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2025 Volume 36 Issue 8
2025, 36(8): 110189
doi: 10.1016/j.cclet.2024.110189
Abstract:
Covalent organic frameworks (COFs), as a burgeoning class of crystalline porous materials have attracted widespread interest due to their designable structures and customized functions. However, the solvothermal synthesis of COFs is often time-consuming and conducted at a high temperature within a sealed vessel, and also requires a large amount of poisonous solvents, which is generally not available for scaling-up production and commercial application. In recent years, great efforts have been made to explore simple, green, and efficient approaches for COFs synthesis. In this comprehensive review, we summarized the advances in emergent strategies by highlighting their distinct features. Fundamental issues and future directions are also discussed with the object of bringing implications for large-scale and sustainable fabrication of COFs.
Covalent organic frameworks (COFs), as a burgeoning class of crystalline porous materials have attracted widespread interest due to their designable structures and customized functions. However, the solvothermal synthesis of COFs is often time-consuming and conducted at a high temperature within a sealed vessel, and also requires a large amount of poisonous solvents, which is generally not available for scaling-up production and commercial application. In recent years, great efforts have been made to explore simple, green, and efficient approaches for COFs synthesis. In this comprehensive review, we summarized the advances in emergent strategies by highlighting their distinct features. Fundamental issues and future directions are also discussed with the object of bringing implications for large-scale and sustainable fabrication of COFs.
2025, 36(8): 110220
doi: 10.1016/j.cclet.2024.110220
Abstract:
In the realm of advanced electrochemical energy storage, the study of diverse electrolyte salts as integral components of electrolyte engineering has garnered immense attention. Notably, lithium di(fluoro)oxalateborate (LiDFOB) as the representative DFOB− contained electrolyte salts, which possesses structural attributes resembling both lithium bis(oxalate)borate (LiBOB) and lithium tetrafluoroborate (LiBF4), has garnered significant attention initially as a classical additive for the formation of solid electrolyte interface (SEI) films in graphite anodes. However, its unique properties have also piqued interest in other battery components, encompassing current collectors, capacity-enhanced cathodes or anodes, polymer solid-state electrolytes, and the full batteries. The introduction of LiDFOB or NaDFOB into these batteries exhibits a dual-faceted effect, with the beneficial aspect outweighing the potential drawbacks. Herein, we present a comprehensive overview of the research advancements surrounding LiDFOB, including the synthesis techniques of LiDFOB, the inherent properties of LiDFOB and LiDFOB-based electrolyte solutions, and the impact of LiDFOB on the performance of traditional graphite anodes, capacity-enlarged anodes, various classic cathodes, and the full batteries. And sectional content is about the usage of NaDFOB in Na-ion batteries. This review aims to aid readers in understanding the pivotal role of LiDFOB and NaDFOB as a constituent of electrolytes and how its utilization can influence electrode materials and other components, ultimately altering the electrochemical energy storage device's performance.
In the realm of advanced electrochemical energy storage, the study of diverse electrolyte salts as integral components of electrolyte engineering has garnered immense attention. Notably, lithium di(fluoro)oxalateborate (LiDFOB) as the representative DFOB− contained electrolyte salts, which possesses structural attributes resembling both lithium bis(oxalate)borate (LiBOB) and lithium tetrafluoroborate (LiBF4), has garnered significant attention initially as a classical additive for the formation of solid electrolyte interface (SEI) films in graphite anodes. However, its unique properties have also piqued interest in other battery components, encompassing current collectors, capacity-enhanced cathodes or anodes, polymer solid-state electrolytes, and the full batteries. The introduction of LiDFOB or NaDFOB into these batteries exhibits a dual-faceted effect, with the beneficial aspect outweighing the potential drawbacks. Herein, we present a comprehensive overview of the research advancements surrounding LiDFOB, including the synthesis techniques of LiDFOB, the inherent properties of LiDFOB and LiDFOB-based electrolyte solutions, and the impact of LiDFOB on the performance of traditional graphite anodes, capacity-enlarged anodes, various classic cathodes, and the full batteries. And sectional content is about the usage of NaDFOB in Na-ion batteries. This review aims to aid readers in understanding the pivotal role of LiDFOB and NaDFOB as a constituent of electrolytes and how its utilization can influence electrode materials and other components, ultimately altering the electrochemical energy storage device's performance.
2025, 36(8): 110247
doi: 10.1016/j.cclet.2024.110247
Abstract:
Metal organic frameworks (MOFs) are crystalline materials with three-dimensional porous network structure. They are obtained by self-assembly of coordinate bond with metal ions as the nodes and organic ligands as the connecting chains. MOFs have attracted extensive attention from researchers over the years due to their clear pore and rich topological structure. As the typical powder materials, a specific separator manufacturing process must be possessed when incorporating MOFs into lithium sulfur batteries separator. This mini review summarized the manufacturing process of MOFs separator for LSBs in recent years, and summed up the effects and mechanisms of separators prepared by various separator-forming processes on the performance of LSBs, the potential for industrialization of different separator manufacturing processes is also mentioned briefly.
Metal organic frameworks (MOFs) are crystalline materials with three-dimensional porous network structure. They are obtained by self-assembly of coordinate bond with metal ions as the nodes and organic ligands as the connecting chains. MOFs have attracted extensive attention from researchers over the years due to their clear pore and rich topological structure. As the typical powder materials, a specific separator manufacturing process must be possessed when incorporating MOFs into lithium sulfur batteries separator. This mini review summarized the manufacturing process of MOFs separator for LSBs in recent years, and summed up the effects and mechanisms of separators prepared by various separator-forming processes on the performance of LSBs, the potential for industrialization of different separator manufacturing processes is also mentioned briefly.
2025, 36(8): 110276
doi: 10.1016/j.cclet.2024.110276
Abstract:
Electrochemical reduction of air-abundant molecules (e.g., CO2, N2, and O2) offers a sustainable solution to address global energy and environmental challenges, where high current density and energy efficiency are highly desirable. However, commercially-relevant current density will cause dramatic change of cation, solvent, pH, and reactant molecular distribution near electrode, resulting in severe concentration polarization and sluggish reaction kinetics. In this case, mass transfer such as molecule migration pathway in electrolytes, electrodes, and devices need to be rationally designed and systematically optimized. Here this review will present a systematical introduction on regulating mass transfer on electrochemical fixation of air-abundant molecules. We firstly discuss the fundamental mass transport from bulk electrolyte to catalyst surface and within electric double layer (EDL) and review the recent advances in regulating mass transport behaviors and optimizing strategy of mass transfer on the catalytic surface. Then we compare the mass transport differences among different cell architectures combining with innovative prospect for transfer pathway towards breaking natural limitation of gas solubility over electroactive interfaces. It is expected that this review can inspire research on comprehensive understanding of fundamental mass transport mechanism at catalyst/electrolyte interface and shed light on optimizing the catalytical device towards practical application for electrochemical fixation of air-abundant molecules.
Electrochemical reduction of air-abundant molecules (e.g., CO2, N2, and O2) offers a sustainable solution to address global energy and environmental challenges, where high current density and energy efficiency are highly desirable. However, commercially-relevant current density will cause dramatic change of cation, solvent, pH, and reactant molecular distribution near electrode, resulting in severe concentration polarization and sluggish reaction kinetics. In this case, mass transfer such as molecule migration pathway in electrolytes, electrodes, and devices need to be rationally designed and systematically optimized. Here this review will present a systematical introduction on regulating mass transfer on electrochemical fixation of air-abundant molecules. We firstly discuss the fundamental mass transport from bulk electrolyte to catalyst surface and within electric double layer (EDL) and review the recent advances in regulating mass transport behaviors and optimizing strategy of mass transfer on the catalytic surface. Then we compare the mass transport differences among different cell architectures combining with innovative prospect for transfer pathway towards breaking natural limitation of gas solubility over electroactive interfaces. It is expected that this review can inspire research on comprehensive understanding of fundamental mass transport mechanism at catalyst/electrolyte interface and shed light on optimizing the catalytical device towards practical application for electrochemical fixation of air-abundant molecules.
2025, 36(8): 110453
doi: 10.1016/j.cclet.2024.110453
Abstract:
Biological sensing technology plays a crucial role in various key areas such as disease diagnosis, environmental monitoring, and biotechnology. Luminescent metal-organic frameworks (LMOFs), with their remarkable advantages including large surface area, customizable pore structures, and highly active functional sites, have emerged as a frontier in biosensor research. This review clarifies the potential of LMOFs in biological sensing applications, with particular emphasis on their efficient performance in detecting amino acids, biomarkers, and drugs, explore the possibility of integrating LMOFs with portable analytical techniques, providing an innovative perspective for advancing luminescence detection technology. Some effective characterization methods to encode these sensing mechanisms including Förster resonance energy transfer (FRET), photoinduced electron transfer (PET) and thermally activated energy back transfer (BENT) highlighted their connection and difference. Finally, the article summarizes the achievements of LMOFs in biological sensing and provides a perspective on future research directions and potential applications, aiming to propel the continuous development of this field.
Biological sensing technology plays a crucial role in various key areas such as disease diagnosis, environmental monitoring, and biotechnology. Luminescent metal-organic frameworks (LMOFs), with their remarkable advantages including large surface area, customizable pore structures, and highly active functional sites, have emerged as a frontier in biosensor research. This review clarifies the potential of LMOFs in biological sensing applications, with particular emphasis on their efficient performance in detecting amino acids, biomarkers, and drugs, explore the possibility of integrating LMOFs with portable analytical techniques, providing an innovative perspective for advancing luminescence detection technology. Some effective characterization methods to encode these sensing mechanisms including Förster resonance energy transfer (FRET), photoinduced electron transfer (PET) and thermally activated energy back transfer (BENT) highlighted their connection and difference. Finally, the article summarizes the achievements of LMOFs in biological sensing and provides a perspective on future research directions and potential applications, aiming to propel the continuous development of this field.
2025, 36(8): 110524
doi: 10.1016/j.cclet.2024.110524
Abstract:
DNA probes display advantages including flexible design, wide range of targets and high selectivity, but free DNA probes are confined to in vitro detection due to their poor cell penetration and low nuclease resistance. Nanomaterials-loaded DNA probes can effectively solve above limitations and promote them in vivo applications. Gold nanoparticles-based probes have been intensely investigated in the past, and AuNP@DNA nanoflare as one of the most powerful tools for biomedical study has been developed. So far, towards AuNP@DNA nanoflare, significant advances in preparation (e.g., salt-aging, low pH-assisted and freezing-directed linking) and application (e.g., sensing and therapeutic nanoflares) have been achieved since first report. In addition, scientific challenges involved in AuNP@DNA nanoflares have been concerned and some endeavor has been made recently. Here, a historical review is provided for AuNP@DNA nanoflares: methodology in preparation and applications in bioanalysis and biomedicine are delineated, challenges and outlook are also discussed, which are expected to improve the further development of this fertile research area.
DNA probes display advantages including flexible design, wide range of targets and high selectivity, but free DNA probes are confined to in vitro detection due to their poor cell penetration and low nuclease resistance. Nanomaterials-loaded DNA probes can effectively solve above limitations and promote them in vivo applications. Gold nanoparticles-based probes have been intensely investigated in the past, and AuNP@DNA nanoflare as one of the most powerful tools for biomedical study has been developed. So far, towards AuNP@DNA nanoflare, significant advances in preparation (e.g., salt-aging, low pH-assisted and freezing-directed linking) and application (e.g., sensing and therapeutic nanoflares) have been achieved since first report. In addition, scientific challenges involved in AuNP@DNA nanoflares have been concerned and some endeavor has been made recently. Here, a historical review is provided for AuNP@DNA nanoflares: methodology in preparation and applications in bioanalysis and biomedicine are delineated, challenges and outlook are also discussed, which are expected to improve the further development of this fertile research area.
2025, 36(8): 110526
doi: 10.1016/j.cclet.2024.110526
Abstract:
In recent years, machine learning (ML) techniques have demonstrated a strong ability to solve highly complex and non-linear problems by analyzing large datasets and learning their intrinsic patterns and relationships. Particularly in chemical engineering and materials science, ML can be used to discover microstructural composition, optimize chemical processes, and create novel synthetic pathways. Electrochemical processes offer the advantages of precise process control, environmental friendliness, high energy conversion efficiency and low cost. This review article provides the first systematic summary of ML in the application of electrochemical oxidation, including pollutant removal, battery remediation, substance synthesis and material characterization prediction. Hot trends at the intersection of ML and electrochemical oxidation were analyzed through bibliometrics. Common ML models were outlined. The role of ML in improving removal efficiency, optimizing experimental conditions, aiding battery diagnosis and predictive maintenance, and revealing material characterization was highlighted. In addition, current issues and future perspectives were presented in relation to the strengths and weaknesses of ML algorithms applied to electrochemical oxidation. In order to further support the sustainable growth of electrochemistry from basic research to useful applications, this review attempts to make it easier to integrate ML into electrochemical oxidation.
In recent years, machine learning (ML) techniques have demonstrated a strong ability to solve highly complex and non-linear problems by analyzing large datasets and learning their intrinsic patterns and relationships. Particularly in chemical engineering and materials science, ML can be used to discover microstructural composition, optimize chemical processes, and create novel synthetic pathways. Electrochemical processes offer the advantages of precise process control, environmental friendliness, high energy conversion efficiency and low cost. This review article provides the first systematic summary of ML in the application of electrochemical oxidation, including pollutant removal, battery remediation, substance synthesis and material characterization prediction. Hot trends at the intersection of ML and electrochemical oxidation were analyzed through bibliometrics. Common ML models were outlined. The role of ML in improving removal efficiency, optimizing experimental conditions, aiding battery diagnosis and predictive maintenance, and revealing material characterization was highlighted. In addition, current issues and future perspectives were presented in relation to the strengths and weaknesses of ML algorithms applied to electrochemical oxidation. In order to further support the sustainable growth of electrochemistry from basic research to useful applications, this review attempts to make it easier to integrate ML into electrochemical oxidation.
2025, 36(8): 110546
doi: 10.1016/j.cclet.2024.110546
Abstract:
Site-specific protein labeling plays important roles in drug discovery and illuminating biological processes at the molecular level. However, it is challenging to label proteins with high specificity while not affecting their structures and biochemical activities. Over the last few years, a variety of promising strategies have been devised that address these challenges including those that involve introduction of small-size peptide tags or unnatural amino acids (UAAs), chemical labeling of specific protein residues, and affinity-driven labeling. This review summarizes recent developments made in the area of site-specific protein labeling utilizing genetically encoding- and chemical-based methods, and discusses future issues that need to be addressed by researchers in this field.
Site-specific protein labeling plays important roles in drug discovery and illuminating biological processes at the molecular level. However, it is challenging to label proteins with high specificity while not affecting their structures and biochemical activities. Over the last few years, a variety of promising strategies have been devised that address these challenges including those that involve introduction of small-size peptide tags or unnatural amino acids (UAAs), chemical labeling of specific protein residues, and affinity-driven labeling. This review summarizes recent developments made in the area of site-specific protein labeling utilizing genetically encoding- and chemical-based methods, and discusses future issues that need to be addressed by researchers in this field.
2025, 36(8): 110548
doi: 10.1016/j.cclet.2024.110548
Abstract:
Ferrate [Fe(Ⅵ)] has demonstrated its efficacy as a potent oxidizing agent in the treatment of wastewater, showcasing its potential for application in environmental remediation. The self-decomposition of Fe(Ⅵ) results in the formation of Fe(Ⅳ)/Fe(Ⅴ), which exhibits remarkable reactivity and selectivity towards the degradation of electron-rich micro-pollutants. Here we presented a comprehensive review on the removal of micro-pollutants in Fe(Ⅵ)/carbon materials (CMs) systems, encompassing an analysis of the oxidation mechanism and mutual activation, thereby providing guidance for the efficient elimination of recalcitrant micro-pollutants. The combnation of Fe(Ⅵ) and CMs can significantly enhanced the removal efficiency of various pollutants, with an increase ranges from 30% to 70%. The rate constants for pseudo-first order reactions were increased ranging from 3 to 14 times, while the total organic carbon (TOC) removal rate was effectively doubled. The presence of active species, including hydroxyl radicals, superoxide radical and Fe(Ⅳ)/Fe(Ⅴ) generated by Fe(Ⅵ) and CMs, can significantly enhance the oxidation efficiency of micro-pollutants which are not easily degraded solely by Fe(Ⅵ) or CMs. Furthermore, Fe(Ⅵ) can enhance the surface area and void volume of CMs, thereby reinforcing the adsorption capacity towards micro-pollutants.
Ferrate [Fe(Ⅵ)] has demonstrated its efficacy as a potent oxidizing agent in the treatment of wastewater, showcasing its potential for application in environmental remediation. The self-decomposition of Fe(Ⅵ) results in the formation of Fe(Ⅳ)/Fe(Ⅴ), which exhibits remarkable reactivity and selectivity towards the degradation of electron-rich micro-pollutants. Here we presented a comprehensive review on the removal of micro-pollutants in Fe(Ⅵ)/carbon materials (CMs) systems, encompassing an analysis of the oxidation mechanism and mutual activation, thereby providing guidance for the efficient elimination of recalcitrant micro-pollutants. The combnation of Fe(Ⅵ) and CMs can significantly enhanced the removal efficiency of various pollutants, with an increase ranges from 30% to 70%. The rate constants for pseudo-first order reactions were increased ranging from 3 to 14 times, while the total organic carbon (TOC) removal rate was effectively doubled. The presence of active species, including hydroxyl radicals, superoxide radical and Fe(Ⅳ)/Fe(Ⅴ) generated by Fe(Ⅵ) and CMs, can significantly enhance the oxidation efficiency of micro-pollutants which are not easily degraded solely by Fe(Ⅵ) or CMs. Furthermore, Fe(Ⅵ) can enhance the surface area and void volume of CMs, thereby reinforcing the adsorption capacity towards micro-pollutants.
2025, 36(8): 110565
doi: 10.1016/j.cclet.2024.110565
Abstract:
At present, many parts of the world are seriously short of water resources. Photothermal seawater desalination has been considered to be an efficient and clean way to solve water shortages. Transition metal dichalcogenides (TMDs) has excellent photothermal properties and plays a key role in photothermal seawater desalination. In recent years, a lot of progress has been made regarding TMDs in photothermal seawater desalination, so it is necessary to review the progress of TMDs structure regulation in improving photothermal properties to further enhance the development of this filed. In this review, firstly, various structural regulation methods of TMDs to optimize its properties and improve the performance of photothermal seawater desalination are comprehensively summarized. Secondly, the relationship between unique structure and its photothermal properties of TMDs is further detailedly discussed. Last but not least, we have provided some suggestions in the solar desalination applying TMDs in future. This review would provide a very important reference for the research of structure regulation of TMDs for effective photothermal seawater desalination.
At present, many parts of the world are seriously short of water resources. Photothermal seawater desalination has been considered to be an efficient and clean way to solve water shortages. Transition metal dichalcogenides (TMDs) has excellent photothermal properties and plays a key role in photothermal seawater desalination. In recent years, a lot of progress has been made regarding TMDs in photothermal seawater desalination, so it is necessary to review the progress of TMDs structure regulation in improving photothermal properties to further enhance the development of this filed. In this review, firstly, various structural regulation methods of TMDs to optimize its properties and improve the performance of photothermal seawater desalination are comprehensively summarized. Secondly, the relationship between unique structure and its photothermal properties of TMDs is further detailedly discussed. Last but not least, we have provided some suggestions in the solar desalination applying TMDs in future. This review would provide a very important reference for the research of structure regulation of TMDs for effective photothermal seawater desalination.
2025, 36(8): 110571
doi: 10.1016/j.cclet.2024.110571
Abstract:
Electrochemical sensors, with their outstanding sensitivity, excellent selectivity, ease of operation, and lower manufacturing costs, have found widespread applications in fields such as disease diagnosis, environmental monitoring, and food safety. In the development of sensing materials, metal-organic frameworks (MOFs) have become a research hotspot due to their high specific surface area, tunable pore structures, and high designability. Recently, conductive metal-organic frameworks (CMOFs) have brought innovative opportunities to the field of electrochemical sensing, attributing to their remarkable capabilities in catalysis, electron transport, and signal amplification. This review summarizes the significant progress of CMOFs in the field of electrochemical sensing. Firstly, the design and synthesis strategies for CMOFs used in electrochemical sensing are explored, including enhancing the electrochemical properties of MOFs through precise design of different metal nodes and ligands or via post-synthetic modification techniques, covering Cu-based CMOFs, Ni-based CMOFs, Fe-based CMOFs, and CMOF composites. Furthermore, this article elaborately discusses the breakthrough achievements of electrochemical sensors based on CMOFs in applications such as the determination of inorganic ions, detection of organic pollutants, and recognition of gases and biomolecules, and introduces the principles of electrochemical sensing methods and the role of CMOFs in enhancing the performance of electrochemical sensors. Finally, this review analyzes the main challenges currently faced by CMOFs in the field of electrochemical sensors and offers perspectives on their future development. These challenges mainly include stability, selectivity, production costs, and the realization of their large-scale application. CMOFs provide new ideas and material platforms for the development of electrochemical sensors. As researchers deepen their understanding of their properties and technological advances continue, the application prospects of CMOF-based electrochemical sensors will be even broader.
Electrochemical sensors, with their outstanding sensitivity, excellent selectivity, ease of operation, and lower manufacturing costs, have found widespread applications in fields such as disease diagnosis, environmental monitoring, and food safety. In the development of sensing materials, metal-organic frameworks (MOFs) have become a research hotspot due to their high specific surface area, tunable pore structures, and high designability. Recently, conductive metal-organic frameworks (CMOFs) have brought innovative opportunities to the field of electrochemical sensing, attributing to their remarkable capabilities in catalysis, electron transport, and signal amplification. This review summarizes the significant progress of CMOFs in the field of electrochemical sensing. Firstly, the design and synthesis strategies for CMOFs used in electrochemical sensing are explored, including enhancing the electrochemical properties of MOFs through precise design of different metal nodes and ligands or via post-synthetic modification techniques, covering Cu-based CMOFs, Ni-based CMOFs, Fe-based CMOFs, and CMOF composites. Furthermore, this article elaborately discusses the breakthrough achievements of electrochemical sensors based on CMOFs in applications such as the determination of inorganic ions, detection of organic pollutants, and recognition of gases and biomolecules, and introduces the principles of electrochemical sensing methods and the role of CMOFs in enhancing the performance of electrochemical sensors. Finally, this review analyzes the main challenges currently faced by CMOFs in the field of electrochemical sensors and offers perspectives on their future development. These challenges mainly include stability, selectivity, production costs, and the realization of their large-scale application. CMOFs provide new ideas and material platforms for the development of electrochemical sensors. As researchers deepen their understanding of their properties and technological advances continue, the application prospects of CMOF-based electrochemical sensors will be even broader.
2025, 36(8): 110587
doi: 10.1016/j.cclet.2024.110587
Abstract:
Neural injuries can be induced by various neurological disorders and traumas, such as brain and spinal cord injuries, cerebrovascular diseases, and neurodegeneration. Due to the designable physicochemical properties, biomaterials are applied for various purposes in neural repair, including promoting axonal regeneration, reducing glial scar formation, delivering drugs, and providing temporary mechanical support to the injured tissue. They need to match the extracellular matrix (ECM) environment, support three-dimensional (3D) cell growth, repair the cellular microenvironment, mimic the tissue's biomechanical forces, and possess biodegradability and plasticity suitable for local intracavity applications. Meanwhile, functionalized biomaterials have been conducted to mimic the structural components of cellular ecological niches and the specific functions of the ECM. They can be engineered to carry a variety of bioactive components, such as stem cells and extracellular vesicles, which are used in neuroscience-related tissue engineering. Researchers also have developed biomaterial-based brain-like organs for high-throughput drug screening and pathological mechanistic studies. This review will discuss the interactions between biomaterials and cells, as well as the advances in neural injuries and engineered microtissues.
Neural injuries can be induced by various neurological disorders and traumas, such as brain and spinal cord injuries, cerebrovascular diseases, and neurodegeneration. Due to the designable physicochemical properties, biomaterials are applied for various purposes in neural repair, including promoting axonal regeneration, reducing glial scar formation, delivering drugs, and providing temporary mechanical support to the injured tissue. They need to match the extracellular matrix (ECM) environment, support three-dimensional (3D) cell growth, repair the cellular microenvironment, mimic the tissue's biomechanical forces, and possess biodegradability and plasticity suitable for local intracavity applications. Meanwhile, functionalized biomaterials have been conducted to mimic the structural components of cellular ecological niches and the specific functions of the ECM. They can be engineered to carry a variety of bioactive components, such as stem cells and extracellular vesicles, which are used in neuroscience-related tissue engineering. Researchers also have developed biomaterial-based brain-like organs for high-throughput drug screening and pathological mechanistic studies. This review will discuss the interactions between biomaterials and cells, as well as the advances in neural injuries and engineered microtissues.
2025, 36(8): 110607
doi: 10.1016/j.cclet.2024.110607
Abstract:
Repairing and regenerating cartilage defects in osteoarthritis patients remains challenging. Traditional treatments primarily offer symptom relief without addressing the underlying progression of the disease. Stem cell therapies provide a promising solution, yet they face limitations such as short retention times, low survival rates in vivo, and insufficient extracellular matrix (ECM) production. Stem cell-based hydrogel therapy offers a controlled microenvironment that can mitigate these challenges and enhance cell therapy effectiveness. This review evaluates the advantages and limitations of various stem cell types and hydrogel materials, summarizing recent advances in their combination for cartilage repair. The potential of stem cell-hydrogel therapies is highlighted, along with the remaining challenges and future directions for improving their clinical application.
Repairing and regenerating cartilage defects in osteoarthritis patients remains challenging. Traditional treatments primarily offer symptom relief without addressing the underlying progression of the disease. Stem cell therapies provide a promising solution, yet they face limitations such as short retention times, low survival rates in vivo, and insufficient extracellular matrix (ECM) production. Stem cell-based hydrogel therapy offers a controlled microenvironment that can mitigate these challenges and enhance cell therapy effectiveness. This review evaluates the advantages and limitations of various stem cell types and hydrogel materials, summarizing recent advances in their combination for cartilage repair. The potential of stem cell-hydrogel therapies is highlighted, along with the remaining challenges and future directions for improving their clinical application.
2025, 36(8): 110619
doi: 10.1016/j.cclet.2024.110619
Abstract:
Heavy metal pollution poses serious risks to the human health and the natural environment, and there is an urgent need to develop efficient heavy metal removal technologies. The adsorption strategy is one of the most famous strategies for the capture of heavy metal ions. In recent years, hyper crosslinked polymers (HCPs), a kind of hyper crosslinked porous material prepared by Friedel-Crafts alkylation reaction, have attracted more and more attention because of their advantages of ultra-light framework, wide range of building monomers, easy modification and functionalization. This review focuses on the advances of HCPs in the efficient applications to the removal of heavy metal ions. The fundamentals are presented including physicochemical properties, adsorption mechanism, and preparation strategies. Subsequently, the application and influencing factors of HCPs toward heavy metal ion adsorption are discussed in detail. Furthermore, the opportunities and challenges of HCPs in this promising research field are summarized and anticipated. We are convinced that the advanced HCP-based materials will make further contributions to heavy metal removal in wastewater treatment, further paving the way of advancing researches in this field.
Heavy metal pollution poses serious risks to the human health and the natural environment, and there is an urgent need to develop efficient heavy metal removal technologies. The adsorption strategy is one of the most famous strategies for the capture of heavy metal ions. In recent years, hyper crosslinked polymers (HCPs), a kind of hyper crosslinked porous material prepared by Friedel-Crafts alkylation reaction, have attracted more and more attention because of their advantages of ultra-light framework, wide range of building monomers, easy modification and functionalization. This review focuses on the advances of HCPs in the efficient applications to the removal of heavy metal ions. The fundamentals are presented including physicochemical properties, adsorption mechanism, and preparation strategies. Subsequently, the application and influencing factors of HCPs toward heavy metal ion adsorption are discussed in detail. Furthermore, the opportunities and challenges of HCPs in this promising research field are summarized and anticipated. We are convinced that the advanced HCP-based materials will make further contributions to heavy metal removal in wastewater treatment, further paving the way of advancing researches in this field.
2025, 36(8): 110644
doi: 10.1016/j.cclet.2024.110644
Abstract:
Organic small molecule fluorophores have been widely used in biology and biochemistry to study cellular structures and processes at high spatial and temporal resolution. Small-molecule dyes offer various benefits, such as high photostability, low molecular weight, and great biocompatibility. However, the poor brightness of most of conventional dyes in biological environments limits their use in high-quality super-resolution fluorescence imaging. Chemists have conceived and developed many methods to enhance the brightness of fluorophores, including structural alterations that raise extinction coefficients and quantum yields. This review outlines current attempts and substantial advances achieved by chemists to improve the brightness of organic small-molecule fluorescent dyes, such as scaffold rigidification and twisted intramolecular charge transfer (TICT) inhibition. We think that this review will help researchers understand the chemical mechanisms involved in increasing the brightness of fluorophores for biological applications.
Organic small molecule fluorophores have been widely used in biology and biochemistry to study cellular structures and processes at high spatial and temporal resolution. Small-molecule dyes offer various benefits, such as high photostability, low molecular weight, and great biocompatibility. However, the poor brightness of most of conventional dyes in biological environments limits their use in high-quality super-resolution fluorescence imaging. Chemists have conceived and developed many methods to enhance the brightness of fluorophores, including structural alterations that raise extinction coefficients and quantum yields. This review outlines current attempts and substantial advances achieved by chemists to improve the brightness of organic small-molecule fluorescent dyes, such as scaffold rigidification and twisted intramolecular charge transfer (TICT) inhibition. We think that this review will help researchers understand the chemical mechanisms involved in increasing the brightness of fluorophores for biological applications.
2025, 36(8): 110645
doi: 10.1016/j.cclet.2024.110645
Abstract:
Bacterial infections pose a significant threat to human health and entail substantial economic losses. Due to the broad-spectrum antibacterial effect and low susceptibility to drug resistance, photodynamic therapy (PDT), a nontraditional antibacterial approach, has garnered a lot of attention. In PDT, the selection of photosensitizer (PS) is crucial because it directly affects the efficiency and safety of the treatment. As a versatile fluorophore, the advantages of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) used as a PS for antibacterial PDT are mainly reflected in its high quantum yield of singlet oxygen, easy modification, and exceptional photostability. Through strategic chemical modifications of the BODIPY structures, it is possible to enhance their photodynamic antibacterial activity and refine their selectivity for bacterial killing. This review focuses on the application of BODIPY-based PSs for treating bacterial infections. According to the design strategies of photodynamic antibacterial materials incorporating BODIPY, a variety of representative therapeutic agents having emerged in recent years are classified and discussed, aiming to offer insights for future research and development in this field.
Bacterial infections pose a significant threat to human health and entail substantial economic losses. Due to the broad-spectrum antibacterial effect and low susceptibility to drug resistance, photodynamic therapy (PDT), a nontraditional antibacterial approach, has garnered a lot of attention. In PDT, the selection of photosensitizer (PS) is crucial because it directly affects the efficiency and safety of the treatment. As a versatile fluorophore, the advantages of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) used as a PS for antibacterial PDT are mainly reflected in its high quantum yield of singlet oxygen, easy modification, and exceptional photostability. Through strategic chemical modifications of the BODIPY structures, it is possible to enhance their photodynamic antibacterial activity and refine their selectivity for bacterial killing. This review focuses on the application of BODIPY-based PSs for treating bacterial infections. According to the design strategies of photodynamic antibacterial materials incorporating BODIPY, a variety of representative therapeutic agents having emerged in recent years are classified and discussed, aiming to offer insights for future research and development in this field.
2025, 36(8): 110727
doi: 10.1016/j.cclet.2024.110727
Abstract:
Selenium is an essential trace element for human beings and it plays a significant role for the health of human nervous system. The strong antioxidant effect of selenium endows the element with the ability to treat various diseases, including Alzheimer's disease (AD). In the body, selenium exists in the forms of selenoproteins, which could treat AD through various pathways, such as inhibiting peroxidation, inhibiting apoptosis signal pathway, reducing the levels of Aβ in neurons and alleviating Tau protein caused by pathological damage. This article aims to comprehensively elaborate on the relationship between selenium and AD.
Selenium is an essential trace element for human beings and it plays a significant role for the health of human nervous system. The strong antioxidant effect of selenium endows the element with the ability to treat various diseases, including Alzheimer's disease (AD). In the body, selenium exists in the forms of selenoproteins, which could treat AD through various pathways, such as inhibiting peroxidation, inhibiting apoptosis signal pathway, reducing the levels of Aβ in neurons and alleviating Tau protein caused by pathological damage. This article aims to comprehensively elaborate on the relationship between selenium and AD.
2025, 36(8): 110832
doi: 10.1016/j.cclet.2025.110832
Abstract:
The integration of advanced diagnostic and therapeutic capabilities in oncology has given rise to phototheranostics, a field that combines the precision of imaging with the selectivity of light-activated treatments. Due to their pronounced near-infrared (NIR) absorption, tunable molecular structures, and commendable stability, organic photovoltaic non-fullerene acceptors (NFAs) represent a promising frontier in cancer management. Despite the great potential of NFAs in phototheranostics, there is currently a lack of systematic reviews in this field. This review provides a meticulous examination of the current state of NFAs in the field of phototheranostics, highlighting the strategic approaches to spectral red-shifting that enhance tissue penetration and therapeutic efficacy. It dissects the link between molecular architecture and performance across key therapeutic and diagnostic modalities, including photothermal therapy (PTT), photodynamic therapy (PDT), and fluorescence imaging (FLI). In addition, the review presents a concise analysis of the challenges and milestones in the clinical translation of NFAs, offering insights into the innovations required to overcome existing barriers.
The integration of advanced diagnostic and therapeutic capabilities in oncology has given rise to phototheranostics, a field that combines the precision of imaging with the selectivity of light-activated treatments. Due to their pronounced near-infrared (NIR) absorption, tunable molecular structures, and commendable stability, organic photovoltaic non-fullerene acceptors (NFAs) represent a promising frontier in cancer management. Despite the great potential of NFAs in phototheranostics, there is currently a lack of systematic reviews in this field. This review provides a meticulous examination of the current state of NFAs in the field of phototheranostics, highlighting the strategic approaches to spectral red-shifting that enhance tissue penetration and therapeutic efficacy. It dissects the link between molecular architecture and performance across key therapeutic and diagnostic modalities, including photothermal therapy (PTT), photodynamic therapy (PDT), and fluorescence imaging (FLI). In addition, the review presents a concise analysis of the challenges and milestones in the clinical translation of NFAs, offering insights into the innovations required to overcome existing barriers.
2025, 36(8): 110902
doi: 10.1016/j.cclet.2025.110902
Abstract:
Pyridazine has garnered increasing attention as a privileged scaffold and bioisosterism in drug discovery due to its unique structural characteristics. It can serve as a hydrogen bond acceptor when interacting with receptors due to its two adjacent nitrogen atoms. Upon conversion to pyridazinone, it exhibits the ability to act as both a hydrogen bond acceptor and donor, showcasing its versatility. This inherent flexibility has prompted extensive research exploring its bioactivity in pesticides and pharmaceuticals. In order to promote the development of pyridazine-based pesticides, this review provides a comprehensive summary of advancements for pyridazine-based pesticides on herbicidal (36.9%), insecticidal (26.2%), antifungal and antibacterial (24.6%), plant growth regulatory (10.8%), and antiviral activities (1.5%) from 2000 to 2024. It serves as an invaluable reference and source of inspiration for agricultural scientists conducting future research.
Pyridazine has garnered increasing attention as a privileged scaffold and bioisosterism in drug discovery due to its unique structural characteristics. It can serve as a hydrogen bond acceptor when interacting with receptors due to its two adjacent nitrogen atoms. Upon conversion to pyridazinone, it exhibits the ability to act as both a hydrogen bond acceptor and donor, showcasing its versatility. This inherent flexibility has prompted extensive research exploring its bioactivity in pesticides and pharmaceuticals. In order to promote the development of pyridazine-based pesticides, this review provides a comprehensive summary of advancements for pyridazine-based pesticides on herbicidal (36.9%), insecticidal (26.2%), antifungal and antibacterial (24.6%), plant growth regulatory (10.8%), and antiviral activities (1.5%) from 2000 to 2024. It serves as an invaluable reference and source of inspiration for agricultural scientists conducting future research.
2025, 36(8): 111206
doi: 10.1016/j.cclet.2025.111206
Abstract:
Controllable liquid manipulation is of paramount scientific and technological importance in various fields, such as the chemical industry, biomedicine, and agricultural production. Magnetic actuation, characterized by rapid, contactless, and environmentally benign operation, has emerged as a promising approach for precise liquid control. However, conventional magnetic strategies typically govern droplet movement on open surfaces, facing limitations such as restricted liquid volumes, uncertain flow paths, and inevitable evaporation, thereby constraining their broader practical applications. Recently, a variety of magnetic-driven strategies have been developed to dynamically regulate liquids within enclosed spaces, especially through physicochemical mechanisms. These approaches provide efficient control over liquid behavior by leveraging magnetically induced chemical changes, structural deformations, and dragging motions, opening new opportunities for flexible and versatile fluid management. This review explores the design and mechanisms of magneto-responsive confined interfaces for the manipulation of nonmagnetic liquids, highlighting key advancements and potential applications including liquid valves, liquid mixing, liquid flow regulation, and liquid pumping. Finally, the existing challenges and future prospects in this field are presented.
Controllable liquid manipulation is of paramount scientific and technological importance in various fields, such as the chemical industry, biomedicine, and agricultural production. Magnetic actuation, characterized by rapid, contactless, and environmentally benign operation, has emerged as a promising approach for precise liquid control. However, conventional magnetic strategies typically govern droplet movement on open surfaces, facing limitations such as restricted liquid volumes, uncertain flow paths, and inevitable evaporation, thereby constraining their broader practical applications. Recently, a variety of magnetic-driven strategies have been developed to dynamically regulate liquids within enclosed spaces, especially through physicochemical mechanisms. These approaches provide efficient control over liquid behavior by leveraging magnetically induced chemical changes, structural deformations, and dragging motions, opening new opportunities for flexible and versatile fluid management. This review explores the design and mechanisms of magneto-responsive confined interfaces for the manipulation of nonmagnetic liquids, highlighting key advancements and potential applications including liquid valves, liquid mixing, liquid flow regulation, and liquid pumping. Finally, the existing challenges and future prospects in this field are presented.
2025, 36(8): 110197
doi: 10.1016/j.cclet.2024.110197
Abstract:
The fabrication of bifunctional electrocatalysts for hydrogen and oxygen evolution in aqueous environment has far-reaching significance. Especially, reasonable interface process regulation toward heterogeneous composites can make full use of the active sites and improve the electrocatalytic activity. In this study, we designed and synthesized NiS2-MoS2-based heterogeneous composites as efficient and stable electrocatalysts for hydrogen and oxygen evolution in alkaline electrolyte. The heterostructure was obtained by one-step hydrothermal ulfurization operation towards polymolybdate-based metal-organic complex. The composition and nanostructures can be tailored by modulating experiment parameter, realizing the phase-controlled synthesis and interface regulation: (1) High-percentage of 1T-MoS2 can be achieved via selecting appropriate vulcanization time and thiourea concentration, benifiting for the higher electroconductivity and more active sites; (2) Regular and orderly vulcanization time promotes the gradual growth and aggregation of nanosheets; (3) The existence of nickel hydroxide improves the electrocatalytic stability for oxygen production performance. The optimized heterogeneous interfaces provide sufficient active sites and accelerate electron transfer. Consequently, the optimal heterogeneous nanosheets present low overpotentials of 33 and 122 mV at the catalytic current densities of 10 mA/cm2 for HER and OER, respectively.
The fabrication of bifunctional electrocatalysts for hydrogen and oxygen evolution in aqueous environment has far-reaching significance. Especially, reasonable interface process regulation toward heterogeneous composites can make full use of the active sites and improve the electrocatalytic activity. In this study, we designed and synthesized NiS2-MoS2-based heterogeneous composites as efficient and stable electrocatalysts for hydrogen and oxygen evolution in alkaline electrolyte. The heterostructure was obtained by one-step hydrothermal ulfurization operation towards polymolybdate-based metal-organic complex. The composition and nanostructures can be tailored by modulating experiment parameter, realizing the phase-controlled synthesis and interface regulation: (1) High-percentage of 1T-MoS2 can be achieved via selecting appropriate vulcanization time and thiourea concentration, benifiting for the higher electroconductivity and more active sites; (2) Regular and orderly vulcanization time promotes the gradual growth and aggregation of nanosheets; (3) The existence of nickel hydroxide improves the electrocatalytic stability for oxygen production performance. The optimized heterogeneous interfaces provide sufficient active sites and accelerate electron transfer. Consequently, the optimal heterogeneous nanosheets present low overpotentials of 33 and 122 mV at the catalytic current densities of 10 mA/cm2 for HER and OER, respectively.
2025, 36(8): 110214
doi: 10.1016/j.cclet.2024.110214
Abstract:
Developing candidate materials that are equipped with the ability of both selective detection and efficient removal of pesticides is greatly desirable for the environment and public health. However, most of reported materials usually possess single function, which considerably limits their applications as sensors or captures. Herein, two fluorescent composites, ZIF-8@AuAg NPs and ZIF-8-AuAg NPs, are prepared by the integration of Au/Ag nanoparticles (M NPs) and a zeolite imidazolate framework (ZIF-8), presenting a more stable fluorescent performance compared with pure AuAg NPs. The characterizations unravel that ZIF-8@AuAg NPs exhibits a core shell type structure, whereas ZIF-8-AuAg NPs are indicative of a dispersed loading type motif. ZIF-8-AuAg NPs features a significant fluorescent quenching effect for three commonly used dinitroaniline pesticides in aqueous matrices. Then, pendimethalin (PDA) is selected as a representative of dinitroaniline pesticides to thoroughly develop the potential applications in the fields of detection and extraction. Impressively, ZIF-8-AuAg NPs made of ZIF-8 shell embedded with AuAg NPs can achieve fluorescence sensing for PDA in a low concentration range with the limit of detection (LOD) of 4.2 nmol/L from aqueous solution and agricultural products, attributed to the combination of competition mechanism and electron transfer. Moreover, ZIF-8-AuAg NPs possesses high adsorption capacity of 125 mg/g for PDA at pH 6, depending on the synergistic effect of unique structural frameworks, coordinative interaction and hydrogen bond. The design for present hybrid composites provides a facile strategy to develop difunctional luminescent adsorbents with the merits of selective detection and effective absorption of dinitroaniline pesticides.
Developing candidate materials that are equipped with the ability of both selective detection and efficient removal of pesticides is greatly desirable for the environment and public health. However, most of reported materials usually possess single function, which considerably limits their applications as sensors or captures. Herein, two fluorescent composites, ZIF-8@AuAg NPs and ZIF-8-AuAg NPs, are prepared by the integration of Au/Ag nanoparticles (M NPs) and a zeolite imidazolate framework (ZIF-8), presenting a more stable fluorescent performance compared with pure AuAg NPs. The characterizations unravel that ZIF-8@AuAg NPs exhibits a core shell type structure, whereas ZIF-8-AuAg NPs are indicative of a dispersed loading type motif. ZIF-8-AuAg NPs features a significant fluorescent quenching effect for three commonly used dinitroaniline pesticides in aqueous matrices. Then, pendimethalin (PDA) is selected as a representative of dinitroaniline pesticides to thoroughly develop the potential applications in the fields of detection and extraction. Impressively, ZIF-8-AuAg NPs made of ZIF-8 shell embedded with AuAg NPs can achieve fluorescence sensing for PDA in a low concentration range with the limit of detection (LOD) of 4.2 nmol/L from aqueous solution and agricultural products, attributed to the combination of competition mechanism and electron transfer. Moreover, ZIF-8-AuAg NPs possesses high adsorption capacity of 125 mg/g for PDA at pH 6, depending on the synergistic effect of unique structural frameworks, coordinative interaction and hydrogen bond. The design for present hybrid composites provides a facile strategy to develop difunctional luminescent adsorbents with the merits of selective detection and effective absorption of dinitroaniline pesticides.
2025, 36(8): 110216
doi: 10.1016/j.cclet.2024.110216
Abstract:
Two-dimensional (2D) organic-inorganic hybrid perovskites (OIHPs) have been developed as promising candidates for photodetection, owing to their excellent semiconducting features and structural tunability. However, as an important parameter for photodetection, the photoresponsive range of 2D OIHPs is usually modulated by finite metal-halide combinations, constraining their further development. The emerging aromatic amine-based alternating-cations-interlayered (A-ACI) hybrid perovskites that exhibit excellent charge transport and additional interlayered structural designability, provide an extra solution for achieving ideal photoresponsive range. Herein, for the first time, the photoresponsive range is successfully broadened in A-ACI hybrid perovskites (NMA)4(FA)2Pb3Br12 (2) remolding from (NMA)4(MA)2Pb3Br12 (1) (NMA = N-methylbenzylaminium, FA = formamidinium and MA = methylammonium). Particularly, 1 and 2 adopt an unprecedented configuration that NMA and MA/FA are alternately arranged in the interlayer in a 4:2 manner. Importantly, 2 exhibits a narrower bandgap than 1, which can be ascribed to the low-lying conduct band composed of intercalation FA π* orbitals. Meanwhile, 2 possesses a shorter interlayer distance and flatter inorganic skeleton, synergistically facilitating the wider photo-absorption range and further endowing a broadening photoresponsive range (70 nm). This research not only enriches the perovskite family but also provides insights into structure-property relationships.
Two-dimensional (2D) organic-inorganic hybrid perovskites (OIHPs) have been developed as promising candidates for photodetection, owing to their excellent semiconducting features and structural tunability. However, as an important parameter for photodetection, the photoresponsive range of 2D OIHPs is usually modulated by finite metal-halide combinations, constraining their further development. The emerging aromatic amine-based alternating-cations-interlayered (A-ACI) hybrid perovskites that exhibit excellent charge transport and additional interlayered structural designability, provide an extra solution for achieving ideal photoresponsive range. Herein, for the first time, the photoresponsive range is successfully broadened in A-ACI hybrid perovskites (NMA)4(FA)2Pb3Br12 (2) remolding from (NMA)4(MA)2Pb3Br12 (1) (NMA = N-methylbenzylaminium, FA = formamidinium and MA = methylammonium). Particularly, 1 and 2 adopt an unprecedented configuration that NMA and MA/FA are alternately arranged in the interlayer in a 4:2 manner. Importantly, 2 exhibits a narrower bandgap than 1, which can be ascribed to the low-lying conduct band composed of intercalation FA π* orbitals. Meanwhile, 2 possesses a shorter interlayer distance and flatter inorganic skeleton, synergistically facilitating the wider photo-absorption range and further endowing a broadening photoresponsive range (70 nm). This research not only enriches the perovskite family but also provides insights into structure-property relationships.
2025, 36(8): 110218
doi: 10.1016/j.cclet.2024.110218
Abstract:
Two-dimensional perovskite ferroelectric which strongly couple ferroelectricity with semiconducting properties are promising candidates for optoelectronic applications. However, it is still a great challenge to fabricate self-powered broadband photodetectors with low detection limit. Herein, we successfully realized self-powered broadband photodetection with low detection limit by using a trilayered perovskite ferroelectric (BA)2EA2Pb3I10 (1, BA = n-butylamine, EA = ethylamine). Giving to its large spontaneous polarization (5.6 µC/cm2), 1 exhibits an open-circuit voltage of 0.25 V which provide driving force to separate carriers. Combining with its low dark current (~10−14 A) and narrow bandgap (Eg = 1.86 eV), 1 demonstrates great potential on detecting the broadband weak lights. Thus, a prominent photodetection performance with high open-off ratio (~105), outstanding responsivity (> 10 mA/W), and promising detectivity (> 1011 Jones), as well as the low detecting limit (~nW/cm2) among the wide wavelength from 377 nm to 637 nm was realized based on the single crystal of 1. This work demonstrates the great potential of 2D perovskite ferroelectric on self-powered broadband photodetectors.
Two-dimensional perovskite ferroelectric which strongly couple ferroelectricity with semiconducting properties are promising candidates for optoelectronic applications. However, it is still a great challenge to fabricate self-powered broadband photodetectors with low detection limit. Herein, we successfully realized self-powered broadband photodetection with low detection limit by using a trilayered perovskite ferroelectric (BA)2EA2Pb3I10 (1, BA = n-butylamine, EA = ethylamine). Giving to its large spontaneous polarization (5.6 µC/cm2), 1 exhibits an open-circuit voltage of 0.25 V which provide driving force to separate carriers. Combining with its low dark current (~10−14 A) and narrow bandgap (Eg = 1.86 eV), 1 demonstrates great potential on detecting the broadband weak lights. Thus, a prominent photodetection performance with high open-off ratio (~105), outstanding responsivity (> 10 mA/W), and promising detectivity (> 1011 Jones), as well as the low detecting limit (~nW/cm2) among the wide wavelength from 377 nm to 637 nm was realized based on the single crystal of 1. This work demonstrates the great potential of 2D perovskite ferroelectric on self-powered broadband photodetectors.
2025, 36(8): 110219
doi: 10.1016/j.cclet.2024.110219
Abstract:
Surface adsorption plays a crucial role in various natural and industrial processes, particularly in the field of energy storage. The adsorption of sodium atoms on 2D layered materials can significantly impact their performance as carriers and electrodes in ion batteries. While it is commonly acknowledged that pristine graphene is not favorable for sodium ion adsorption, the suitability of other 2D materials with similar honeycomb symmetry remains unclear. In this study, we employ systematic first-principles calculations to explore interlayer interactions and electron transfer effects on sodium adsorption on 2D van der Waals (vdW) heterostructures (HTSs) surfaces. Our results demonstrate that sodium adsorption is energetically favorable on these substrates. Moreover, we find that the adsorption strength can be effectively tuned by manipulation of the electron accumulation or depletion of the layer directly interacting with the sodium atom. By stacking these layered materials with different electron abundancy to form vdW HTSs, the charge density of the substrate becomes tunable through interlayer charge transfer. In these vdW HTSs, the adsorption behavior of sodium is primarily controlled by the absorption layer and exhibits a linear correlation with its pz-band center. Additionally, we identify linear correlations between the sodium adsorption energies, the electron loss of the sodium atom, the interlayer charge transfer, and the heights of the adsorbed sodium atom. These discoveries underscore the impact of interlayer electron transfer and interactions on sodium ion adsorption on 2D vdW HTSs and providing new insights into material design for alkali atom adsorption.
Surface adsorption plays a crucial role in various natural and industrial processes, particularly in the field of energy storage. The adsorption of sodium atoms on 2D layered materials can significantly impact their performance as carriers and electrodes in ion batteries. While it is commonly acknowledged that pristine graphene is not favorable for sodium ion adsorption, the suitability of other 2D materials with similar honeycomb symmetry remains unclear. In this study, we employ systematic first-principles calculations to explore interlayer interactions and electron transfer effects on sodium adsorption on 2D van der Waals (vdW) heterostructures (HTSs) surfaces. Our results demonstrate that sodium adsorption is energetically favorable on these substrates. Moreover, we find that the adsorption strength can be effectively tuned by manipulation of the electron accumulation or depletion of the layer directly interacting with the sodium atom. By stacking these layered materials with different electron abundancy to form vdW HTSs, the charge density of the substrate becomes tunable through interlayer charge transfer. In these vdW HTSs, the adsorption behavior of sodium is primarily controlled by the absorption layer and exhibits a linear correlation with its pz-band center. Additionally, we identify linear correlations between the sodium adsorption energies, the electron loss of the sodium atom, the interlayer charge transfer, and the heights of the adsorbed sodium atom. These discoveries underscore the impact of interlayer electron transfer and interactions on sodium ion adsorption on 2D vdW HTSs and providing new insights into material design for alkali atom adsorption.
2025, 36(8): 110246
doi: 10.1016/j.cclet.2024.110246
Abstract:
Conjugated microporous polymers (CMPs) have attracted considerable attention as potential organic anode materials for sodium-ion batteries (SIBs) due to their flexible chemical structure, high porosity, environmental friendliness, and cost effectiveness. However, the inherent shortcomings of organic electrodes, such as low conductivity, high solubility in electrolyte, narrow material utilization, etc., limit their further development. In this work, we successfully prepared a novel porous polyimide PPD containing multicarbonyl active centers via the polycondensation of pyromellitic dianhydride (PMDA) and 2,6-diaminoanthraquinone (DAAQ). The stable conjugated structure and multiple redox centers give the polymer high reversible specific capacity (244.6 mAh/g after 100 cycles at 100 mA/g), ultra-long cycle stability (100.7 mAh/g after 2000 cycles at 1.0 A/g), and predominant rate capability. Meanwhile, the sodium storage mechanism of the electrode materials during the charging and discharging process is investigated by ex-situ XPS/FTIR analysis. Due to the exceptional electrochemical properties and simple synthesis method, this work may shed light on the preparation of polyimide-based anodes for high specific capacity and rate capability secondary batteries.
Conjugated microporous polymers (CMPs) have attracted considerable attention as potential organic anode materials for sodium-ion batteries (SIBs) due to their flexible chemical structure, high porosity, environmental friendliness, and cost effectiveness. However, the inherent shortcomings of organic electrodes, such as low conductivity, high solubility in electrolyte, narrow material utilization, etc., limit their further development. In this work, we successfully prepared a novel porous polyimide PPD containing multicarbonyl active centers via the polycondensation of pyromellitic dianhydride (PMDA) and 2,6-diaminoanthraquinone (DAAQ). The stable conjugated structure and multiple redox centers give the polymer high reversible specific capacity (244.6 mAh/g after 100 cycles at 100 mA/g), ultra-long cycle stability (100.7 mAh/g after 2000 cycles at 1.0 A/g), and predominant rate capability. Meanwhile, the sodium storage mechanism of the electrode materials during the charging and discharging process is investigated by ex-situ XPS/FTIR analysis. Due to the exceptional electrochemical properties and simple synthesis method, this work may shed light on the preparation of polyimide-based anodes for high specific capacity and rate capability secondary batteries.
2025, 36(8): 110257
doi: 10.1016/j.cclet.2024.110257
Abstract:
Intrinsic two-dimensional (2D) ferromagnetic (FM) semiconductors have attracted extensive attentions for their potential applications in next-generation spintronics devices. In recent years, the van der Waals material Ⅵ3 has been experimentally found to be an intrinsic FM semiconductor. However, the electronic structure of the Ⅵ3 is not fully understood. To reveal why the Ⅵ3 is a ferromagnetic semiconductor with strong out-of-plane anisotropy, we systematically studied the electronic structure of the monolayer Ⅵ3. Our results confirm that the monolayer Ⅵ3 is a Mott insulator, and d2 electrons occupy ag and egπ+ orbitals. The half-metallic state is a metastable state with a total energy 0.7 eV higher than the ferromagnetic Mott insulating state. Furthermore, our study confirmed that the Ⅵ3 exhibits the out-of-plane magnetic anisotropy, which originates from d2 electrons occupying low-lying ag and egπ+ orbitals. Since the orbital angular momentum of the egπ+ state is not completely quenched, the Ⅵ3 has the out-of-plane anisotropy under interplay between the spin-orbit coupling and crystal field. Our study provides valuable guidance for the design of 2D magnetic materials with pronounced out-of-plane anisotropy.
Intrinsic two-dimensional (2D) ferromagnetic (FM) semiconductors have attracted extensive attentions for their potential applications in next-generation spintronics devices. In recent years, the van der Waals material Ⅵ3 has been experimentally found to be an intrinsic FM semiconductor. However, the electronic structure of the Ⅵ3 is not fully understood. To reveal why the Ⅵ3 is a ferromagnetic semiconductor with strong out-of-plane anisotropy, we systematically studied the electronic structure of the monolayer Ⅵ3. Our results confirm that the monolayer Ⅵ3 is a Mott insulator, and d2 electrons occupy ag and egπ+ orbitals. The half-metallic state is a metastable state with a total energy 0.7 eV higher than the ferromagnetic Mott insulating state. Furthermore, our study confirmed that the Ⅵ3 exhibits the out-of-plane magnetic anisotropy, which originates from d2 electrons occupying low-lying ag and egπ+ orbitals. Since the orbital angular momentum of the egπ+ state is not completely quenched, the Ⅵ3 has the out-of-plane anisotropy under interplay between the spin-orbit coupling and crystal field. Our study provides valuable guidance for the design of 2D magnetic materials with pronounced out-of-plane anisotropy.
2025, 36(8): 110272
doi: 10.1016/j.cclet.2024.110272
Abstract:
Halide electrolytes, renowned for their excellent electrochemical stability and wide voltage window, exhibit significant potential in the development of high energy density solid-state batteries featuring high voltage cathode materials. In this study, we present the development and synthesis of a 0.6Li2S-ZrCl4 solid electrolyte, demonstrating an ion conductivity of 1.9 × 10–3 S/cm at 25 ℃. Under a pressure of 500 MPa, the relative density of the electrolyte can reach 97.37%, showcasing its commendable compressibility. 0.6Li2S-ZrCl4 served as the electrolyte, and we assembled batteries utilizing a LiCoO2 (LCO) positive electrode, Li9.54Si1.74P1.44S11.7Cl0.3 (LSPSCl) coating, and Li-In negative electrode for laboratory testing. At 25 ℃, this all-solid-state battery demonstrated an impressive discharge capacity retention rate of 86.99% (with a final discharge specific capacity of 110.5 mAh/g) after 250 cycles at 24 mA/g and 100 MPa stack pressure. Upon substituting the positive electrode material with LiNi0.8Mn0.1Co0.1O2 (NMC811) and assembling an all-solid-state battery, it demonstrated a discharge capacity retention rate of 74.17% after 200 cycles at 3.6 mA/g and 100 MPa stack pressure in an environment at 25 ℃ (with a final discharge specific capacity of 103.3 mA/g). Our findings hold significant implications for the design of novel superionic conductors, thereby contributing to the advancement of all-solid-state battery technology.
Halide electrolytes, renowned for their excellent electrochemical stability and wide voltage window, exhibit significant potential in the development of high energy density solid-state batteries featuring high voltage cathode materials. In this study, we present the development and synthesis of a 0.6Li2S-ZrCl4 solid electrolyte, demonstrating an ion conductivity of 1.9 × 10–3 S/cm at 25 ℃. Under a pressure of 500 MPa, the relative density of the electrolyte can reach 97.37%, showcasing its commendable compressibility. 0.6Li2S-ZrCl4 served as the electrolyte, and we assembled batteries utilizing a LiCoO2 (LCO) positive electrode, Li9.54Si1.74P1.44S11.7Cl0.3 (LSPSCl) coating, and Li-In negative electrode for laboratory testing. At 25 ℃, this all-solid-state battery demonstrated an impressive discharge capacity retention rate of 86.99% (with a final discharge specific capacity of 110.5 mAh/g) after 250 cycles at 24 mA/g and 100 MPa stack pressure. Upon substituting the positive electrode material with LiNi0.8Mn0.1Co0.1O2 (NMC811) and assembling an all-solid-state battery, it demonstrated a discharge capacity retention rate of 74.17% after 200 cycles at 3.6 mA/g and 100 MPa stack pressure in an environment at 25 ℃ (with a final discharge specific capacity of 103.3 mA/g). Our findings hold significant implications for the design of novel superionic conductors, thereby contributing to the advancement of all-solid-state battery technology.
2025, 36(8): 110275
doi: 10.1016/j.cclet.2024.110275
Abstract:
The core@shell structure materials with the synergistic effect have been confirmed as promising catalysts for oxygen evolution reaction (OER). However, the conventional catalysts with crystalline phase suffer from deficient active sites, elemental dissolution, and structural collapse during OER catalysis, which results in the limited OER performance. Herein, we introduced the amorphous phase structure by controllable wet-chemical sulfuration strategy, thus to prepare the amorphous/crystalline (a/c) AgS@CoS core@shell catalysts. Benefitting from the core@shell construction with synergistic interaction, a/c heterophase with well-balanced catalytic activity and stability, favorable sulfides components with positive oxysulfide reconstructed layer formation, the optimized AgS@CoS-2 catalysts displayed superior OER catalytic behaviors with a low overpotential of 260 mV and Tafel slope of 64.4 mV/dec on the current density of 10 mA/cm2, surpassing the counterpart catalysts and commercial RuO2 catalysts. Meanwhile, the AgS@CoS-2 catalysts possessed remarkable OER catalytic stability, as well as the favorable overall water splitting performance.
The core@shell structure materials with the synergistic effect have been confirmed as promising catalysts for oxygen evolution reaction (OER). However, the conventional catalysts with crystalline phase suffer from deficient active sites, elemental dissolution, and structural collapse during OER catalysis, which results in the limited OER performance. Herein, we introduced the amorphous phase structure by controllable wet-chemical sulfuration strategy, thus to prepare the amorphous/crystalline (a/c) AgS@CoS core@shell catalysts. Benefitting from the core@shell construction with synergistic interaction, a/c heterophase with well-balanced catalytic activity and stability, favorable sulfides components with positive oxysulfide reconstructed layer formation, the optimized AgS@CoS-2 catalysts displayed superior OER catalytic behaviors with a low overpotential of 260 mV and Tafel slope of 64.4 mV/dec on the current density of 10 mA/cm2, surpassing the counterpart catalysts and commercial RuO2 catalysts. Meanwhile, the AgS@CoS-2 catalysts possessed remarkable OER catalytic stability, as well as the favorable overall water splitting performance.
2025, 36(8): 110308
doi: 10.1016/j.cclet.2024.110308
Abstract:
Zn metal batteries are highly attractive because of their high theoretical specific capacity, intrinsic safety and resource availability. However, further development is significantly hindered by low Coulomb efficiency, which is closely linked to reaction processes occurring at electrode/electrolyte interfaces. Herein, we have achieved a real-time visualization and comprehensive analysis of the interfacial evolution of Zn metal anode via in situ AFM in organic and aqueous electrolytes, respectively. The processes of uneven nucleation, dendrite growth, the ZnO formation and the dissolution of Zn substrate are directly probed in aqueous electrolyte, which induces interfacial deterioration and ultimately results in battery failure. In organic electrolyte, the in situ observations show that the homogeneous nuclei form on the Zn surface to induce the dendrite-free deposition, however, exhibiting poor Zn plating/stripping reversibility. This work delves into the dynamic evolution and electrochemical behaviors regulated by solvents, which provides in-depth understanding of structure-reactivity correlations and further interfacial engineering.
Zn metal batteries are highly attractive because of their high theoretical specific capacity, intrinsic safety and resource availability. However, further development is significantly hindered by low Coulomb efficiency, which is closely linked to reaction processes occurring at electrode/electrolyte interfaces. Herein, we have achieved a real-time visualization and comprehensive analysis of the interfacial evolution of Zn metal anode via in situ AFM in organic and aqueous electrolytes, respectively. The processes of uneven nucleation, dendrite growth, the ZnO formation and the dissolution of Zn substrate are directly probed in aqueous electrolyte, which induces interfacial deterioration and ultimately results in battery failure. In organic electrolyte, the in situ observations show that the homogeneous nuclei form on the Zn surface to induce the dendrite-free deposition, however, exhibiting poor Zn plating/stripping reversibility. This work delves into the dynamic evolution and electrochemical behaviors regulated by solvents, which provides in-depth understanding of structure-reactivity correlations and further interfacial engineering.
2025, 36(8): 110517
doi: 10.1016/j.cclet.2024.110517
Abstract:
Flow anodic oxidation system has demonstrated to be a promising and environmental benign water treatment technology because of its advantages of high contaminant removal efficiency and low energy consumption. However, traditional setup needs an external unit for flow anode material separation and recovery, which inevitably increases the capital cost and hinders its continuous operation. Herein, a specific porous cathode is introduced to achieve continuous water purification with high contaminant removal in a flow anodic oxidation system. The effluent concentration of carbamazepine (CBZ), a common and model contaminant widely detected in natural water environment, was reduced by 99%. The linear sweep voltammetry (LSV) and quenching tests demonstrated that HO• was the dominant reactive species. While the removal of contaminants was inhibited in practical surface water, largely related to the quenching by dissolved organic matter and bicarbonate, the flow anodic oxidation process was competent in alleviating the ecotoxicity following oxidation. Our study constructs a modular device for cost-effective continuous water purification and provides insight into the mechanisms of flow andic oxidation.
Flow anodic oxidation system has demonstrated to be a promising and environmental benign water treatment technology because of its advantages of high contaminant removal efficiency and low energy consumption. However, traditional setup needs an external unit for flow anode material separation and recovery, which inevitably increases the capital cost and hinders its continuous operation. Herein, a specific porous cathode is introduced to achieve continuous water purification with high contaminant removal in a flow anodic oxidation system. The effluent concentration of carbamazepine (CBZ), a common and model contaminant widely detected in natural water environment, was reduced by 99%. The linear sweep voltammetry (LSV) and quenching tests demonstrated that HO• was the dominant reactive species. While the removal of contaminants was inhibited in practical surface water, largely related to the quenching by dissolved organic matter and bicarbonate, the flow anodic oxidation process was competent in alleviating the ecotoxicity following oxidation. Our study constructs a modular device for cost-effective continuous water purification and provides insight into the mechanisms of flow andic oxidation.
Theoretical insight into the active sites for chlorobenzene oxidation: From phosphate to M3 clusters
2025, 36(8): 110527
doi: 10.1016/j.cclet.2024.110527
Abstract:
Chlorobenzene is a model molecule for researching harmful chlorinated volatile organic compounds. Designing the chemical adsorption site for complex molecules such as chlorobenzene is challenging without a large dataset and reasonable descriptors. Here, the adsorption of chlorobenzene on a phosphorylated CeO2 catalyst was analyzed using density functional theory calculations. Three different surface phosphate (HxPO4) models were constructed and used to adsorb chlorobenzene. An orbital interaction with fully occupied antibonding is found in one of three physical adsorptions. Based on this, the surface sites of a tri-cluster (M3) located at the CeO2 surface have been suggested to activate chlorobenzene. Three different clusters have been tested, namely Fe3, Ru3, and B3. All these clusters can activate and twist chlorobenzene by donating electrons. Fe3 and Ru3 form bonds with weak covalent and strong ionic characters, while B3 forms strong covalent bonds between boron and carbon. This work not only predicts a class of sites for chlorobenzene activation that may prevent polychlorinated by-products but also gives a template for catalyst rational design according to fundamental catalytic theory.
Chlorobenzene is a model molecule for researching harmful chlorinated volatile organic compounds. Designing the chemical adsorption site for complex molecules such as chlorobenzene is challenging without a large dataset and reasonable descriptors. Here, the adsorption of chlorobenzene on a phosphorylated CeO2 catalyst was analyzed using density functional theory calculations. Three different surface phosphate (HxPO4) models were constructed and used to adsorb chlorobenzene. An orbital interaction with fully occupied antibonding is found in one of three physical adsorptions. Based on this, the surface sites of a tri-cluster (M3) located at the CeO2 surface have been suggested to activate chlorobenzene. Three different clusters have been tested, namely Fe3, Ru3, and B3. All these clusters can activate and twist chlorobenzene by donating electrons. Fe3 and Ru3 form bonds with weak covalent and strong ionic characters, while B3 forms strong covalent bonds between boron and carbon. This work not only predicts a class of sites for chlorobenzene activation that may prevent polychlorinated by-products but also gives a template for catalyst rational design according to fundamental catalytic theory.
2025, 36(8): 110530
doi: 10.1016/j.cclet.2024.110530
Abstract:
Rapid and robust identification of bacteria is crucial for environmental monitoring and clinical diagnosis. Herein, a bioinspired interface-mediated multichannel sensor array was developed based on three-color-emitting antimicrobial functional carbon dots (FCDs) and concanavalin A doped polydopamine nanoparticles (ConA-PDA) for identification of bacteria. In this sensor, the fluorescence intensity of the three FCDs was quenched by the ConA-PDA. Upon addition different types of bacteria, the fluorescence intensity of the three FCDs was restored or further quenched. Recur to statistical analysis methods, it is employed to accurately discriminate 10 types of bacteria (including three probiotics and seven pathogenic bacteria) in natural water samples and human urine samples. The discrimination ability of the sensor array was highly enhanced via different competing binding of the FCDs and the bacteria toward ConA-PDA. The proposed array-based method offers a rapid, high-throughput, and reliable sensing platform for pathogen diagnosis in the field of environmental monitoring and clinical diagnosis.
Rapid and robust identification of bacteria is crucial for environmental monitoring and clinical diagnosis. Herein, a bioinspired interface-mediated multichannel sensor array was developed based on three-color-emitting antimicrobial functional carbon dots (FCDs) and concanavalin A doped polydopamine nanoparticles (ConA-PDA) for identification of bacteria. In this sensor, the fluorescence intensity of the three FCDs was quenched by the ConA-PDA. Upon addition different types of bacteria, the fluorescence intensity of the three FCDs was restored or further quenched. Recur to statistical analysis methods, it is employed to accurately discriminate 10 types of bacteria (including three probiotics and seven pathogenic bacteria) in natural water samples and human urine samples. The discrimination ability of the sensor array was highly enhanced via different competing binding of the FCDs and the bacteria toward ConA-PDA. The proposed array-based method offers a rapid, high-throughput, and reliable sensing platform for pathogen diagnosis in the field of environmental monitoring and clinical diagnosis.
2025, 36(8): 110538
doi: 10.1016/j.cclet.2024.110538
Abstract:
Rational design of complex hollow nanostructures offers a great opportunity to construct various functional nanostructures. A novel in situ disassembly-polymerization-pyrolysis approach was developed to synthesize atomically dispersed Fe single atoms (Fe SAs) and tiny Co nanoparticles (Co NPs) binary sites embedded in double-shelled hollow carbon nanocages (Co NPs/Fe SAs DSCNs) without removing excess templates. The Co NPs/Fe SAs DSCNs displayed excellent bifunctional activity, boosting the realistic rechargeable zinc-air batteries with high efficiency, long-term durability, and reversibility, which is comparable to noble metal catalysts (Pt/C and RuO2). The enhanced catalytic activity should be attributed to as well as the strong interactions between Fe SAs and Co NPs with the nitrogen-doped carbon matrix, the exposure of more active sites, and the high-flux mass transportation. In addition, the confinement effect between the double C–N shells prevented the aggregation and corrosion of metal atoms, thus improving the durability of the Co NPs/Fe SAs DSCNs, further highlighting the structural advantages of carbon nanoreactor. This work provides guidance for further rational design and preparation of complex hollow structure materials with advanced bifunctional air cathodes.
Rational design of complex hollow nanostructures offers a great opportunity to construct various functional nanostructures. A novel in situ disassembly-polymerization-pyrolysis approach was developed to synthesize atomically dispersed Fe single atoms (Fe SAs) and tiny Co nanoparticles (Co NPs) binary sites embedded in double-shelled hollow carbon nanocages (Co NPs/Fe SAs DSCNs) without removing excess templates. The Co NPs/Fe SAs DSCNs displayed excellent bifunctional activity, boosting the realistic rechargeable zinc-air batteries with high efficiency, long-term durability, and reversibility, which is comparable to noble metal catalysts (Pt/C and RuO2). The enhanced catalytic activity should be attributed to as well as the strong interactions between Fe SAs and Co NPs with the nitrogen-doped carbon matrix, the exposure of more active sites, and the high-flux mass transportation. In addition, the confinement effect between the double C–N shells prevented the aggregation and corrosion of metal atoms, thus improving the durability of the Co NPs/Fe SAs DSCNs, further highlighting the structural advantages of carbon nanoreactor. This work provides guidance for further rational design and preparation of complex hollow structure materials with advanced bifunctional air cathodes.
2025, 36(8): 110544
doi: 10.1016/j.cclet.2024.110544
Abstract:
A dual S-scheme g-C3N4/Ag3PO4/g-C3N5 heterojunction was prepared by decomposition methods, and it displayed enhanced performance to degrade tetracycline hydrochloride with the ideal stability under different water substrates and ions. Comparing with three single components, as g-C3N4, g-C3N5, and Ag3PO4, the dual S-scheme g-C3N4/Ag3PO4/g-C3N5 heterojunction displayed 4.4-, 3.4-, and 2.5-times enhancements in the tetracycline hydrochloride removal. Based on the dynamics analyses for charge carriers and band structure calculations, two channels of molecular oxygen activation (MOA) between Ag3PO4 and g-C3N4 (and g-C3N5) were confirmed. More importantly, according to this double consumption process of excited electrons, dual S-scheme g-C3N4/Ag3PO4/g-C3N5 could suppress the charge recombination, which was the key point to boosting photocatalytic activity. Moreover, the determination of intermediates also supported the vital role of MOA during these photocatalytic reactions. this report of two reactive sites in MOA that generate reactive oxygen species in a "V" type band structure. The electronic dynamic in the reaction was also testified by several detections, indicating the enhanced charge separation and migration from internal field effect and electron trapping from dual S-scheme mechanism. This work provides a new research direction for the design and mechanism analysis of dual S-scheme photocatalysts
A dual S-scheme g-C3N4/Ag3PO4/g-C3N5 heterojunction was prepared by decomposition methods, and it displayed enhanced performance to degrade tetracycline hydrochloride with the ideal stability under different water substrates and ions. Comparing with three single components, as g-C3N4, g-C3N5, and Ag3PO4, the dual S-scheme g-C3N4/Ag3PO4/g-C3N5 heterojunction displayed 4.4-, 3.4-, and 2.5-times enhancements in the tetracycline hydrochloride removal. Based on the dynamics analyses for charge carriers and band structure calculations, two channels of molecular oxygen activation (MOA) between Ag3PO4 and g-C3N4 (and g-C3N5) were confirmed. More importantly, according to this double consumption process of excited electrons, dual S-scheme g-C3N4/Ag3PO4/g-C3N5 could suppress the charge recombination, which was the key point to boosting photocatalytic activity. Moreover, the determination of intermediates also supported the vital role of MOA during these photocatalytic reactions. this report of two reactive sites in MOA that generate reactive oxygen species in a "V" type band structure. The electronic dynamic in the reaction was also testified by several detections, indicating the enhanced charge separation and migration from internal field effect and electron trapping from dual S-scheme mechanism. This work provides a new research direction for the design and mechanism analysis of dual S-scheme photocatalysts
2025, 36(8): 110558
doi: 10.1016/j.cclet.2024.110558
Abstract:
From the seeds of Peganum harmala L., three new alkaloids of β-carboline were isolated. Among them, peganumiums A (1) and B (2) were dimers with specific new scaffolds, all with long conjugated systems. Peganumium A and peganumium C (3) were ionic alkaloid salts and peganumium B was a hexacyclic-condensed alkaloid. The biosynthetic pathways of the three compounds above were also speculated. A preliminary cytotoxicity assay revealed that peganumium B had strong in vitro antiproliferative ability against a variety of cancer cells. The analysis of 1H nuclear magnetic resonance (NMR) metabolomics suggested that the antiproliferative mechanism of peganumium B could be associated with the biosynthesis of phenylalanine, tyrosine and tryptophan, the metabolism of glycine, serine, and threonine, the metabolism of taurine and hypotaurine, and the metabolism of nicotinate and nicotinamide. In addition, peganumium B could reduce the mitochondrial content of body-wall muscle cells of a Caenorhabditis elegans (C. elegans) strain in vivo.
From the seeds of Peganum harmala L., three new alkaloids of β-carboline were isolated. Among them, peganumiums A (1) and B (2) were dimers with specific new scaffolds, all with long conjugated systems. Peganumium A and peganumium C (3) were ionic alkaloid salts and peganumium B was a hexacyclic-condensed alkaloid. The biosynthetic pathways of the three compounds above were also speculated. A preliminary cytotoxicity assay revealed that peganumium B had strong in vitro antiproliferative ability against a variety of cancer cells. The analysis of 1H nuclear magnetic resonance (NMR) metabolomics suggested that the antiproliferative mechanism of peganumium B could be associated with the biosynthesis of phenylalanine, tyrosine and tryptophan, the metabolism of glycine, serine, and threonine, the metabolism of taurine and hypotaurine, and the metabolism of nicotinate and nicotinamide. In addition, peganumium B could reduce the mitochondrial content of body-wall muscle cells of a Caenorhabditis elegans (C. elegans) strain in vivo.
2025, 36(8): 110559
doi: 10.1016/j.cclet.2024.110559
Abstract:
Endotracheal intubation-related complications are common in clinical, and there are currently no effective strategies to address these matters. Inspired by the biological characteristics of human airway mucus (HAM), an artificial airway mucus (ARM) coating is straightforwardly constructed by combining carboxymethyl chitosan with methyl cellulose. The ARM coating exhibited excellent lubricity (coefficient of friction (CoF) = 0.05) and hydrophilicity (water contact angle (WCA) = 21.3°), and was capable of coating both the internal and external surfaces of the endotracheal tube (ETT). In vitro experiments demonstrated that the ARM coating not only showed good broad-spectrum antibacterial activity, but also significantly reduced nonspecific protein adhesion. Through an in vivo intubation cynomolgus monkey model, ARM-coated ETT potently mitigated airway injury and inflammation, and was highly potential to prevent bacterial infection and catheter blockage. This work offers a promising avenue for the development of airway-friendly invasive devices.
Endotracheal intubation-related complications are common in clinical, and there are currently no effective strategies to address these matters. Inspired by the biological characteristics of human airway mucus (HAM), an artificial airway mucus (ARM) coating is straightforwardly constructed by combining carboxymethyl chitosan with methyl cellulose. The ARM coating exhibited excellent lubricity (coefficient of friction (CoF) = 0.05) and hydrophilicity (water contact angle (WCA) = 21.3°), and was capable of coating both the internal and external surfaces of the endotracheal tube (ETT). In vitro experiments demonstrated that the ARM coating not only showed good broad-spectrum antibacterial activity, but also significantly reduced nonspecific protein adhesion. Through an in vivo intubation cynomolgus monkey model, ARM-coated ETT potently mitigated airway injury and inflammation, and was highly potential to prevent bacterial infection and catheter blockage. This work offers a promising avenue for the development of airway-friendly invasive devices.
2025, 36(8): 110563
doi: 10.1016/j.cclet.2024.110563
Abstract:
Granular sludges can resist the toxicity inhibition of medium-chain fatty acids (MCFAs) and enhance the chain elongation (CE) process. However, the granulation process is time-consuming and requires a suitable facilitating granulation mean. This study proposed two continuous fed Expanded Granular Sludge Bed bioreactors, one with electric field (EF) and one without, to demonstrate the promotion of sludge granulation by EF and the enhancement of MCFAs production efficiency by the anaerobic granular sludge (AnGS). Through more than 50 days of operation, the EF was demonstrated to be able to promote the granulation, and the formed AnGS enhanced MCFAs yield by 36%. Besides, mechanism analysis indicated that the EF promoted microbial aggregation and extracellular polymeric substances (EPS) synthesis, which enabled AnGS to form more easily. Besides, AnGS formed with EF improved extracellular electron transfer capacity and microbial function activity, which also contributed to the production of more MCFAs. Overall, this study provides a method to facilitate AnGS granulation and revealed the underlying mechanisms, and offers important support for the diverse applications of AnGS in other bioresources recovery bioprocesses.
Granular sludges can resist the toxicity inhibition of medium-chain fatty acids (MCFAs) and enhance the chain elongation (CE) process. However, the granulation process is time-consuming and requires a suitable facilitating granulation mean. This study proposed two continuous fed Expanded Granular Sludge Bed bioreactors, one with electric field (EF) and one without, to demonstrate the promotion of sludge granulation by EF and the enhancement of MCFAs production efficiency by the anaerobic granular sludge (AnGS). Through more than 50 days of operation, the EF was demonstrated to be able to promote the granulation, and the formed AnGS enhanced MCFAs yield by 36%. Besides, mechanism analysis indicated that the EF promoted microbial aggregation and extracellular polymeric substances (EPS) synthesis, which enabled AnGS to form more easily. Besides, AnGS formed with EF improved extracellular electron transfer capacity and microbial function activity, which also contributed to the production of more MCFAs. Overall, this study provides a method to facilitate AnGS granulation and revealed the underlying mechanisms, and offers important support for the diverse applications of AnGS in other bioresources recovery bioprocesses.
2025, 36(8): 110564
doi: 10.1016/j.cclet.2024.110564
Abstract:
An all-solid-state ion-selective electrode (ISE) for the detection of potassium ions in complex media was developed based on functional peptides with both antibacterial and antifouling properties. While exhibiting unique antifouling property, the ISE capitalized on the high surface area of the conductive metal-organic framework (MOF) solid transducer layer to facilitate rapid ion-electron transfer, consequently improving the electrode stability. For a short period, the application of a ± 1 nA current to the ISE resulted in a slight potential drift of 2.5 µV/s, while for a long-term stability test, the ISE maintained a stable Nernstian response slope over 8 days. The antifouling and antibacterial peptide effectively eradicated bacteria from the electrode surface while inhibited the adhesion of bacteria and other biological organisms. Both theoretical calculations and experimental results indicated that the incorporation of peptides in the sensing membrane did not compromise the detection performance of the ISE. The prepared antifouling potassium ion-selective electrode exhibited a Nernstian response range spanning from 1.0 × 10–8 mol/L to 1.0 × 10–3 mol/L, with a detection limit of 2.51 nmol/L. Crucially, the prepared solid-contact ISE maintained excellent antifouling and sensing capabilities in actual seawater and human urine, indicating a promising feasibility of this strategy for constructing ISEs suitable for practical application in complex systems.
An all-solid-state ion-selective electrode (ISE) for the detection of potassium ions in complex media was developed based on functional peptides with both antibacterial and antifouling properties. While exhibiting unique antifouling property, the ISE capitalized on the high surface area of the conductive metal-organic framework (MOF) solid transducer layer to facilitate rapid ion-electron transfer, consequently improving the electrode stability. For a short period, the application of a ± 1 nA current to the ISE resulted in a slight potential drift of 2.5 µV/s, while for a long-term stability test, the ISE maintained a stable Nernstian response slope over 8 days. The antifouling and antibacterial peptide effectively eradicated bacteria from the electrode surface while inhibited the adhesion of bacteria and other biological organisms. Both theoretical calculations and experimental results indicated that the incorporation of peptides in the sensing membrane did not compromise the detection performance of the ISE. The prepared antifouling potassium ion-selective electrode exhibited a Nernstian response range spanning from 1.0 × 10–8 mol/L to 1.0 × 10–3 mol/L, with a detection limit of 2.51 nmol/L. Crucially, the prepared solid-contact ISE maintained excellent antifouling and sensing capabilities in actual seawater and human urine, indicating a promising feasibility of this strategy for constructing ISEs suitable for practical application in complex systems.
2025, 36(8): 110570
doi: 10.1016/j.cclet.2024.110570
Abstract:
Most anti-tumor agents suffer from systemic non-specific distribution and low aggregation in tumors, which not only decreases the therapeutic efficacy, but also causes systemic toxic side effects in the treatments of tumors. In recent years, the rapid development of nanotechnology has brought new ideas for the application of anti-tumor drugs. Nanomedicines, such as liposomes and micelles, can improve drug targeting and prolong systemic circulation time to promote anti-tumor efficacy and reduce toxic side effects. However, conventional micelles bear the risk of instability and premature drug leaking in the blood circulation. We designed a reduction-responsive core-cross-linked micelle PTX@Fmoc-LA-PEG efficiently encapsulating Paclitaxel (PTX) via π-π stacking and hydrophobic interactions of Fmoc and PTX. Moreover, the micelle was further locked based on the cross-linking properties of the disulfide bonds formed by lipoic acid (LA). As expected, the core-cross-linked micelles PTX@Fmoc-LA-PEG remained stable in normal physiological environments, while restoring the normal drug release rate of micelles under the highly reducing environment due to LA unlocking. The blank micelles (Fmoc-LA-PEG) exhibited excellent biocompatibility, while the drug-loaded micelles (PTX@Fmoc-LA-PEG) displayed a remarkable anti-tumor effect in vitro and in vivo experiments. These results suggested that core-cross-linked micelles PTX@Fmoc-LA-PEG have great potential to improve the targeting and stability of anti-tumor drugs.
Most anti-tumor agents suffer from systemic non-specific distribution and low aggregation in tumors, which not only decreases the therapeutic efficacy, but also causes systemic toxic side effects in the treatments of tumors. In recent years, the rapid development of nanotechnology has brought new ideas for the application of anti-tumor drugs. Nanomedicines, such as liposomes and micelles, can improve drug targeting and prolong systemic circulation time to promote anti-tumor efficacy and reduce toxic side effects. However, conventional micelles bear the risk of instability and premature drug leaking in the blood circulation. We designed a reduction-responsive core-cross-linked micelle PTX@Fmoc-LA-PEG efficiently encapsulating Paclitaxel (PTX) via π-π stacking and hydrophobic interactions of Fmoc and PTX. Moreover, the micelle was further locked based on the cross-linking properties of the disulfide bonds formed by lipoic acid (LA). As expected, the core-cross-linked micelles PTX@Fmoc-LA-PEG remained stable in normal physiological environments, while restoring the normal drug release rate of micelles under the highly reducing environment due to LA unlocking. The blank micelles (Fmoc-LA-PEG) exhibited excellent biocompatibility, while the drug-loaded micelles (PTX@Fmoc-LA-PEG) displayed a remarkable anti-tumor effect in vitro and in vivo experiments. These results suggested that core-cross-linked micelles PTX@Fmoc-LA-PEG have great potential to improve the targeting and stability of anti-tumor drugs.
2025, 36(8): 110578
doi: 10.1016/j.cclet.2024.110578
Abstract:
A novel Cu-t-ZrO2 catalyst with enhanced electronic metal-support interaction (EMSI) is designed for efficient electrocatalytic conversion of nitrate (NO3−) to ammonia (NH3), achieving a remarkable Faradaic efficiency and yield rate of 97.54% and 33.64 mg h−1 mgcat−1, respectively. Electrons are more likely to be transferred from Cu to t-ZrO2 at the electron-rich interface due to the lower work function, which promotes the formation of highly active Cu species and facilitates NO3− adsorption, ensuring selective conversion into NH3.
A novel Cu-t-ZrO2 catalyst with enhanced electronic metal-support interaction (EMSI) is designed for efficient electrocatalytic conversion of nitrate (NO3−) to ammonia (NH3), achieving a remarkable Faradaic efficiency and yield rate of 97.54% and 33.64 mg h−1 mgcat−1, respectively. Electrons are more likely to be transferred from Cu to t-ZrO2 at the electron-rich interface due to the lower work function, which promotes the formation of highly active Cu species and facilitates NO3− adsorption, ensuring selective conversion into NH3.
2025, 36(8): 110583
doi: 10.1016/j.cclet.2024.110583
Abstract:
Polyvinyl chloride is the most widely used general-purpose plastic and plays a vital role in various industries. Mercury-based catalysts severely limit the green sustainability of industry. Non-metallic carbon materials are very promising alternatives in acetylene hydrochlorination, but their stability remains a challenge of major concern at present. Based on the principle of green chemistry, structurally tunable and defect-rich carbon materials were synthesized by hydrothermal carbonization and pyrolysis using glucose as carbon source and m-phenylenediamine as nitrogen source and cross-linking agent. Experimental characterization and density functional theory confirmed that pyridinic N was the main active site. The introduction of N not only regulated the formation of the hierarchically porous structure of the carbon material, but also increased the adsorption of HCl and decreased the adsorption strength of C2H2. The synergistic effect of high N content and porous structure significantly enhanced the catalytic performance of the catalysts in acetylene hydrochlorination. The C2H2 conversion was maintained at around 98% after 100 h under the reaction conditions (T = 220 ℃, GHSV(C2H2) = 30 h-1, VHCl/VC2H2 = 1.15). Thus, the one-pot synthesis process used here is a good benchmark for future catalyst research.
Polyvinyl chloride is the most widely used general-purpose plastic and plays a vital role in various industries. Mercury-based catalysts severely limit the green sustainability of industry. Non-metallic carbon materials are very promising alternatives in acetylene hydrochlorination, but their stability remains a challenge of major concern at present. Based on the principle of green chemistry, structurally tunable and defect-rich carbon materials were synthesized by hydrothermal carbonization and pyrolysis using glucose as carbon source and m-phenylenediamine as nitrogen source and cross-linking agent. Experimental characterization and density functional theory confirmed that pyridinic N was the main active site. The introduction of N not only regulated the formation of the hierarchically porous structure of the carbon material, but also increased the adsorption of HCl and decreased the adsorption strength of C2H2. The synergistic effect of high N content and porous structure significantly enhanced the catalytic performance of the catalysts in acetylene hydrochlorination. The C2H2 conversion was maintained at around 98% after 100 h under the reaction conditions (T = 220 ℃, GHSV(C2H2) = 30 h-1, VHCl/VC2H2 = 1.15). Thus, the one-pot synthesis process used here is a good benchmark for future catalyst research.
2025, 36(8): 110584
doi: 10.1016/j.cclet.2024.110584
Abstract:
Six rearranged nor-diterpenoids with 5/6/6-fused tricyclic system (1–6), and one unprecedented dimer with 5/6/6/6/6/5-fused carbon core (7) were isolated from Strophioblachia glandulosa. Spectroscopic techniques, electronic circular dichroism (ECD), quantum chemical calculations, and single-crystal X-ray diffraction analysis were used to elucidate their structures. A preliminary bioactivity assay revealed compounds 2 and 3 exhibited potent anti-myocardial hypertrophy effect in vitro by significantly inhibiting the expression levels of atrial natriuretic peptide (ANP) and myosin heavy chain 7 (MYH7) proteins. Additionally, mitogen-activated protein kinase 14 (Mapk14) may be involved in the regulation of compound 3 on cardiac hypertrophic disease by network pharmacology prediction and experimental verification.
Six rearranged nor-diterpenoids with 5/6/6-fused tricyclic system (1–6), and one unprecedented dimer with 5/6/6/6/6/5-fused carbon core (7) were isolated from Strophioblachia glandulosa. Spectroscopic techniques, electronic circular dichroism (ECD), quantum chemical calculations, and single-crystal X-ray diffraction analysis were used to elucidate their structures. A preliminary bioactivity assay revealed compounds 2 and 3 exhibited potent anti-myocardial hypertrophy effect in vitro by significantly inhibiting the expression levels of atrial natriuretic peptide (ANP) and myosin heavy chain 7 (MYH7) proteins. Additionally, mitogen-activated protein kinase 14 (Mapk14) may be involved in the regulation of compound 3 on cardiac hypertrophic disease by network pharmacology prediction and experimental verification.
2025, 36(8): 110585
doi: 10.1016/j.cclet.2024.110585
Abstract:
Triple-negative breast cancer (TNBC) is one of the most lethal diseases and lack of feasible therapeutic methods. Herein, we developed a bioactive covalent organic framework (COF) for adoptive cell therapy (ACT) of TNBC. In our design, Mn2+ functionalized COF was employed as a bioactive CpG carrier, which could simultaneously engineer and polarize macrophages to the antitumor phenotype, via the synergistic interaction of CpG and Mn2+. In the in vitro experiments, the engineered macrophages were found to secret high levels of antitumor cytokines for efficient TNBC cell inhibition. In the in vivo antitumor model, bioactive COF-engineered macrophages were found to relieve the hypoxia tumor microenvironment, enabling prevention of immune cell depletion during ACT. Thus, we realized efficient TNBC therapy and metastasis inhibition with the engineered macrophages in a long-term therapy model. This work provides a promising strategy for metastatic TNBC treatment and highlights the importance of bioactive COF in biomedicine.
Triple-negative breast cancer (TNBC) is one of the most lethal diseases and lack of feasible therapeutic methods. Herein, we developed a bioactive covalent organic framework (COF) for adoptive cell therapy (ACT) of TNBC. In our design, Mn2+ functionalized COF was employed as a bioactive CpG carrier, which could simultaneously engineer and polarize macrophages to the antitumor phenotype, via the synergistic interaction of CpG and Mn2+. In the in vitro experiments, the engineered macrophages were found to secret high levels of antitumor cytokines for efficient TNBC cell inhibition. In the in vivo antitumor model, bioactive COF-engineered macrophages were found to relieve the hypoxia tumor microenvironment, enabling prevention of immune cell depletion during ACT. Thus, we realized efficient TNBC therapy and metastasis inhibition with the engineered macrophages in a long-term therapy model. This work provides a promising strategy for metastatic TNBC treatment and highlights the importance of bioactive COF in biomedicine.
2025, 36(8): 110586
doi: 10.1016/j.cclet.2024.110586
Abstract:
Idiopathic pulmonary fibrosis (IPF) is a progressive lung disease and its incidence rate is rapidly rising. However, effective therapies for the treatment of IPF are still lacking. Phosphodiesterase 4 (PDE4) inhibitors were reported to be potential anti-fibrotic agents. Herein, structure-based hit-to-lead optimization of natural isoaurostatin (8.98 µmol/L) resulted in several potent inhibitors of PDE4 with half maximal inhibitory concentration (IC50) values ranging from 35 nmol/L to 126 nmol/L. Co-crystal structures revealed that isoaurostatin compounds exhibited different binding patterns from the classic PDE4 inhibitor rolipram and the analogues would favor to be Z configurations other than the corresponding E isomers. Finally, lead 2–9 showed remarkable in vitro/in vivo anti-fibrotic effects indicating its potential as a novel anti-IPF agent.
Idiopathic pulmonary fibrosis (IPF) is a progressive lung disease and its incidence rate is rapidly rising. However, effective therapies for the treatment of IPF are still lacking. Phosphodiesterase 4 (PDE4) inhibitors were reported to be potential anti-fibrotic agents. Herein, structure-based hit-to-lead optimization of natural isoaurostatin (8.98 µmol/L) resulted in several potent inhibitors of PDE4 with half maximal inhibitory concentration (IC50) values ranging from 35 nmol/L to 126 nmol/L. Co-crystal structures revealed that isoaurostatin compounds exhibited different binding patterns from the classic PDE4 inhibitor rolipram and the analogues would favor to be Z configurations other than the corresponding E isomers. Finally, lead 2–9 showed remarkable in vitro/in vivo anti-fibrotic effects indicating its potential as a novel anti-IPF agent.
2025, 36(8): 110594
doi: 10.1016/j.cclet.2024.110594
Abstract:
Osteogenic ability impairment and myelosuppression are common complications of chemotherapy and many chemotherapeutics can affect the skeletal system. Skeletal system protection is necessary for cancer chemotherapy. In this study, osteogenic growth peptide (OGP) and tetrahedral framework nucleic-acid nanostructures (tFNAs) are combined to form a peptide-DNA complex OGP-tFNAs, which aims to combine the positive biological effect on tissue protection and regeneration. The bone marrow protection and bone formation effect of OGP-tFNAs are investigated in chemotherapy-induced myelosuppressive mice. The results show that OGP-tFNAs could reduce the cell damage degree from 5-fluorouracil (5-FU) in vitro and maintained the osteogenic differentiation potential. Furthermore, OGP-tFNAs accelerate bone defect regeneration in myelosuppressive mice. In conclusion, OGP-tFNAs could protect the osteogenic differentiation potential of bone marrow stromal cells (BMSCs) from 5-FU injury and maintain the bone formation ability of myelosuppressive mice suffering from chemotherapy.
Osteogenic ability impairment and myelosuppression are common complications of chemotherapy and many chemotherapeutics can affect the skeletal system. Skeletal system protection is necessary for cancer chemotherapy. In this study, osteogenic growth peptide (OGP) and tetrahedral framework nucleic-acid nanostructures (tFNAs) are combined to form a peptide-DNA complex OGP-tFNAs, which aims to combine the positive biological effect on tissue protection and regeneration. The bone marrow protection and bone formation effect of OGP-tFNAs are investigated in chemotherapy-induced myelosuppressive mice. The results show that OGP-tFNAs could reduce the cell damage degree from 5-fluorouracil (5-FU) in vitro and maintained the osteogenic differentiation potential. Furthermore, OGP-tFNAs accelerate bone defect regeneration in myelosuppressive mice. In conclusion, OGP-tFNAs could protect the osteogenic differentiation potential of bone marrow stromal cells (BMSCs) from 5-FU injury and maintain the bone formation ability of myelosuppressive mice suffering from chemotherapy.
2025, 36(8): 110595
doi: 10.1016/j.cclet.2024.110595
Abstract:
Seed germination plays a pivotal role in plant growth and undergoes many intricate biochemical changes including lipid metabolism. Nevertheless, little is known about lipid changes and distributions in different structures of soybean seeds during germination. Here, we applied mass spectrometry imaging (MSI) in conjunction with MS-based lipidomics to examine the lipid alterations in the embryo and cotyledon of soybean seeds during germination. To expand the coverage of lipid detection in soybean seeds, we used the novel techniques of matrix-assisted laser desorption/ionization (MALDI) and MALDI coupled with laser-postionization (MALDI-2). The results revealed that compared to MALDI, MALDI-2 enhanced the detected numbers and intensities of lipid species in various lipid classes, except for a few classes (e.g., sphingomyelin and phosphatidylcholine). Lipidomic data showed that compared to the embryo, the cotyledon demonstrated slower but similar lipid changes during germination. These changes included the reduced levels of glycerolipids, phospholipids, and sterols, as well as the increased levels of lysophospholipids. Data from MALDI&MALDI-2 MSI supported and complemented these lipidomic findings. Our work highlights the significance of integrating lipid profiles and distributions to enhance our understanding of the metabolic pathways involved in seed germination.
Seed germination plays a pivotal role in plant growth and undergoes many intricate biochemical changes including lipid metabolism. Nevertheless, little is known about lipid changes and distributions in different structures of soybean seeds during germination. Here, we applied mass spectrometry imaging (MSI) in conjunction with MS-based lipidomics to examine the lipid alterations in the embryo and cotyledon of soybean seeds during germination. To expand the coverage of lipid detection in soybean seeds, we used the novel techniques of matrix-assisted laser desorption/ionization (MALDI) and MALDI coupled with laser-postionization (MALDI-2). The results revealed that compared to MALDI, MALDI-2 enhanced the detected numbers and intensities of lipid species in various lipid classes, except for a few classes (e.g., sphingomyelin and phosphatidylcholine). Lipidomic data showed that compared to the embryo, the cotyledon demonstrated slower but similar lipid changes during germination. These changes included the reduced levels of glycerolipids, phospholipids, and sterols, as well as the increased levels of lysophospholipids. Data from MALDI&MALDI-2 MSI supported and complemented these lipidomic findings. Our work highlights the significance of integrating lipid profiles and distributions to enhance our understanding of the metabolic pathways involved in seed germination.
2025, 36(8): 110610
doi: 10.1016/j.cclet.2024.110610
Abstract:
The sensitive and selective monitoring of nitrogen dioxide (NO2) can have a significant impact on environmental monitoring and health protection. Unfortunately, commercial NO2 sensors largely suffer from poor detection sensitivity and high operating temperatures. In this study, we developed a sensitive room-temperature NO2 sensor based on an n-n heterojunction comprised of a Cs2AgInCl6 perovskite with chlorine vacancies (VCl) and TiO2 nanotube arrays (VCl-Cs2AgInCl6/TiO2 NTs). In this design, the large number of chlorine vacancies in the Cs2AgInCl6 perovskite act as active sites for oxygen adsorption and the subsequent sensing reaction. Benefitting from the formation of the n-n type heterojunction and the one-dimensional structure of the TiO2 nanotubes, the Fermi levels are aligned, thereby facilitating the efficient transport of charge carriers between the target gas and the sensing interface. The resulting VCl-Cs2AgInCl6/TiO2 NTs demonstrate a high response of 7.26 toward 1ppm of NO2 at room temperature, possess a detection limit as low as 20 ppb, and have outstanding performance stability. This work widens the application of perovskite materials and indicates their potential application in medical diagnostics, environmental monitoring, and smart sensing systems.
The sensitive and selective monitoring of nitrogen dioxide (NO2) can have a significant impact on environmental monitoring and health protection. Unfortunately, commercial NO2 sensors largely suffer from poor detection sensitivity and high operating temperatures. In this study, we developed a sensitive room-temperature NO2 sensor based on an n-n heterojunction comprised of a Cs2AgInCl6 perovskite with chlorine vacancies (VCl) and TiO2 nanotube arrays (VCl-Cs2AgInCl6/TiO2 NTs). In this design, the large number of chlorine vacancies in the Cs2AgInCl6 perovskite act as active sites for oxygen adsorption and the subsequent sensing reaction. Benefitting from the formation of the n-n type heterojunction and the one-dimensional structure of the TiO2 nanotubes, the Fermi levels are aligned, thereby facilitating the efficient transport of charge carriers between the target gas and the sensing interface. The resulting VCl-Cs2AgInCl6/TiO2 NTs demonstrate a high response of 7.26 toward 1ppm of NO2 at room temperature, possess a detection limit as low as 20 ppb, and have outstanding performance stability. This work widens the application of perovskite materials and indicates their potential application in medical diagnostics, environmental monitoring, and smart sensing systems.
2025, 36(8): 110613
doi: 10.1016/j.cclet.2024.110613
Abstract:
Common activations of sulfite (S(Ⅳ))-based advanced oxidation processes (AOPs) utilized metal ions and oxides as catalysts, which are constrained by challenges in catalyst recovery, inadequate stability, and susceptibility to secondary pollution in application. Calcium sulfite (CaSO3), one of the byproducts of flue gas desulfurization, is of interest in AOPs because of its ability to slowly release S(Ⅳ), low toxicity, and cost-effectiveness. Therefore, a heterogenous activator, molybdenum carbide (Mo2C) was selected to stimulate CaSO3 for typical antibiotic elimination. Benefiting from the dissociation form of HSO3− from CaSO3 and improved electron transfer of Mo2C at pH 6, the simulated target metronidazole (MTZ) can be removed by 85.65% with rate constant of 0.02424 min−1 under near-neutral circumstance. The combining determinations of quenching test, electron spin resonance spectrum, and reactive species probe demonstrated singlet oxygen (1O2) and sulfate radicals played leading role for MTZ decontamination. Characterization and theoretical calculation suggested the alteration of Mo valence state drove the activation of S(Ⅳ), and revealed that dissolved oxygen promoted the adsorption of HSO3− on the surface of Mo2C, then facilitating production of 1O2. The favorable stability and applicability for Mo2C/CaSO3 process indicated an applied prospect in actual pharmaceutical wastewater.
Common activations of sulfite (S(Ⅳ))-based advanced oxidation processes (AOPs) utilized metal ions and oxides as catalysts, which are constrained by challenges in catalyst recovery, inadequate stability, and susceptibility to secondary pollution in application. Calcium sulfite (CaSO3), one of the byproducts of flue gas desulfurization, is of interest in AOPs because of its ability to slowly release S(Ⅳ), low toxicity, and cost-effectiveness. Therefore, a heterogenous activator, molybdenum carbide (Mo2C) was selected to stimulate CaSO3 for typical antibiotic elimination. Benefiting from the dissociation form of HSO3− from CaSO3 and improved electron transfer of Mo2C at pH 6, the simulated target metronidazole (MTZ) can be removed by 85.65% with rate constant of 0.02424 min−1 under near-neutral circumstance. The combining determinations of quenching test, electron spin resonance spectrum, and reactive species probe demonstrated singlet oxygen (1O2) and sulfate radicals played leading role for MTZ decontamination. Characterization and theoretical calculation suggested the alteration of Mo valence state drove the activation of S(Ⅳ), and revealed that dissolved oxygen promoted the adsorption of HSO3− on the surface of Mo2C, then facilitating production of 1O2. The favorable stability and applicability for Mo2C/CaSO3 process indicated an applied prospect in actual pharmaceutical wastewater.
2025, 36(8): 110614
doi: 10.1016/j.cclet.2024.110614
Abstract:
Neuronal mitochondrial damage is the primary characteristic of Alzheimer's disease (AD); as mitochondrial microRNAs (miRNAs) are crucial for maintaining mitochondrial function, developing a detection system for mitochondrial miRNAs and applying it for AD treatment is of great significance. Herein, we report CeO2-DNA-RNA hybrid chain (DRP)/mitochondrial aptamers (MA) nanoclusters, formed using specially modified 5 nm sized cerium dioxide (CeO2) nanoparticles, to achieve AD diagnosis and treatment by targeting mitochondrial miRNA-204. First, nanomaterials with unique reactive oxygen species-scavenging functions could easily enter the central nervous system, and surface modification with mitochondrial aptamers facilitated successful mitochondrial targeting. Furthermore, surface modification of nanomaterials with DNA-RNA hybrid biological detection probes was used to detect miRNA-204 in AD and simultaneously perform gene-silencing therapy. In 3×Tg-AD model mice, CeO2-DRP/MA aggregated into neuronal mitochondria, silenced mitochondrial miRNA-204, and restored the damaged mitochondria for AD treatment. The promising diagnostic and therapeutic functions of CeO2-DRP/MA demonstrate its better performance as a diagnostic and therapeutic system targeting mitochondrial miRNA.
Neuronal mitochondrial damage is the primary characteristic of Alzheimer's disease (AD); as mitochondrial microRNAs (miRNAs) are crucial for maintaining mitochondrial function, developing a detection system for mitochondrial miRNAs and applying it for AD treatment is of great significance. Herein, we report CeO2-DNA-RNA hybrid chain (DRP)/mitochondrial aptamers (MA) nanoclusters, formed using specially modified 5 nm sized cerium dioxide (CeO2) nanoparticles, to achieve AD diagnosis and treatment by targeting mitochondrial miRNA-204. First, nanomaterials with unique reactive oxygen species-scavenging functions could easily enter the central nervous system, and surface modification with mitochondrial aptamers facilitated successful mitochondrial targeting. Furthermore, surface modification of nanomaterials with DNA-RNA hybrid biological detection probes was used to detect miRNA-204 in AD and simultaneously perform gene-silencing therapy. In 3×Tg-AD model mice, CeO2-DRP/MA aggregated into neuronal mitochondria, silenced mitochondrial miRNA-204, and restored the damaged mitochondria for AD treatment. The promising diagnostic and therapeutic functions of CeO2-DRP/MA demonstrate its better performance as a diagnostic and therapeutic system targeting mitochondrial miRNA.
2025, 36(8): 110615
doi: 10.1016/j.cclet.2024.110615
Abstract:
Micellar nanostructures formed by amphiphilic polymers are prone to dissociation when the in vivo environment changes. Polyprodrug micelles can cross-link with other hydrophobic drugs through non-covalent bonds, which has the advantage of fixed structure and avoids the use of chemical cross-linking agents. In this study, we prepared a polyprodrug with hydrophobic curcumin (CUR) and hydrophilic poly(ethylene glycol) (PEG) in the main chain through a click reaction between CUR derivatives containing azide groups and di-alkynly-capped PEG. Due to the presence of benzene rings in the structure of CUR, the polyprodrug can form non-covalent cross-linked nanoparticles (NCCL-CUR NPs) through hydrophobic and π-π stacking interaction. The structure, molecular weight, and self-assembly properties of the polyprodrug were characterized. The anti-cancer drug camptothecin (CPT) was encapsulated in the polyprodrug nanoparticles, producing dual-drug-loaded nanoparticles (abbreviated as CPT@NCCL-CUR NPs). The test results indicate that the NPs have reductive responsiveness and can release the original drugs CUR and CPT in phosphate buffer (PB) solution containing glutathione (GSH), while remaining stability in physiological environment. Cell and in vivo experiments further demonstrate that the dual-drug-loaded CPT@NCCL-CUR NPs can inhibit the growth of tumor through synergistic effects. This work provides a valuable approach for the preparation of amphiphilic polyprodrug with anti-tumor CUR as the backbone, and the stable dual-drug-loaded NPs containing both CUR and CPT through non-covalent cross-linking for synergistic therapy.
Micellar nanostructures formed by amphiphilic polymers are prone to dissociation when the in vivo environment changes. Polyprodrug micelles can cross-link with other hydrophobic drugs through non-covalent bonds, which has the advantage of fixed structure and avoids the use of chemical cross-linking agents. In this study, we prepared a polyprodrug with hydrophobic curcumin (CUR) and hydrophilic poly(ethylene glycol) (PEG) in the main chain through a click reaction between CUR derivatives containing azide groups and di-alkynly-capped PEG. Due to the presence of benzene rings in the structure of CUR, the polyprodrug can form non-covalent cross-linked nanoparticles (NCCL-CUR NPs) through hydrophobic and π-π stacking interaction. The structure, molecular weight, and self-assembly properties of the polyprodrug were characterized. The anti-cancer drug camptothecin (CPT) was encapsulated in the polyprodrug nanoparticles, producing dual-drug-loaded nanoparticles (abbreviated as CPT@NCCL-CUR NPs). The test results indicate that the NPs have reductive responsiveness and can release the original drugs CUR and CPT in phosphate buffer (PB) solution containing glutathione (GSH), while remaining stability in physiological environment. Cell and in vivo experiments further demonstrate that the dual-drug-loaded CPT@NCCL-CUR NPs can inhibit the growth of tumor through synergistic effects. This work provides a valuable approach for the preparation of amphiphilic polyprodrug with anti-tumor CUR as the backbone, and the stable dual-drug-loaded NPs containing both CUR and CPT through non-covalent cross-linking for synergistic therapy.
2025, 36(8): 110617
doi: 10.1016/j.cclet.2024.110617
Abstract:
Fluorescence-based imaging applications have been benefiting greatly from donor-acceptor (D-A)/donor-π-acceptor (D-π-A) fluorescent probes owing to their intramolecular charge transfer (ICT) nature and self-assembly behavior. In this study, we design and synthesize a hydrophilic D-A fluorescent probe, namely CHBA, which would self-assemble into interlaced textures down to nanoscale but disassemble by trace amount of water in fingertip area. Upon finger-pressing, it enables fingerprint imaging and covers level-1/2/3 fingerprint information, wherein the sweat pores can be mapped in both bright field model and fluorescence mode, capable of naked-eye-based similarity analysis for personal identity verification (PIV). Spectroscopic analysis and morphology study show that the working mechanism can be attributed to the selective water-erosion effect on the solid-liquid interphase under physical contact. The sweat pore information can be digitized by polar coordinate conversion, further allowing machine-learning-based analysis for PIV application. The final PIV accuracy reaches 100% for all the involved machine-learning models, with no erroneous judgements. A prototype of PIV system is constructed by integrating CHBA with artificial intelligence hardware, wherein the sweat pore imaging, data processing and the decision-making could be run in parallel, suggesting high feasibility in real-world application.
Fluorescence-based imaging applications have been benefiting greatly from donor-acceptor (D-A)/donor-π-acceptor (D-π-A) fluorescent probes owing to their intramolecular charge transfer (ICT) nature and self-assembly behavior. In this study, we design and synthesize a hydrophilic D-A fluorescent probe, namely CHBA, which would self-assemble into interlaced textures down to nanoscale but disassemble by trace amount of water in fingertip area. Upon finger-pressing, it enables fingerprint imaging and covers level-1/2/3 fingerprint information, wherein the sweat pores can be mapped in both bright field model and fluorescence mode, capable of naked-eye-based similarity analysis for personal identity verification (PIV). Spectroscopic analysis and morphology study show that the working mechanism can be attributed to the selective water-erosion effect on the solid-liquid interphase under physical contact. The sweat pore information can be digitized by polar coordinate conversion, further allowing machine-learning-based analysis for PIV application. The final PIV accuracy reaches 100% for all the involved machine-learning models, with no erroneous judgements. A prototype of PIV system is constructed by integrating CHBA with artificial intelligence hardware, wherein the sweat pore imaging, data processing and the decision-making could be run in parallel, suggesting high feasibility in real-world application.
2025, 36(8): 110620
doi: 10.1016/j.cclet.2024.110620
Abstract:
Ferroptosis is a new regulated cell death process executed by lipid peroxidation (LPO) of polyunsaturated fatty acids. Lipid droplets (LDs), as an important organelle for lipid storage and metabolism, are probably a major site of LPO and play critical roles in the regulation of ferroptosis. However, the detailed study on LPO in LDs has not been carried out because of the lack of LD-targeting tools for the in situ monitoring of LPO. Herein, the first LD-targeting LPO fluorescence probe (LD-LPO) has been developed. LD-LPO exhibits a rapid and selective fluorescence enhancement at 518 nm, which is unaffected by highly destructive reactive oxygen species (e.g., hydroxyl radical) and environmental factor changes (e.g., polarity and viscosity). LD-LPO is capable of targeting LDs and visualizing LPO within LDs in situ during erastin- or (1S,3R)-RSL3 (RSL3)-induced ferroptosis. Moreover, LD-LPO has also been used to image LPO in the ferroptosis-associated non-alcoholic fatty liver disease (NAFLD), and to evaluate the medicine treatment of NAFLD with saroglitazar, demonstrating its utility for monitoring LPO levels in biosystems. The favorable analytical and imaging performance of LD-LPO may allow its application in more ferroptosis-associated physiological and pathological processes.
Ferroptosis is a new regulated cell death process executed by lipid peroxidation (LPO) of polyunsaturated fatty acids. Lipid droplets (LDs), as an important organelle for lipid storage and metabolism, are probably a major site of LPO and play critical roles in the regulation of ferroptosis. However, the detailed study on LPO in LDs has not been carried out because of the lack of LD-targeting tools for the in situ monitoring of LPO. Herein, the first LD-targeting LPO fluorescence probe (LD-LPO) has been developed. LD-LPO exhibits a rapid and selective fluorescence enhancement at 518 nm, which is unaffected by highly destructive reactive oxygen species (e.g., hydroxyl radical) and environmental factor changes (e.g., polarity and viscosity). LD-LPO is capable of targeting LDs and visualizing LPO within LDs in situ during erastin- or (1S,3R)-RSL3 (RSL3)-induced ferroptosis. Moreover, LD-LPO has also been used to image LPO in the ferroptosis-associated non-alcoholic fatty liver disease (NAFLD), and to evaluate the medicine treatment of NAFLD with saroglitazar, demonstrating its utility for monitoring LPO levels in biosystems. The favorable analytical and imaging performance of LD-LPO may allow its application in more ferroptosis-associated physiological and pathological processes.
2025, 36(8): 110642
doi: 10.1016/j.cclet.2024.110642
Abstract:
Enantiomer identification is of paramount industrial value and physiological significance. Construction of sensitive chiral sensors with high enantiomeric discrimination ability is highly desirable. In this work, a chiral covalent organic framework/anodic aluminum oxide (c-COF/AAO) membrane was prepared for electrochemical enantioselective recognition and sensing. Benefiting from the remarkable asymmetry, the as-prepared nanofluidic c-COF/AAO presents a distinct ion current rectification (ICR) characteristic, enabling sensitive bioanalysis. In addition, owing to the large surface area, high chemical stability and perfect ion selectivity of chiral COF, the prepared c-COF/AAO membrane presents exceptionally selective mass transport and thereby enables excellent chiral discrimination for S-/R-Naproxen (S-/R-Npx) enantiomers. It is especially noteworthy that the detection limit is achieved as low as 3.88 pmol/L. These results raise the possibility for a facile, stable and low-cost method to carry out sensitive enantioselective recognition and detection.
Enantiomer identification is of paramount industrial value and physiological significance. Construction of sensitive chiral sensors with high enantiomeric discrimination ability is highly desirable. In this work, a chiral covalent organic framework/anodic aluminum oxide (c-COF/AAO) membrane was prepared for electrochemical enantioselective recognition and sensing. Benefiting from the remarkable asymmetry, the as-prepared nanofluidic c-COF/AAO presents a distinct ion current rectification (ICR) characteristic, enabling sensitive bioanalysis. In addition, owing to the large surface area, high chemical stability and perfect ion selectivity of chiral COF, the prepared c-COF/AAO membrane presents exceptionally selective mass transport and thereby enables excellent chiral discrimination for S-/R-Naproxen (S-/R-Npx) enantiomers. It is especially noteworthy that the detection limit is achieved as low as 3.88 pmol/L. These results raise the possibility for a facile, stable and low-cost method to carry out sensitive enantioselective recognition and detection.
2025, 36(8): 110643
doi: 10.1016/j.cclet.2024.110643
Abstract:
Monitoring the dynamics of cellular pseudopodia at nanoscale has become essential for understanding their diverse and complex functions in living cells. This is made possible by combining single-molecule localization microscopy (SMLM) with self-blinking dyes. However, existing self-blinking dyes often face limitations, such as nonspecific blinking and low photostability, which can bring background noise and yield erroneous localization signals, hindering their effectiveness for nanoscale visualization. Here, we present a method for long-term SMLM imaging of cellular pseudopodia dynamics using a blinkogenic probe that exhibits self-blinking activation upon molecular recognition. This approach enabled the precise tracking of various pseudopodia structures, including filopodia, lamellipodia, and (tunneling nanotubes)-nanoscale (TNTs), in living cells. We monitored the growth and fusion of filopodia, as well as the extension and shrinkage of lamellipodia, in real-time. Additionally, we identified two distinct fusion modes between filopodia and lamellipodia and captured the formation of TNTs and their interactions with filopodia, demonstrating the probe's utility in visualizing real-time pseudopodia dynamics at nanoscale.
Monitoring the dynamics of cellular pseudopodia at nanoscale has become essential for understanding their diverse and complex functions in living cells. This is made possible by combining single-molecule localization microscopy (SMLM) with self-blinking dyes. However, existing self-blinking dyes often face limitations, such as nonspecific blinking and low photostability, which can bring background noise and yield erroneous localization signals, hindering their effectiveness for nanoscale visualization. Here, we present a method for long-term SMLM imaging of cellular pseudopodia dynamics using a blinkogenic probe that exhibits self-blinking activation upon molecular recognition. This approach enabled the precise tracking of various pseudopodia structures, including filopodia, lamellipodia, and (tunneling nanotubes)-nanoscale (TNTs), in living cells. We monitored the growth and fusion of filopodia, as well as the extension and shrinkage of lamellipodia, in real-time. Additionally, we identified two distinct fusion modes between filopodia and lamellipodia and captured the formation of TNTs and their interactions with filopodia, demonstrating the probe's utility in visualizing real-time pseudopodia dynamics at nanoscale.
2025, 36(8): 110647
doi: 10.1016/j.cclet.2024.110647
Abstract:
Pyrazolidinones, as significant analogs of β-lactam antibiotics, have garnered substantial interest for their enantioselective synthesis. Azomethine imines, recognized as valuable building blocks for the construction of these nitrogen-containing compounds, underscore the continuous pursuit of novel building blocks and reaction methodologies within the chemical community. In this paper, we present a cascade cyclization between alkenyl azomethine imines and furan-2(5H)-one to generate chiral coronal polyheterocyclic compounds with high yields and enantioselectivities, catalyzed by dipeptide-derived phosphonium salts. In-vitro biological activity assays highlight the potential of these chiral compounds in drug discovery. Additionally, density functional theory (DFT) calculations elucidate the pivotal role of phosphonium salts, demonstrating their cooperative activations via hydrogen bonding and ion-pairing interactions.
Pyrazolidinones, as significant analogs of β-lactam antibiotics, have garnered substantial interest for their enantioselective synthesis. Azomethine imines, recognized as valuable building blocks for the construction of these nitrogen-containing compounds, underscore the continuous pursuit of novel building blocks and reaction methodologies within the chemical community. In this paper, we present a cascade cyclization between alkenyl azomethine imines and furan-2(5H)-one to generate chiral coronal polyheterocyclic compounds with high yields and enantioselectivities, catalyzed by dipeptide-derived phosphonium salts. In-vitro biological activity assays highlight the potential of these chiral compounds in drug discovery. Additionally, density functional theory (DFT) calculations elucidate the pivotal role of phosphonium salts, demonstrating their cooperative activations via hydrogen bonding and ion-pairing interactions.
2025, 36(8): 110648
doi: 10.1016/j.cclet.2024.110648
Abstract:
Herein, a ternary supramolecular assembly (BPP-BQ⊂CB[8]-SCD) is successfully constructed by a bromophenylpyridine-tethered-bromoisoquinoline (BPP-BQ), cucurbit[8]uril (CB[8]) and sulfonated β-cyclodextrin (SCD) via successive assembling way, exhibiting progressively enhanced green room-temperature phosphorescence (RTP). The self-aggregates of BPP-BQ⊂CB[8]-SCD accommodate an energy acceptor rhodamine B (RhB) to form a light-harvesting system (BPP-BQ⊂CB[8]-SCD@RhB) with further enhanced yellow long-lifetime luminescence with large Stokes shift based on triplet-singlet Förster resonance energy transfer (TS-FRET). Crucially, the introduction of a photoactive diarylethene achieves the long-lived photoluminescence of BPP-BQ⊂CB[8]-SCD@RhB to be switched with the efficiency of up to 98% through logically ordered lowering/enhancing RTP performance of the energy donor and intercepting/restoring TS-FRET pathway, when stimulated by host-guest competition and light illumination in sequence. Moreover, BPP-BQ⊂CB[8]-SCD@RhB is evenly doped into polyvinyl alcohol or polyacrylamide to obtain high-performance luminescent films with long afterglow. The abovementioned logically ordered stimulus-switched long-lived emission enables the light-harvesting system in both solution and solid state to be applied in high-security-level information encryption and transformation, and anti-counterfeiting.
Herein, a ternary supramolecular assembly (BPP-BQ⊂CB[8]-SCD) is successfully constructed by a bromophenylpyridine-tethered-bromoisoquinoline (BPP-BQ), cucurbit[8]uril (CB[8]) and sulfonated β-cyclodextrin (SCD) via successive assembling way, exhibiting progressively enhanced green room-temperature phosphorescence (RTP). The self-aggregates of BPP-BQ⊂CB[8]-SCD accommodate an energy acceptor rhodamine B (RhB) to form a light-harvesting system (BPP-BQ⊂CB[8]-SCD@RhB) with further enhanced yellow long-lifetime luminescence with large Stokes shift based on triplet-singlet Förster resonance energy transfer (TS-FRET). Crucially, the introduction of a photoactive diarylethene achieves the long-lived photoluminescence of BPP-BQ⊂CB[8]-SCD@RhB to be switched with the efficiency of up to 98% through logically ordered lowering/enhancing RTP performance of the energy donor and intercepting/restoring TS-FRET pathway, when stimulated by host-guest competition and light illumination in sequence. Moreover, BPP-BQ⊂CB[8]-SCD@RhB is evenly doped into polyvinyl alcohol or polyacrylamide to obtain high-performance luminescent films with long afterglow. The abovementioned logically ordered stimulus-switched long-lived emission enables the light-harvesting system in both solution and solid state to be applied in high-security-level information encryption and transformation, and anti-counterfeiting.
2025, 36(8): 110649
doi: 10.1016/j.cclet.2024.110649
Abstract:
Covalent organic frameworks (COFs) have demonstrated great potential in chromatographic separation because of unique structure and superior performance. Herein, single-crystal three-dimensional (3D) COFs with regular morphology, good monodispersity and high specific surface area, were used as a stationary phase for high-performance liquid chromatography (HPLC). The single-crystal 3D COFs packed column not only exhibits high efficiency in separating hydrophobic molecules involving substituted benzenes, halogenated benzenes, halogenated nitrobenzenes, aromatic amines, aromatic hydrocarbons (PAHs) and phthalate esters (PAEs), but also achieves baseline separation of acenaphthene and acenaphthylene with similar physical and chemical properties as well as environmental pollutants, which cannot be quickly separated on commercial C18 column and a polycrystalline 3D COFs packed column. Especially, the column efficiency of 17303-24255 plates/m was obtained for PAEs, and the resolution values for acenaphthene and acenaphthylene, and carbamazepine (CBZ) and carbamazepine-10, 11-epoxide (CBZEP) were 1.7 and 2.2, respectively. This successful application not only confirmed the great potential of the single-crystal 3D COFs in HPLC separation of the organic molecules, but also facilitates the application of COFs in separation science.
Covalent organic frameworks (COFs) have demonstrated great potential in chromatographic separation because of unique structure and superior performance. Herein, single-crystal three-dimensional (3D) COFs with regular morphology, good monodispersity and high specific surface area, were used as a stationary phase for high-performance liquid chromatography (HPLC). The single-crystal 3D COFs packed column not only exhibits high efficiency in separating hydrophobic molecules involving substituted benzenes, halogenated benzenes, halogenated nitrobenzenes, aromatic amines, aromatic hydrocarbons (PAHs) and phthalate esters (PAEs), but also achieves baseline separation of acenaphthene and acenaphthylene with similar physical and chemical properties as well as environmental pollutants, which cannot be quickly separated on commercial C18 column and a polycrystalline 3D COFs packed column. Especially, the column efficiency of 17303-24255 plates/m was obtained for PAEs, and the resolution values for acenaphthene and acenaphthylene, and carbamazepine (CBZ) and carbamazepine-10, 11-epoxide (CBZEP) were 1.7 and 2.2, respectively. This successful application not only confirmed the great potential of the single-crystal 3D COFs in HPLC separation of the organic molecules, but also facilitates the application of COFs in separation science.
2025, 36(8): 110650
doi: 10.1016/j.cclet.2024.110650
Abstract:
N-doped graphite carbon sphere coated cobalt nanoparticle catalyst (Co@C-N-900), prepared by solvothermal-calcination method, is applied to activate peroxymonosulfate (PMS) for bisphenol A (BPA) elimination. The outcomes demonstrate that the Co@C-N-900 could effectively activate PMS, thereby causing efficient removal of BPA in water. In addition, the Co@C-N-900/PMS system also has the advantages of low metal leaching, applicability in high salinity environments, good selectivity and stability. Further investigations using electron paramagnetic resonance, chronoamperometry, and quenching experiments demonstrated that the Co@C-N-900/PMS system is a typical non-radical route with singlet oxygen (1O2) as the main reactive oxygen species (ROS). Density functional theory calculations (DFT) indicate that N-doping can effectively regulate the charge distribution on the catalyst surface, generating acidic/alkaline sites favorable for PMS adsorption and activation. Furthermore, it also can enhance the interaction and charge transfer capacity between the Co@C-N-900 and PMS. Lastly, LC-QTOF-MS/MS analysis revealed two possible BPA degradation pathways: (1) 1O2 attacked the isopropyl group in BPA between the two phenyl groups, causing β-scission to occur. (2) Following the oxidation of the hydroxyl group in the aromatic ring of BPA, 1O2 could cause further β-scission. The prepared Co@C-N-900 catalyst is a very promising catalyst, which would offer a workable remedy for treating water pollution.
N-doped graphite carbon sphere coated cobalt nanoparticle catalyst (Co@C-N-900), prepared by solvothermal-calcination method, is applied to activate peroxymonosulfate (PMS) for bisphenol A (BPA) elimination. The outcomes demonstrate that the Co@C-N-900 could effectively activate PMS, thereby causing efficient removal of BPA in water. In addition, the Co@C-N-900/PMS system also has the advantages of low metal leaching, applicability in high salinity environments, good selectivity and stability. Further investigations using electron paramagnetic resonance, chronoamperometry, and quenching experiments demonstrated that the Co@C-N-900/PMS system is a typical non-radical route with singlet oxygen (1O2) as the main reactive oxygen species (ROS). Density functional theory calculations (DFT) indicate that N-doping can effectively regulate the charge distribution on the catalyst surface, generating acidic/alkaline sites favorable for PMS adsorption and activation. Furthermore, it also can enhance the interaction and charge transfer capacity between the Co@C-N-900 and PMS. Lastly, LC-QTOF-MS/MS analysis revealed two possible BPA degradation pathways: (1) 1O2 attacked the isopropyl group in BPA between the two phenyl groups, causing β-scission to occur. (2) Following the oxidation of the hydroxyl group in the aromatic ring of BPA, 1O2 could cause further β-scission. The prepared Co@C-N-900 catalyst is a very promising catalyst, which would offer a workable remedy for treating water pollution.
2025, 36(8): 110651
doi: 10.1016/j.cclet.2024.110651
Abstract:
Despite the considerable potentiality of photodynamic therapy (PDT) in cancer treatment, conventional hydrophobic photosensitizers cause obstacles for in vivo application, while their inert structures are difficult to chemically modify. Additionally, undesirable tumor hypoxia resulting from oxygen consumption also discounts the therapeutic efficacy of PDT. Herein, we developed a self-strengthened nanogel with reactive oxygen species (ROS) trigger-explosive property. IR780 was spontaneous assembled within the conical cavity of cyclodextrin (β-CD) using host-guest interactions, while adjacent IR780 molecules on the dextrin backbone with hydrophobic interaction and π conjugation induced nanogel formation. Simultaneously, hydrophilic compound tirapazamine (TPZ) was incorporated into nanogel for synergistic tumor treatment. The inherent high levels of ROS in tumor can break down boronic ester bond linker of nanogel, initiating its disintegration. Furthermore, our findings indicate the ROS level (including H2O2 and 1O2) can be transiently enhanced during PDT process at the animal level, which accelerates the explosion of nanogel. Notably, the IR780@β-CD module exhibited enhanced ROS generation efficiency during PDT with the continues explosion of nanogel, which further strengthens nanogel disintegration, tumor phototherapy and cargo releasement. Additionally, the released TPZ is activated under hypoxic conditions after PDT treatment, addressing the limitations of PDT and facilitating multi-synergistic tumor treatment.
Despite the considerable potentiality of photodynamic therapy (PDT) in cancer treatment, conventional hydrophobic photosensitizers cause obstacles for in vivo application, while their inert structures are difficult to chemically modify. Additionally, undesirable tumor hypoxia resulting from oxygen consumption also discounts the therapeutic efficacy of PDT. Herein, we developed a self-strengthened nanogel with reactive oxygen species (ROS) trigger-explosive property. IR780 was spontaneous assembled within the conical cavity of cyclodextrin (β-CD) using host-guest interactions, while adjacent IR780 molecules on the dextrin backbone with hydrophobic interaction and π conjugation induced nanogel formation. Simultaneously, hydrophilic compound tirapazamine (TPZ) was incorporated into nanogel for synergistic tumor treatment. The inherent high levels of ROS in tumor can break down boronic ester bond linker of nanogel, initiating its disintegration. Furthermore, our findings indicate the ROS level (including H2O2 and 1O2) can be transiently enhanced during PDT process at the animal level, which accelerates the explosion of nanogel. Notably, the IR780@β-CD module exhibited enhanced ROS generation efficiency during PDT with the continues explosion of nanogel, which further strengthens nanogel disintegration, tumor phototherapy and cargo releasement. Additionally, the released TPZ is activated under hypoxic conditions after PDT treatment, addressing the limitations of PDT and facilitating multi-synergistic tumor treatment.
In-situ reconstructed Cu/NiO nanosheets synergistically boosting nitrate electroreduction to ammonia
2025, 36(8): 110657
doi: 10.1016/j.cclet.2024.110657
Abstract:
Electrochemical reduction of nitrate (NO3−) serves as an eco-friendly friendly alternative to the conventional Haber-Bosch ammonia (NH3) synthesis process. The Cu electrocatalyst is widely recognized for its strong adsorption capacity towards nitrate, but its limited H adsorption and slow hydrogenation of oxynitride intermediates hinder the efficiency of converting NO3− into NH3. Herein, a series of nanocomposite catalysts composed of CuO nanostructure with low NiO content that grow in-situ on carbon paper (CuO/NiOx-CP) were synthesized via hydrothermal method and calcination for enhanced nitrate electroreduction utilizing the strong nitrate adsorption capacity of copper and excellent water dissociation ability of NiO to supply hydrogen free radicals (•H). In-situ Raman spectroscopy reveals dynamic reconstruction of Cu/NiOx during the electrochemical nitrate reduction process from CuO/NiOx. Due to the synergistic effect of Cu and NiO, a high Faradaic efficiency (FE, ~97.9%) and yield rate (YR, 391.5 µmol h−1 cm−2) of ammonia are achieved on CuO/NiO2.3%-CP. Electron paramagnetic resonance (EPR) proves that the presence of NiO enhances the generation of •H, which can be rapidly consumed during nitrate reduction process. Density functional theory (DFT) calculations indicate that the activation energy of NiO (0.57 eV) is much lower than Cu (0.84 eV) for water splitting to generate •H, thus facilitating *NO hydrogenations. This drives us to create more effective catalysts for nitrate reduction under neutral conditions by promoting H2O dissociation.
Electrochemical reduction of nitrate (NO3−) serves as an eco-friendly friendly alternative to the conventional Haber-Bosch ammonia (NH3) synthesis process. The Cu electrocatalyst is widely recognized for its strong adsorption capacity towards nitrate, but its limited H adsorption and slow hydrogenation of oxynitride intermediates hinder the efficiency of converting NO3− into NH3. Herein, a series of nanocomposite catalysts composed of CuO nanostructure with low NiO content that grow in-situ on carbon paper (CuO/NiOx-CP) were synthesized via hydrothermal method and calcination for enhanced nitrate electroreduction utilizing the strong nitrate adsorption capacity of copper and excellent water dissociation ability of NiO to supply hydrogen free radicals (•H). In-situ Raman spectroscopy reveals dynamic reconstruction of Cu/NiOx during the electrochemical nitrate reduction process from CuO/NiOx. Due to the synergistic effect of Cu and NiO, a high Faradaic efficiency (FE, ~97.9%) and yield rate (YR, 391.5 µmol h−1 cm−2) of ammonia are achieved on CuO/NiO2.3%-CP. Electron paramagnetic resonance (EPR) proves that the presence of NiO enhances the generation of •H, which can be rapidly consumed during nitrate reduction process. Density functional theory (DFT) calculations indicate that the activation energy of NiO (0.57 eV) is much lower than Cu (0.84 eV) for water splitting to generate •H, thus facilitating *NO hydrogenations. This drives us to create more effective catalysts for nitrate reduction under neutral conditions by promoting H2O dissociation.
2025, 36(8): 110660
doi: 10.1016/j.cclet.2024.110660
Abstract:
Mechanically robust transparent materials that can be repaired have many advantages for practical applications. In this study, a supramolecular strategy is used to introduce healing capacity and mechanical toughness into artificial glass. Non-covalent/dynamic covalent polymerization of thioctic acid (TA) and (±)-trans-1,2-diaminocyclohexane (DC) generates supramolecular glass with versatile attractive properties, including high optical transmittance (>90%), strong impact resistance (2.47 kJ/m2), good mechanical strength (21.6 MPa), and high rigidity (65 HD on Shore hardness). The adhesive bonding of poly[TA], along with its photopolymerization behavior, enables damaged areas in poly[DC/TA] to be rebuilt in-situ. Subsequent solidification and hardening of the repaired areas are notably accelerated by hydrogen bonding between poly[TA] and DC. The newly healed poly[DC/TA] exhibits considerable optical and mechanical properties compared to those of untreated poly[DC/TA]. This study presents a new design concept for constructing the high-performance glass from low-molecular-weight organic compounds.
Mechanically robust transparent materials that can be repaired have many advantages for practical applications. In this study, a supramolecular strategy is used to introduce healing capacity and mechanical toughness into artificial glass. Non-covalent/dynamic covalent polymerization of thioctic acid (TA) and (±)-trans-1,2-diaminocyclohexane (DC) generates supramolecular glass with versatile attractive properties, including high optical transmittance (>90%), strong impact resistance (2.47 kJ/m2), good mechanical strength (21.6 MPa), and high rigidity (65 HD on Shore hardness). The adhesive bonding of poly[TA], along with its photopolymerization behavior, enables damaged areas in poly[DC/TA] to be rebuilt in-situ. Subsequent solidification and hardening of the repaired areas are notably accelerated by hydrogen bonding between poly[TA] and DC. The newly healed poly[DC/TA] exhibits considerable optical and mechanical properties compared to those of untreated poly[DC/TA]. This study presents a new design concept for constructing the high-performance glass from low-molecular-weight organic compounds.
2025, 36(8): 110662
doi: 10.1016/j.cclet.2024.110662
Abstract:
Radioactive microspheres have demonstrated excellent therapeutic effects and good tolerance in the treatment of unresectable primary and secondary liver malignancies. This is attributed to precise embolization and potent anti-tumor effect. However, certain limitations such as unstable loading, perfusion stasis, heterogeneous distribution, ectopic distribution, and insufficient dosage, restrict their clinical application. Herein, a novel personalized Y-90 carbon microsphere with high uniformity, high specific activity and high availability (90Y-HUACM) is presented. It is synthesized through planar molecular complex adsorption and chemical deposition solidification. 90Y-HUACM exhibited controllable size, excellent biocompatibility, outstanding in vitro and in vivo stability. The radiolabeling efficiency of Y-90 exceeded 99% and the leaching rate of Y-90 is far below 0.1%. Furthermore, the excellent anti-tumor effect, nuclide loading stability, anti-reflux characteristics, precise embolization, and biosafety of 90Y-HUACM were validated in a rabbit VX2 liver tumor model. In summary, this new, high-performance, and customizable radioactive microsphere provides a superior choice for selective internal radiation treatment of advanced liver cancer is expected to be rapidly applied in clinical practice.
Radioactive microspheres have demonstrated excellent therapeutic effects and good tolerance in the treatment of unresectable primary and secondary liver malignancies. This is attributed to precise embolization and potent anti-tumor effect. However, certain limitations such as unstable loading, perfusion stasis, heterogeneous distribution, ectopic distribution, and insufficient dosage, restrict their clinical application. Herein, a novel personalized Y-90 carbon microsphere with high uniformity, high specific activity and high availability (90Y-HUACM) is presented. It is synthesized through planar molecular complex adsorption and chemical deposition solidification. 90Y-HUACM exhibited controllable size, excellent biocompatibility, outstanding in vitro and in vivo stability. The radiolabeling efficiency of Y-90 exceeded 99% and the leaching rate of Y-90 is far below 0.1%. Furthermore, the excellent anti-tumor effect, nuclide loading stability, anti-reflux characteristics, precise embolization, and biosafety of 90Y-HUACM were validated in a rabbit VX2 liver tumor model. In summary, this new, high-performance, and customizable radioactive microsphere provides a superior choice for selective internal radiation treatment of advanced liver cancer is expected to be rapidly applied in clinical practice.
2025, 36(8): 110676
doi: 10.1016/j.cclet.2024.110676
Abstract:
Purely organic room-temperature phosphorescence (RTP) is current hotspot in the research fields of chemistry, biology, materials etc. Herein, we report that photo-thermal double response reversible ultralong RTP flexible elastic material with multicolor delayed fluorescence, which is constructed by 4-biphenylboronic acid (BOH), polyethylene glycol, 2,2-bis(hydroxymethyl)propionic acid, isophorone diamine and isophorone diisocyanate copolymer. Importantly, the supramolecular phosphorescent elastomer not only exhibits extending RTP emission with a lifetime up to 1.21 s, but also gives a visible afterglow of 20 s via encapsulation of BOH unities by the deep cavities of hydroxypropyl-β-cyclodextrin (β-CD-HP) and in situ polymerization. Especially, after doping organic dyes (Fluorescein isothiocyanate, Sulforhodamine 101, Rhodamine B), supramolecular phosphorescent elastomer achieves multicolor delayed fluorescence realized by RTP energy transfer from phosphorescent donor to dye acceptors, which possesses reversible photo-thermal responsiveness and maintains high efficiency in delayed emission even after dozens of cycles. Present research provides a new approach for constructing multicolor delayed fluorescent supramolecular elastomers.
Purely organic room-temperature phosphorescence (RTP) is current hotspot in the research fields of chemistry, biology, materials etc. Herein, we report that photo-thermal double response reversible ultralong RTP flexible elastic material with multicolor delayed fluorescence, which is constructed by 4-biphenylboronic acid (BOH), polyethylene glycol, 2,2-bis(hydroxymethyl)propionic acid, isophorone diamine and isophorone diisocyanate copolymer. Importantly, the supramolecular phosphorescent elastomer not only exhibits extending RTP emission with a lifetime up to 1.21 s, but also gives a visible afterglow of 20 s via encapsulation of BOH unities by the deep cavities of hydroxypropyl-β-cyclodextrin (β-CD-HP) and in situ polymerization. Especially, after doping organic dyes (Fluorescein isothiocyanate, Sulforhodamine 101, Rhodamine B), supramolecular phosphorescent elastomer achieves multicolor delayed fluorescence realized by RTP energy transfer from phosphorescent donor to dye acceptors, which possesses reversible photo-thermal responsiveness and maintains high efficiency in delayed emission even after dozens of cycles. Present research provides a new approach for constructing multicolor delayed fluorescent supramolecular elastomers.
2025, 36(8): 110705
doi: 10.1016/j.cclet.2024.110705
Abstract:
A wide range of isoquinoline ring-modified Quinap oxides with different steric and electronic variations have been constructed through a palladium-catalyzed imidoylative cyclization of arylethenyl isocyanides with 2-diphenylphosphinyl-1-naphthyl bromides. The Pd-catalysis plays dual roles in the formation of both axial C–C bond and isoquinoline ring. This de novo synthetic strategy features good functional group tolerance, high yields and easy scale-up, providing Quinap derivatives with substitution patterns that could not be obtained using coupling reactions. Chiral ligands 7 and 12 can be readily prepared by transformation of the resulting Quinap oxide to their BINOL esters, and have been proven to be superb chiral ligands for the copper-catalyzed enantioselective A3-coupling and alkynylation of quinoline reactions. In general, the enantioselectivies obtained using ligands 7 and 12 are excellent, and the ee values are higher than those using Quinap as ligand, even three times higher in some cases. Mechanism studies revealed that a monomeric copper(Ⅰ) complex bearing a single chiral ligand was formed and served as the catalytically active species.
A wide range of isoquinoline ring-modified Quinap oxides with different steric and electronic variations have been constructed through a palladium-catalyzed imidoylative cyclization of arylethenyl isocyanides with 2-diphenylphosphinyl-1-naphthyl bromides. The Pd-catalysis plays dual roles in the formation of both axial C–C bond and isoquinoline ring. This de novo synthetic strategy features good functional group tolerance, high yields and easy scale-up, providing Quinap derivatives with substitution patterns that could not be obtained using coupling reactions. Chiral ligands 7 and 12 can be readily prepared by transformation of the resulting Quinap oxide to their BINOL esters, and have been proven to be superb chiral ligands for the copper-catalyzed enantioselective A3-coupling and alkynylation of quinoline reactions. In general, the enantioselectivies obtained using ligands 7 and 12 are excellent, and the ee values are higher than those using Quinap as ligand, even three times higher in some cases. Mechanism studies revealed that a monomeric copper(Ⅰ) complex bearing a single chiral ligand was formed and served as the catalytically active species.
2025, 36(8): 110706
doi: 10.1016/j.cclet.2024.110706
Abstract:
In the current era marked by energy shortages, the advancement of nuclear energy stands as an inevitable progression. The reprocessing of spent nuclear fuel plays a crucial role in determining the sustainability of nuclear energy as a viable energy source. Among these processes, the separation and recovery of Pu(Ⅳ) from high-level liquid waste (HLLW) hold paramount significance in terms of safety and strategic implications. Herein, this work focused on the synthesis of two acid- and radiation-resistant pyridine-based sp2c-COFs (COF-IHEP3 and COF-IHEP4), followed by the creation of two pyridine-based ionized sp2c-COFs named COF-IHEP3-CH3NO3 and COF-IHEP4-CH3NO3 through post-modification. These materials have potential anion exchange capacity for the selective separation of Pu(Ⅳ) in highly acidic conditions. Notably, in 8 mol/L nitric acid solution, COF-IHEP3-CH3NO3 demonstrated the capability to eliminate plutonium within 20 min in 98% removal efficiency with a Kd value of 2450 mL/g. Experimental and theoretical analysis suggest that the ionized sp2c-COFs exhibit exceptional stability, selectivity, and prevention of secondary contamination towards Pu(Ⅳ) in the presence of multiple ions environments. In short, this work provides an appropriate anion exchange strategy to design ionic sp2c-COFs as a promising platform for Pu(Ⅳ) recovery from HLLW.
In the current era marked by energy shortages, the advancement of nuclear energy stands as an inevitable progression. The reprocessing of spent nuclear fuel plays a crucial role in determining the sustainability of nuclear energy as a viable energy source. Among these processes, the separation and recovery of Pu(Ⅳ) from high-level liquid waste (HLLW) hold paramount significance in terms of safety and strategic implications. Herein, this work focused on the synthesis of two acid- and radiation-resistant pyridine-based sp2c-COFs (COF-IHEP3 and COF-IHEP4), followed by the creation of two pyridine-based ionized sp2c-COFs named COF-IHEP3-CH3NO3 and COF-IHEP4-CH3NO3 through post-modification. These materials have potential anion exchange capacity for the selective separation of Pu(Ⅳ) in highly acidic conditions. Notably, in 8 mol/L nitric acid solution, COF-IHEP3-CH3NO3 demonstrated the capability to eliminate plutonium within 20 min in 98% removal efficiency with a Kd value of 2450 mL/g. Experimental and theoretical analysis suggest that the ionized sp2c-COFs exhibit exceptional stability, selectivity, and prevention of secondary contamination towards Pu(Ⅳ) in the presence of multiple ions environments. In short, this work provides an appropriate anion exchange strategy to design ionic sp2c-COFs as a promising platform for Pu(Ⅳ) recovery from HLLW.
2025, 36(8): 110707
doi: 10.1016/j.cclet.2024.110707
Abstract:
Designing efficient, recyclable, and low-cost catalysts is crucial for the synthesis of quinoxaline derivatives. In this context, a novel N-stable Co2P nano-catalyst (CoP@NC-1.5) was developed using a template-sacrificial approach. The catalyst demonstrated a broad substrate scope and good functional group tolerance, achieving yields of up to 84%. Additionally, the catalyst exhibited reusability and can be recycled up to three times. The CoP@NC-1.5 was characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results indicated that the catalyst contained Co2P nanoparticles. The X-ray photoelectron spectroscopy (XPS) further confirms the presence of Co-P. Analysis of the characterization data and experimental results revealed that the active site of the catalyst comprises N-stable Co2P nanoparticles.
Designing efficient, recyclable, and low-cost catalysts is crucial for the synthesis of quinoxaline derivatives. In this context, a novel N-stable Co2P nano-catalyst (CoP@NC-1.5) was developed using a template-sacrificial approach. The catalyst demonstrated a broad substrate scope and good functional group tolerance, achieving yields of up to 84%. Additionally, the catalyst exhibited reusability and can be recycled up to three times. The CoP@NC-1.5 was characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results indicated that the catalyst contained Co2P nanoparticles. The X-ray photoelectron spectroscopy (XPS) further confirms the presence of Co-P. Analysis of the characterization data and experimental results revealed that the active site of the catalyst comprises N-stable Co2P nanoparticles.
2025, 36(8): 110730
doi: 10.1016/j.cclet.2024.110730
Abstract:
The development of organic frameworks with radical skeletons is desired. In this study, we report the development of a novel two-dimensional radical halogen-bonded organic framework (XOF). The radical monomer, benzimidazole triphenylmethyl (BTTM), was synthesized through the coupling of TTM radicals with benzimidazole. Initially, the benzimidazole units were coordinated with Ag+ ions to create a [N···Ag···N]+ framework. Subsequently, the addition of iodine led to the in situ replacement of Ag+ with I+ ions, forming [N···I···N]+ linkers and resulting in the creation of the XOF structure. The resulting XOF-HBTTM and XOF-BTTM structures demonstrated good-crystallinity, confirmed by PXRD, HR-TEM, SEAD, and SAXS analyses. EPR measurements confirmed the preservation of radical characteristics within the XOF framework. Furthermore, SQUID measurements indicated that XOF-BTTM exhibits spin moments of S = 1/2 at 2 K, with a saturated magnetization strength peaking at 4.10 emu/g, a notable enhancement compared to 1.87 emu/g for the BTTM monomer. This improvement in magnetism is attributed to the extended spin density distribution and the presence of [N···I···N]+ interactions, as suggested by DFT calculations. Additionally, the radical XOF-BTTM exhibited significantly enhanced electrical conductivity, reaching up to 1.30 × 10−4 S/cm, which is two orders of magnitude higher than that of XOF-HBTTM. This increased conductivity is linked to a reduced HOMO-LUMO gap, higher carrier density, and the incorporation of triphenylmethyl radicals within the framework. This research highlights the potential of benzimidazolyl motifs in constructing functional XOFs and advances our understanding of radical organic frameworks.
The development of organic frameworks with radical skeletons is desired. In this study, we report the development of a novel two-dimensional radical halogen-bonded organic framework (XOF). The radical monomer, benzimidazole triphenylmethyl (BTTM), was synthesized through the coupling of TTM radicals with benzimidazole. Initially, the benzimidazole units were coordinated with Ag+ ions to create a [N···Ag···N]+ framework. Subsequently, the addition of iodine led to the in situ replacement of Ag+ with I+ ions, forming [N···I···N]+ linkers and resulting in the creation of the XOF structure. The resulting XOF-HBTTM and XOF-BTTM structures demonstrated good-crystallinity, confirmed by PXRD, HR-TEM, SEAD, and SAXS analyses. EPR measurements confirmed the preservation of radical characteristics within the XOF framework. Furthermore, SQUID measurements indicated that XOF-BTTM exhibits spin moments of S = 1/2 at 2 K, with a saturated magnetization strength peaking at 4.10 emu/g, a notable enhancement compared to 1.87 emu/g for the BTTM monomer. This improvement in magnetism is attributed to the extended spin density distribution and the presence of [N···I···N]+ interactions, as suggested by DFT calculations. Additionally, the radical XOF-BTTM exhibited significantly enhanced electrical conductivity, reaching up to 1.30 × 10−4 S/cm, which is two orders of magnitude higher than that of XOF-HBTTM. This increased conductivity is linked to a reduced HOMO-LUMO gap, higher carrier density, and the incorporation of triphenylmethyl radicals within the framework. This research highlights the potential of benzimidazolyl motifs in constructing functional XOFs and advances our understanding of radical organic frameworks.
2025, 36(8): 110734
doi: 10.1016/j.cclet.2024.110734
Abstract:
Glycosyl imidates are among the pioneering donors for catalytic glycosylation. We report a new generation of imidates featuring the presence of a pentafluorophenyl group, introduced via substitution on imidoyl fluoride which is easily prepared, stable and user-friendly. The resulting donors exhibit exceptional shelf stability while can be readily activated to achieve high-yielding glycosylation, encompassing comprehensively aldosyl, ketosyl and ulosonyl donors, and both O- and N-glycosylation acceptors. Notably, the reactivity gradient across different generations of imidates, coupled with the accessible imidate acceptor from selective reaction of imidoyl fluoride at the anomeric hydroxyl group, enables a fully catalytic one-pot synthesis of oligosaccharides.
Glycosyl imidates are among the pioneering donors for catalytic glycosylation. We report a new generation of imidates featuring the presence of a pentafluorophenyl group, introduced via substitution on imidoyl fluoride which is easily prepared, stable and user-friendly. The resulting donors exhibit exceptional shelf stability while can be readily activated to achieve high-yielding glycosylation, encompassing comprehensively aldosyl, ketosyl and ulosonyl donors, and both O- and N-glycosylation acceptors. Notably, the reactivity gradient across different generations of imidates, coupled with the accessible imidate acceptor from selective reaction of imidoyl fluoride at the anomeric hydroxyl group, enables a fully catalytic one-pot synthesis of oligosaccharides.
2025, 36(8): 110741
doi: 10.1016/j.cclet.2024.110741
Abstract:
The development of multi-stimuli-responsive luminescent system to address emerging demands is essential in anti-counterfeiting field. Herein, a photoswitchable system was reported, which was constructed from photoacid sulfonato-merocyanine (MEH-D) serving as H+ donor and diarylethene derivative (DAE-A1) as acceptor. After capturing 2 equiv. HCl, the obtained fluorescent molecule DAE-A1-H showed solvatochromic property. Further on, benefiting from that MEH-D released protons and became a ring-closed isomer spiropyran (SP-D) under 440 nm irradiation, DAE-A1 was protonated, turning on fluorescence effect was realized in DAE-A1/MEH-D. In dark, a photo-activated reversible process was realized with SP-D changed to MEH-D in situ system. In addition, the OF-DAE-A1-H/SP-D could efficiently and reversibly switch on/off its luminescence upon irradiation by UV–vis light. Significantly, the multi-stimuli-responsive system was successfully applied in logic gate and fluorescence ink, making it an efficient strategy for information encryption and decryption with higher security requirements.
The development of multi-stimuli-responsive luminescent system to address emerging demands is essential in anti-counterfeiting field. Herein, a photoswitchable system was reported, which was constructed from photoacid sulfonato-merocyanine (MEH-D) serving as H+ donor and diarylethene derivative (DAE-A1) as acceptor. After capturing 2 equiv. HCl, the obtained fluorescent molecule DAE-A1-H showed solvatochromic property. Further on, benefiting from that MEH-D released protons and became a ring-closed isomer spiropyran (SP-D) under 440 nm irradiation, DAE-A1 was protonated, turning on fluorescence effect was realized in DAE-A1/MEH-D. In dark, a photo-activated reversible process was realized with SP-D changed to MEH-D in situ system. In addition, the OF-DAE-A1-H/SP-D could efficiently and reversibly switch on/off its luminescence upon irradiation by UV–vis light. Significantly, the multi-stimuli-responsive system was successfully applied in logic gate and fluorescence ink, making it an efficient strategy for information encryption and decryption with higher security requirements.
2025, 36(8): 110757
doi: 10.1016/j.cclet.2024.110757
Abstract:
Uronic acids are prevalent components of crucial glycoconjugates, pivotal in various biological processes. In nature, NDP-uronic acids, the nucleosides-activated uronic acids, serve as glycosylation donors catalyzed by uronosyltransferases (UATs) to construct glycans containing uronic acids. Despite their biological importance, the synthesis of naturally occurring NDP-uronic acids on a large scale remains challenging. Here, we developed an oxidation reaction insertion strategy for the efficient synthesis of NDP-uronic acids, and 11 NDP-uronic acids were successfully prepared in good yield and on a large scale. The prepared NDP-uronic acids can be used to explore new uronosyltransferases and synthesize uronic acids containing carbohydrates for fundamental research.
Uronic acids are prevalent components of crucial glycoconjugates, pivotal in various biological processes. In nature, NDP-uronic acids, the nucleosides-activated uronic acids, serve as glycosylation donors catalyzed by uronosyltransferases (UATs) to construct glycans containing uronic acids. Despite their biological importance, the synthesis of naturally occurring NDP-uronic acids on a large scale remains challenging. Here, we developed an oxidation reaction insertion strategy for the efficient synthesis of NDP-uronic acids, and 11 NDP-uronic acids were successfully prepared in good yield and on a large scale. The prepared NDP-uronic acids can be used to explore new uronosyltransferases and synthesize uronic acids containing carbohydrates for fundamental research.
2025, 36(8): 110758
doi: 10.1016/j.cclet.2024.110758
Abstract:
Imposing conformational constraints on sp3-rich structures is emerging as an important strategy for structural modification and optimization, which can improve the bioactivity of drugs. Herein, we report a visible-light-induced photosensitized [2 + 2] homo-cycloaddition and cross-cycloaddition of cyclopropenes to synthesize tricyclo[3.1.0.02,4]hexanes as rigidified 3,3,6,6-tetrasubstituted cyclohexanes. Trifluoroacetylsilanes, previously known as trifluoromethyl siloxycarbene precursors, were used as photocatalysts for the first time. The mechanism study supports that the aggregation of cyclopropenes is important to promote their sensitization by trifluoroacetylsilanes through energy transfer.
Imposing conformational constraints on sp3-rich structures is emerging as an important strategy for structural modification and optimization, which can improve the bioactivity of drugs. Herein, we report a visible-light-induced photosensitized [2 + 2] homo-cycloaddition and cross-cycloaddition of cyclopropenes to synthesize tricyclo[3.1.0.02,4]hexanes as rigidified 3,3,6,6-tetrasubstituted cyclohexanes. Trifluoroacetylsilanes, previously known as trifluoromethyl siloxycarbene precursors, were used as photocatalysts for the first time. The mechanism study supports that the aggregation of cyclopropenes is important to promote their sensitization by trifluoroacetylsilanes through energy transfer.
2025, 36(8): 110759
doi: 10.1016/j.cclet.2024.110759
Abstract:
Herein we report an environmentally friendly and energy-efficient method for the adsorptive separation of toluene from toluene-alcohol azeotropes using porous crystalline fluorinated leaning pillar[6]arene (FLP6α), achieving up to 100% purity. Moreover, FLP6α demonstrates rapid adsorption and excellent recyclability.
Herein we report an environmentally friendly and energy-efficient method for the adsorptive separation of toluene from toluene-alcohol azeotropes using porous crystalline fluorinated leaning pillar[6]arene (FLP6α), achieving up to 100% purity. Moreover, FLP6α demonstrates rapid adsorption and excellent recyclability.
2025, 36(8): 110767
doi: 10.1016/j.cclet.2024.110767
Abstract:
Skin protection and wound healing in harsh environments such as seawater, cold, and dryness face great challenges. However, traditional hydrogels tend to lose adhesion underwater, freeze at low temperatures, and dehydrate in dry environments, severely limiting their applications. Inspired by marine barnacles, a chitosan (CTS)‑butyl acrylate (BA)-glycerol gel (CB-G-Gel) is fabricated, which mimic the electrostatic and hydrophobic interactions of barnacle cement proteins using CTS and BA respectively to enhance adhesion underwater, and employ a glycerol/water solvent exchange strategy to endow the gel with anti-freezing and water-retaining properties. CB-G-Gel exhibits strong underwater adhesion and good antibacterial activity, and promotes seawater-immersed wound healing. CB-G-Gel protects the skin from frostbite and scald (−196~120 ℃), and has excellent water retention under dry conditions of 20% relative humidity and 60 ℃. This strategy of combining barnacle biomimicry with glycerol/water solvent exchange provides a guidance for skin protection and wound healing in harsh environments.
Skin protection and wound healing in harsh environments such as seawater, cold, and dryness face great challenges. However, traditional hydrogels tend to lose adhesion underwater, freeze at low temperatures, and dehydrate in dry environments, severely limiting their applications. Inspired by marine barnacles, a chitosan (CTS)‑butyl acrylate (BA)-glycerol gel (CB-G-Gel) is fabricated, which mimic the electrostatic and hydrophobic interactions of barnacle cement proteins using CTS and BA respectively to enhance adhesion underwater, and employ a glycerol/water solvent exchange strategy to endow the gel with anti-freezing and water-retaining properties. CB-G-Gel exhibits strong underwater adhesion and good antibacterial activity, and promotes seawater-immersed wound healing. CB-G-Gel protects the skin from frostbite and scald (−196~120 ℃), and has excellent water retention under dry conditions of 20% relative humidity and 60 ℃. This strategy of combining barnacle biomimicry with glycerol/water solvent exchange provides a guidance for skin protection and wound healing in harsh environments.
2025, 36(8): 110888
doi: 10.1016/j.cclet.2025.110888
Abstract:
Heterogeneous catalysts have attracted wide attention due to their remarkable oxygen evolution reaction (OER) capabilities. Herein, a one-step strategy involving the coupling of NixSey with CeO2 is proposed to concurrently construct heterogeneous interfaces, adjust phase structure, and regulate electronic configuration, thereby enhancing OER performance. Thanks to the role of CeO2 coupling in reducing the activation-energy and accelerating the reaction kinetics, the heterogeneous NixSey/CeO2 catalyst exhibits a low overpotential of 218 mV at 10 mA/cm2 and long-term stability (> 400 h) in 1.0 mol/L KOH for OER. Moreover, the post-OER characterization reveals that the NixSey matrix is reconstructed into NiOOH, while the incorporated CeO2 nanocrystals self-assemble into larger polycrystalline particles. Theoretical analysis further demonstrates that the optimized electronic states at NiOOH/CeO2 interfaces can modulate intermediate chemisorption toward favorable OER kinetics. This study offers fresh perspectives on the synthesis and structure-activity relationship of CeO2-coupled electrocatalysts.
Heterogeneous catalysts have attracted wide attention due to their remarkable oxygen evolution reaction (OER) capabilities. Herein, a one-step strategy involving the coupling of NixSey with CeO2 is proposed to concurrently construct heterogeneous interfaces, adjust phase structure, and regulate electronic configuration, thereby enhancing OER performance. Thanks to the role of CeO2 coupling in reducing the activation-energy and accelerating the reaction kinetics, the heterogeneous NixSey/CeO2 catalyst exhibits a low overpotential of 218 mV at 10 mA/cm2 and long-term stability (> 400 h) in 1.0 mol/L KOH for OER. Moreover, the post-OER characterization reveals that the NixSey matrix is reconstructed into NiOOH, while the incorporated CeO2 nanocrystals self-assemble into larger polycrystalline particles. Theoretical analysis further demonstrates that the optimized electronic states at NiOOH/CeO2 interfaces can modulate intermediate chemisorption toward favorable OER kinetics. This study offers fresh perspectives on the synthesis and structure-activity relationship of CeO2-coupled electrocatalysts.
2025, 36(8): 110976
doi: 10.1016/j.cclet.2025.110976
Abstract:
Super-fine electrohydrodynamic inkjet (SIJ) printing of perovskite nanocrystal (PNC) colloid ink exhibits significant potential in the fabrication of high-resolution color conversion microstructures arrays for full-color micro-LED displays. However, the impact of solvent on both the printing process and the morphology of SIJ-printed PNC color conversion microstructures remains underexplored. In this study, we prepared samples of CsPbBr3 PNC colloid inks in various solvents and investigated the solvent’s impact on SIJ printed PNC microstructures. Our findings reveal that the boiling point of the solvent is crucial to the SIJ printing process of PNC colloid inks. Only does the boiling point of the solvent fall in the optimal range, the regular positioned, micron-scaled, conical PNC microstructures can be successfully printed. Below this optimal range, the ink is unable to be ejected from the nozzle; while above this range, irregular positioned microstructures with nanoscale height and coffee-ring-like morphology are produced. Based on these observations, high-resolution color conversion PNC microstructures were effectively prepared using SIJ printing of PNC colloid ink dispersed in dimethylbenzene solvent.
Super-fine electrohydrodynamic inkjet (SIJ) printing of perovskite nanocrystal (PNC) colloid ink exhibits significant potential in the fabrication of high-resolution color conversion microstructures arrays for full-color micro-LED displays. However, the impact of solvent on both the printing process and the morphology of SIJ-printed PNC color conversion microstructures remains underexplored. In this study, we prepared samples of CsPbBr3 PNC colloid inks in various solvents and investigated the solvent’s impact on SIJ printed PNC microstructures. Our findings reveal that the boiling point of the solvent is crucial to the SIJ printing process of PNC colloid inks. Only does the boiling point of the solvent fall in the optimal range, the regular positioned, micron-scaled, conical PNC microstructures can be successfully printed. Below this optimal range, the ink is unable to be ejected from the nozzle; while above this range, irregular positioned microstructures with nanoscale height and coffee-ring-like morphology are produced. Based on these observations, high-resolution color conversion PNC microstructures were effectively prepared using SIJ printing of PNC colloid ink dispersed in dimethylbenzene solvent.
2025, 36(8): 110989
doi: 10.1016/j.cclet.2025.110989
Abstract:
Zinc-ion battery (ZIB) has been regarded as one of the most promising sustainable energy storage systems due to its low cost, safety, and attractive electrochemical performance. However, the metallic zinc anode with uneven deposition during cycling would result in significant capacity decay, low Coulombic efficiency, and electrolyte consumption, thus the undesirable cyclability severely hampers the practical applications. Herein, a phosphorus-doped carbon protective layer was coated onto the surface of Zn anode via using the plasma-enhanced chemical vapor deposition (PECVD) approach. Enhanced conductivity and lower nucleation overpotential induced by the P-doped carbon protective layer can effectively facilitate the ion diffusion kinetics and suppress side reactions. The as-fabricated P-C/Zn anode demonstrated excellent cycling stability during the zinc plating/stripping process, maintaining a low voltage hysteresis (34.8 mV) for over 1000 h under a current density of 2 mA/cm2 and a capacity of 2 mAh/cm2. Moreover, the P-C/ZnMnO2 full cell exhibited high specific capacity of about 252.5 mAh/g at 2 A/g upon 700 long cycles. This study is helpful to design more efficient zinc-ion batteries towards the future applications.
Zinc-ion battery (ZIB) has been regarded as one of the most promising sustainable energy storage systems due to its low cost, safety, and attractive electrochemical performance. However, the metallic zinc anode with uneven deposition during cycling would result in significant capacity decay, low Coulombic efficiency, and electrolyte consumption, thus the undesirable cyclability severely hampers the practical applications. Herein, a phosphorus-doped carbon protective layer was coated onto the surface of Zn anode via using the plasma-enhanced chemical vapor deposition (PECVD) approach. Enhanced conductivity and lower nucleation overpotential induced by the P-doped carbon protective layer can effectively facilitate the ion diffusion kinetics and suppress side reactions. The as-fabricated P-C/Zn anode demonstrated excellent cycling stability during the zinc plating/stripping process, maintaining a low voltage hysteresis (34.8 mV) for over 1000 h under a current density of 2 mA/cm2 and a capacity of 2 mAh/cm2. Moreover, the P-C/ZnMnO2 full cell exhibited high specific capacity of about 252.5 mAh/g at 2 A/g upon 700 long cycles. This study is helpful to design more efficient zinc-ion batteries towards the future applications.
2025, 36(8): 110993
doi: 10.1016/j.cclet.2025.110993
Abstract:
P2-type layered transition-metal oxides with high energy density and rich variety have attracted extensive attention for sodium-ion batteries (SIBs) in grid-scale energy storage application, but they usually suffer from sluggish kinetics and large volume change upon cycling. Herein, we designed a high-performance P2-type Na0.67Ni0.31Mn0.67Mo0.02O2 (NNMMO) cathode with regulated electronic environment and Na+ zigzag ordering modulation via high-valence Mo6+ stabilization engineering. The achieved NNMMO cathode exhibits a high-rate capability with a reversible capacity of 77.2 mAh/g at 10 C and a long cycle life with a capacity retention of 75% at 2 C after 1000 cycles. In addition, in situ X-ray diffraction and ex-situ X-ray absorption fine structure spectroscopy characterizations verify that the presence of Mo6+ also stabilizes the desodiated structure through a pinning effect, achieving an extremely low volume change of 1.04% upon Na+ extraction. The quantified diffusional analysis and theoretical calculations demonstrate that the Mo6+-doping improves the Na+ diffusion kinetics, optimizes the energy band structure and enhances the TM-O bond strength. Additionally, the as-fabricated pouch cells by paring NNMMO cathode and hard carbon anode show impressive cycling stability with an energy density of 296.7 Wh/kg. This study broadens the perspective for high-valence metal ion doping to obtain superior cathode materials and pave the way for developing high-energy-density SIBs.
P2-type layered transition-metal oxides with high energy density and rich variety have attracted extensive attention for sodium-ion batteries (SIBs) in grid-scale energy storage application, but they usually suffer from sluggish kinetics and large volume change upon cycling. Herein, we designed a high-performance P2-type Na0.67Ni0.31Mn0.67Mo0.02O2 (NNMMO) cathode with regulated electronic environment and Na+ zigzag ordering modulation via high-valence Mo6+ stabilization engineering. The achieved NNMMO cathode exhibits a high-rate capability with a reversible capacity of 77.2 mAh/g at 10 C and a long cycle life with a capacity retention of 75% at 2 C after 1000 cycles. In addition, in situ X-ray diffraction and ex-situ X-ray absorption fine structure spectroscopy characterizations verify that the presence of Mo6+ also stabilizes the desodiated structure through a pinning effect, achieving an extremely low volume change of 1.04% upon Na+ extraction. The quantified diffusional analysis and theoretical calculations demonstrate that the Mo6+-doping improves the Na+ diffusion kinetics, optimizes the energy band structure and enhances the TM-O bond strength. Additionally, the as-fabricated pouch cells by paring NNMMO cathode and hard carbon anode show impressive cycling stability with an energy density of 296.7 Wh/kg. This study broadens the perspective for high-valence metal ion doping to obtain superior cathode materials and pave the way for developing high-energy-density SIBs.
2025, 36(8): 111018
doi: 10.1016/j.cclet.2025.111018
Abstract:
Sorafenib (Sora) not only has an inhibitory effect on angiogenesis via indirectly inhibiting tumor growth through antiangiogenesis, but also can inactivate the glutathione peroxidase 4 (GPX4) to induce ferroptosis. Nonetheless, the therapeutic efficacy is hampered by a plethora of factors, including low bioavailability and tumor microenvironment (TME). Of particular note is the hypoxic and reductive TME, which acts as a significant impediment and poses formidable challenges to attain the most optimal treatment outcomes. Herein, we developed a novel therapeutic platform based on Sora-loaded mesoporous ferromanganese nanoparticles (PMFNs@Sora). PMFNs mimics both catalase and GPX activities. The self-sustained catalase activity enables continuous decomposition of hydrogen peroxide to generate oxygen, which alleviates hypoxia microenvironment. The GPX activity simultaneously amplifies the therapeutic efficacy of Sora. The as-synthesized PMFNs@Sora demonstrates significantly enhanced antitumor effect in vitro through apoptosis-ferroptosis, revealed by Western blot. Furthermore, PMFNs@Sora also showed effective tumor growth inhibition in vivo. This multifunctional nanoplatform offers a promising strategy for modulating the TME and enhancing cancer treatment in clinical application.
Sorafenib (Sora) not only has an inhibitory effect on angiogenesis via indirectly inhibiting tumor growth through antiangiogenesis, but also can inactivate the glutathione peroxidase 4 (GPX4) to induce ferroptosis. Nonetheless, the therapeutic efficacy is hampered by a plethora of factors, including low bioavailability and tumor microenvironment (TME). Of particular note is the hypoxic and reductive TME, which acts as a significant impediment and poses formidable challenges to attain the most optimal treatment outcomes. Herein, we developed a novel therapeutic platform based on Sora-loaded mesoporous ferromanganese nanoparticles (PMFNs@Sora). PMFNs mimics both catalase and GPX activities. The self-sustained catalase activity enables continuous decomposition of hydrogen peroxide to generate oxygen, which alleviates hypoxia microenvironment. The GPX activity simultaneously amplifies the therapeutic efficacy of Sora. The as-synthesized PMFNs@Sora demonstrates significantly enhanced antitumor effect in vitro through apoptosis-ferroptosis, revealed by Western blot. Furthermore, PMFNs@Sora also showed effective tumor growth inhibition in vivo. This multifunctional nanoplatform offers a promising strategy for modulating the TME and enhancing cancer treatment in clinical application.
2025, 36(8): 111096
doi: 10.1016/j.cclet.2025.111096
Abstract:
The ineluctable introduction of lithium salt to polymer solid-state electrolytes incurs a compromise between strength, ionic conductivity, and thickness. Here, we propose Al2O3-coated polyimide (AO/PI) porous film as a high-strength substrate to support fast-ion-conducting polymer-in-salt (PIS) solid-state electrolytes, aiming to suppress lithium dendrite growth and improve full-cell performance. The Al2O3 coating layer not only refines the wettability of polyimide porous film to PIS, but also performs as a high modulus protective layer to suppress the growth of lithium dendrites. The resulting PI/AO@PIS exhibits a small thickness of only 35 µm with an outstanding tensile strength of 11.3 MPa and Young's modulus of 537.6 MPa. In addition, the PI/AO@PIS delivers a high ionic conductivity of 0.1 mS/cm at 25 ℃. As a result, the PI/AO@PIS enables symmetric Li cells to achieve exceptional cyclability for over 1000 h at 0.1 mA/cm2 without noticeable lithium dendrite formation. Moreover, the PI/AO@PIS-based LiFePO4Li full cells demonstrate outstanding rate performance (125.7 mAh/g at 5 C) and impressive cycling stability (96.1% capacity retention at 1 C after 200 cycles). This work highlights the efficacy of enhancing the mechanical properties of polymer matrices and extending cell performance through the incorporation of a dense inorganic interface layer.
The ineluctable introduction of lithium salt to polymer solid-state electrolytes incurs a compromise between strength, ionic conductivity, and thickness. Here, we propose Al2O3-coated polyimide (AO/PI) porous film as a high-strength substrate to support fast-ion-conducting polymer-in-salt (PIS) solid-state electrolytes, aiming to suppress lithium dendrite growth and improve full-cell performance. The Al2O3 coating layer not only refines the wettability of polyimide porous film to PIS, but also performs as a high modulus protective layer to suppress the growth of lithium dendrites. The resulting PI/AO@PIS exhibits a small thickness of only 35 µm with an outstanding tensile strength of 11.3 MPa and Young's modulus of 537.6 MPa. In addition, the PI/AO@PIS delivers a high ionic conductivity of 0.1 mS/cm at 25 ℃. As a result, the PI/AO@PIS enables symmetric Li cells to achieve exceptional cyclability for over 1000 h at 0.1 mA/cm2 without noticeable lithium dendrite formation. Moreover, the PI/AO@PIS-based LiFePO4Li full cells demonstrate outstanding rate performance (125.7 mAh/g at 5 C) and impressive cycling stability (96.1% capacity retention at 1 C after 200 cycles). This work highlights the efficacy of enhancing the mechanical properties of polymer matrices and extending cell performance through the incorporation of a dense inorganic interface layer.
2025, 36(8): 111118
doi: 10.1016/j.cclet.2025.111118
Abstract:
Available online Further oxidation of NH3 produced via photocatalytic N2 fixation represents a promising strategy to enhance the economic value of N2 fixation. This work employs first-principles density functional theory (DFT) calculations to demonstrate that incorporating Co into NiO improves both N2 adsorption and activation as well as M-N electron exchange intensity. Guided by these predictions, a novel Co single-atom photocatalyst supported by nanoconfined NiO@C nanosheets was synthesized using a direct metal atomization method, achieving high HNO3 production (60.54%). NH4+ and NO3− production rates during N2 photofixation reached 67.97 µmol gcat−1 h−1 and 104.28 µmol gcat−1 h−1, respectively. The overall N2 → NH3 → HNO3 photofixation pathway was validated through in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and 15N isotopic labeling. Mechanistic studies reveal that Co single-atom introduction serves as an electron trap, enhancing photogenerated electron accumulation with a five-fold increase in carrier density compared to NiO@C, as observed via in-situ X-ray photoelectron spectroscopy (XPS). This synergistic effect between electron traps and N2 adsorption/activation sites at Co single-atom centers supports rapid N2 reduction kinetics. Additionally, nanoconfined ink-bottle pores in the carbon layer impede NH3 desorption, further boosting NO3− production. This work offers a comprehensive approach to optimizing N2 photofixation through electron regulation and surface reaction kinetics.
Available online Further oxidation of NH3 produced via photocatalytic N2 fixation represents a promising strategy to enhance the economic value of N2 fixation. This work employs first-principles density functional theory (DFT) calculations to demonstrate that incorporating Co into NiO improves both N2 adsorption and activation as well as M-N electron exchange intensity. Guided by these predictions, a novel Co single-atom photocatalyst supported by nanoconfined NiO@C nanosheets was synthesized using a direct metal atomization method, achieving high HNO3 production (60.54%). NH4+ and NO3− production rates during N2 photofixation reached 67.97 µmol gcat−1 h−1 and 104.28 µmol gcat−1 h−1, respectively. The overall N2 → NH3 → HNO3 photofixation pathway was validated through in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and 15N isotopic labeling. Mechanistic studies reveal that Co single-atom introduction serves as an electron trap, enhancing photogenerated electron accumulation with a five-fold increase in carrier density compared to NiO@C, as observed via in-situ X-ray photoelectron spectroscopy (XPS). This synergistic effect between electron traps and N2 adsorption/activation sites at Co single-atom centers supports rapid N2 reduction kinetics. Additionally, nanoconfined ink-bottle pores in the carbon layer impede NH3 desorption, further boosting NO3− production. This work offers a comprehensive approach to optimizing N2 photofixation through electron regulation and surface reaction kinetics.
2025, 36(8): 111122
doi: 10.1016/j.cclet.2025.111122
Abstract:
The hydrogenation of dimethyl oxalate (DMO) to ethanol (EtOH) represents a promising avenue for syngas conversion and plays a pivotal role in advancing sustainable energy economies. Nevertheless, designing catalysts with high EtOH yields at low temperatures remains a significant challenge. This study introduces an efficient catalyst featuring a rich SiO2-Ni3Mo3N interface, which achieved a remarkable 97.5% EtOH yield at 210 °C and 2 MPa. Impressively, an EtOH yield of 95% was also obtained at 210 °C and 1.5 MPa. The research demonstrates that the addition of SiO2 fosters the development of a rich SiO2-Ni3Mo3N interface, which enhances the concentration of Lewis acid sites (L-acid) and Brønsted acids sites (B-acid) within the catalyst. This enhancement promotes the adsorption of raw material and intermediate products while increasing H2 adsorption, thereby boosting the catalyst's deep hydrogenation capacity. Density functional theory (DFT) simulations indicate that SiO2 incorporation modifies the catalyst's metal d-band center through electron transfer, increasing its adsorption capability for raw materials and intermediates and facilitating EtOH production. Consequently, this study achieves high EtOH yields at low temperatures, advances the industrialization process of syngas to EtOH conversion, and offers novel insights into constructing highly active catalytic interfaces for DMO hydrogenation.
The hydrogenation of dimethyl oxalate (DMO) to ethanol (EtOH) represents a promising avenue for syngas conversion and plays a pivotal role in advancing sustainable energy economies. Nevertheless, designing catalysts with high EtOH yields at low temperatures remains a significant challenge. This study introduces an efficient catalyst featuring a rich SiO2-Ni3Mo3N interface, which achieved a remarkable 97.5% EtOH yield at 210 °C and 2 MPa. Impressively, an EtOH yield of 95% was also obtained at 210 °C and 1.5 MPa. The research demonstrates that the addition of SiO2 fosters the development of a rich SiO2-Ni3Mo3N interface, which enhances the concentration of Lewis acid sites (L-acid) and Brønsted acids sites (B-acid) within the catalyst. This enhancement promotes the adsorption of raw material and intermediate products while increasing H2 adsorption, thereby boosting the catalyst's deep hydrogenation capacity. Density functional theory (DFT) simulations indicate that SiO2 incorporation modifies the catalyst's metal d-band center through electron transfer, increasing its adsorption capability for raw materials and intermediates and facilitating EtOH production. Consequently, this study achieves high EtOH yields at low temperatures, advances the industrialization process of syngas to EtOH conversion, and offers novel insights into constructing highly active catalytic interfaces for DMO hydrogenation.
2025, 36(8): 111123
doi: 10.1016/j.cclet.2025.111123
Abstract:
It is necessary to adopt a specific strategy to construct an efficient and low-cost transition metal-based composite to replace the precious metal-based electrocatalyst for OER catalytic processes. In this work, a beaded stream-like N and P-codoped carbon-coated Fe3O4 nanocomposite (N,P-Fe3O4@C) is derived from MIL-88A by two-step annealing. The unique 3D nanostructure and amorphous N-doped carbon layer enlarge the number of active sites, and P doping changes the pathway from AEM to LOM. The synergistic effect of these factors results in N,P-Fe3O4@C presenting excellent OER catalytic activity with an overpotential of 201 mV (η10), a Tafel slope of 57.1 mV/dec and stable operation for 100 h (the current density is 10 mA/cm2). Density functional theory calculations and electrochemical tests reveal that the P doping enhances the overlap of Fe 3d orbital bands and O 2p orbitals, and thus significantly increases the metal-oxygen covalency, triggering the pathway transition from AEM to LOM. This work provides a new way to construct more efficient transition metal-based composite carbon materials.
It is necessary to adopt a specific strategy to construct an efficient and low-cost transition metal-based composite to replace the precious metal-based electrocatalyst for OER catalytic processes. In this work, a beaded stream-like N and P-codoped carbon-coated Fe3O4 nanocomposite (N,P-Fe3O4@C) is derived from MIL-88A by two-step annealing. The unique 3D nanostructure and amorphous N-doped carbon layer enlarge the number of active sites, and P doping changes the pathway from AEM to LOM. The synergistic effect of these factors results in N,P-Fe3O4@C presenting excellent OER catalytic activity with an overpotential of 201 mV (η10), a Tafel slope of 57.1 mV/dec and stable operation for 100 h (the current density is 10 mA/cm2). Density functional theory calculations and electrochemical tests reveal that the P doping enhances the overlap of Fe 3d orbital bands and O 2p orbitals, and thus significantly increases the metal-oxygen covalency, triggering the pathway transition from AEM to LOM. This work provides a new way to construct more efficient transition metal-based composite carbon materials.
2025, 36(8): 111138
doi: 10.1016/j.cclet.2025.111138
Abstract:
Abundant efforts have been devoted to improving the efficiency of organic light-emitting diodes (OLEDs), however, approaches to control the device efficiency roll-off are still extremely limited, especially in non-doped blue OLEDs. In this work, three blue emitters (TAT, TAMT and TAMT-CN) with "hot exciton" properties are designed and synthesized based on [1,2,4]triazolo[1,5-a]pyridine (TP) as a regulating unit as well as anthracene-triphenylamine (An-TPA) as the chromophore. By adjusting the linkage mode and modifying the TP unit, the excited state properties, carrier transfer abilities, horizontal orientation, and device efficiency roll-off were precisely controlled. Among these materials, emitters that directly connect the fused TP unit exhibit balanced charge-transporting ability, higher photoluminescent quantum yield and improved horizontal orientation, resulting in better electroluminescence (EL) performance in non-doped blue OLEDs. As a result, non-doped blue OLEDs exhibit excellent performance with external quantum efficiencies of over 6%, brightness of over 30,000 cd/m2 and EL peaks of around 476 nm. More importantly, the device based on TAMT-CN exhibits an ultra-low efficiency roll-off of 2.97% at a high brightness of 10,000 cd/m2. The accessible molecular unit and feasible design strategy in this work are of great significance for designing highly efficient and ultra-low efficiency roll-off non-doped blue OLEDs.
Abundant efforts have been devoted to improving the efficiency of organic light-emitting diodes (OLEDs), however, approaches to control the device efficiency roll-off are still extremely limited, especially in non-doped blue OLEDs. In this work, three blue emitters (TAT, TAMT and TAMT-CN) with "hot exciton" properties are designed and synthesized based on [1,2,4]triazolo[1,5-a]pyridine (TP) as a regulating unit as well as anthracene-triphenylamine (An-TPA) as the chromophore. By adjusting the linkage mode and modifying the TP unit, the excited state properties, carrier transfer abilities, horizontal orientation, and device efficiency roll-off were precisely controlled. Among these materials, emitters that directly connect the fused TP unit exhibit balanced charge-transporting ability, higher photoluminescent quantum yield and improved horizontal orientation, resulting in better electroluminescence (EL) performance in non-doped blue OLEDs. As a result, non-doped blue OLEDs exhibit excellent performance with external quantum efficiencies of over 6%, brightness of over 30,000 cd/m2 and EL peaks of around 476 nm. More importantly, the device based on TAMT-CN exhibits an ultra-low efficiency roll-off of 2.97% at a high brightness of 10,000 cd/m2. The accessible molecular unit and feasible design strategy in this work are of great significance for designing highly efficient and ultra-low efficiency roll-off non-doped blue OLEDs.
2025, 36(8): 111162
doi: 10.1016/j.cclet.2025.111162
Abstract:
A meticulous design of the local environment at the interface between active species and the support, aimed at optimizing the adsorption of H2O molecules and BH4− anion, offers an ideal strategy for enhancing hydrogen generation via NaBH4 hydrolysis through dual activation pathways. Theoretical predictions based on d-band center analysis and electron transfer calculations suggest that introducing -OH functional groups induce charge redistribution, enhancing charge concentration on alk-Ti3C2 and facilitating the adsorption and activation of dual active species, H2O molecules and BH4− anion. Inspired by these predictions, the optimized alk-Ti3C2/RuOx catalyst demonstrates the highest catalytic activity, achieving a hydrogen generation rate (HGR) of 9468 mL min−1 gcat.−1. Both experimental data and theoretical analyses confirm that the -OH functional groups promote charge enrichment on alk-Ti3C2, optimizing the adsorption of H2O molecules and BH4− anion, and reducing the dissociation energy barrier of the *OHH-TS intermediate. This dual activation pathways mechanism lowers the activation energy for NaBH4 hydrolysis, significantly enhancing the HGR performance. These findings, guided by theoretical insights, establish alk-Ti3C2/RuOx as an efficient catalyst for NaBH4 hydrolysis and provide a strong foundation for future hydrogen generation catalyst designs.
A meticulous design of the local environment at the interface between active species and the support, aimed at optimizing the adsorption of H2O molecules and BH4− anion, offers an ideal strategy for enhancing hydrogen generation via NaBH4 hydrolysis through dual activation pathways. Theoretical predictions based on d-band center analysis and electron transfer calculations suggest that introducing -OH functional groups induce charge redistribution, enhancing charge concentration on alk-Ti3C2 and facilitating the adsorption and activation of dual active species, H2O molecules and BH4− anion. Inspired by these predictions, the optimized alk-Ti3C2/RuOx catalyst demonstrates the highest catalytic activity, achieving a hydrogen generation rate (HGR) of 9468 mL min−1 gcat.−1. Both experimental data and theoretical analyses confirm that the -OH functional groups promote charge enrichment on alk-Ti3C2, optimizing the adsorption of H2O molecules and BH4− anion, and reducing the dissociation energy barrier of the *OHH-TS intermediate. This dual activation pathways mechanism lowers the activation energy for NaBH4 hydrolysis, significantly enhancing the HGR performance. These findings, guided by theoretical insights, establish alk-Ti3C2/RuOx as an efficient catalyst for NaBH4 hydrolysis and provide a strong foundation for future hydrogen generation catalyst designs.
2025, 36(8): 111193
doi: 10.1016/j.cclet.2025.111193
Abstract:
Cu2+ in copper-based catalysts can facilitate the hydrogenation of the CH4 production pathway via the electrochemical carbon dioxide reduction reaction (ECRR). However, Cu2+ species in copper oxides are unstable and have been revealed to reduce to Cu0 under the applied cathodic potential. In this work, we reported an A-site modulation strategy to stabilize Cu2+ in perovskite for efficient ECRR to CH4. After the introduction of Ca2+ in La2CuO4, the obtained LaCa0.4CuO3-δ is stable during ECRR. We achieved a 59.6% ± 3.8% CH4 faradaic efficiency at -1.30 V versus reversible hydrogen electrode in H-cell and a partial current density of 155.0 mA/cm2 in membrane electrode assembly. DFT calculations and in situ Raman spectroscopy show that Cu2+ facilitates the hydrogenation of *CH2O to *CH3O and the further production of CH4. This work introduces an efficient strategy to stabilize Cu2+ and provides an understanding of Cu2+ in promoting ECRR to CH4.
Cu2+ in copper-based catalysts can facilitate the hydrogenation of the CH4 production pathway via the electrochemical carbon dioxide reduction reaction (ECRR). However, Cu2+ species in copper oxides are unstable and have been revealed to reduce to Cu0 under the applied cathodic potential. In this work, we reported an A-site modulation strategy to stabilize Cu2+ in perovskite for efficient ECRR to CH4. After the introduction of Ca2+ in La2CuO4, the obtained LaCa0.4CuO3-δ is stable during ECRR. We achieved a 59.6% ± 3.8% CH4 faradaic efficiency at -1.30 V versus reversible hydrogen electrode in H-cell and a partial current density of 155.0 mA/cm2 in membrane electrode assembly. DFT calculations and in situ Raman spectroscopy show that Cu2+ facilitates the hydrogenation of *CH2O to *CH3O and the further production of CH4. This work introduces an efficient strategy to stabilize Cu2+ and provides an understanding of Cu2+ in promoting ECRR to CH4.
2025, 36(8): 111208
doi: 10.1016/j.cclet.2025.111208
Abstract:
In view of the dearth of active components and the unsatisfactory dispersion of Cu-based catalysts, it is imperative to undertake a detailed investigation of catalysts with enhanced catalytic performance. In order to achieve a balance between the catalytic activity and stability in the reaction process, a series of P-atom doped Cu0/Cuδ+ binary Cu-based catalysts were prepared by means of heteroatom introduction and heat treatment. The introduction of P enhanced the stability of Cu during heat treatment, thereby inhibiting the excessive agglomeration of Cu. The structure of the Cu0/Cuδ+ binary catalyst was modified through heat treatment and HCl activation, and the relationship between its structure and catalytic activity was subsequently investigated. The activation process of HCl facilitated the conversion of the Cu0 state to the Cu-Cl state and augmented the valence state of Cu. The valence modulation of the Cu site by HCl during the reaction prevented the over-reduction of the Cu site by acetylene and enhanced the stability of the catalyst. The 3Cu/5CuP/AC-800 catalyst was operated for 50 h without significant deactivation under the reaction conditions of T = 180 ℃, V(HCl)/V(C2H2) = 1.15 and GHSV(C2H2) = 180 h-1. This design strategy provides a novel reference point for further studies of CuCl2 based catalysts for acetylene hydrochlorination.
In view of the dearth of active components and the unsatisfactory dispersion of Cu-based catalysts, it is imperative to undertake a detailed investigation of catalysts with enhanced catalytic performance. In order to achieve a balance between the catalytic activity and stability in the reaction process, a series of P-atom doped Cu0/Cuδ+ binary Cu-based catalysts were prepared by means of heteroatom introduction and heat treatment. The introduction of P enhanced the stability of Cu during heat treatment, thereby inhibiting the excessive agglomeration of Cu. The structure of the Cu0/Cuδ+ binary catalyst was modified through heat treatment and HCl activation, and the relationship between its structure and catalytic activity was subsequently investigated. The activation process of HCl facilitated the conversion of the Cu0 state to the Cu-Cl state and augmented the valence state of Cu. The valence modulation of the Cu site by HCl during the reaction prevented the over-reduction of the Cu site by acetylene and enhanced the stability of the catalyst. The 3Cu/5CuP/AC-800 catalyst was operated for 50 h without significant deactivation under the reaction conditions of T = 180 ℃, V(HCl)/V(C2H2) = 1.15 and GHSV(C2H2) = 180 h-1. This design strategy provides a novel reference point for further studies of CuCl2 based catalysts for acetylene hydrochlorination.
2025, 36(8): 111231
doi: 10.1016/j.cclet.2025.111231
Abstract:
Layered ammonium vanadate has become a promising cathode material for aqueous zinc ion batteries (ZIBs) due to its small mass and large ionic radius of ammonium ions as well as the consequent large layer spacing and high specific capacity. However, the irreversible de-ammoniation caused by N·H···O bonds damaged would impair cycle life of ZIBs and the strong electrostatic interaction between Zn2+ and V-O frame could slower the mobility of Zn2+. Furthermore, the thermal instability of ammonium vanadate also limits the use of common carbon coating modification method to solve the problem. Herein, V2CTX MXene was innovatively selected as a bifunctional source to in-situ derivatized (NH4)2V8O20·xH2O with amorphous carbon-coated (NHVO@C) via one-step hydrothermal method in relatively moderate temperature. The amorphous carbon shell derived from the V2CTX MXene as a conductive framework to effectively improve the diffusion kinetics of Zn2+ and the robust carbon skeleton could alleviate the ammonium dissolution during long-term cycling. As a result, zinc ion batteries using NHVO@C as cathode exhibit superior electrochemical performance. Moreover, the assembled foldable or high loading (10.2 mg/cm2) soft-packed ZIBs further demonstrates its practical application. This study provided new insights into the development of the carbon cladding process for thermally unstable materials in moderate temperatures.
Layered ammonium vanadate has become a promising cathode material for aqueous zinc ion batteries (ZIBs) due to its small mass and large ionic radius of ammonium ions as well as the consequent large layer spacing and high specific capacity. However, the irreversible de-ammoniation caused by N·H···O bonds damaged would impair cycle life of ZIBs and the strong electrostatic interaction between Zn2+ and V-O frame could slower the mobility of Zn2+. Furthermore, the thermal instability of ammonium vanadate also limits the use of common carbon coating modification method to solve the problem. Herein, V2CTX MXene was innovatively selected as a bifunctional source to in-situ derivatized (NH4)2V8O20·xH2O with amorphous carbon-coated (NHVO@C) via one-step hydrothermal method in relatively moderate temperature. The amorphous carbon shell derived from the V2CTX MXene as a conductive framework to effectively improve the diffusion kinetics of Zn2+ and the robust carbon skeleton could alleviate the ammonium dissolution during long-term cycling. As a result, zinc ion batteries using NHVO@C as cathode exhibit superior electrochemical performance. Moreover, the assembled foldable or high loading (10.2 mg/cm2) soft-packed ZIBs further demonstrates its practical application. This study provided new insights into the development of the carbon cladding process for thermally unstable materials in moderate temperatures.
2025, 36(8): 111226
doi: 10.1016/j.cclet.2025.111226
Abstract:
2025, 36(8): 111255
doi: 10.1016/j.cclet.2025.111255
Abstract:
The role of oceanic carbon pumps in Earth’s climate system: Impact and feedback under climate change
2025, 36(8): 111300
doi: 10.1016/j.cclet.2025.111300
Abstract:
2025, 36(8): 111316
doi: 10.1016/j.cclet.2025.111316
Abstract:
