-covalent ligand binding structures and affinities. (c) The scaffolding function of proteins is proposed as a new avenue for drug design, with a focus on modulating protein-protein interactions through small molecules and proteolysis targeting chimeras (PROTACs). (d) The concept of pro-PROTACs is explored as a promising strategy for cancer therapy, combining the principles of prodrugs and PROTACs to enhance specificity and reduce toxicity. (e) The design of prodrugs through carbon-carbon bond cleavage is discussed, offering a new perspective for the activation of drugs with limited modifiable functional groups. (f) The targeting of programmed cell death pathways in cancer therapies with small molecules is reviewed, emphasizing the induction of autophagy-dependent cell death, ferroptosis, and cuproptosis. These insights collectively contribute to a deeper understanding of the dynamic landscape of drug discovery.
2025, 36(3): 110533
doi: 10.1016/j.cclet.2024.110533
Abstract:
The realization of high-efficiency photocatalysis is greatly meaningful to overcome the issues of current energy and environment, in which the core factor is the exploration of photocatalysts with promising semiconductor properties. The Cu-based metal sulfide photocatalysts of CuSbS2 and its derivative of bournonite CuPbSbS3 possess the features of earth-abundant elements, strong photostability, visible-light range bandgap, and high absorption coefficient, possessing great potential for the realization of efficient photocatalytic applications. Although the photocatalysts of CuSbS2 and CuPbSbS3 have been investigated in photocatalysis application of hydrogen production and degradation, the exploration process is still in the early-development stage. In this review, the design concept and semiconductor properties of CuSbS2 and CuPbSbS3 are firstly introduced. Subsequently, the photocatalytic applications of CuSbS2 and CuPbSbS3 photocatalysts, mainly including hydrogen production and degradation, are systematically reviewed. Finally, the challenges and prospects for the further exploration of CuSbS2 and CuPbSbS3 photocatalysts are provided.
The realization of high-efficiency photocatalysis is greatly meaningful to overcome the issues of current energy and environment, in which the core factor is the exploration of photocatalysts with promising semiconductor properties. The Cu-based metal sulfide photocatalysts of CuSbS2 and its derivative of bournonite CuPbSbS3 possess the features of earth-abundant elements, strong photostability, visible-light range bandgap, and high absorption coefficient, possessing great potential for the realization of efficient photocatalytic applications. Although the photocatalysts of CuSbS2 and CuPbSbS3 have been investigated in photocatalysis application of hydrogen production and degradation, the exploration process is still in the early-development stage. In this review, the design concept and semiconductor properties of CuSbS2 and CuPbSbS3 are firstly introduced. Subsequently, the photocatalytic applications of CuSbS2 and CuPbSbS3 photocatalysts, mainly including hydrogen production and degradation, are systematically reviewed. Finally, the challenges and prospects for the further exploration of CuSbS2 and CuPbSbS3 photocatalysts are provided.
2025, 36(3): 109858
doi: 10.1016/j.cclet.2024.109858
Abstract:
Chemical investigation of the marine-derived fungus Chaetomium globosum HBU-45 led to the discovery of chaeglobol A (1). Its structure was determined by spectroscopic analysis, computational electronic circular dichroism (ECD)/optical rotatory dispersion (ORD) methods, and X-ray crystallography. Compound 1 represents a new skeleton with an uncommon 6/6/6/5/6/5/6/5 octacyclic system, which is presumably biosynthesized via a [4 + 2] cycloaddition and an enzymatic cyclization. Chaeglobol A (1) exhibited inhibitory activity against B. dothidea by destroying cell membrane integrity and causing oxidative damage within the cells.
Chemical investigation of the marine-derived fungus Chaetomium globosum HBU-45 led to the discovery of chaeglobol A (1). Its structure was determined by spectroscopic analysis, computational electronic circular dichroism (ECD)/optical rotatory dispersion (ORD) methods, and X-ray crystallography. Compound 1 represents a new skeleton with an uncommon 6/6/6/5/6/5/6/5 octacyclic system, which is presumably biosynthesized via a [4 + 2] cycloaddition and an enzymatic cyclization. Chaeglobol A (1) exhibited inhibitory activity against B. dothidea by destroying cell membrane integrity and causing oxidative damage within the cells.
2025, 36(3): 109859
doi: 10.1016/j.cclet.2024.109859
Abstract:
Hymoins A–C (1–3), three unusual polycyclic polyprenylated acylphloroglucinols (PPAPs) were isolated from the flowers of Hypericum monogynum. Hymoin A features the first intriguing 6/5/5/5/7 pentacyclic caged PPAP. Hymoin B is characterized by an unprecedented rearranged 5/6/8 tricyclic ring system, while hymoin C represents the first rearranged PPAP with a fantastic spirocyclic 5/6/7 ring system. Their structures were established by extensive spectroscopic analysis, X-ray crystallography, and computational methods. The plausible biosynthetic routes for the compounds were also proposed. In oleic acid (OA)-induced HepG2 cells, all compounds exhibited significant lipid-lowering activity at the concentrations of 2–8 µmol/L. Further mechanistic study implied that compound 1 exhibited excellent lipid-lowering activity in OA-induced HepG2 cells through inhibiting the proteins of free fatty acids synthesis and improving lipidolysis.
Hymoins A–C (1–3), three unusual polycyclic polyprenylated acylphloroglucinols (PPAPs) were isolated from the flowers of Hypericum monogynum. Hymoin A features the first intriguing 6/5/5/5/7 pentacyclic caged PPAP. Hymoin B is characterized by an unprecedented rearranged 5/6/8 tricyclic ring system, while hymoin C represents the first rearranged PPAP with a fantastic spirocyclic 5/6/7 ring system. Their structures were established by extensive spectroscopic analysis, X-ray crystallography, and computational methods. The plausible biosynthetic routes for the compounds were also proposed. In oleic acid (OA)-induced HepG2 cells, all compounds exhibited significant lipid-lowering activity at the concentrations of 2–8 µmol/L. Further mechanistic study implied that compound 1 exhibited excellent lipid-lowering activity in OA-induced HepG2 cells through inhibiting the proteins of free fatty acids synthesis and improving lipidolysis.
2025, 36(3): 109869
doi: 10.1016/j.cclet.2024.109869
Abstract:
Systemic administration of the anti-rheumatic drug methotrexate (MTX) for a long period of time may lead to therapeutic tolerance, various adverse effects, and potential harm to the immune system. Therapeutic nano-delivery carriers constructed based on biologically active phenols provide a promising approach to enhance the therapeutic effect of anti-rheumatic drugs. Caffeic acid, a natural compound with anti-inflammatory properties, holds significant potential in the treatment of diverse inflammatory conditions. In this paper, we first constructed a nano-delivery platform for MTX using caffeic acid-based polyphenol polymer Ph-CaA-OH (PCOH), and investigated the treatment of rheumatoid arthritis (RA) at low drug administration doses (2.5 mg/kg). PCOH nanoparticles (NPs) could inhibit lipopolysaccharidesstimulated macrophage inducible nitric oxide synthase (iNOS) expression and pro-inflammatory differentiation in vitro. In vivo imaging revealed the rapid accumulation and sustained presence of PCOH NPs at inflamed joints in collagen induced-arthritis (CIA) mice. Therapeutic evaluation of CIA mice demonstrated that MTX@PCOH NPs were superior to free MTX in reducing the progression of RA and decreasing the expression of multiple pro-inflammatory cytokines without significant toxic effects. By enhancing drug aggregation at inflammatory joints and capitalizing on the synergistic effects of active carriers, MTX@PCOH NPs effectively minimized the required drug dosage and mitigated toxic side effects in RA treatment. The application of PCOH NPs to RA treatment provides a new strategy for the development of safer and more effective anti-RA nanomedicines.
Systemic administration of the anti-rheumatic drug methotrexate (MTX) for a long period of time may lead to therapeutic tolerance, various adverse effects, and potential harm to the immune system. Therapeutic nano-delivery carriers constructed based on biologically active phenols provide a promising approach to enhance the therapeutic effect of anti-rheumatic drugs. Caffeic acid, a natural compound with anti-inflammatory properties, holds significant potential in the treatment of diverse inflammatory conditions. In this paper, we first constructed a nano-delivery platform for MTX using caffeic acid-based polyphenol polymer Ph-CaA-OH (PCOH), and investigated the treatment of rheumatoid arthritis (RA) at low drug administration doses (2.5 mg/kg). PCOH nanoparticles (NPs) could inhibit lipopolysaccharidesstimulated macrophage inducible nitric oxide synthase (iNOS) expression and pro-inflammatory differentiation in vitro. In vivo imaging revealed the rapid accumulation and sustained presence of PCOH NPs at inflamed joints in collagen induced-arthritis (CIA) mice. Therapeutic evaluation of CIA mice demonstrated that MTX@PCOH NPs were superior to free MTX in reducing the progression of RA and decreasing the expression of multiple pro-inflammatory cytokines without significant toxic effects. By enhancing drug aggregation at inflammatory joints and capitalizing on the synergistic effects of active carriers, MTX@PCOH NPs effectively minimized the required drug dosage and mitigated toxic side effects in RA treatment. The application of PCOH NPs to RA treatment provides a new strategy for the development of safer and more effective anti-RA nanomedicines.
2025, 36(3): 109902
doi: 10.1016/j.cclet.2024.109902
Abstract:
Photodynamic therapy (PDT) not only directly eradicates tumor cells but also boosts immunogenicity, promoting antigen presentation and immune cell infiltration. However, the robust antioxidant defense mechanisms within tumor cells significantly weaken the efficacy of photodynamic immunotherapy. Herein, a supramolecular hybrid nanoassembly is constructed by exploring the synergistic effects of the photodynamic photosensitizer (pyropheophorbide a, PPa) and the ferroptosis inducer (erastin). The erastin-mediated inhibition of system Xc− significantly downregulates glutathione (GSH) expression, amplifying intracellular oxidative stress, leading to pronounced cell apoptosis, and promoting the release of damage-associated molecular patterns (DAMPs). Additionally, the precise cooperation of PPa and erastin enhances ferroptosis efficiency, exacerbating the accumulation of lipid peroxides (LPOs). Ultimately, LPOs serve as a "find me" signal, while DMAPs act as an "eat me" signal, collectively promoting dendritic cell maturation, enhancing infiltration of the cytotoxic T lymphocytes, and eliciting a robust immune response. This study opens new horizons for enhancing tumor immunotherapy through simultaneous ferroptosis-PDT.
Photodynamic therapy (PDT) not only directly eradicates tumor cells but also boosts immunogenicity, promoting antigen presentation and immune cell infiltration. However, the robust antioxidant defense mechanisms within tumor cells significantly weaken the efficacy of photodynamic immunotherapy. Herein, a supramolecular hybrid nanoassembly is constructed by exploring the synergistic effects of the photodynamic photosensitizer (pyropheophorbide a, PPa) and the ferroptosis inducer (erastin). The erastin-mediated inhibition of system Xc− significantly downregulates glutathione (GSH) expression, amplifying intracellular oxidative stress, leading to pronounced cell apoptosis, and promoting the release of damage-associated molecular patterns (DAMPs). Additionally, the precise cooperation of PPa and erastin enhances ferroptosis efficiency, exacerbating the accumulation of lipid peroxides (LPOs). Ultimately, LPOs serve as a "find me" signal, while DMAPs act as an "eat me" signal, collectively promoting dendritic cell maturation, enhancing infiltration of the cytotoxic T lymphocytes, and eliciting a robust immune response. This study opens new horizons for enhancing tumor immunotherapy through simultaneous ferroptosis-PDT.
2025, 36(3): 110021
doi: 10.1016/j.cclet.2024.110021
Abstract:
Oral ulcers are a common ulcerative injury that occurs in the oral mucosa. When occurring, they can cause mucosal pain and affect eating and communication. The oral cavity, characterized by its moist environment and constant movement of the lips and tongue, presents challenges for conventional drug delivery systems due to its suboptimal adhesion. Therefore, there is a need for the development of adhesive materials specifically designed for use within the oral cavity. In this research, a sticky coacervate incorporating tea polyphenols (TP) was formulated based on the adhesive properties observed in sandcastle worms. The coacervate is composed of Pluronic F68 (F68) and TP, synthesized through the coacervation reaction. The F68-TP coacervates are attached to porcine skin easily. It also reduces bacterial viability and has the ability to clear reactive oxygen species. In animal ulcer models, these coacervates demonstrate anti-inflammatory effects and enhance collagen and muscle fiber synthesis. Overall, these adhesive coacervates with antioxidative and antibacterial properties hold potential as a therapeutic option for oral ulcers in the oral cavity.
Oral ulcers are a common ulcerative injury that occurs in the oral mucosa. When occurring, they can cause mucosal pain and affect eating and communication. The oral cavity, characterized by its moist environment and constant movement of the lips and tongue, presents challenges for conventional drug delivery systems due to its suboptimal adhesion. Therefore, there is a need for the development of adhesive materials specifically designed for use within the oral cavity. In this research, a sticky coacervate incorporating tea polyphenols (TP) was formulated based on the adhesive properties observed in sandcastle worms. The coacervate is composed of Pluronic F68 (F68) and TP, synthesized through the coacervation reaction. The F68-TP coacervates are attached to porcine skin easily. It also reduces bacterial viability and has the ability to clear reactive oxygen species. In animal ulcer models, these coacervates demonstrate anti-inflammatory effects and enhance collagen and muscle fiber synthesis. Overall, these adhesive coacervates with antioxidative and antibacterial properties hold potential as a therapeutic option for oral ulcers in the oral cavity.
2025, 36(3): 110180
doi: 10.1016/j.cclet.2024.110180
Abstract:
Colon-targeted oral drug delivery systems are one of the most promising therapeutic strategies for alleviating and curing inflammatory bowel disease (IBD), but they still face challenges in successfully passing through the harsh gastrointestinal environment and intestinal mucus barrier. To overcome the gastrointestinal barriers for oral drug delivery mentioned above, a "spore-like" oral nanodrug delivery platform (Cur/COS/SC NPs) has been developed. Firstly, chitooligosaccharides (COS) are encapsulated on the surface of Curcumin nanoparticles (Cur NPs) to form carrier-free nanoparticles (Cur/COS NPs). Subsequently, inspired by the natural high resistance of spore coat (SC), SC is chosen as the "protective umbrella" to encapsulate Cur/COS NPs for precision targeted therapy of IBD. After oral administration, SC can effectively protect NPs through the rugged gastrointestinal environment and exhibit excellent intestinal mucus penetration characteristics. Moreover, the negatively-charged Cur/COS/SC NPs specifically target positively-charged inflamed colon via electrostatic interactions. It is demonstrated that Cur/COS/SC NPs can promote the expression of tight junction proteins, inhibit aberrant activation of the Toll-like receptor 4/myeloid differentiation primary response gene 88/nuclear factor-κB (TLR4/MyD88/NF-κB) signaling pathway, and downregulate the levels of pro-inflammatory factors, exhibiting excellent anti-inflammatory effects. Notably, it is found that Cur/COS/SC NPs can significantly increase the richness and diversity of gut microbiota, and restore the homeostasis of gut microbiota by inhibiting pathogenic bacteria and promoting probiotics. Hence, Cur/COS/SC NPs provide a safe, efficient, and feasible new strategy for IBD treatment.
Colon-targeted oral drug delivery systems are one of the most promising therapeutic strategies for alleviating and curing inflammatory bowel disease (IBD), but they still face challenges in successfully passing through the harsh gastrointestinal environment and intestinal mucus barrier. To overcome the gastrointestinal barriers for oral drug delivery mentioned above, a "spore-like" oral nanodrug delivery platform (Cur/COS/SC NPs) has been developed. Firstly, chitooligosaccharides (COS) are encapsulated on the surface of Curcumin nanoparticles (Cur NPs) to form carrier-free nanoparticles (Cur/COS NPs). Subsequently, inspired by the natural high resistance of spore coat (SC), SC is chosen as the "protective umbrella" to encapsulate Cur/COS NPs for precision targeted therapy of IBD. After oral administration, SC can effectively protect NPs through the rugged gastrointestinal environment and exhibit excellent intestinal mucus penetration characteristics. Moreover, the negatively-charged Cur/COS/SC NPs specifically target positively-charged inflamed colon via electrostatic interactions. It is demonstrated that Cur/COS/SC NPs can promote the expression of tight junction proteins, inhibit aberrant activation of the Toll-like receptor 4/myeloid differentiation primary response gene 88/nuclear factor-κB (TLR4/MyD88/NF-κB) signaling pathway, and downregulate the levels of pro-inflammatory factors, exhibiting excellent anti-inflammatory effects. Notably, it is found that Cur/COS/SC NPs can significantly increase the richness and diversity of gut microbiota, and restore the homeostasis of gut microbiota by inhibiting pathogenic bacteria and promoting probiotics. Hence, Cur/COS/SC NPs provide a safe, efficient, and feasible new strategy for IBD treatment.
2025, 36(3): 110228
doi: 10.1016/j.cclet.2024.110228
Abstract:
Gliomas are the most common intracranial tumors with poor survival and high mortality. Furthermore, the clinical efficacy of current drugs is still not ideal; despite the development of several therapeutic drugs over the past decades and tumor progression or recurrence is inevitable in many patients. RNAi-based therapy presents a novel disease-related gene targeting therapy, including otherwise undruggable genes, and generates therapeutic options. However, the therapeutic effect of siRNA is hindered by multiple biological barriers, primarily the blood-brain barrier (BBB). A glycoprotein-derived peptide-mediated delivery system is the preferred option to resolve this phenomenon. RDP, a polypeptide composed of 15 amino acids derived from rabies virus glycoprotein (RVG), possesses an N-type acetylcholine receptor (nAChR)-binding efficiency similar to that of RVG29. Given its lower cost and small particle size when used as a ligand, RDP should be extensively evaluated. First, we verified the brain-targeting efficacyy of RDP at the cellular and animal levels and further explored the possibility of using the RDP-oligoarginine peptide (designated RDP-5R) as a bio-safe vehicle to deliver therapeutic siRNA into glioma cells in vitro and in vivo. The polypeptide carrier possesses a diblock design composed of oligoarginine for binding siRNA through electrostatic interactions and RDP for cascade BBB- and glioma cell-targeting. The results indicated that RDP-R5/siRNA nanoparticles exhibited stable and suitable physicochemical properties for in vivo application, desirable glioma-targeting effects, and therapeutic efficiency. As a novel and efficient polypeptide carrier, RDP-based polypeptides hold great promise as a noninvasive, safe, and efficient treatment for various brain diseases.
Gliomas are the most common intracranial tumors with poor survival and high mortality. Furthermore, the clinical efficacy of current drugs is still not ideal; despite the development of several therapeutic drugs over the past decades and tumor progression or recurrence is inevitable in many patients. RNAi-based therapy presents a novel disease-related gene targeting therapy, including otherwise undruggable genes, and generates therapeutic options. However, the therapeutic effect of siRNA is hindered by multiple biological barriers, primarily the blood-brain barrier (BBB). A glycoprotein-derived peptide-mediated delivery system is the preferred option to resolve this phenomenon. RDP, a polypeptide composed of 15 amino acids derived from rabies virus glycoprotein (RVG), possesses an N-type acetylcholine receptor (nAChR)-binding efficiency similar to that of RVG29. Given its lower cost and small particle size when used as a ligand, RDP should be extensively evaluated. First, we verified the brain-targeting efficacyy of RDP at the cellular and animal levels and further explored the possibility of using the RDP-oligoarginine peptide (designated RDP-5R) as a bio-safe vehicle to deliver therapeutic siRNA into glioma cells in vitro and in vivo. The polypeptide carrier possesses a diblock design composed of oligoarginine for binding siRNA through electrostatic interactions and RDP for cascade BBB- and glioma cell-targeting. The results indicated that RDP-R5/siRNA nanoparticles exhibited stable and suitable physicochemical properties for in vivo application, desirable glioma-targeting effects, and therapeutic efficiency. As a novel and efficient polypeptide carrier, RDP-based polypeptides hold great promise as a noninvasive, safe, and efficient treatment for various brain diseases.
2025, 36(3): 110300
doi: 10.1016/j.cclet.2024.110300
Abstract:
CO2 electrolysis into formate is a promising technology with the potential to simultaneously alleviate energy shortages and global warming. However, the limited stability of the catalysts during long-term electrolysis hinders their widespread implementation. Herein, we show that a core-shell bimetallic BiAg catalyst with a multifaceted Janus structure at its core can achieve a stability of up to 300 h with a formate faradaic efficiency (FEformate) over 90% at −0.75 V vs. RHE (reversible hydrogen electrode) in an H-type cell. Our investigations reveal the important role of the Janus structure on the transfer of electrons, favoring their delocalization across the catalyst and enhancing their mobility. We propose that the compressive strain inclined to grain boundaries within this structure would lower the energy barrier for electrons transfer and promotes the cooperation between Ag and Bi. Indeed, Ag initiates the activation of CO2 through a series of cascade reactions and is subsequently hydrogenated on Bi. Additionally, our study suggests that Ag plays a crucial role in stabilizing the catalyst structure after long-term electrolysis. This work highlights a new strategy for tandem CO2 electrolysis, providing novel insights for the design of formate formation catalysts.
CO2 electrolysis into formate is a promising technology with the potential to simultaneously alleviate energy shortages and global warming. However, the limited stability of the catalysts during long-term electrolysis hinders their widespread implementation. Herein, we show that a core-shell bimetallic BiAg catalyst with a multifaceted Janus structure at its core can achieve a stability of up to 300 h with a formate faradaic efficiency (FEformate) over 90% at −0.75 V vs. RHE (reversible hydrogen electrode) in an H-type cell. Our investigations reveal the important role of the Janus structure on the transfer of electrons, favoring their delocalization across the catalyst and enhancing their mobility. We propose that the compressive strain inclined to grain boundaries within this structure would lower the energy barrier for electrons transfer and promotes the cooperation between Ag and Bi. Indeed, Ag initiates the activation of CO2 through a series of cascade reactions and is subsequently hydrogenated on Bi. Additionally, our study suggests that Ag plays a crucial role in stabilizing the catalyst structure after long-term electrolysis. This work highlights a new strategy for tandem CO2 electrolysis, providing novel insights for the design of formate formation catalysts.
2025, 36(3): 110448
doi: 10.1016/j.cclet.2024.110448
Abstract:
The escalation in the incidence of multidrug-resistant Gram-negative bacteria is becoming a pressing global concern. Polymyxin B (PMB), a conventional antibiotic with notable therapeutic efficacy against Gram-negative bacterial infections, serves as a crucial final recourse against carbapenem-resistant Klebsiella pneumoniae (CRKP) infections. Nevertheless, the clinical usage of PMB is impeded by its pronounced nephrotoxicity and poor infection site targeting. This investigation is geared to construct a nanoparticle formulation (named HA-PMB@H) comprising hyaluronic acid (HA) and PMB via a simple Schiff base reaction and further coating HA by electrostatic action. HA-PMB@H shows an average size of (153.8 ± 24.3) nm, and a mean zeta potential of (−25.6 ± 5.2) mV. Additionally, PMB can be released from HA-PMB@H more thoroughly and efficiently at pH 5.5 compared to pH 7.4, which demonstrates the Schiff base modification of PMB paves the way for its release at focus of infection. The uptake ratio of HA-PMB@H by alveolar epithelial cells (RLE-6TN) surpassed that of free PMB devoid of HA, which facilitates to the intracellular sterilization of PMB. Furthermore, the employment of HA-PMB@H ameliorated the toxicity of PMB towards human embryonic kidney cells (HEK 293) and pulmonary microvascular endothelial cells (HULEC-5a). What is more, HA-PMB@H effectively managed severe pneumonia induced by CRKP samples from clinical patients diagnosed with CRKP infection in vivo, substantially enhancing the survival rate of mice. Consequently, this nano-delivery system holds promising clinical significance in the combat against drug-resistant bacterial infections.
The escalation in the incidence of multidrug-resistant Gram-negative bacteria is becoming a pressing global concern. Polymyxin B (PMB), a conventional antibiotic with notable therapeutic efficacy against Gram-negative bacterial infections, serves as a crucial final recourse against carbapenem-resistant Klebsiella pneumoniae (CRKP) infections. Nevertheless, the clinical usage of PMB is impeded by its pronounced nephrotoxicity and poor infection site targeting. This investigation is geared to construct a nanoparticle formulation (named HA-PMB@H) comprising hyaluronic acid (HA) and PMB via a simple Schiff base reaction and further coating HA by electrostatic action. HA-PMB@H shows an average size of (153.8 ± 24.3) nm, and a mean zeta potential of (−25.6 ± 5.2) mV. Additionally, PMB can be released from HA-PMB@H more thoroughly and efficiently at pH 5.5 compared to pH 7.4, which demonstrates the Schiff base modification of PMB paves the way for its release at focus of infection. The uptake ratio of HA-PMB@H by alveolar epithelial cells (RLE-6TN) surpassed that of free PMB devoid of HA, which facilitates to the intracellular sterilization of PMB. Furthermore, the employment of HA-PMB@H ameliorated the toxicity of PMB towards human embryonic kidney cells (HEK 293) and pulmonary microvascular endothelial cells (HULEC-5a). What is more, HA-PMB@H effectively managed severe pneumonia induced by CRKP samples from clinical patients diagnosed with CRKP infection in vivo, substantially enhancing the survival rate of mice. Consequently, this nano-delivery system holds promising clinical significance in the combat against drug-resistant bacterial infections.
2025, 36(3): 110553
doi: 10.1016/j.cclet.2024.110553
Abstract:
Double redox-mediated intrinsic semiconductor photocatalysis: Practical semi-heterogeneous synthesis
2025, 36(3): 110621
doi: 10.1016/j.cclet.2024.110621
Abstract:
2025, 36(3): 110597
doi: 10.1016/j.cclet.2024.110597
Abstract:
