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Chinese Chemical Letters
Chinese Chemical Letters
主管 : 中国科学技术协会
刊期 : 月刊主编 : 钱旭红
语种 : 英文主办 : 中国化学会、中国医学科学院药物研究所
ISSN : 1001-8417 CN : 11-2710/O6本刊创办于1990年7月，是由中国化学会主办，中国医学科学院药物研究所承办的核心期刊。本刊由著名化学家梁晓天院士任主编，其内容涵盖化学研究的各个领域，及时报道我国化学界各个研究领域的最新进展及世界上一些化学研究的热点问题。本刊自1993年起为SCI、CA、日本科技文献速报等收录，2000年美国化学文摘引用中国期刊频次中位列第四。展开 > - 影响因子: 8.9
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期刊内热点文章
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Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
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Recent progress in the synthesis of sulfonyl fluorides for SuFEx click chemistry
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Development of electron and hole selective contact materials for perovskite solar cells
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Superiority of poly(L-lactic acid) microspheres as dermal fillers
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期刊内下载排行
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Synthesis of a new ratiometric emission Ca2+ indicator for in vivo bioimaging
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Synthesis of a water-soluble macromolecular light stabilizer containing hindered amine structures
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Fluorine-containing agrochemicals in the last decade and approaches for fluorine incorporation
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Superiority of poly(L-lactic acid) microspheres as dermal fillers
2026, 37(10): 111432
doi: 10.1016/j.cclet.2025.111432
摘要:
Proton exchange membrane fuel cell (PEMFC) has attracted great attention as an energy conversion technology, especially in the fields of new energy vehicles. The core component of PEMFC is membrane electrode assembly (MEA), which is consist of proton exchange membrane (PEM), gas diffusion layer (GDL) and catalyst layer (CL). Notably, the catalyst layer serves as the center for electrochemical reactions that generate electricity. Besides the state-of-the-art materials, the catalyst ink properties and CL structure also have a great effect on performance, durability, and cost of PEMFC. However, it is not very clear how the interactions between different components of catalyst ink, the CL formation procedure as well as inhomogeneous CL structure affect the overall performance. This review, therefore, mainly focuses on recent advancements in catalyst ink dispersion methods, complex interactions between the ink materials and new processes to improve the stability of catalyst ink. In addition, this review will highlight advanced CL structure designs, their impact on the fuel cell performance, and introducing advanced techniques for a deeper analysis of the CL structure. Finally, this review emphasizes the challenges and perspectives in catalyst ink and CL studies, which are crucial for the regulation and development of high-performing PEMFCs.
Proton exchange membrane fuel cell (PEMFC) has attracted great attention as an energy conversion technology, especially in the fields of new energy vehicles. The core component of PEMFC is membrane electrode assembly (MEA), which is consist of proton exchange membrane (PEM), gas diffusion layer (GDL) and catalyst layer (CL). Notably, the catalyst layer serves as the center for electrochemical reactions that generate electricity. Besides the state-of-the-art materials, the catalyst ink properties and CL structure also have a great effect on performance, durability, and cost of PEMFC. However, it is not very clear how the interactions between different components of catalyst ink, the CL formation procedure as well as inhomogeneous CL structure affect the overall performance. This review, therefore, mainly focuses on recent advancements in catalyst ink dispersion methods, complex interactions between the ink materials and new processes to improve the stability of catalyst ink. In addition, this review will highlight advanced CL structure designs, their impact on the fuel cell performance, and introducing advanced techniques for a deeper analysis of the CL structure. Finally, this review emphasizes the challenges and perspectives in catalyst ink and CL studies, which are crucial for the regulation and development of high-performing PEMFCs.
2026, 37(10): 111533
doi: 10.1016/j.cclet.2025.111533
摘要:
Low-temperature energy storage technology plays a crucial role in sustaining energy supply for interstellar exploration, polar research stations, military facilities in extremely cold regions. Sodium-ion batteries (SIBs) are regarded as potential candidates for large-scale energy storage systems under extreme low-temperature conditions due to their abundant sodium resources, low cost and superior temperature tolerance. As a critical component of SIBs, the electrolyte is closely related to the charge transfer kinetics within the battery and significantly influences its low-temperature electrochemical performance. Herein, we present a comprehensive review focusing on recent advances in organic liquid electrolytes for enhancing the low-temperature performance of SIBs. Firstly, the failure mechanisms of SIBs at low temperatures are systematically analyzed from the perspective of charge transfer kinetics. Subsequently, the electrolyte design strategies for low-temperature SIBs are introduced based on two evaluation dimensions: half cell and full cell systems. Finally, the future research directions for developing advanced electrolytes to improve the low-temperature performance of SIBs are proposed. This review provides valuable insights into electrolyte optimization strategies, which are expected to accelerate the development of high-performance SIBs for reliable energy storage in extreme cold environments.
Low-temperature energy storage technology plays a crucial role in sustaining energy supply for interstellar exploration, polar research stations, military facilities in extremely cold regions. Sodium-ion batteries (SIBs) are regarded as potential candidates for large-scale energy storage systems under extreme low-temperature conditions due to their abundant sodium resources, low cost and superior temperature tolerance. As a critical component of SIBs, the electrolyte is closely related to the charge transfer kinetics within the battery and significantly influences its low-temperature electrochemical performance. Herein, we present a comprehensive review focusing on recent advances in organic liquid electrolytes for enhancing the low-temperature performance of SIBs. Firstly, the failure mechanisms of SIBs at low temperatures are systematically analyzed from the perspective of charge transfer kinetics. Subsequently, the electrolyte design strategies for low-temperature SIBs are introduced based on two evaluation dimensions: half cell and full cell systems. Finally, the future research directions for developing advanced electrolytes to improve the low-temperature performance of SIBs are proposed. This review provides valuable insights into electrolyte optimization strategies, which are expected to accelerate the development of high-performance SIBs for reliable energy storage in extreme cold environments.
2026, 37(10): 111605
doi: 10.1016/j.cclet.2025.111605
摘要:
In response to the increasing societal demand for efficient power and energy storage solutions, the development of novel battery technologies to complement existing lithium-ion batteries (LIBs) has emerged as a pivotal area of research. Sodium-ion batteries (SIBs), owing to the similarities in the physicochemical properties of sodium and lithium, have interpreted as promising candidates for next-generation secondary batteries. However, current research predominantly concentrates on the optimization of cathode and anode materials, as well as electrolytes, with insufficient attention paid to the critical role of inactive materials, such as binders, conductive agents, and separators. While electrode and electrolyte materials are undeniably crucial in determining the electrochemical behavior of batteries, the presence of these inactive components exerts a significant influence on factors including cost, performance and safety. This review aims to offer a comprehensive overview of the development, classification, and challenges associated with these key inactive components, with particular focus on cross-material synergies on battery performance. It is anticipated that this review will provide valuable insights to facilitate the enhancement of SIB performance and contribute to the optimization of battery systems as a whole.
In response to the increasing societal demand for efficient power and energy storage solutions, the development of novel battery technologies to complement existing lithium-ion batteries (LIBs) has emerged as a pivotal area of research. Sodium-ion batteries (SIBs), owing to the similarities in the physicochemical properties of sodium and lithium, have interpreted as promising candidates for next-generation secondary batteries. However, current research predominantly concentrates on the optimization of cathode and anode materials, as well as electrolytes, with insufficient attention paid to the critical role of inactive materials, such as binders, conductive agents, and separators. While electrode and electrolyte materials are undeniably crucial in determining the electrochemical behavior of batteries, the presence of these inactive components exerts a significant influence on factors including cost, performance and safety. This review aims to offer a comprehensive overview of the development, classification, and challenges associated with these key inactive components, with particular focus on cross-material synergies on battery performance. It is anticipated that this review will provide valuable insights to facilitate the enhancement of SIB performance and contribute to the optimization of battery systems as a whole.
2026, 37(10): 111653
doi: 10.1016/j.cclet.2025.111653
摘要:
Lithium metal batteries are widely recognized as a promising candidate for next-generation energy storage systems due to their exceptional theoretical energy density. However, the uncontrollable dendritic growth of lithium metal anodes remains a critical safety hazard, significantly impeding their practical implementation. The unique open-channel structures and functional moieties within metal-organic framework (MOF)-based solid-state electrolytes enable precise regulation of lithium-ion transport, offering a novel approach to address the lithium dendrite issue. This review systematically summarizes recent advances in MOF-based solid-state electrolytes that are categorized into three representative systems: pristine MOF-based electrolytes, MOF/ionic-liquid hybrid electrolytes, and MOF/polymer composite electrolytes. The discussion focuses on design principles and ion conduction mechanisms of MOF-based solid-state electrolytes, emphasizing the correlation between structural features and electrochemical performance. Furthermore, prospects for MOF-based electrolytes are discussed, highlighting future research directions towards high-performance MOF-based electrolytes for lithium metal batteries with high safety and high energy density.
Lithium metal batteries are widely recognized as a promising candidate for next-generation energy storage systems due to their exceptional theoretical energy density. However, the uncontrollable dendritic growth of lithium metal anodes remains a critical safety hazard, significantly impeding their practical implementation. The unique open-channel structures and functional moieties within metal-organic framework (MOF)-based solid-state electrolytes enable precise regulation of lithium-ion transport, offering a novel approach to address the lithium dendrite issue. This review systematically summarizes recent advances in MOF-based solid-state electrolytes that are categorized into three representative systems: pristine MOF-based electrolytes, MOF/ionic-liquid hybrid electrolytes, and MOF/polymer composite electrolytes. The discussion focuses on design principles and ion conduction mechanisms of MOF-based solid-state electrolytes, emphasizing the correlation between structural features and electrochemical performance. Furthermore, prospects for MOF-based electrolytes are discussed, highlighting future research directions towards high-performance MOF-based electrolytes for lithium metal batteries with high safety and high energy density.
2026, 37(10): 112095
doi: 10.1016/j.cclet.2025.112095
摘要:
Elucidating drug mechanisms of action and evaluating therapeutic efficacy require advanced techniques for real-time, dynamic monitoring of drug-target interactions in living systems. Recent advances in optical molecular probes have yielded powerful tools to visualize drug targets, quantify pharmacodynamic profiles, and track drug metabolism. In this review, we first summarize the major categories of optical imaging targets for chemotherapy assessment, followed by a systematic discussion of optical probe design strategies tailored to these targets. We then comprehensively review probe applications in drug screening, target validation, efficacy assessment, adverse effect evaluation, biodistribution analysis, and metabolic pathway tracking. Finally, we discuss the prospects and challenges of molecular optical imaging in precision medicine and clinical applications, while proposing potential breakthroughs and future directions. This review serves as a valuable reference for advancing optical probe design and application in drug development.
Elucidating drug mechanisms of action and evaluating therapeutic efficacy require advanced techniques for real-time, dynamic monitoring of drug-target interactions in living systems. Recent advances in optical molecular probes have yielded powerful tools to visualize drug targets, quantify pharmacodynamic profiles, and track drug metabolism. In this review, we first summarize the major categories of optical imaging targets for chemotherapy assessment, followed by a systematic discussion of optical probe design strategies tailored to these targets. We then comprehensively review probe applications in drug screening, target validation, efficacy assessment, adverse effect evaluation, biodistribution analysis, and metabolic pathway tracking. Finally, we discuss the prospects and challenges of molecular optical imaging in precision medicine and clinical applications, while proposing potential breakthroughs and future directions. This review serves as a valuable reference for advancing optical probe design and application in drug development.
2026, 37(10): 112102
doi: 10.1016/j.cclet.2025.112102
摘要:
Tetrahedral framework nucleic acids (tFNAs) have emerged as a promising platform for a wide range of biomedical applications due to their unique structural stability, ease of synthesis, and excellent biocompatibility. This review provides a comprehensive overview of the various modification strategies for tFNAs, including vertex modification, edge functional loading, internal encapsulation, and surface coating. These modifications enable precise control over their biological activity, facilitating advancements in drug delivery, gene therapy, tissue engineering, and diagnostic imaging. Additionally, the structural engineering of tFNAs has enabled their integration into theranostic platforms, offering significant potential for personalized medicine. The review also discusses the challenges involved in the clinical translation of tFNAs, such as scalability, pharmacokinetic optimization, and regulatory approval, and presents a forward-looking perspective on the emerging trends that could further broaden the scope of tFNAs in clinical applications. Finally, we conclude by outlining the future prospects of tFNAs in next-generation therapeutic and diagnostic systems, highlighting their transformative potential in the biomedical field.
Tetrahedral framework nucleic acids (tFNAs) have emerged as a promising platform for a wide range of biomedical applications due to their unique structural stability, ease of synthesis, and excellent biocompatibility. This review provides a comprehensive overview of the various modification strategies for tFNAs, including vertex modification, edge functional loading, internal encapsulation, and surface coating. These modifications enable precise control over their biological activity, facilitating advancements in drug delivery, gene therapy, tissue engineering, and diagnostic imaging. Additionally, the structural engineering of tFNAs has enabled their integration into theranostic platforms, offering significant potential for personalized medicine. The review also discusses the challenges involved in the clinical translation of tFNAs, such as scalability, pharmacokinetic optimization, and regulatory approval, and presents a forward-looking perspective on the emerging trends that could further broaden the scope of tFNAs in clinical applications. Finally, we conclude by outlining the future prospects of tFNAs in next-generation therapeutic and diagnostic systems, highlighting their transformative potential in the biomedical field.
2026, 37(10): 112135
doi: 10.1016/j.cclet.2025.112135
摘要:
Immune-mediated inflammatory diseases (IMIDs) are a class of chronic, relapsing disorders characterized by dysregulated immune activation and persistent inflammation. These conditions affect multiple organs, severely compromising patients' quality of life and increasing the global healthcare burden. Conventional treatments, such as glucocorticoids, immunosuppressants, and biologics, face limitations including low delivery efficiency, off-target effects, and poor patient adherence, whether administered topically or systemically. With the growing recognition of IMID pathogenesis as a multitargeted process, precision-based strategies and localized, patient-friendly drug delivery systems are increasingly needed. Microneedle (MN) technology has emerged as a promising transdermal and transmucosal platform for minimally invasive, site-specific therapeutic delivery in IMID treatment. By precisely targeting immune cells in the skin, oral mucosa, and eyes, MNs offer a novel approach to precision immunotherapy. This review explores recent advances in MN-based therapies for IMIDs, emphasizing their potential to transform the management of allergic conditions, autoimmune diseases, inflammatory skin disorders, infection-related chronic inflammation, oral disorders, and ocular disorders. Furthermore, the challenges hindering the clinical translation of MNs are discussed, along with perspectives on their future development. We anticipate that this review will provide innovative insights into precision immunotherapy for IMIDs.
Immune-mediated inflammatory diseases (IMIDs) are a class of chronic, relapsing disorders characterized by dysregulated immune activation and persistent inflammation. These conditions affect multiple organs, severely compromising patients' quality of life and increasing the global healthcare burden. Conventional treatments, such as glucocorticoids, immunosuppressants, and biologics, face limitations including low delivery efficiency, off-target effects, and poor patient adherence, whether administered topically or systemically. With the growing recognition of IMID pathogenesis as a multitargeted process, precision-based strategies and localized, patient-friendly drug delivery systems are increasingly needed. Microneedle (MN) technology has emerged as a promising transdermal and transmucosal platform for minimally invasive, site-specific therapeutic delivery in IMID treatment. By precisely targeting immune cells in the skin, oral mucosa, and eyes, MNs offer a novel approach to precision immunotherapy. This review explores recent advances in MN-based therapies for IMIDs, emphasizing their potential to transform the management of allergic conditions, autoimmune diseases, inflammatory skin disorders, infection-related chronic inflammation, oral disorders, and ocular disorders. Furthermore, the challenges hindering the clinical translation of MNs are discussed, along with perspectives on their future development. We anticipate that this review will provide innovative insights into precision immunotherapy for IMIDs.
2026, 37(10): 112137
doi: 10.1016/j.cclet.2025.112137
摘要:
Bioluminescence imaging has emerged as a vital tool for studying molecular dynamics in living organisms, owing to its high sensitivity, absence of background fluorescence, and independence from external excitation light sources, demonstrating significant potential for propelling self-illuminated theranostic applications. Among bioluminescent systems, NanoLuc luciferase (NLuc) demonstrates significant advantages over traditional luciferases due to its exceptional catalytic efficiency, small molecular size (19 kDa), stability, and ATP independence. However, its short emission wavelength (ca. 460 nm) is susceptible to tissue attenuation, which hinders deep-tissue applications, severely impeding its application in deep-tissue imaging and theranostics. Fortunately, bioluminescence resonance energy transfer (BRET) technology, combined with fluorescent protein fusions, protein tag techniques, and site-specific labeling with fluorescent dyes, effectively extends emission wavelengths, greatly enriching the toolkit for bioluminescence-based integrated theranostics. This review, for the first time, systematically summarizes groundbreaking strategies for engineered NLuc in “self-illuminating” theranostic applications. By elucidating its structure-function relationships, we focus on developments in NLuc engineering, substrate optimization, and the construction of BRET systems. The review critically assesses progress in deep-tissue imaging and spatiotemporally controlled phototherapy, providing a forward-looking roadmap for clinical translation in diagnostics and precision medicine.
Bioluminescence imaging has emerged as a vital tool for studying molecular dynamics in living organisms, owing to its high sensitivity, absence of background fluorescence, and independence from external excitation light sources, demonstrating significant potential for propelling self-illuminated theranostic applications. Among bioluminescent systems, NanoLuc luciferase (NLuc) demonstrates significant advantages over traditional luciferases due to its exceptional catalytic efficiency, small molecular size (19 kDa), stability, and ATP independence. However, its short emission wavelength (ca. 460 nm) is susceptible to tissue attenuation, which hinders deep-tissue applications, severely impeding its application in deep-tissue imaging and theranostics. Fortunately, bioluminescence resonance energy transfer (BRET) technology, combined with fluorescent protein fusions, protein tag techniques, and site-specific labeling with fluorescent dyes, effectively extends emission wavelengths, greatly enriching the toolkit for bioluminescence-based integrated theranostics. This review, for the first time, systematically summarizes groundbreaking strategies for engineered NLuc in “self-illuminating” theranostic applications. By elucidating its structure-function relationships, we focus on developments in NLuc engineering, substrate optimization, and the construction of BRET systems. The review critically assesses progress in deep-tissue imaging and spatiotemporally controlled phototherapy, providing a forward-looking roadmap for clinical translation in diagnostics and precision medicine.
2026, 37(10): 112138
doi: 10.1016/j.cclet.2025.112138
摘要:
Liver disease remains one of the most prevalent health concerns, attracting significant attention for its treatment options. As an emerging technology, messenger RNA (mRNA) technology has shown remarkable potential in the biomedical field, with RNA drugs offering distinct advantages such as rapid onset, safety, multiple target options, and ease of clinical translation. However, the inherent instability and susceptibility to degradation of mRNA molecules pose significant challenges for efficient and targeted delivery. Nanotechnology offers innovative solutions to these challenges, not only overcoming physiological barriers but also significantly enhancing the efficacy of mRNA drugs. As an ideal strategy for treating liver diseases, lipid nanoparticle (LNP)-encapsulated mRNA can activate regenerative pathways in hepatocytes within a short time frame, facilitating the treatment of liver injuries from various causes. This review highlights recent advancements in LNP-based mRNA delivery systems for treating different liver diseases. It begins with an introduction to mRNA drugs and their delivery systems, followed by a discussion on the targeting capabilities of LNP. It also emphasizes the application of LNP-based mRNA delivery systems in treating liver diseases. Finally, It outlines the current challenges faced by LNP-based mRNA delivery systems in liver disease treatment and anticipates future applications in addressing liver-related disorders. It is hoped that these insights presented here will help to further improve the application of mRNA-LNP technology in disease treatment. This review aims to provide a reference for researchers and clinicians in related fields and promotes the further development of this technology.
Liver disease remains one of the most prevalent health concerns, attracting significant attention for its treatment options. As an emerging technology, messenger RNA (mRNA) technology has shown remarkable potential in the biomedical field, with RNA drugs offering distinct advantages such as rapid onset, safety, multiple target options, and ease of clinical translation. However, the inherent instability and susceptibility to degradation of mRNA molecules pose significant challenges for efficient and targeted delivery. Nanotechnology offers innovative solutions to these challenges, not only overcoming physiological barriers but also significantly enhancing the efficacy of mRNA drugs. As an ideal strategy for treating liver diseases, lipid nanoparticle (LNP)-encapsulated mRNA can activate regenerative pathways in hepatocytes within a short time frame, facilitating the treatment of liver injuries from various causes. This review highlights recent advancements in LNP-based mRNA delivery systems for treating different liver diseases. It begins with an introduction to mRNA drugs and their delivery systems, followed by a discussion on the targeting capabilities of LNP. It also emphasizes the application of LNP-based mRNA delivery systems in treating liver diseases. Finally, It outlines the current challenges faced by LNP-based mRNA delivery systems in liver disease treatment and anticipates future applications in addressing liver-related disorders. It is hoped that these insights presented here will help to further improve the application of mRNA-LNP technology in disease treatment. This review aims to provide a reference for researchers and clinicians in related fields and promotes the further development of this technology.
2026, 37(10): 112152
doi: 10.1016/j.cclet.2025.112152
摘要:
Exosome-based therapies stand at the forefront of precision medicine, offering tailored solutions for disease-specific drug delivery and personalized treatment strategies. Addressing challenges such as the non-specific targeting of exosomes in brain diseases is crucial for optimizing therapeutic efficacy. Chemical modification of exosomes enables specific targeting of brain diseases via precise chemical reactions to conjugate brain disease-targeting ligands, functional molecules, or responsive moieties. The modification efficiency and outcomes are inherently contingent upon varying chemical reaction conditions, while the modification process itself exerts profound influences on the stability, biological activity, and functional expression of exosomes. Advanced chemical modification strategies have been demonstrated to effectively cross the blood-brain barrier (BBB), enabling spatiotemporally precise targeting of intracerebral lesion sites while maintaining their optimal biological activity and structural stability. By integrating the latest research achievements, this study reveals the unique advantages and mechanistic pathways of chemical modification in constructing highly specific targeted delivery systems for brain diseases, providing a precisely controllable novel approach for the precision therapy of brain diseases. Despite existing challenges, these advancements in chemically modified exosome research hold promise for ushering in safer, highly precise, and personalized therapies, thereby propelling the further advancement of exosomes in the therapeutic landscape of brain diseases.
Exosome-based therapies stand at the forefront of precision medicine, offering tailored solutions for disease-specific drug delivery and personalized treatment strategies. Addressing challenges such as the non-specific targeting of exosomes in brain diseases is crucial for optimizing therapeutic efficacy. Chemical modification of exosomes enables specific targeting of brain diseases via precise chemical reactions to conjugate brain disease-targeting ligands, functional molecules, or responsive moieties. The modification efficiency and outcomes are inherently contingent upon varying chemical reaction conditions, while the modification process itself exerts profound influences on the stability, biological activity, and functional expression of exosomes. Advanced chemical modification strategies have been demonstrated to effectively cross the blood-brain barrier (BBB), enabling spatiotemporally precise targeting of intracerebral lesion sites while maintaining their optimal biological activity and structural stability. By integrating the latest research achievements, this study reveals the unique advantages and mechanistic pathways of chemical modification in constructing highly specific targeted delivery systems for brain diseases, providing a precisely controllable novel approach for the precision therapy of brain diseases. Despite existing challenges, these advancements in chemically modified exosome research hold promise for ushering in safer, highly precise, and personalized therapies, thereby propelling the further advancement of exosomes in the therapeutic landscape of brain diseases.
2026, 37(10): 112170
doi: 10.1016/j.cclet.2025.112170
摘要:
Transdermal drug delivery provides a non-invasive route to circumvent gastrointestinal irritation and first-pass metabolism. This review presents a unique framework by categorizing delivery strategies into biological, chemical, and physical domains, a synthesis complemented by an original analysis of U.S. Food and Drug Administration approved drugs and over 1100 clinical trials. We systematically evaluate representative delivery strategy including microneedles, peptides, and liposomes highlighting their developmental trajectories, advantages, limitations, and clinical adoption status. Furthermore, the review focuses on three paradigmatic drugs (insulin, donepezil, and cannabinoids) to assess their cutting-edge transdermal research and commercialization progress. The insights gathered herein not only summarize the current state but also identify key challenges and opportunities, offering valuable guidance for accelerating the translation of novel transdermal systems.
Transdermal drug delivery provides a non-invasive route to circumvent gastrointestinal irritation and first-pass metabolism. This review presents a unique framework by categorizing delivery strategies into biological, chemical, and physical domains, a synthesis complemented by an original analysis of U.S. Food and Drug Administration approved drugs and over 1100 clinical trials. We systematically evaluate representative delivery strategy including microneedles, peptides, and liposomes highlighting their developmental trajectories, advantages, limitations, and clinical adoption status. Furthermore, the review focuses on three paradigmatic drugs (insulin, donepezil, and cannabinoids) to assess their cutting-edge transdermal research and commercialization progress. The insights gathered herein not only summarize the current state but also identify key challenges and opportunities, offering valuable guidance for accelerating the translation of novel transdermal systems.
2026, 37(10): 112425
doi: 10.1016/j.cclet.2026.112425
摘要:
Zinc plays a pivotal role in maintaining skin homeostasis, wound healing, and immune regulation, making it a promising therapeutic agent for diverse dermatological conditions. Despite its wide clinical application, conventional zinc formulations face significant limitations, including low bioavailability, systemic side effects, rapid ion release, and poor skin penetration. These shortcomings restrict their clinical efficacy and translation. Engineered carriers such as nanoparticles (NPs), hydrogels, and microneedles (MNs) offer opportunities to achieve controlled zinc release, enhance transdermal penetration, reduce local irritation, and enable combinational therapies with synergistic bioactivities. This review provides a comprehensive overview of zinc’s biological functions in skin physiology and pathology, critically discusses the bottlenecks of current zinc-containing medical materials, and highlights emerging delivery platforms designed to unlock its therapeutic potential. We further propose future research directions focusing on precision-targeted delivery, integration with advanced biomaterials, and exploration of zinc-based synergistic therapies.
Zinc plays a pivotal role in maintaining skin homeostasis, wound healing, and immune regulation, making it a promising therapeutic agent for diverse dermatological conditions. Despite its wide clinical application, conventional zinc formulations face significant limitations, including low bioavailability, systemic side effects, rapid ion release, and poor skin penetration. These shortcomings restrict their clinical efficacy and translation. Engineered carriers such as nanoparticles (NPs), hydrogels, and microneedles (MNs) offer opportunities to achieve controlled zinc release, enhance transdermal penetration, reduce local irritation, and enable combinational therapies with synergistic bioactivities. This review provides a comprehensive overview of zinc’s biological functions in skin physiology and pathology, critically discusses the bottlenecks of current zinc-containing medical materials, and highlights emerging delivery platforms designed to unlock its therapeutic potential. We further propose future research directions focusing on precision-targeted delivery, integration with advanced biomaterials, and exploration of zinc-based synergistic therapies.
2026, 37(10): 112463
doi: 10.1016/j.cclet.2026.112463
摘要:
In the context of dwindling energy resources and worsening environmental conditions, the dual-functional photocatalysis for hydrogen production and pollutant degradation has garnered widespread attention. This review systematically summarizes the latest advancements in photocatalytic technology in these two fields. The article first introduces the preparation methods of photocatalysts, focusing on several promising fundamental materials such as graphitic carbon nitride, metal organic frameworks, and metal oxides/sulfides. It also discusses in detail the synthesis methods of these materials, including pyrolysis, wet chemistry, and deposition methods, which are crucial for enhancing the performance of photocatalysts. Next, the article delves into the applications of dual-functional photocatalysts in hydrogen production and pollutant degradation, particularly the mechanisms and effects of simultaneous hydrogen generation and pollutant degradation. It emphasizes the performance and potential of dual-functional catalysts in these two processes, especially how photocatalysts can achieve both hydrogen evolution and pollutant degradation concurrently. Finally, the article looks ahead to future research directions, highlighting the challenges faced by dual-functional catalysts in technological applications, including the source of H atoms in hydrogen production, the common patterns of reaction sites during pollutant degradation, and the differing properties of oxidation products. It also underscores the potential development opportunities by utilizing hydrogen sources from pollutants and optimizing catalyst design.
In the context of dwindling energy resources and worsening environmental conditions, the dual-functional photocatalysis for hydrogen production and pollutant degradation has garnered widespread attention. This review systematically summarizes the latest advancements in photocatalytic technology in these two fields. The article first introduces the preparation methods of photocatalysts, focusing on several promising fundamental materials such as graphitic carbon nitride, metal organic frameworks, and metal oxides/sulfides. It also discusses in detail the synthesis methods of these materials, including pyrolysis, wet chemistry, and deposition methods, which are crucial for enhancing the performance of photocatalysts. Next, the article delves into the applications of dual-functional photocatalysts in hydrogen production and pollutant degradation, particularly the mechanisms and effects of simultaneous hydrogen generation and pollutant degradation. It emphasizes the performance and potential of dual-functional catalysts in these two processes, especially how photocatalysts can achieve both hydrogen evolution and pollutant degradation concurrently. Finally, the article looks ahead to future research directions, highlighting the challenges faced by dual-functional catalysts in technological applications, including the source of H atoms in hydrogen production, the common patterns of reaction sites during pollutant degradation, and the differing properties of oxidation products. It also underscores the potential development opportunities by utilizing hydrogen sources from pollutants and optimizing catalyst design.
2026, 37(10): 112501
doi: 10.1016/j.cclet.2026.112501
摘要:
Oligonucleotide therapy offers a promising approach for the treatment of various diseases by specifically targeting genes or pathogenic molecules with therapeutic oligonucleotides, demonstrating significant therapeutic efficacy and application potential. To date, the Food and Drug Administration (FDA) has approved over 20 oligonucleotide-based drugs. Pharmacokinetics plays a critical role in the regulatory approval of these drugs, which necessitates robust bioanalytical techniques. In this review, we first elucidate the mechanisms and representative drugs associated with different classes of therapeutic oligonucleotides, alongside an overview of their commonly used delivery systems. Subsequently, we provide a systematic overview of current bioanalytical methodologies, including sample preparation, separation, and detection, and highlight advantages, recent advancements, and challenges. Finally, we discuss future directions for analytical technique development for oligonucleotides.
Oligonucleotide therapy offers a promising approach for the treatment of various diseases by specifically targeting genes or pathogenic molecules with therapeutic oligonucleotides, demonstrating significant therapeutic efficacy and application potential. To date, the Food and Drug Administration (FDA) has approved over 20 oligonucleotide-based drugs. Pharmacokinetics plays a critical role in the regulatory approval of these drugs, which necessitates robust bioanalytical techniques. In this review, we first elucidate the mechanisms and representative drugs associated with different classes of therapeutic oligonucleotides, alongside an overview of their commonly used delivery systems. Subsequently, we provide a systematic overview of current bioanalytical methodologies, including sample preparation, separation, and detection, and highlight advantages, recent advancements, and challenges. Finally, we discuss future directions for analytical technique development for oligonucleotides.
2026, 37(10): 112502
doi: 10.1016/j.cclet.2026.112502
摘要:
Emerging contaminants (ECs) present significant environmental and health risks due to their widespread impact. Catalytic Fenton-like reactions using carbon-based catalysts offer a promising and sustainable solution for EC removal. This review synthesizes recent advancements in heteroatom-doped carbon (HDC) catalysts for peroxymonosulfate (PMS) activation, critically evaluating the merits and limitations of HDC-mediated Fenton-like reactions. The review explores how doping affects catalyst porosity, electronic properties, PMS activation efficiency, and overall effectiveness in EC removal. Innovative strategies for identifying key reactive species in HDC/PMS systems are discussed, including the use of chemical probes, spin-trapping agents, and SETP-based methodologies. Additionally, density functional theory (DFT) is utilized to investigate the electronic structures of ECs and their interactions with reactive oxygen species (ROS). The practical potential of HDCs in remediating contaminated groundwater and wastewater is also addressed, alongside a discussion of the challenges and future research directions to enhance their scalable applications, offering a roadmap for advancing sustainable environmental remediation technologies.
Emerging contaminants (ECs) present significant environmental and health risks due to their widespread impact. Catalytic Fenton-like reactions using carbon-based catalysts offer a promising and sustainable solution for EC removal. This review synthesizes recent advancements in heteroatom-doped carbon (HDC) catalysts for peroxymonosulfate (PMS) activation, critically evaluating the merits and limitations of HDC-mediated Fenton-like reactions. The review explores how doping affects catalyst porosity, electronic properties, PMS activation efficiency, and overall effectiveness in EC removal. Innovative strategies for identifying key reactive species in HDC/PMS systems are discussed, including the use of chemical probes, spin-trapping agents, and SETP-based methodologies. Additionally, density functional theory (DFT) is utilized to investigate the electronic structures of ECs and their interactions with reactive oxygen species (ROS). The practical potential of HDCs in remediating contaminated groundwater and wastewater is also addressed, alongside a discussion of the challenges and future research directions to enhance their scalable applications, offering a roadmap for advancing sustainable environmental remediation technologies.
2026, 37(10): 112516
doi: 10.1016/j.cclet.2026.112516
摘要:
Climate change and global warming constitute formidable global challenges, predominantly driven by the excessive dependence on conventional fossil fuels, which results in substantial carbon dioxide (CO2) emissions. Addressing these environmental issues is a paramount priority for researchers. Single-atom catalysts (SACs) have attracted significant attention due to their high atomic efficiency and unique performance in various catalytic reactions. As an emerging two-dimensional (2D) carbon material, graphdiyne (GDY) has gained favor in environmental remediation applications in recent years. GDY comprises sp- and sp2-hybridized carbon atoms, which form benzene rings and diacetylenic linkages (–C≡C–C≡C–) within a two-dimensional planar network, endowing it with high π-conjugation, distinctive and tunable electronic properties, and excellent chemical and thermal stability. In this review, we investigate the environmental catalytic reactions and applications of GDY-based SACs. We provide a detailed account of the current methodologies for synthesizing GDY and examine the catalytic applications of GDY-based SACs in CO2 reduction reactions. Specifically, we systematically categorize the photocatalytic and electrocatalytic CO2 reduction processes using metal-doped GDY and metal-free doped GDY. Finally, we discuss the challenges and future developments of GDY within the context of SACs.
Climate change and global warming constitute formidable global challenges, predominantly driven by the excessive dependence on conventional fossil fuels, which results in substantial carbon dioxide (CO2) emissions. Addressing these environmental issues is a paramount priority for researchers. Single-atom catalysts (SACs) have attracted significant attention due to their high atomic efficiency and unique performance in various catalytic reactions. As an emerging two-dimensional (2D) carbon material, graphdiyne (GDY) has gained favor in environmental remediation applications in recent years. GDY comprises sp- and sp2-hybridized carbon atoms, which form benzene rings and diacetylenic linkages (–C≡C–C≡C–) within a two-dimensional planar network, endowing it with high π-conjugation, distinctive and tunable electronic properties, and excellent chemical and thermal stability. In this review, we investigate the environmental catalytic reactions and applications of GDY-based SACs. We provide a detailed account of the current methodologies for synthesizing GDY and examine the catalytic applications of GDY-based SACs in CO2 reduction reactions. Specifically, we systematically categorize the photocatalytic and electrocatalytic CO2 reduction processes using metal-doped GDY and metal-free doped GDY. Finally, we discuss the challenges and future developments of GDY within the context of SACs.
2026, 37(10): 112522
doi: 10.1016/j.cclet.2026.112522
摘要:
Micro/nano plastics as an emerging contaminant have attracted the attention of researchers worldwide. However, a variety of detection methods have been derived based on the properties of micro/nano plastics, such as micro-infrared spectroscopy, micro-Raman spectroscopy, gas chromatography-mass spectrometry, liquid chromatograph-mass spectrometry, optical-photothermal infrared. Compared with spectroscopy and mass spectrometry detection methods, many new detection methods have emerged with the advantages of low cost, high speed, and high sensitivity. But the detection process often only reflects part of the properties of micro/nano plastics, which limits our comprehensive understanding of the environmental behaviors of micro/nano plastics such as carrying contamination and interfacial properties. In this review, we critically summarize the existing literature on traditional and rapid detection methods, focusing on their current research status, applicability conditions, detection limits, and mechanisms. We emphasize that weathering behavior, migration behavior, deposition, adhesion, and adsorption of micro/nano plastics in the environment will change the physicochemical properties of micro/nano plastics, which will have an impact on current rapid detection and analysis methods. Rapid detection and analysis methods require consideration of the interfacial evolution behavior of micro/nano plastics in the environment to enhance the universality of their application. In addition, rapid detection methods are complementary to traditional standardized detection methods. After understanding the types of micro/nano plastics, we are more concerned about the quantity, dispersion behavior, carrying contamination, and interfacial properties in the environment. These properties are crucial for the environmental assessment and prevention of micro/nano plastics. It is recommended that further comprehensive research be conducted based on the optical and interfacial properties of micro/nano plastics, combined with machine learning and computer modeling, to provide a reliable basis for micro/nano plastic research.
Micro/nano plastics as an emerging contaminant have attracted the attention of researchers worldwide. However, a variety of detection methods have been derived based on the properties of micro/nano plastics, such as micro-infrared spectroscopy, micro-Raman spectroscopy, gas chromatography-mass spectrometry, liquid chromatograph-mass spectrometry, optical-photothermal infrared. Compared with spectroscopy and mass spectrometry detection methods, many new detection methods have emerged with the advantages of low cost, high speed, and high sensitivity. But the detection process often only reflects part of the properties of micro/nano plastics, which limits our comprehensive understanding of the environmental behaviors of micro/nano plastics such as carrying contamination and interfacial properties. In this review, we critically summarize the existing literature on traditional and rapid detection methods, focusing on their current research status, applicability conditions, detection limits, and mechanisms. We emphasize that weathering behavior, migration behavior, deposition, adhesion, and adsorption of micro/nano plastics in the environment will change the physicochemical properties of micro/nano plastics, which will have an impact on current rapid detection and analysis methods. Rapid detection and analysis methods require consideration of the interfacial evolution behavior of micro/nano plastics in the environment to enhance the universality of their application. In addition, rapid detection methods are complementary to traditional standardized detection methods. After understanding the types of micro/nano plastics, we are more concerned about the quantity, dispersion behavior, carrying contamination, and interfacial properties in the environment. These properties are crucial for the environmental assessment and prevention of micro/nano plastics. It is recommended that further comprehensive research be conducted based on the optical and interfacial properties of micro/nano plastics, combined with machine learning and computer modeling, to provide a reliable basis for micro/nano plastic research.
2026, 37(10): 112553
doi: 10.1016/j.cclet.2026.112553
摘要:
Extracellular vesicles (EVs) released by cells are widely present in body fluids and serve as mediators of cell communication and markers in disease diagnosis. However, it remains challenging to separate high-purity and structurally intact EVs from complex biological samples. Recently, microfluidics has shown excellent performance in the separation and analysis of EVs due to its precise control and integration capabilities. Microfluidic methods hold promise for clinical diagnostics owing to their integrated and convenient properties. In this review, we first introduce microfluidic-based label-free and affinity-based strategies for EV separation. Next, the common EV analysis methods integrated with microfluidics are summarized, including fluorescence, electrochemistry, surface plasmon resonance (SPR), and surface-enhanced Raman spectroscopy (SERS). Then, some microfluidics-based systems (valves, traps, and droplets) for single-cell EV analysis are concluded. Finally, we present the challenges and trends of microfluidics in EV research.
Extracellular vesicles (EVs) released by cells are widely present in body fluids and serve as mediators of cell communication and markers in disease diagnosis. However, it remains challenging to separate high-purity and structurally intact EVs from complex biological samples. Recently, microfluidics has shown excellent performance in the separation and analysis of EVs due to its precise control and integration capabilities. Microfluidic methods hold promise for clinical diagnostics owing to their integrated and convenient properties. In this review, we first introduce microfluidic-based label-free and affinity-based strategies for EV separation. Next, the common EV analysis methods integrated with microfluidics are summarized, including fluorescence, electrochemistry, surface plasmon resonance (SPR), and surface-enhanced Raman spectroscopy (SERS). Then, some microfluidics-based systems (valves, traps, and droplets) for single-cell EV analysis are concluded. Finally, we present the challenges and trends of microfluidics in EV research.
2026, 37(10): 112555
doi: 10.1016/j.cclet.2026.112555
摘要:
Nitrous oxide (N2O), a potent greenhouse gas, requires urgent and effective mitigation strategies. Among traditional (high-temperature thermal decomposition, selective catalytic reduction (SCR), direct catalytic decomposition, etc.) and emerging (biological treatment, photo/electrocatalysis, plasma-assisted decomposition, etc.) technologies, direct catalytic decomposition stands out as a highly promising approach thanks to its energy efficiency and environmental benefits. This review systematically summarizes recent progress in the catalytic decomposition of N2O, with emphasis on catalysts, including noble metal catalysts, transition metal oxide catalysts, zeolite-based catalysts, and emerging catalytic materials. Atomic-level active site engineering, oxygen vacancy modulation, and active site-support interactions, which determine catalytic performances and reaction mechanisms, are critically delineated. Furthermore, practical challenges of catalyst designs and integrated reaction systems are addressed. By establishing connections between fundamental research and industrial applications, this review proposes a comprehensive framework for the development of next-generation N2O decomposition catalysts, thereby supporting global efforts to cut greenhouse gas emissions.
Nitrous oxide (N2O), a potent greenhouse gas, requires urgent and effective mitigation strategies. Among traditional (high-temperature thermal decomposition, selective catalytic reduction (SCR), direct catalytic decomposition, etc.) and emerging (biological treatment, photo/electrocatalysis, plasma-assisted decomposition, etc.) technologies, direct catalytic decomposition stands out as a highly promising approach thanks to its energy efficiency and environmental benefits. This review systematically summarizes recent progress in the catalytic decomposition of N2O, with emphasis on catalysts, including noble metal catalysts, transition metal oxide catalysts, zeolite-based catalysts, and emerging catalytic materials. Atomic-level active site engineering, oxygen vacancy modulation, and active site-support interactions, which determine catalytic performances and reaction mechanisms, are critically delineated. Furthermore, practical challenges of catalyst designs and integrated reaction systems are addressed. By establishing connections between fundamental research and industrial applications, this review proposes a comprehensive framework for the development of next-generation N2O decomposition catalysts, thereby supporting global efforts to cut greenhouse gas emissions.
2026, 37(10): 112556
doi: 10.1016/j.cclet.2026.112556
摘要:
Piezocatalysis based on electrode polarization processes represents a highly promising approach for in-situ H2O2 generation. The efficiency of piezocatalytic H2O2 generation faces dual constraints from extrinsic operational parameters like excitation frequency and intrinsic material properties, particularly crystallographic characteristics and polarization magnitude governing charge separation kinetics. Consequently, structural optimization targeting enhanced polarization response, accelerated charge transfer, and strengthened reactant adsorption at active sites has become a central research imperative. This review evaluates piezoelectric material design strategies, establishes structure-function relationships spanning multiscale features and H2O2 production efficiency, and assesses technological viability for advanced wastewater remediation. By systematically analyzing core structural determinants, including crystal symmetry, heterojunction, surface functionalization, polymerization degree, and microstructural parameters (porosity/thickness), across diverse piezocatalytic systems, we elucidate governing structure-function interdependencies for H2O2 production. These determinants have been further validated in material classes spanning perovskites, bismuth-based layered compounds, wurtzite-type materials, transition metal dichalcogenides, carbon-based materials, polymers, metal-organic frameworks, and MAX phase materials. These insights will establish mechanistic foundations for in-situ H2O2 synthesis, advancing sustainable water remediation via piezocatalysis.
Piezocatalysis based on electrode polarization processes represents a highly promising approach for in-situ H2O2 generation. The efficiency of piezocatalytic H2O2 generation faces dual constraints from extrinsic operational parameters like excitation frequency and intrinsic material properties, particularly crystallographic characteristics and polarization magnitude governing charge separation kinetics. Consequently, structural optimization targeting enhanced polarization response, accelerated charge transfer, and strengthened reactant adsorption at active sites has become a central research imperative. This review evaluates piezoelectric material design strategies, establishes structure-function relationships spanning multiscale features and H2O2 production efficiency, and assesses technological viability for advanced wastewater remediation. By systematically analyzing core structural determinants, including crystal symmetry, heterojunction, surface functionalization, polymerization degree, and microstructural parameters (porosity/thickness), across diverse piezocatalytic systems, we elucidate governing structure-function interdependencies for H2O2 production. These determinants have been further validated in material classes spanning perovskites, bismuth-based layered compounds, wurtzite-type materials, transition metal dichalcogenides, carbon-based materials, polymers, metal-organic frameworks, and MAX phase materials. These insights will establish mechanistic foundations for in-situ H2O2 synthesis, advancing sustainable water remediation via piezocatalysis.
2026, 37(10): 112585
doi: 10.1016/j.cclet.2026.112585
摘要:
Nanozymes have been widely used in tumor theranostics because of their enzyme-like catalytic properties and the ease of preparation and stability, which are superior to those of natural enzymes. The complex tumor microenvironment limits the therapeutic efficacy in various ways, while carbon-based nanozymes stand out among the nanozymes due to their high specific surface area, strong drug-carrying capacity, easy-to-modify surfaces, excellent biocompatibility, and unique optical-photothermal conversion efficiency. In recent years, significant progress has been made in the application of carbon nanozymes (CNs) in tumor therapy. This article mainly reviews the classification, characteristics, catalytic mechanism and the latest applications of CNs in tumor theranostics. Additionally, it analyzes the prospects and challenges faced by CNs.
Nanozymes have been widely used in tumor theranostics because of their enzyme-like catalytic properties and the ease of preparation and stability, which are superior to those of natural enzymes. The complex tumor microenvironment limits the therapeutic efficacy in various ways, while carbon-based nanozymes stand out among the nanozymes due to their high specific surface area, strong drug-carrying capacity, easy-to-modify surfaces, excellent biocompatibility, and unique optical-photothermal conversion efficiency. In recent years, significant progress has been made in the application of carbon nanozymes (CNs) in tumor therapy. This article mainly reviews the classification, characteristics, catalytic mechanism and the latest applications of CNs in tumor theranostics. Additionally, it analyzes the prospects and challenges faced by CNs.
2026, 37(10): 112691
doi: 10.1016/j.cclet.2026.112691
摘要:
Hydrogen energy is a key clean and sustainable alternative to fossil fuels. Producing “green hydrogen” via water electrolysis using renewable energy is a leading approach, but high costs and reliance on scarce precious metal catalysts like platinum and iridium remain major barriers. Developing affordable, efficient, and stable non-precious metal catalysts is therefore essential for scaling up green hydrogen technology. Nickel-based materials have emerged as promising candidates due to their good electrocatalytic activity for both hydrogen and oxygen evolution reactions, corrosion resistance, and low cost. Recent studies have focused on nickel-based compounds such as hydroxides, sulfides, selenides, and phosphates as bifunctional catalysts. However, their performance still lags precious metals in activity and stability, necessitating further improvement through material modification. This review examines the fundamental mechanisms of electrocatalysis and explores strategies to enhance nickel-based catalysts, including anion/cation doping, microstructure control, and heterointerface engineering. These approaches help optimize electronic structures, increase surface area, and improve mass transfer, thereby boosting catalytic activity and durability. Finally, the practical potential and development pathway of high-performance nickel-based electrocatalysts for large-scale green hydrogen production are discussed.
Hydrogen energy is a key clean and sustainable alternative to fossil fuels. Producing “green hydrogen” via water electrolysis using renewable energy is a leading approach, but high costs and reliance on scarce precious metal catalysts like platinum and iridium remain major barriers. Developing affordable, efficient, and stable non-precious metal catalysts is therefore essential for scaling up green hydrogen technology. Nickel-based materials have emerged as promising candidates due to their good electrocatalytic activity for both hydrogen and oxygen evolution reactions, corrosion resistance, and low cost. Recent studies have focused on nickel-based compounds such as hydroxides, sulfides, selenides, and phosphates as bifunctional catalysts. However, their performance still lags precious metals in activity and stability, necessitating further improvement through material modification. This review examines the fundamental mechanisms of electrocatalysis and explores strategies to enhance nickel-based catalysts, including anion/cation doping, microstructure control, and heterointerface engineering. These approaches help optimize electronic structures, increase surface area, and improve mass transfer, thereby boosting catalytic activity and durability. Finally, the practical potential and development pathway of high-performance nickel-based electrocatalysts for large-scale green hydrogen production are discussed.
2026, 37(10): 112695
doi: 10.1016/j.cclet.2026.112695
摘要:
Over the past few decades, various forms of selenium, including organic and inorganic types, have been extensively researched for their impact on synthetic chemistry. Organic selenium has evolved from being a niche and pungent chemical compound to being recognized as an environmentally sustainable tool that facilitates greener organic synthesis. Chemists have made substantial advancements in selenium chemistry, advancing from stoichiometric to catalytic processes and from racemic to asymmetric transformations. To address the limitations in asymmetric reactions, a group of scientists led by Denmark, Breder, Yeung, Chen, Zhao and Shirakawa introduced a range of chiral selenium catalysts. These catalysts, each with distinct structures, exhibit varying levels of reaction activity and catalyze different types of reactions. Despite these differences, the majority of reactions focus on olefin substrates and arenes. The selenium-mediated transformations demonstrate high chemoselectivity, regioselectivity, and stereoselectivity. This review summarizes recent advances in selenium-catalyzed enantioselective reactions, categorizing them by selenium properties, reaction types, and proposed mechanisms.
Over the past few decades, various forms of selenium, including organic and inorganic types, have been extensively researched for their impact on synthetic chemistry. Organic selenium has evolved from being a niche and pungent chemical compound to being recognized as an environmentally sustainable tool that facilitates greener organic synthesis. Chemists have made substantial advancements in selenium chemistry, advancing from stoichiometric to catalytic processes and from racemic to asymmetric transformations. To address the limitations in asymmetric reactions, a group of scientists led by Denmark, Breder, Yeung, Chen, Zhao and Shirakawa introduced a range of chiral selenium catalysts. These catalysts, each with distinct structures, exhibit varying levels of reaction activity and catalyze different types of reactions. Despite these differences, the majority of reactions focus on olefin substrates and arenes. The selenium-mediated transformations demonstrate high chemoselectivity, regioselectivity, and stereoselectivity. This review summarizes recent advances in selenium-catalyzed enantioselective reactions, categorizing them by selenium properties, reaction types, and proposed mechanisms.
2026, 37(10): 112696
doi: 10.1016/j.cclet.2026.112696
摘要:
Triplet-triplet annihilation upconversion (TTA-UC), a process capable of converting low-energy photons into higher-energy light, has garnered significant interest for applications in photovoltaics, bioimaging, and photopolymerization. This phenomenon relies on the concerted interaction between a sensitizer (energy donor) and an annihilator (energy acceptor). While considerable research has been devoted to developing diverse molecular derivatives of photosensitizers with tailored photophysical properties, the deliberate structural design of annihilators has remained relatively underexplored. However, in molecular diffusion-limited systems, such as in solid-state matrices, rational annihilator design becomes crucial. This review summarizes recent advances in the structural design of triplet annihilators for TTA-UC systems. We categorize these emerging annihilators into three groups based on their design principles: (1) Multichromophoric annihilators engineered for intramolecular TTA, (2) supramolecular macrocycle-based annihilators that enhance both triplet-triplet energy transfer and TTA processes, and (3) annihilators designed with ordered molecular arrangements to achieve efficient TTA-UC in diffusion-limited environments.
Triplet-triplet annihilation upconversion (TTA-UC), a process capable of converting low-energy photons into higher-energy light, has garnered significant interest for applications in photovoltaics, bioimaging, and photopolymerization. This phenomenon relies on the concerted interaction between a sensitizer (energy donor) and an annihilator (energy acceptor). While considerable research has been devoted to developing diverse molecular derivatives of photosensitizers with tailored photophysical properties, the deliberate structural design of annihilators has remained relatively underexplored. However, in molecular diffusion-limited systems, such as in solid-state matrices, rational annihilator design becomes crucial. This review summarizes recent advances in the structural design of triplet annihilators for TTA-UC systems. We categorize these emerging annihilators into three groups based on their design principles: (1) Multichromophoric annihilators engineered for intramolecular TTA, (2) supramolecular macrocycle-based annihilators that enhance both triplet-triplet energy transfer and TTA processes, and (3) annihilators designed with ordered molecular arrangements to achieve efficient TTA-UC in diffusion-limited environments.
2026, 37(10): 112897
doi: 10.1016/j.cclet.2026.112897
摘要:
Alkali metal batteries (AMBs) have emerged as promising candidates for next-generation high-energy-density energy storage systems due to their high theoretical specific capacity and high output voltage. However, further application of AMBs is hindered by severe dendritic growth and large volume expansion of alkali metal anodes (AMAs) during cycling, as well as their unstable interphases. In this context, carbon dot-based nanomaterials (CDNMs), with their superior specific surface area, tunable heteroatom doping, and abundant surface functional groups, have been extensively investigated to stabilize AMAs, demonstrating remarkable potential in addressing aforementioned issues. Considering the rapidly growing research enthusiasm in this topic in recent years, here, we comprehensively summarize recent progress in application of CDNMs in stable and dendrite-free AMAs. First, the critical challenges of alkali metal anodes and the corresponding modification strategies in alkali metal batteries are discussed. Furthermore, the structure and properties of carbon dots (CDs) are introduced, as well as the advantages, disadvantages, and research progress of various CDs preparation methods are summarized from both the top-down and bottom-up perspectives. In addition, the relationship between fabrication methods, micro/nanostructure, and electrochemical performance are systematically summarized and discussed. Finally, in light of the current research status, the challenges and opportunities of the application of CDNMs in AMBs are proposed.
Alkali metal batteries (AMBs) have emerged as promising candidates for next-generation high-energy-density energy storage systems due to their high theoretical specific capacity and high output voltage. However, further application of AMBs is hindered by severe dendritic growth and large volume expansion of alkali metal anodes (AMAs) during cycling, as well as their unstable interphases. In this context, carbon dot-based nanomaterials (CDNMs), with their superior specific surface area, tunable heteroatom doping, and abundant surface functional groups, have been extensively investigated to stabilize AMAs, demonstrating remarkable potential in addressing aforementioned issues. Considering the rapidly growing research enthusiasm in this topic in recent years, here, we comprehensively summarize recent progress in application of CDNMs in stable and dendrite-free AMAs. First, the critical challenges of alkali metal anodes and the corresponding modification strategies in alkali metal batteries are discussed. Furthermore, the structure and properties of carbon dots (CDs) are introduced, as well as the advantages, disadvantages, and research progress of various CDs preparation methods are summarized from both the top-down and bottom-up perspectives. In addition, the relationship between fabrication methods, micro/nanostructure, and electrochemical performance are systematically summarized and discussed. Finally, in light of the current research status, the challenges and opportunities of the application of CDNMs in AMBs are proposed.
2026, 37(10): 111530
doi: 10.1016/j.cclet.2025.111530
摘要:
Molecular-based ferroelectrics have received extensive attention from materials scientists in recent years due to their light weight, high flexibility, and environmental friendliness. However, the precise design of molecular-based ferroelectrics by using crown ether supramolecular systems remains a huge challenge. In this work, L-valine (L-Val) and 18-crown-6 were selected as the guest and host molecules, respectively, for constructing crown ether complexes: [L-Val]2+(18-crown-6)3(H2O)2[FeX4]2- (X = Cl (1), Br (2)) by halogen modulation. The results indicated that compound 1 exhibits a reversible phase transition accompanied by symmetry evolution from P1 to I2/m at room temperature. The implementation of halogen substitution strategy resulted in compound 2 crystallizes in C2/m space group, and the phase transition temperature was changed by 30 K. Meanwhile, oscillations of supramolecular groups within the framework conferred significant coupled physical properties, including reversible dielectric anomalies, reversible magnetic transfers, spin crossovers (SCOs), the band gap value decreases, paraelectric–ferroelectric phase transitions, and a second-harmonic generation (SHG) response. In short, this work provides a brand new perspective on expanding the multifunctionality of crown ether supramolecular systems.
Molecular-based ferroelectrics have received extensive attention from materials scientists in recent years due to their light weight, high flexibility, and environmental friendliness. However, the precise design of molecular-based ferroelectrics by using crown ether supramolecular systems remains a huge challenge. In this work, L-valine (L-Val) and 18-crown-6 were selected as the guest and host molecules, respectively, for constructing crown ether complexes: [L-Val]2+(18-crown-6)3(H2O)2[FeX4]2- (X = Cl (1), Br (2)) by halogen modulation. The results indicated that compound 1 exhibits a reversible phase transition accompanied by symmetry evolution from P1 to I2/m at room temperature. The implementation of halogen substitution strategy resulted in compound 2 crystallizes in C2/m space group, and the phase transition temperature was changed by 30 K. Meanwhile, oscillations of supramolecular groups within the framework conferred significant coupled physical properties, including reversible dielectric anomalies, reversible magnetic transfers, spin crossovers (SCOs), the band gap value decreases, paraelectric–ferroelectric phase transitions, and a second-harmonic generation (SHG) response. In short, this work provides a brand new perspective on expanding the multifunctionality of crown ether supramolecular systems.
2026, 37(10): 111531
doi: 10.1016/j.cclet.2025.111531
摘要:
Rare-earth-doped fluorescent hydrogels, while effective for optical sensing, often have limited functionality due to weak physical crosslinking. Stretchable chemically crosslinked conductive hydrogel sensors, essential for adhering to the human body to monitor movements, typically hinder fluorescence. This is caused by the opacity of conductive components, and adhesion molecules like catechol may quench fluorescence. These constraints limit the multifunctional applications of hydrogels that combine both physical and chemical crosslinking. In this study, we blend and polymerize acrylamide (AM), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), and iminodiacetic acid (IDA)-modified carboxymethyl cellulose sodium (CMC—Na) to form hydrogels, while introducing rare-earth elements to achieve synergistic benefits. This novel approach yields hydrogels with low hysteresis, high strain (1150%), ultra-fast response capability (50 ms), and high sensitivity (GF = 5.03), facilitated by the physical crosslinking of rare-earth ions. By adjusting the IDA content or the Eu3+/Tb3+ ratio, we can precisely control the hydrogel’s brightness, achieving tunable red/yellow/green fluorescence variations through radiative transitions. Additionally, we have developed, for the first time, a fluorescence/conductivity dual-channel sensor that responds to pressure changes by displaying color shifts. This represents a new strategy for multifunctional rare-earth-doped hydrogels and flexible sensing applications.
Rare-earth-doped fluorescent hydrogels, while effective for optical sensing, often have limited functionality due to weak physical crosslinking. Stretchable chemically crosslinked conductive hydrogel sensors, essential for adhering to the human body to monitor movements, typically hinder fluorescence. This is caused by the opacity of conductive components, and adhesion molecules like catechol may quench fluorescence. These constraints limit the multifunctional applications of hydrogels that combine both physical and chemical crosslinking. In this study, we blend and polymerize acrylamide (AM), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), and iminodiacetic acid (IDA)-modified carboxymethyl cellulose sodium (CMC—Na) to form hydrogels, while introducing rare-earth elements to achieve synergistic benefits. This novel approach yields hydrogels with low hysteresis, high strain (1150%), ultra-fast response capability (50 ms), and high sensitivity (GF = 5.03), facilitated by the physical crosslinking of rare-earth ions. By adjusting the IDA content or the Eu3+/Tb3+ ratio, we can precisely control the hydrogel’s brightness, achieving tunable red/yellow/green fluorescence variations through radiative transitions. Additionally, we have developed, for the first time, a fluorescence/conductivity dual-channel sensor that responds to pressure changes by displaying color shifts. This represents a new strategy for multifunctional rare-earth-doped hydrogels and flexible sensing applications.
2026, 37(10): 111532
doi: 10.1016/j.cclet.2025.111532
摘要:
The most notable structural features of polyoxometalates (POMs) are their large molecular size and relatively low effective surface charge density. These properties endow POMs with excellent Brønsted acidity and proton mobility, making them ideal materials for proton conductors. In this study, a series of homotrimeric complexes were successfully synthesized through Ln3+/Bi3+ induced assembly of a suitable organic ligand 1-hydroxyethylidene 1,1-diphosphonic acid (HEDP): H9[La(Mo2O4)6(H2O)6(HEDP)6](LaO9H6)·18H2O (complex 1), H9[Nd(Mo2O4)6(H2O)6(HEDP)6](NdO6H12)·15H2O (complex 2), and H9[Bi(Mo2O4)6(H2O)6(HEDP)6] (complex 3). Notably, the presence of free rare earth ions in the asymmetric unit of complexes 1 and 2 is a structural feature that results in a tighter hydrogen-bonding network in their three-dimensional stacking structures, which in turn significantly enhances the proton conductivity. Complexes 1–3 exhibit excellent proton conductivity, with measured values of 3.35 × 10–2, 3.81 × 10–2, and 2.37 × 10–2 S/cm under 98% relative humidity at 80 ℃. This study establishes a promising strategy for designing molybdate cluster-based materials with enhanced proton conduction properties.
The most notable structural features of polyoxometalates (POMs) are their large molecular size and relatively low effective surface charge density. These properties endow POMs with excellent Brønsted acidity and proton mobility, making them ideal materials for proton conductors. In this study, a series of homotrimeric complexes were successfully synthesized through Ln3+/Bi3+ induced assembly of a suitable organic ligand 1-hydroxyethylidene 1,1-diphosphonic acid (HEDP): H9[La(Mo2O4)6(H2O)6(HEDP)6](LaO9H6)·18H2O (complex 1), H9[Nd(Mo2O4)6(H2O)6(HEDP)6](NdO6H12)·15H2O (complex 2), and H9[Bi(Mo2O4)6(H2O)6(HEDP)6] (complex 3). Notably, the presence of free rare earth ions in the asymmetric unit of complexes 1 and 2 is a structural feature that results in a tighter hydrogen-bonding network in their three-dimensional stacking structures, which in turn significantly enhances the proton conductivity. Complexes 1–3 exhibit excellent proton conductivity, with measured values of 3.35 × 10–2, 3.81 × 10–2, and 2.37 × 10–2 S/cm under 98% relative humidity at 80 ℃. This study establishes a promising strategy for designing molybdate cluster-based materials with enhanced proton conduction properties.
2026, 37(10): 111534
doi: 10.1016/j.cclet.2025.111534
摘要:
The conjugation of metal-organic architectures with metal nanoparticles into a multicomponent system is an attractive route for designing myriad materials with structural complexity, integrated properties, and important applications. Herein, we report a single-crystal to single-crystal transition from the thiacalixarene-based octahedral coordination cage Co24-Na to Co24-Ag and the construction of nanohybrids (Co24-Ag@Ag-NPs) by combining Co24-Ag with silver nanoparticles (Ag NPs) for photothermal conversion. The multicomponent Co24-Ag@Ag-NPs not only combined and enhanced the light absorption effect of Co24-Ag and the plasmon effect of Ag NPs but also offered the Mott-Schottky heterojunction. Benefiting from the improved photo-response ability and the protective effect of calixarene in preventing heat loss, Co24-Ag@Ag-NPs exhibited significant visible light photothermal conversion performance.
The conjugation of metal-organic architectures with metal nanoparticles into a multicomponent system is an attractive route for designing myriad materials with structural complexity, integrated properties, and important applications. Herein, we report a single-crystal to single-crystal transition from the thiacalixarene-based octahedral coordination cage Co24-Na to Co24-Ag and the construction of nanohybrids (Co24-Ag@Ag-NPs) by combining Co24-Ag with silver nanoparticles (Ag NPs) for photothermal conversion. The multicomponent Co24-Ag@Ag-NPs not only combined and enhanced the light absorption effect of Co24-Ag and the plasmon effect of Ag NPs but also offered the Mott-Schottky heterojunction. Benefiting from the improved photo-response ability and the protective effect of calixarene in preventing heat loss, Co24-Ag@Ag-NPs exhibited significant visible light photothermal conversion performance.
2026, 37(10): 111535
doi: 10.1016/j.cclet.2025.111535
摘要:
Cyclic trinuclear complexes (CTCs) are coordination compounds composed of three metal atoms arranged in a cyclic structure, which imparts them with significant potential for catalytic applications. However, their practical use is often hindered by issues of low chemical stability and poor dispersity. In this work, we present an efficient strategy for stabilizing trinuclear copper complexes [tris(µ2–4-carboxaldehyde-pyrazolato-N,N’)-tri-copper(Ⅰ) monohydrate, Cu3(PyCA)3·H2O] by chemically incorporating them into the core of diblock copolymer aggregates. Specifically, we utilize reversible addition-fragmentation chain transfer (RAFT) polymerization to synthesize poly(2-aminoethyl methacrylate hydrochloride)50-block-poly(glycerol monomethacrylate)52 (A50-G52) diblock copolymers. The subsequent reaction between primary amine groups of the A50 block and aldehyde groups of the Cu3(PyCA)3·H2O leads to the formation of A50-G52-Cu3(PyCA)3 hybrid nanoparticles, in which the G52 blocks serve as steric coronas, while the Cu3(PyCA)3·H2O are incorporated within the core domain. Notably, these hybrid nanoparticles exhibit enhanced stability and improved catalytic performance in the Sonogashira cross-coupling reaction in air. Through the precise design of reactive block copolymers, this study presents a novel strategy for the particleization of CTCs, thereby enabling the practical and scalable preparation of a diverse range of CTCs-based functional materials with enhanced properties.
Cyclic trinuclear complexes (CTCs) are coordination compounds composed of three metal atoms arranged in a cyclic structure, which imparts them with significant potential for catalytic applications. However, their practical use is often hindered by issues of low chemical stability and poor dispersity. In this work, we present an efficient strategy for stabilizing trinuclear copper complexes [tris(µ2–4-carboxaldehyde-pyrazolato-N,N’)-tri-copper(Ⅰ) monohydrate, Cu3(PyCA)3·H2O] by chemically incorporating them into the core of diblock copolymer aggregates. Specifically, we utilize reversible addition-fragmentation chain transfer (RAFT) polymerization to synthesize poly(2-aminoethyl methacrylate hydrochloride)50-block-poly(glycerol monomethacrylate)52 (A50-G52) diblock copolymers. The subsequent reaction between primary amine groups of the A50 block and aldehyde groups of the Cu3(PyCA)3·H2O leads to the formation of A50-G52-Cu3(PyCA)3 hybrid nanoparticles, in which the G52 blocks serve as steric coronas, while the Cu3(PyCA)3·H2O are incorporated within the core domain. Notably, these hybrid nanoparticles exhibit enhanced stability and improved catalytic performance in the Sonogashira cross-coupling reaction in air. Through the precise design of reactive block copolymers, this study presents a novel strategy for the particleization of CTCs, thereby enabling the practical and scalable preparation of a diverse range of CTCs-based functional materials with enhanced properties.
2026, 37(10): 111557
doi: 10.1016/j.cclet.2025.111557
摘要:
Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)-based solid polymer electrolytes show great potential for high energy lithium metal batteries, however, the residual solvent and related severe side reactions limit its development. Herein, a PVDF-HFP-based solid polymer electrolyte modified by fluorobenzene (FB) co-solvent is designed to address these problems. The introduced FB with weak solvation interaction regulates the coordination environment and induces anions to enter the solvation structure, generating more contact ion pairs (CIPs) and aggregates (AGGs). In addition, the anions-derived LiF-rich interphases help to improve the interface stability against Li metal. As a result, the FB-PVDF-HFP achieves high ionic conductivity (4.1 × 10−4 S/cm) and low activation energy (0.125 eV) at room temperature. In addition, Li||Li symmetric cells using FB-PVDF-HFP electrolyte can achieve uniform and dendrite-free lithium deposition/stripping in the long-term cycling over 2300 h. The assembled solid-state Li|FB-PVDF-HFP|LFP full cell shows improved rate performance and cycling performance (600 cycles at 0.5 C and 450 cycles at 3 C) at room temperature. This work verifies the feasibility of fluorinated terminated solid polymer electrolytes on its lithium-ion transport and interfacial stability in lithium metal batteries.
Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)-based solid polymer electrolytes show great potential for high energy lithium metal batteries, however, the residual solvent and related severe side reactions limit its development. Herein, a PVDF-HFP-based solid polymer electrolyte modified by fluorobenzene (FB) co-solvent is designed to address these problems. The introduced FB with weak solvation interaction regulates the coordination environment and induces anions to enter the solvation structure, generating more contact ion pairs (CIPs) and aggregates (AGGs). In addition, the anions-derived LiF-rich interphases help to improve the interface stability against Li metal. As a result, the FB-PVDF-HFP achieves high ionic conductivity (4.1 × 10−4 S/cm) and low activation energy (0.125 eV) at room temperature. In addition, Li||Li symmetric cells using FB-PVDF-HFP electrolyte can achieve uniform and dendrite-free lithium deposition/stripping in the long-term cycling over 2300 h. The assembled solid-state Li|FB-PVDF-HFP|LFP full cell shows improved rate performance and cycling performance (600 cycles at 0.5 C and 450 cycles at 3 C) at room temperature. This work verifies the feasibility of fluorinated terminated solid polymer electrolytes on its lithium-ion transport and interfacial stability in lithium metal batteries.
2026, 37(10): 111558
doi: 10.1016/j.cclet.2025.111558
摘要:
Solid-state electrolytes composed of earth-abundant elements offer significant cost advantages for large-scale energy storage applications. However, their widespread adoption is hindered by inherently low ionic conductivity. In this study, we report a low-cost solid-state electrolyte, LixAlCl3-xOx (0.6 ≤ x ≤ 1.1), with dramatically enhanced ionic conductivity achieved through the construction of fast ion-conducting channels via an innovative anion mixing strategy. First-principles calculations and experimental characterizations reveal that the Cl−/O2− anion mixing expands the distribution of Li+ ions within the lattice while reducing the distance between adjacent sites. This structural optimization results in a low Li+ migration activation energy of 0.3 eV and elevates the ionic conductivity from 10−3 mS/cm to 1.5 mS/cm. Furthermore, the Cl-/O2- mixing synergistically combines the advantages of both anions, endowing the LixAlCl3-xOx electrolyte with high-voltage stability (up to 3.96 V vs. Li+/Li), robust interfacial compatibility, and air stability. When integrated into all-solid-state batteries with a LiCoO2Li0.8AlCl2.2O0.8Li6PS5ClLi-Si configuration, it delivers an initial capacity of 127 mAh/g and retains 94.4% of its discharge capacity after 180 cycles at 0.3 C.
Solid-state electrolytes composed of earth-abundant elements offer significant cost advantages for large-scale energy storage applications. However, their widespread adoption is hindered by inherently low ionic conductivity. In this study, we report a low-cost solid-state electrolyte, LixAlCl3-xOx (0.6 ≤ x ≤ 1.1), with dramatically enhanced ionic conductivity achieved through the construction of fast ion-conducting channels via an innovative anion mixing strategy. First-principles calculations and experimental characterizations reveal that the Cl−/O2− anion mixing expands the distribution of Li+ ions within the lattice while reducing the distance between adjacent sites. This structural optimization results in a low Li+ migration activation energy of 0.3 eV and elevates the ionic conductivity from 10−3 mS/cm to 1.5 mS/cm. Furthermore, the Cl-/O2- mixing synergistically combines the advantages of both anions, endowing the LixAlCl3-xOx electrolyte with high-voltage stability (up to 3.96 V vs. Li+/Li), robust interfacial compatibility, and air stability. When integrated into all-solid-state batteries with a LiCoO2Li0.8AlCl2.2O0.8Li6PS5ClLi-Si configuration, it delivers an initial capacity of 127 mAh/g and retains 94.4% of its discharge capacity after 180 cycles at 0.3 C.
2026, 37(10): 111560
doi: 10.1016/j.cclet.2025.111560
摘要:
Piezoelectric materials have wide commercial applications involving our everyday lives. The common categorized "soft" and "hard" piezoelectric materials have distinct even contradictory performance parameters typically exemplified by piezoelectric coefficient d33 and mechanical quality factor Qm. However, for some special devices operated in resonant mode, simultaneously high or at least balanced performance parameters are needed. Here, we show the transition from "soft" to "hard" performance in 2 mol% Sm doped (0.36-x)Pb(Ni1/3Nb2/3)O3-xPb(Mn1/3Nb2/3)O3–0.28PbZrO3–0.36PbTiO3 quaternary solid solution piezoceramics, for which the d33 and planar electromechanical coupling factor kp decrease, while Qm and Curie temperature Tc increase monotonously with increasing x value. As the results, balanced performance with moderate d33 = 446 pC/N, kp = 0.49, Qm = 425, and Tc = 170 ℃ are achieved around x = 0.03. This work not only shows the feasibility for combining "soft" and "hard" performance by forming appropriate solid solutions, but also provides a suitable material basis for further simultaneously optimizing piezoelectric parameters.
Piezoelectric materials have wide commercial applications involving our everyday lives. The common categorized "soft" and "hard" piezoelectric materials have distinct even contradictory performance parameters typically exemplified by piezoelectric coefficient d33 and mechanical quality factor Qm. However, for some special devices operated in resonant mode, simultaneously high or at least balanced performance parameters are needed. Here, we show the transition from "soft" to "hard" performance in 2 mol% Sm doped (0.36-x)Pb(Ni1/3Nb2/3)O3-xPb(Mn1/3Nb2/3)O3–0.28PbZrO3–0.36PbTiO3 quaternary solid solution piezoceramics, for which the d33 and planar electromechanical coupling factor kp decrease, while Qm and Curie temperature Tc increase monotonously with increasing x value. As the results, balanced performance with moderate d33 = 446 pC/N, kp = 0.49, Qm = 425, and Tc = 170 ℃ are achieved around x = 0.03. This work not only shows the feasibility for combining "soft" and "hard" performance by forming appropriate solid solutions, but also provides a suitable material basis for further simultaneously optimizing piezoelectric parameters.
2026, 37(10): 111561
doi: 10.1016/j.cclet.2025.111561
摘要:
Charge transfer cocrystals offer an opportunity to construct high performance organic photothermal materials and hold great promise toward various applications, including photothermal imaging, photothermal therapy, seawater desalination. However, the photothermal cocrystal materials are still in infancy and it is necessary to further explore them and develop more novel applications. Herein, a charge transfer cocrystal of anthracene and 7,7′,8,8′-tetracyanoquinodimethane was constructed and has a strong D−A interactions and a small HOMO−LUMO gap (1.46 eV) and thus displays a broad absorption over 300–821 nm range. The near-infrared photothermal conversion performance was evaluated under 808 nm laser illumination and the conversion efficiency reaches 58.3%, with the temperature increases to 72.1 ℃ in 145 s. The cocrystal was successfully employed as a versatile photothermal material for imaging and functional electrical device control, paving the way for the development of emerging applications in related fields.
Charge transfer cocrystals offer an opportunity to construct high performance organic photothermal materials and hold great promise toward various applications, including photothermal imaging, photothermal therapy, seawater desalination. However, the photothermal cocrystal materials are still in infancy and it is necessary to further explore them and develop more novel applications. Herein, a charge transfer cocrystal of anthracene and 7,7′,8,8′-tetracyanoquinodimethane was constructed and has a strong D−A interactions and a small HOMO−LUMO gap (1.46 eV) and thus displays a broad absorption over 300–821 nm range. The near-infrared photothermal conversion performance was evaluated under 808 nm laser illumination and the conversion efficiency reaches 58.3%, with the temperature increases to 72.1 ℃ in 145 s. The cocrystal was successfully employed as a versatile photothermal material for imaging and functional electrical device control, paving the way for the development of emerging applications in related fields.
2026, 37(10): 111562
doi: 10.1016/j.cclet.2025.111562
摘要:
The oxygen evolution reaction (OER), as the rate-determining step in water electrolysis, demands efficient non-precious catalysts to replace conventional Ru/Ir-based materials. While transition metal sulfides (TMS) show promise application prospect, but is limited by sulfur leaching-induced degradation. We address this challenge through a cyanide-mediated stabilization strategy, developing a Ni-CN/Ni3S2 catalyst where sacrificial C≡N groups transform into C═O moieties during OER. This structural evolution effectively suppresses sulfur leaching while enabling the formation of highly active Ni-SO4-OH species rather than conventional NiOOH. The optimized catalyst demonstrates exceptional performance with a 209 mV overpotential at 10 mA/cm2, outperforming both RuO2 (241 mV) and pristine Ni3S2 (311 mV), and maintains 200 h stability at 100 mA/cm2. When integrated into an anion exchange membrane (AEM) electrolyzer, the catalyst achieves 1 A/cm2 at 1.71 V with 200 h durability (35 µV/h voltage decay). Combined experimental and theoretical analyses reveal that the sulfur-anchored structure enables exceptional stability through controlled surface reconstruction and suppressed element dissolution. This work provides critical insights into designing durable, high-performance OER electrocatalysts through dynamic interface engineering.
The oxygen evolution reaction (OER), as the rate-determining step in water electrolysis, demands efficient non-precious catalysts to replace conventional Ru/Ir-based materials. While transition metal sulfides (TMS) show promise application prospect, but is limited by sulfur leaching-induced degradation. We address this challenge through a cyanide-mediated stabilization strategy, developing a Ni-CN/Ni3S2 catalyst where sacrificial C≡N groups transform into C═O moieties during OER. This structural evolution effectively suppresses sulfur leaching while enabling the formation of highly active Ni-SO4-OH species rather than conventional NiOOH. The optimized catalyst demonstrates exceptional performance with a 209 mV overpotential at 10 mA/cm2, outperforming both RuO2 (241 mV) and pristine Ni3S2 (311 mV), and maintains 200 h stability at 100 mA/cm2. When integrated into an anion exchange membrane (AEM) electrolyzer, the catalyst achieves 1 A/cm2 at 1.71 V with 200 h durability (35 µV/h voltage decay). Combined experimental and theoretical analyses reveal that the sulfur-anchored structure enables exceptional stability through controlled surface reconstruction and suppressed element dissolution. This work provides critical insights into designing durable, high-performance OER electrocatalysts through dynamic interface engineering.
2026, 37(10): 111563
doi: 10.1016/j.cclet.2025.111563
摘要:
Metal-oxo clusters (MOCs), particularly those with renowned Keggin-type architecture, have been extensively studied for their facile synthesis, robust stability, and diverse applications. However, the isolation of thorium-oxo clusters with novel structural motifs remains elusive due to the distinctive hydrolytic behaviour of Th4+ ions. Herein, we report nine electropositive α-Keggin-type thorium-oxo clusters, M@Th12@L8 (where M is fully or co-occupied by Al3+, W6+, Mo6+, V5+, Cr3+, or Mn4+; L = Al or Ga), synthesized via aluminate-regulated Th4+ hydrolysis. Unlike Th6(O/OH)8-based structures for most reported thorium-oxo clusters, M@Th12@L8 features an unprecedented triple-layered Platonic architecture: a central MO6 octahedron, a Th12 icosahedron, and an outer cube of eight LO5 ligands. Structural rigidity maintains invariant M–O bond lengths despite variable MO6 and LO5 units, while the central M ion dictates solution pH during cluster formation, crystallization kinetics, crystal yield, and tunable optical properties. Time-resolved small-angle X-ray scattering (SAXS) and 27Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) unveil the partial decomposition of aluminate precursors and the synchronized self-assembly of M@Th12@L8. This work advances our understanding of thorium hydrolysis in heterometallic systems and establishes a modular strategy to prepare MOCs with tailored architectures and functionalities.
Metal-oxo clusters (MOCs), particularly those with renowned Keggin-type architecture, have been extensively studied for their facile synthesis, robust stability, and diverse applications. However, the isolation of thorium-oxo clusters with novel structural motifs remains elusive due to the distinctive hydrolytic behaviour of Th4+ ions. Herein, we report nine electropositive α-Keggin-type thorium-oxo clusters, M@Th12@L8 (where M is fully or co-occupied by Al3+, W6+, Mo6+, V5+, Cr3+, or Mn4+; L = Al or Ga), synthesized via aluminate-regulated Th4+ hydrolysis. Unlike Th6(O/OH)8-based structures for most reported thorium-oxo clusters, M@Th12@L8 features an unprecedented triple-layered Platonic architecture: a central MO6 octahedron, a Th12 icosahedron, and an outer cube of eight LO5 ligands. Structural rigidity maintains invariant M–O bond lengths despite variable MO6 and LO5 units, while the central M ion dictates solution pH during cluster formation, crystallization kinetics, crystal yield, and tunable optical properties. Time-resolved small-angle X-ray scattering (SAXS) and 27Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) unveil the partial decomposition of aluminate precursors and the synchronized self-assembly of M@Th12@L8. This work advances our understanding of thorium hydrolysis in heterometallic systems and establishes a modular strategy to prepare MOCs with tailored architectures and functionalities.
2026, 37(10): 111592
doi: 10.1016/j.cclet.2025.111592
摘要:
Composite solid electrolytes are the most promising candidates for next-generation commercial electrolytes in Li metal batteries. However, the inevitable layered-structure caused by the agglomeration or sedimentation severely impairs the stability and ion conductivity. In this work, by using the phase-inversion within 20 s, we successfully uniformly dispersed Li6.5La3Zr1.5Ta0.5O12 (LLZTO) nano-powders into cellulose acetate, generating a highly conductive and stable 3D composite skeleton film with the thickness of 50 µm. Due to the high heating/cooling rate of 104 ℃/min, the ultrafast high-temperature sintering (UHS) enables the LLZTO powders with high crystallinity and a size of ~500 nm. Filling the PEGDA polymer, the resulting composite electrolyte films exhibit an ion conductivity of 1.2 mS/cm, nearly 6 times that of the electrolyte film without LLZTO. The composite electrolyte films exhibit excellent stability with Li metal, resulting in a reversible cycling over 2200 h at 0.2 mA/cm2. Using LiFePO4 and Li metal, the full cell shows a high capacity retention of 99.6% after 200 cycles and a high rate performance of 1 C. Pairing with NCM811, the cell stable cycles over 110 cycles with a Coulombic efficiency of 99.2%. This work provides a novel strategy for designing high-performance composite solid electrolytes and paves the way for developing practical SSLMBs with enhanced safety, high energy density, and long cycle life.
Composite solid electrolytes are the most promising candidates for next-generation commercial electrolytes in Li metal batteries. However, the inevitable layered-structure caused by the agglomeration or sedimentation severely impairs the stability and ion conductivity. In this work, by using the phase-inversion within 20 s, we successfully uniformly dispersed Li6.5La3Zr1.5Ta0.5O12 (LLZTO) nano-powders into cellulose acetate, generating a highly conductive and stable 3D composite skeleton film with the thickness of 50 µm. Due to the high heating/cooling rate of 104 ℃/min, the ultrafast high-temperature sintering (UHS) enables the LLZTO powders with high crystallinity and a size of ~500 nm. Filling the PEGDA polymer, the resulting composite electrolyte films exhibit an ion conductivity of 1.2 mS/cm, nearly 6 times that of the electrolyte film without LLZTO. The composite electrolyte films exhibit excellent stability with Li metal, resulting in a reversible cycling over 2200 h at 0.2 mA/cm2. Using LiFePO4 and Li metal, the full cell shows a high capacity retention of 99.6% after 200 cycles and a high rate performance of 1 C. Pairing with NCM811, the cell stable cycles over 110 cycles with a Coulombic efficiency of 99.2%. This work provides a novel strategy for designing high-performance composite solid electrolytes and paves the way for developing practical SSLMBs with enhanced safety, high energy density, and long cycle life.
2026, 37(10): 111594
doi: 10.1016/j.cclet.2025.111594
摘要:
Olivine-type LiMnxFe1-xPO4 (LMFP) cathode materials with high energy density (≈700 Wh/kg) and high discharge platform (4.1 V vs. Li+/Li), have attracted considerable interest and prominence in the realm of lithium-ion batteries (LIBs). Nevertheless, the cycling stability of LMFP highly associated with electrolyte compatibility, which suffers from the subsistent transition-metal dissolution under hydrofluoric acid (HF) corrosion and unstable interface formation, posing significant challenges. Herein, we demonstrate that a multifunctional electrolyte additive, (Trimethylsilyl)methyl acetate (TMSA), possesses the good compatibility with LiMn0.60Fe0.40PO4 cathode material. Its features are embodied in the HF elimination, proton coordination and hierarchic cathode electrolyte interface (CEI) formation to prevent electrolyte decomposition and swelling of conductive carbon layer inside materials. Therefore, the LiMn0.60Fe0.40PO4ǁLi batteries can sustain the significantly enhanced capacity retentions of 67.5% after 500 cycles at room temperature (25 ℃) and 74.4% after 400 cycles at high temperature of 55 ℃, even contributing to an improved specific capacity of 113.8 mAh/g at 15 C rate (vs. 88.1 mAh/g in the counterpart). Impressively, LiMn0.60Fe0.40PO4ǁgraphite pouch cell retains a 93.76% capacity after 300 cycles. These much better electrochemical performances from the facile yet available design of electrolyte additive shows the great importance and potential for the developments of LiMn0.60Fe0.40PO4-based LIBs.
Olivine-type LiMnxFe1-xPO4 (LMFP) cathode materials with high energy density (≈700 Wh/kg) and high discharge platform (4.1 V vs. Li+/Li), have attracted considerable interest and prominence in the realm of lithium-ion batteries (LIBs). Nevertheless, the cycling stability of LMFP highly associated with electrolyte compatibility, which suffers from the subsistent transition-metal dissolution under hydrofluoric acid (HF) corrosion and unstable interface formation, posing significant challenges. Herein, we demonstrate that a multifunctional electrolyte additive, (Trimethylsilyl)methyl acetate (TMSA), possesses the good compatibility with LiMn0.60Fe0.40PO4 cathode material. Its features are embodied in the HF elimination, proton coordination and hierarchic cathode electrolyte interface (CEI) formation to prevent electrolyte decomposition and swelling of conductive carbon layer inside materials. Therefore, the LiMn0.60Fe0.40PO4ǁLi batteries can sustain the significantly enhanced capacity retentions of 67.5% after 500 cycles at room temperature (25 ℃) and 74.4% after 400 cycles at high temperature of 55 ℃, even contributing to an improved specific capacity of 113.8 mAh/g at 15 C rate (vs. 88.1 mAh/g in the counterpart). Impressively, LiMn0.60Fe0.40PO4ǁgraphite pouch cell retains a 93.76% capacity after 300 cycles. These much better electrochemical performances from the facile yet available design of electrolyte additive shows the great importance and potential for the developments of LiMn0.60Fe0.40PO4-based LIBs.
2026, 37(10): 111601
doi: 10.1016/j.cclet.2025.111601
摘要:
The orbital differentiation of transition metal ions demonstrates a critical role in modulating the structure and properties of two-dimensional π-d conjugated metal-organic frameworks (2D c-MOFs), which is possible to achieve the high-capacity and high-voltage features in rechargeable metal-ion batteries. Herein, we propose and demonstrate the strategy of coordination chemistry with different transition metal ions to construct metal phthalocyanine-based 2D c-MOFs (NiPc-8O-Cu, NiPc-8O-Ni and CuPc-8O-Cu) with different central and peripheral metal-coordination redox-active sites, which were discussed for the first time as the advanced cathode materials for potassium-ion batteries (PIBs). Benefiting from the low-spin state and the closed-shell d-orbital of central metal, NiPc-8O-Cu has higher electron/ion conductivity and stronger electron delocalization, demonstrating fascinating electrochemical performance, including a high reversible specific capacity (194 mAh/g at 0.2 A/g) and a well long-term cycling performance (over 3000 cycles at 5.0 A/g). It is worth noting that NiPc-8O-Cu can also showcase the good cycle performance at wide-temperature (−20~60 ℃). These findings provide a general guideline for the development of high-performance 2D c-MOFs as electrode materials for metal-ion batteries by engineering "inside and outside" active-site strategy.
The orbital differentiation of transition metal ions demonstrates a critical role in modulating the structure and properties of two-dimensional π-d conjugated metal-organic frameworks (2D c-MOFs), which is possible to achieve the high-capacity and high-voltage features in rechargeable metal-ion batteries. Herein, we propose and demonstrate the strategy of coordination chemistry with different transition metal ions to construct metal phthalocyanine-based 2D c-MOFs (NiPc-8O-Cu, NiPc-8O-Ni and CuPc-8O-Cu) with different central and peripheral metal-coordination redox-active sites, which were discussed for the first time as the advanced cathode materials for potassium-ion batteries (PIBs). Benefiting from the low-spin state and the closed-shell d-orbital of central metal, NiPc-8O-Cu has higher electron/ion conductivity and stronger electron delocalization, demonstrating fascinating electrochemical performance, including a high reversible specific capacity (194 mAh/g at 0.2 A/g) and a well long-term cycling performance (over 3000 cycles at 5.0 A/g). It is worth noting that NiPc-8O-Cu can also showcase the good cycle performance at wide-temperature (−20~60 ℃). These findings provide a general guideline for the development of high-performance 2D c-MOFs as electrode materials for metal-ion batteries by engineering "inside and outside" active-site strategy.
2026, 37(10): 111602
doi: 10.1016/j.cclet.2025.111602
摘要:
Solid polymer electrolytes present transformative potential for all-solid-state sodium metal batteries (ASSMBs) owing to their molecular tailorability, cost-effectiveness and ease of processability, yet face critical challenges including sluggish Na+ diffusion kinetics at room temperature, high-voltage oxidation tendency, and uncontrolled Na dendrite growth. To address these limitations, we propose an anion-regulation strategy through a hierarchically engineered composite polymer electrolyte (CPE) that strategically integrates (1) a high-concentration NaTFSI− optimized polyethylene oxide (PEO) matrix (EO: Na+ = 6:1) and (2) a mechanically reinforced polyacrylonitrile (PAN) scaffold embedded with uniformly dispersed UIO-66 metal–organic framework nanoparticles (UIO-66@PAN). High-concentration TFSI− dissociation activates mobile anion-Na+ cluster species that form dynamic percolation networks, establishing low-energy-barrier pathways for accelerated Na+ migration (1.01 mS/cm at 30 ℃). Meanwhile, the UIO-66@PAN scaffold delivers exceptional tensile resilience (3.46 MPa) for the CPE membrane, meanwhile sub-nanometer precision of porous architecture (7.5–8.1 Å in UIO-66 vs. 7.9 Å for TFSI−) enables steric-electronic dual-anchoring effects for TFSI− immobilization, achieving a high Na+ transference number (tNa+ = 0.76). In a solvent-free, layer-stacked ASSMB assembly with sodium vanadium phosphate (NVP) cathode (1 mAh/cm2), 25 µm CPE and the Na foil, the prototype achieves 91.3% capacity retention over 200 cycles at room temperature, rate behavior up to 1 C as well as robust cyclability across a wide temperature range (25–80 ℃). This molecular-scale engineering of anion behavior in the CPE design thus establishes a new paradigm for the practical ASSMB prototyping.
Solid polymer electrolytes present transformative potential for all-solid-state sodium metal batteries (ASSMBs) owing to their molecular tailorability, cost-effectiveness and ease of processability, yet face critical challenges including sluggish Na+ diffusion kinetics at room temperature, high-voltage oxidation tendency, and uncontrolled Na dendrite growth. To address these limitations, we propose an anion-regulation strategy through a hierarchically engineered composite polymer electrolyte (CPE) that strategically integrates (1) a high-concentration NaTFSI− optimized polyethylene oxide (PEO) matrix (EO: Na+ = 6:1) and (2) a mechanically reinforced polyacrylonitrile (PAN) scaffold embedded with uniformly dispersed UIO-66 metal–organic framework nanoparticles (UIO-66@PAN). High-concentration TFSI− dissociation activates mobile anion-Na+ cluster species that form dynamic percolation networks, establishing low-energy-barrier pathways for accelerated Na+ migration (1.01 mS/cm at 30 ℃). Meanwhile, the UIO-66@PAN scaffold delivers exceptional tensile resilience (3.46 MPa) for the CPE membrane, meanwhile sub-nanometer precision of porous architecture (7.5–8.1 Å in UIO-66 vs. 7.9 Å for TFSI−) enables steric-electronic dual-anchoring effects for TFSI− immobilization, achieving a high Na+ transference number (tNa+ = 0.76). In a solvent-free, layer-stacked ASSMB assembly with sodium vanadium phosphate (NVP) cathode (1 mAh/cm2), 25 µm CPE and the Na foil, the prototype achieves 91.3% capacity retention over 200 cycles at room temperature, rate behavior up to 1 C as well as robust cyclability across a wide temperature range (25–80 ℃). This molecular-scale engineering of anion behavior in the CPE design thus establishes a new paradigm for the practical ASSMB prototyping.
2026, 37(10): 111603
doi: 10.1016/j.cclet.2025.111603
摘要:
A facile ammonium salt-mediated double-deck stacking strategy is first put forward to fabricate Li3YCl6 (LYC) halide solid electrolyte (HSE), which capitalizes on the dual functionality of NH4Cl in terms of dehydration and chlorination. It is worth mentioning that the obtained LYC features nanoparticles (< 400 nm) and demonstrates an excellent ionic conductivity of 2.33 × 10–4 S/cm at 25 ℃. In addition, the integration of LYC into all-solid-state cell with LiCoO2 cathode and Li anode delivers a high initial discharge specific capacity of 139.5 mAh/g at 0.1 C with a capacity retention ratio of 87.7% after 50 cycles. Encouragingly, the well-designed strategy not only enables the adoption of low-cost metal oxides and hydrates as raw materials, but also realizes the regeneration of damp LYC HSE. Hence, these encouraging results manifest that the proposed synthesis strategy delivers extremely economic benefits and valuable insights for developing HSEs.
A facile ammonium salt-mediated double-deck stacking strategy is first put forward to fabricate Li3YCl6 (LYC) halide solid electrolyte (HSE), which capitalizes on the dual functionality of NH4Cl in terms of dehydration and chlorination. It is worth mentioning that the obtained LYC features nanoparticles (< 400 nm) and demonstrates an excellent ionic conductivity of 2.33 × 10–4 S/cm at 25 ℃. In addition, the integration of LYC into all-solid-state cell with LiCoO2 cathode and Li anode delivers a high initial discharge specific capacity of 139.5 mAh/g at 0.1 C with a capacity retention ratio of 87.7% after 50 cycles. Encouragingly, the well-designed strategy not only enables the adoption of low-cost metal oxides and hydrates as raw materials, but also realizes the regeneration of damp LYC HSE. Hence, these encouraging results manifest that the proposed synthesis strategy delivers extremely economic benefits and valuable insights for developing HSEs.
2026, 37(10): 111606
doi: 10.1016/j.cclet.2025.111606
摘要:
Achieving optimal reactive oxygen species (ROS) production requires carefully balancing these interactions to maximize therapeutic efficacy. Herein, we have successfully developed a nanosystem through defect substitution using CuCoFe-layered double hydroxides (LDHs) as a template, followed by Pt reduction on the layer, the resulting nanoalloy, denoted as CuPt alloy@LDHs, demonstrating remarkable ROS production activity. This superior ROS production was attributed to its low Gibbs free energy barrier for generating hydroxyl radical (·OH), as confirmed by both characterizations and density functional theory (DFT) calculations. Additionally, the nanoalloy exhibits good (NOx)-like activity, effectively disrupting the intracellular NADH/NAD+ cycling balance and enabling self-cycling of endogenous H2O2. This work highlights that CuPt alloy@LDHs can effectively disrupt the redox homeostasis in tumor regions, significantly improving therapeutic efficacy and overcoming the limitations of current nanoalloy catalytic therapies.
Achieving optimal reactive oxygen species (ROS) production requires carefully balancing these interactions to maximize therapeutic efficacy. Herein, we have successfully developed a nanosystem through defect substitution using CuCoFe-layered double hydroxides (LDHs) as a template, followed by Pt reduction on the layer, the resulting nanoalloy, denoted as CuPt alloy@LDHs, demonstrating remarkable ROS production activity. This superior ROS production was attributed to its low Gibbs free energy barrier for generating hydroxyl radical (·OH), as confirmed by both characterizations and density functional theory (DFT) calculations. Additionally, the nanoalloy exhibits good (NOx)-like activity, effectively disrupting the intracellular NADH/NAD+ cycling balance and enabling self-cycling of endogenous H2O2. This work highlights that CuPt alloy@LDHs can effectively disrupt the redox homeostasis in tumor regions, significantly improving therapeutic efficacy and overcoming the limitations of current nanoalloy catalytic therapies.
2026, 37(10): 111639
doi: 10.1016/j.cclet.2025.111639
摘要:
The development of high-performance nonlinear optical (NLO) crystals for the short-wave ultraviolet (UV) region remains a significant challenge. In this work, four novel organic-inorganic metal halides, (3-QUO)2MX4 (3-QUO = 1-azabicyclo[2.2.2]octan-3-one; M = Zn, Cd; X = Br, I), were developed. Our initial efforts with the iodide compounds, (3-QUO)2ZnI4 and (3-QUO)2CdI4, yielded materials with modest second-harmonic generation (SHG) responses and, critically, they were non-phase-matchable. To overcome this, we employed a halogen-substitution strategy, replacing iodine with bromine, guided by the principle of bandgap widening. This approach successfully yielded (3-QUO)2ZnBr4 and (3-QUO)2CdBr4, which exhibit superior short-wave UV transparency and achieve phase-matchable SHG. Specifically, (3-QUO)2ZnBr4 shows a wide bandgap of 5.10 eV (UV cutoff: 220 nm) and a phase-matchable SHG response of 1.5 times that of KH2PO4 (KDP). Similarly, (3-QUO)2CdBr4 possesses a bandgap of 4.55 eV (UV cutoff: 245 nm) and an SHG response of 1.8 × KDP. Furthermore, these materials exhibit yellowish-white fluorescence under blue light excitation. This work demonstrates an effective approach to simultaneously tune bandgap, SHG response, and phase-matching capabilities for short-wave UV NLO applications.
The development of high-performance nonlinear optical (NLO) crystals for the short-wave ultraviolet (UV) region remains a significant challenge. In this work, four novel organic-inorganic metal halides, (3-QUO)2MX4 (3-QUO = 1-azabicyclo[2.2.2]octan-3-one; M = Zn, Cd; X = Br, I), were developed. Our initial efforts with the iodide compounds, (3-QUO)2ZnI4 and (3-QUO)2CdI4, yielded materials with modest second-harmonic generation (SHG) responses and, critically, they were non-phase-matchable. To overcome this, we employed a halogen-substitution strategy, replacing iodine with bromine, guided by the principle of bandgap widening. This approach successfully yielded (3-QUO)2ZnBr4 and (3-QUO)2CdBr4, which exhibit superior short-wave UV transparency and achieve phase-matchable SHG. Specifically, (3-QUO)2ZnBr4 shows a wide bandgap of 5.10 eV (UV cutoff: 220 nm) and a phase-matchable SHG response of 1.5 times that of KH2PO4 (KDP). Similarly, (3-QUO)2CdBr4 possesses a bandgap of 4.55 eV (UV cutoff: 245 nm) and an SHG response of 1.8 × KDP. Furthermore, these materials exhibit yellowish-white fluorescence under blue light excitation. This work demonstrates an effective approach to simultaneously tune bandgap, SHG response, and phase-matching capabilities for short-wave UV NLO applications.
2026, 37(10): 111640
doi: 10.1016/j.cclet.2025.111640
摘要:
Environmental remediation demands efficient strategies for antibiotic degradation. Herein, we report the successful selective loading of nano zero-valent iron (nZVI) into the lumen of halloysite nanotubes (HNTs) via vacuum-assisted infusion and thermal reduction (denoted as nZVI@HNTs). This confined nanoreactor architecture simultaneously acts as a robust reductant and a Fenton-like catalyst. The tubular structure of HNTs enhanced nZVI dispersion and stability while leveraging its nanoconfinement effect to concentrate pollutants and suppress parasitic reactions between nZVI and H2O2. For tetracycline (TC) degradation, the nZVI@HNTs+H2O2 system achieved 86.61% removal within 90 min (20 mg/L TC, pH 5.5), outperforming surface-loaded controls by >19%. Crucially, the HNT lumen provides dual protection: Spatial isolation suppresses non-target nZVI consumption by O2/H2O, while constrained diffusion delays H2O2 contact, prioritizing contaminant reduction before controlled Fe2+-activated oxidation. Reactive oxygen species (ROS), including ·OH, ·O2−, and 1O2, synergistically drove TC degradation through radical and nonradical pathways. LC-MS analysis identified intermediates formed via demethylation, ring opening, and hydroxylation, with toxicity assessments confirming reduced acute toxicity, mutagenicity, and developmental toxicity of byproducts. Notably, nZVI@HNTs retained 64.03% efficiency after five cycles, demonstrating superior reusability. This work provides a novel strategy to enhance nZVI’s environmental applicability by combining confinement engineering with redox-coupled processes, offering broad prospects for sustainable water purification.
Environmental remediation demands efficient strategies for antibiotic degradation. Herein, we report the successful selective loading of nano zero-valent iron (nZVI) into the lumen of halloysite nanotubes (HNTs) via vacuum-assisted infusion and thermal reduction (denoted as nZVI@HNTs). This confined nanoreactor architecture simultaneously acts as a robust reductant and a Fenton-like catalyst. The tubular structure of HNTs enhanced nZVI dispersion and stability while leveraging its nanoconfinement effect to concentrate pollutants and suppress parasitic reactions between nZVI and H2O2. For tetracycline (TC) degradation, the nZVI@HNTs+H2O2 system achieved 86.61% removal within 90 min (20 mg/L TC, pH 5.5), outperforming surface-loaded controls by >19%. Crucially, the HNT lumen provides dual protection: Spatial isolation suppresses non-target nZVI consumption by O2/H2O, while constrained diffusion delays H2O2 contact, prioritizing contaminant reduction before controlled Fe2+-activated oxidation. Reactive oxygen species (ROS), including ·OH, ·O2−, and 1O2, synergistically drove TC degradation through radical and nonradical pathways. LC-MS analysis identified intermediates formed via demethylation, ring opening, and hydroxylation, with toxicity assessments confirming reduced acute toxicity, mutagenicity, and developmental toxicity of byproducts. Notably, nZVI@HNTs retained 64.03% efficiency after five cycles, demonstrating superior reusability. This work provides a novel strategy to enhance nZVI’s environmental applicability by combining confinement engineering with redox-coupled processes, offering broad prospects for sustainable water purification.
2026, 37(10): 111650
doi: 10.1016/j.cclet.2025.111650
摘要:
Aqueous polysulfide/iodide redox flow batteries (SIRFBs) have been identified as a promising solution for scalable energy storage, exhibiting high energy density and cost-effectiveness, attracting considerable attention. Nonetheless, their practical applicability hindered by the suboptimal redox reaction kinetics, leading to constrained energy efficiency (EE) and power density. Herein, this study proposes a novel approach for coupling of graphene oxide with abundant sulfur vacancies in MoS2 nanosheets (VS-MoS2@GO). The bifunctional catalysts enhancing the transformation of S2−/Sx2− and I−/I3− redox couples while concomitantly improving the reaction kinetics. The experimental and theoretical calculation analyses elucidate that the GO bond with VS-MoS2 induces C-O-Mo and results in generating abundant sites, which attribute to the enhanced adsorption of crucial reaction intermediates and improved charge transfer. Consequently, the SIRFB derived notable EEs of 95.4%, 90.2%, and 75.6% at 10, 20, and 50 mA/cm2 with 50% state of charge, respectively. Furthermore, these batteries exhibit remarkable power density (93.2 mW/cm2), ultralow overpotential (100 mV), and an extended cycling life that exceeds 500 cycles. This work presents an innovative perspective to design high-active electrode materials that have potential for broad application in sundry flow battery chemistry, which would facilitate technological breakthroughs and advancements in the field of RFB.
Aqueous polysulfide/iodide redox flow batteries (SIRFBs) have been identified as a promising solution for scalable energy storage, exhibiting high energy density and cost-effectiveness, attracting considerable attention. Nonetheless, their practical applicability hindered by the suboptimal redox reaction kinetics, leading to constrained energy efficiency (EE) and power density. Herein, this study proposes a novel approach for coupling of graphene oxide with abundant sulfur vacancies in MoS2 nanosheets (VS-MoS2@GO). The bifunctional catalysts enhancing the transformation of S2−/Sx2− and I−/I3− redox couples while concomitantly improving the reaction kinetics. The experimental and theoretical calculation analyses elucidate that the GO bond with VS-MoS2 induces C-O-Mo and results in generating abundant sites, which attribute to the enhanced adsorption of crucial reaction intermediates and improved charge transfer. Consequently, the SIRFB derived notable EEs of 95.4%, 90.2%, and 75.6% at 10, 20, and 50 mA/cm2 with 50% state of charge, respectively. Furthermore, these batteries exhibit remarkable power density (93.2 mW/cm2), ultralow overpotential (100 mV), and an extended cycling life that exceeds 500 cycles. This work presents an innovative perspective to design high-active electrode materials that have potential for broad application in sundry flow battery chemistry, which would facilitate technological breakthroughs and advancements in the field of RFB.
2026, 37(10): 111651
doi: 10.1016/j.cclet.2025.111651
摘要:
Biomass-derived hard carbons (HCs) have emerged as highly promising anode materials for sodium-ion batteries (SIBs), owing to their high reversible capacities as well as low cost. However, the complex internal structure of biomass precursors presents significant challenges for precise control of microstructure as well as energy storage performance of the final HC products. To address this issue, in this study, three anthraquinone (AQ)-based organic small molecules, namely AQ, 2,6-dihydroxyanthraquinone (DQ) and 2,6-diaminoanthraquinone (DAAQ), are selected as crosslinking agents of bamboo biomass, to reveal the unique role of functional groups in these molecules for the precise regulation of microstructure of the bamboo-derived HCs. The results demonstrate that, under the same aromatic carbon skeleton, hydroxyl and amino groups have significant influence on the pore structure, graphitization degree, and electrochemical performance of HCs. Among them, DAAQ with amino functional groups exhibits the best crosslinking efficiency, resulting in a more ordered carbon structure along with successful N-heteroatom doping. Consequently, the HC prepared from DAAQ-crosslinked bamboo achieves a remarkable reversible capacity of 351 mAh/g and a high initial Coulombic efficiency of 86.4% at 20 mA/g. This work demonstrates the significant potential of functionalized AQ-based molecules as efficient crosslinkers in regulating the microstructure of biomass-derived HCs.
Biomass-derived hard carbons (HCs) have emerged as highly promising anode materials for sodium-ion batteries (SIBs), owing to their high reversible capacities as well as low cost. However, the complex internal structure of biomass precursors presents significant challenges for precise control of microstructure as well as energy storage performance of the final HC products. To address this issue, in this study, three anthraquinone (AQ)-based organic small molecules, namely AQ, 2,6-dihydroxyanthraquinone (DQ) and 2,6-diaminoanthraquinone (DAAQ), are selected as crosslinking agents of bamboo biomass, to reveal the unique role of functional groups in these molecules for the precise regulation of microstructure of the bamboo-derived HCs. The results demonstrate that, under the same aromatic carbon skeleton, hydroxyl and amino groups have significant influence on the pore structure, graphitization degree, and electrochemical performance of HCs. Among them, DAAQ with amino functional groups exhibits the best crosslinking efficiency, resulting in a more ordered carbon structure along with successful N-heteroatom doping. Consequently, the HC prepared from DAAQ-crosslinked bamboo achieves a remarkable reversible capacity of 351 mAh/g and a high initial Coulombic efficiency of 86.4% at 20 mA/g. This work demonstrates the significant potential of functionalized AQ-based molecules as efficient crosslinkers in regulating the microstructure of biomass-derived HCs.
2026, 37(10): 111656
doi: 10.1016/j.cclet.2025.111656
摘要:
Spin crossover (SCO) metal-organic frameworks (MOFs) exhibit significant potential for applications in data storage, displays, switches, actuators and sensors. However, designing novel SCO MOFs with new framework topologies remains a considerable challenge. Herein, the self-assembly of FeBr2 and Fe(ClO4)2·6H2O with K[Ag(CN)2] and N1,N1,N3,N3-tetra(pyridin-4-yl)benzene-1,3-diamine (i-TPBA) resulted in two distinct MOFs: [FeⅡ3{Ag8Br8(CN)6}(i-TPBA)3]·4DEF (1, DEF = N,N-diethylformamide) and [FeⅡ{Ag(CN)2}(i-TPBA)]ClO4·2H2O·0.5DEF (2). In 1, the hexatopic cluster anions [Ag8Br8(CN)6]6−, tetratopic ligands i-TPBA and hexatopic Fe(Ⅱ) ions are linked to form a cluster-based MOF with the urk topology. In contrast, the [Ag(CN)2]− units in 2 axially bridge the Fe(Ⅱ) ions, constructing one-dimensional right-handed 31 helical chains, which are further linked by tetratopic i-TPBA connectors to generate a three-dimensional chiral framework with a previously unreported topology, designated as sco1. Moreover, the SCO behavior can be effectively modulated by thiophene guest molecules, leading to the observation of a rare scan rate-dependent hysteretic SCO behavior in 2_thio. Thus, this study demonstrates that multidentate ligands can be employed to construct SCO MOFs with new topologies, offering a versatile platform for the advancement of multifunctional SCO materials
Spin crossover (SCO) metal-organic frameworks (MOFs) exhibit significant potential for applications in data storage, displays, switches, actuators and sensors. However, designing novel SCO MOFs with new framework topologies remains a considerable challenge. Herein, the self-assembly of FeBr2 and Fe(ClO4)2·6H2O with K[Ag(CN)2] and N1,N1,N3,N3-tetra(pyridin-4-yl)benzene-1,3-diamine (i-TPBA) resulted in two distinct MOFs: [FeⅡ3{Ag8Br8(CN)6}(i-TPBA)3]·4DEF (1, DEF = N,N-diethylformamide) and [FeⅡ{Ag(CN)2}(i-TPBA)]ClO4·2H2O·0.5DEF (2). In 1, the hexatopic cluster anions [Ag8Br8(CN)6]6−, tetratopic ligands i-TPBA and hexatopic Fe(Ⅱ) ions are linked to form a cluster-based MOF with the urk topology. In contrast, the [Ag(CN)2]− units in 2 axially bridge the Fe(Ⅱ) ions, constructing one-dimensional right-handed 31 helical chains, which are further linked by tetratopic i-TPBA connectors to generate a three-dimensional chiral framework with a previously unreported topology, designated as sco1. Moreover, the SCO behavior can be effectively modulated by thiophene guest molecules, leading to the observation of a rare scan rate-dependent hysteretic SCO behavior in 2_thio. Thus, this study demonstrates that multidentate ligands can be employed to construct SCO MOFs with new topologies, offering a versatile platform for the advancement of multifunctional SCO materials
2026, 37(10): 111657
doi: 10.1016/j.cclet.2025.111657
摘要:
The large-scale deployment of proton-exchange membrane water electrolysis (PEMWE) is plagued by the exclusively rely on Ir for anode water oxidation. Platinum (Pt), as one of the few acid stable elements, has long been ignored as a possible alternative due to its surface oxidation and passivation. In this study, we incorporate boron (B) and strontium (Sr) into Pt to achieve notable promotion in catalytic activity and long-term anti-passivation feature. While B serves as an electron reservoir by donating charge to Pt sites, Sr induces compressive strain to suppress lattice oxygen formation. The synergistic effects of B and Sr effectively modulate Pt-O orbital coupling from oxidative passivation and confer the best water oxidation activity and stability. Notably, the B,Sr-Pt catalyst achieves a low overpotential of 308 mV at 10 mA/cm2 in 0.5 mol/L H2SO4, approaching those of the Ir based catalysts. In PEMWE devices, B,Sr-Pt exhibits an operating voltage of 2.061V at 1 A/cm2 and operate stably for 240h at 1 A/cm2. These findings offer a promising strategy for enhancing the OER efficiency and durability of Pt-based catalysts by effectively addressing Pt site passivation.
The large-scale deployment of proton-exchange membrane water electrolysis (PEMWE) is plagued by the exclusively rely on Ir for anode water oxidation. Platinum (Pt), as one of the few acid stable elements, has long been ignored as a possible alternative due to its surface oxidation and passivation. In this study, we incorporate boron (B) and strontium (Sr) into Pt to achieve notable promotion in catalytic activity and long-term anti-passivation feature. While B serves as an electron reservoir by donating charge to Pt sites, Sr induces compressive strain to suppress lattice oxygen formation. The synergistic effects of B and Sr effectively modulate Pt-O orbital coupling from oxidative passivation and confer the best water oxidation activity and stability. Notably, the B,Sr-Pt catalyst achieves a low overpotential of 308 mV at 10 mA/cm2 in 0.5 mol/L H2SO4, approaching those of the Ir based catalysts. In PEMWE devices, B,Sr-Pt exhibits an operating voltage of 2.061V at 1 A/cm2 and operate stably for 240h at 1 A/cm2. These findings offer a promising strategy for enhancing the OER efficiency and durability of Pt-based catalysts by effectively addressing Pt site passivation.
2026, 37(10): 111785
doi: 10.1016/j.cclet.2025.111785
摘要:
Advancing low-cost and efficient electrocatalysts for the hydrogen evolution reaction (HER) in alkaline media is essential for sustainable hydrogen production, particularly in the context of anion exchange membrane (AEM) water electrolysis systems. Among various candidates, cobalt-based phosphides, particularly CoP, have drawn significant attention as cost-effective alternatives to platinum-based HER electrocatalysts due to their excellent catalytic performance. However, improving both water dissociation kinetics and hydrogen adsorption free energies remains a challenge. In this study, we introduce lead (Pb), a non-transition metal with higher electronegativity and a similar ionic radius to Co, to modify the electronic structure of CoP at both Co and P sites. Pb doping significantly optimizes both water dissociation and adsorption free energy in the alkaline HER process. The optimized Pb-CoP/CC electrocatalyst reduces the overpotential from 100 mV to 53 mV and achieves a Tafel slope of 57 mV/dec in alkaline electrolyte. Additionally, it exhibits excellent durability, maintaining stable performance for over 120 h. The improved HER performance of Pb-CoP/CC can be ascribed to the synergistic interactions between its components: accelerated water dissociation on Co sites, optimized hydrogen intermediate adsorption on P sites, and improved charge transfer abilities. These findings are supported by experimental data and DFT calculations. When used as the cathode in an AEM electrolyzer, Pb-CoP/CC achieves a current density of 500 mA/cm2 at 1.95 V, demonstrating excellent stability. This work highlights the efficacy of metal ion doping with higher electronegativity in improving HER performance and establishes a versatile strategy for other non-precious metal-based transition metal compounds, paving the way for high-performance AEM electrolyzers.
Advancing low-cost and efficient electrocatalysts for the hydrogen evolution reaction (HER) in alkaline media is essential for sustainable hydrogen production, particularly in the context of anion exchange membrane (AEM) water electrolysis systems. Among various candidates, cobalt-based phosphides, particularly CoP, have drawn significant attention as cost-effective alternatives to platinum-based HER electrocatalysts due to their excellent catalytic performance. However, improving both water dissociation kinetics and hydrogen adsorption free energies remains a challenge. In this study, we introduce lead (Pb), a non-transition metal with higher electronegativity and a similar ionic radius to Co, to modify the electronic structure of CoP at both Co and P sites. Pb doping significantly optimizes both water dissociation and adsorption free energy in the alkaline HER process. The optimized Pb-CoP/CC electrocatalyst reduces the overpotential from 100 mV to 53 mV and achieves a Tafel slope of 57 mV/dec in alkaline electrolyte. Additionally, it exhibits excellent durability, maintaining stable performance for over 120 h. The improved HER performance of Pb-CoP/CC can be ascribed to the synergistic interactions between its components: accelerated water dissociation on Co sites, optimized hydrogen intermediate adsorption on P sites, and improved charge transfer abilities. These findings are supported by experimental data and DFT calculations. When used as the cathode in an AEM electrolyzer, Pb-CoP/CC achieves a current density of 500 mA/cm2 at 1.95 V, demonstrating excellent stability. This work highlights the efficacy of metal ion doping with higher electronegativity in improving HER performance and establishes a versatile strategy for other non-precious metal-based transition metal compounds, paving the way for high-performance AEM electrolyzers.
2026, 37(10): 111952
doi: 10.1016/j.cclet.2025.111952
摘要:
Argyrodite sulfide solid electrolytes are highly favored by the researchers in the field of all-solid-state lithium metal battery due to their high ionic conductivity, relatively stable electrochemical window, and excellent processability. However, argyrodite sulfide solid electrolytes still face some technical difficulties that urgently need to be overcome, such as poor air stability and interface compatibility. This work reports a novel Li6+2xP1–xGaxS5–1.5xO1.5xCl (i.e., LPSC-xGa2O3) electrolyte via modifying Li6PS5Cl electrolyte with Ga2O3. The experimental results show that the prepared solid electrolyte has the highest ionic conductivity when the doping content of Ga2O3 reaches to x = 0.05. In addition, LPSC-0.05Ga2O3 has been proven to have good ability to suppress Li dendrites and improve cathode and anode interface compatibilities. The assembled all-solid-state lithium metal battery using LPSC-0.05Ga2O3 can maintain long-term stability for >200 cycles at 0.5 C. This work has laid the vital foundation for designing a high-performance solid-state electrolyte and promoting development of power battery industry.
Argyrodite sulfide solid electrolytes are highly favored by the researchers in the field of all-solid-state lithium metal battery due to their high ionic conductivity, relatively stable electrochemical window, and excellent processability. However, argyrodite sulfide solid electrolytes still face some technical difficulties that urgently need to be overcome, such as poor air stability and interface compatibility. This work reports a novel Li6+2xP1–xGaxS5–1.5xO1.5xCl (i.e., LPSC-xGa2O3) electrolyte via modifying Li6PS5Cl electrolyte with Ga2O3. The experimental results show that the prepared solid electrolyte has the highest ionic conductivity when the doping content of Ga2O3 reaches to x = 0.05. In addition, LPSC-0.05Ga2O3 has been proven to have good ability to suppress Li dendrites and improve cathode and anode interface compatibilities. The assembled all-solid-state lithium metal battery using LPSC-0.05Ga2O3 can maintain long-term stability for >200 cycles at 0.5 C. This work has laid the vital foundation for designing a high-performance solid-state electrolyte and promoting development of power battery industry.
2026, 37(10): 111994
doi: 10.1016/j.cclet.2025.111994
摘要:
Hydrazine oxidation reaction (HzOR) is highly thermodynamically favorable, but typically kinetically slow with a significant overpotential at most electrodes. Developing and illustrating a generic methodology for reducing the overpotential is of great significance but challenging. Here we designed a Fe-tannic acid (Fe-TA) buffering coating for carbon-hybridized Fe3O4 (C-Fe3O4) particles to reduce the overpotential of the multiple-proton-involved HzOR, which was further applied to highly efficient hydrazine-assisted hydrogen production and electrochemical hydrazine detection. A series of comparative experiments confirmed that the Fe-TA coating significantly reduces the isoelectric point, enhances the wettability, increases the electric double-layer capacitance, and decreases the charge transfer resistance, thereby lowering the resistance overpotential. Notably, C-Fe3O4@Fe-TA exhibited an excellent buffering effect that effectively decreases the concentration overpotential for electrochemical HzOR, which can be attributed to the reversible transformations among the mono-, bis-, and tris-complexes of Fe(Ⅲ) with tannic acid. Correspondingly, C-Fe3O4@Fe-TA achieved current density of 10 mA/cm2 at 23 mV (vs. RHE) in the electrolyte containing 1.0 mol/L KOH and 0.3 mol/L hydrazine. Coupled with HzOR, the C-Fe3O4@Fe-TA║Pt wire electrolysis system required a low working voltage of only 0.22 V at 10 mA/cm2 for synchronous hydrogen production, which was significantly lower than that of a traditional overall water splitting system (1.23 V). Moreover, C-Fe3O4@Fe-TA showed good performance in electrochemical hydrazine detection, simultaneously exhibiting high sensitivity (1478 µA L mmol−1 cm−2), a low detection limit (0.15 µmol/L), high selectivity, excellent stability, and high reliability for the analysis of real samples. This study reveals that the Fe-TA buffering coating can effectively decrease both the concentration and resistance overpotentials in electrochemical HzOR, demonstrating its potential as a general methodology for reducing the overpotential in this class of multiple-proton-involved reactions.
Hydrazine oxidation reaction (HzOR) is highly thermodynamically favorable, but typically kinetically slow with a significant overpotential at most electrodes. Developing and illustrating a generic methodology for reducing the overpotential is of great significance but challenging. Here we designed a Fe-tannic acid (Fe-TA) buffering coating for carbon-hybridized Fe3O4 (C-Fe3O4) particles to reduce the overpotential of the multiple-proton-involved HzOR, which was further applied to highly efficient hydrazine-assisted hydrogen production and electrochemical hydrazine detection. A series of comparative experiments confirmed that the Fe-TA coating significantly reduces the isoelectric point, enhances the wettability, increases the electric double-layer capacitance, and decreases the charge transfer resistance, thereby lowering the resistance overpotential. Notably, C-Fe3O4@Fe-TA exhibited an excellent buffering effect that effectively decreases the concentration overpotential for electrochemical HzOR, which can be attributed to the reversible transformations among the mono-, bis-, and tris-complexes of Fe(Ⅲ) with tannic acid. Correspondingly, C-Fe3O4@Fe-TA achieved current density of 10 mA/cm2 at 23 mV (vs. RHE) in the electrolyte containing 1.0 mol/L KOH and 0.3 mol/L hydrazine. Coupled with HzOR, the C-Fe3O4@Fe-TA║Pt wire electrolysis system required a low working voltage of only 0.22 V at 10 mA/cm2 for synchronous hydrogen production, which was significantly lower than that of a traditional overall water splitting system (1.23 V). Moreover, C-Fe3O4@Fe-TA showed good performance in electrochemical hydrazine detection, simultaneously exhibiting high sensitivity (1478 µA L mmol−1 cm−2), a low detection limit (0.15 µmol/L), high selectivity, excellent stability, and high reliability for the analysis of real samples. This study reveals that the Fe-TA buffering coating can effectively decrease both the concentration and resistance overpotentials in electrochemical HzOR, demonstrating its potential as a general methodology for reducing the overpotential in this class of multiple-proton-involved reactions.
2026, 37(10): 112057
doi: 10.1016/j.cclet.2025.112057
摘要:
Cu-Zn solid solutions are investigated as advanced current collector materials for anode-free Li metal batteries (AFLMBs), addressing the limited lithiophilicity and slow Li+ diffusion kinetics inherent to conventional Cu foil. Benefiting from the uniform distribution of lithiophilic Zn, Cu-Zn solid solutions demonstrated enhanced lithiophilicity and accelerated Li+ diffusion, which effectively facilitated uniform and reversible lithium deposition. First-principles calculations confirmed that Cu-Zn solid solutions, particularly Cu62Zn38, exhibited stronger Li adsorption and reduced diffusion barriers compared to Cu. Unlike alloy-prone metal coatings (e.g., Cu@Zn and thermally processed Cu@Zn) that sacrifice interfacial stability for lithiophilicity, Cu-Zn solid solution maintains robust electrode-electrolyte interfaces due to its alloying inertness. Ex-situ SEM and COMSOL simulations revealed dendrite-suppressed and homogeneous Li deposition on Cu62Zn38. In anode-free full cells, Cu62Zn38 achieves a capacity retention of 55.1% after 150 cycles, far exceeding Cu foil (13.8%). This work establishes Cu-Zn solid solutions current collectors as a scalable solution for high-energy-density AFLMBs.
Cu-Zn solid solutions are investigated as advanced current collector materials for anode-free Li metal batteries (AFLMBs), addressing the limited lithiophilicity and slow Li+ diffusion kinetics inherent to conventional Cu foil. Benefiting from the uniform distribution of lithiophilic Zn, Cu-Zn solid solutions demonstrated enhanced lithiophilicity and accelerated Li+ diffusion, which effectively facilitated uniform and reversible lithium deposition. First-principles calculations confirmed that Cu-Zn solid solutions, particularly Cu62Zn38, exhibited stronger Li adsorption and reduced diffusion barriers compared to Cu. Unlike alloy-prone metal coatings (e.g., Cu@Zn and thermally processed Cu@Zn) that sacrifice interfacial stability for lithiophilicity, Cu-Zn solid solution maintains robust electrode-electrolyte interfaces due to its alloying inertness. Ex-situ SEM and COMSOL simulations revealed dendrite-suppressed and homogeneous Li deposition on Cu62Zn38. In anode-free full cells, Cu62Zn38 achieves a capacity retention of 55.1% after 150 cycles, far exceeding Cu foil (13.8%). This work establishes Cu-Zn solid solutions current collectors as a scalable solution for high-energy-density AFLMBs.
2026, 37(10): 112084
doi: 10.1016/j.cclet.2025.112084
摘要:
Acaualblides A–E (1–5), five architecturally unprecedented macrolides, were isolated from fungus Acaulium album 429 and comprehensively characterized. Their structures were elucidated by high-resolution electrospray ionization mass spectrometry (HRESIMS), extensive spectroscopic analyses, and single-crystal X-ray diffraction. Compounds 1–3 possess unusual fourteen-membered macrolide frameworks bearing pyridine or thiophene moieties. Compound 4 represents the first heterodimer featuring a macrolide unit covalently linked to an aflatoxin B1 moiety through a C–C bond, while compound 5 is a unique homodimeric macrolide in which two identical units are connected by both a C-9/C-9′ carbon-carbon bond and a C-8/C-8′ thioether bridge. Plausible biosynthetic pathways for compounds 1–5 are proposed. Notably, compound 1 displayed significant immunosuppressive activity by inhibiting B-cell proliferation and activation through modulation of the B-cell receptor (BCR) signaling pathway.
Acaualblides A–E (1–5), five architecturally unprecedented macrolides, were isolated from fungus Acaulium album 429 and comprehensively characterized. Their structures were elucidated by high-resolution electrospray ionization mass spectrometry (HRESIMS), extensive spectroscopic analyses, and single-crystal X-ray diffraction. Compounds 1–3 possess unusual fourteen-membered macrolide frameworks bearing pyridine or thiophene moieties. Compound 4 represents the first heterodimer featuring a macrolide unit covalently linked to an aflatoxin B1 moiety through a C–C bond, while compound 5 is a unique homodimeric macrolide in which two identical units are connected by both a C-9/C-9′ carbon-carbon bond and a C-8/C-8′ thioether bridge. Plausible biosynthetic pathways for compounds 1–5 are proposed. Notably, compound 1 displayed significant immunosuppressive activity by inhibiting B-cell proliferation and activation through modulation of the B-cell receptor (BCR) signaling pathway.
2026, 37(10): 112085
doi: 10.1016/j.cclet.2025.112085
摘要:
The nose-to-brain drug delivery system has emerged as a transformative strategy for central nervous system (CNS) diseases therapy by leveraging the olfactory pathway to circumvent the blood-brain barrier. However, its clinical translation remains impeded by suboptimal olfactory deposition efficiency. A critical but poorly understood challenge lies in rational formulation design, particularly regarding how key physicochemical properties like viscosity govern the nasal drug delivery processes. Using rizatriptan nasal sprays as a viscosity-regulated model system (2–250 mPa s), we dissected how formulation viscosity governs olfactory deposition through synchronized macro-micro spray characteristics. A module 3D-printed human nasal cast was utilized to assess the olfactory deposition efficiency. Additionally, the spray pattern, plume geometry and real-time droplet size distribution were examined using laser diffraction analysis. The results demonstrate a non-monotonic olfactory deposition dependence on viscosity, peaking at 40 mPa s with 31.64% efficiency (31-fold enhancement vs. 2 mPa s). Furthermore, the increase of viscosity led to a reduction in plume angle and spray area, while simultaneously decreasing the stabilization stage fraction of droplets. Mechanistic analysis revealed two competing viscosity-mediated effects: (1) Macroscale plume narrowing that minimized anterior nasal losses; (2) Microscale destabilization of droplets that impaired turbinate transportation. This study elucidates that the viscosity-regulated precision olfactory deposition results from the equilibrium between macroscopic spray geometry and microscopic droplet dynamic, challenging the conventional single-parameter optimization paradigm. Our findings advance nose-to-brain drug delivery by deciphering the viscosity-regulated deposition mechanism, thereby paving the way for rationally designed nasal sprays with enhanced targeting efficiency for CNS diseases.
The nose-to-brain drug delivery system has emerged as a transformative strategy for central nervous system (CNS) diseases therapy by leveraging the olfactory pathway to circumvent the blood-brain barrier. However, its clinical translation remains impeded by suboptimal olfactory deposition efficiency. A critical but poorly understood challenge lies in rational formulation design, particularly regarding how key physicochemical properties like viscosity govern the nasal drug delivery processes. Using rizatriptan nasal sprays as a viscosity-regulated model system (2–250 mPa s), we dissected how formulation viscosity governs olfactory deposition through synchronized macro-micro spray characteristics. A module 3D-printed human nasal cast was utilized to assess the olfactory deposition efficiency. Additionally, the spray pattern, plume geometry and real-time droplet size distribution were examined using laser diffraction analysis. The results demonstrate a non-monotonic olfactory deposition dependence on viscosity, peaking at 40 mPa s with 31.64% efficiency (31-fold enhancement vs. 2 mPa s). Furthermore, the increase of viscosity led to a reduction in plume angle and spray area, while simultaneously decreasing the stabilization stage fraction of droplets. Mechanistic analysis revealed two competing viscosity-mediated effects: (1) Macroscale plume narrowing that minimized anterior nasal losses; (2) Microscale destabilization of droplets that impaired turbinate transportation. This study elucidates that the viscosity-regulated precision olfactory deposition results from the equilibrium between macroscopic spray geometry and microscopic droplet dynamic, challenging the conventional single-parameter optimization paradigm. Our findings advance nose-to-brain drug delivery by deciphering the viscosity-regulated deposition mechanism, thereby paving the way for rationally designed nasal sprays with enhanced targeting efficiency for CNS diseases.
2026, 37(10): 112093
doi: 10.1016/j.cclet.2025.112093
摘要:
Precise gene therapy for hepatocellular carcinoma (HCC) remains challenging due to the lack of tumor-selective activation and biosafety concerns of conventional DNAzyme systems. Herein, we report a logic-gated, triple-responsive nanoplatform that enables spatiotemporal control of DNAzyme activation exclusively within the tumor microenvironment. The DNAzyme is rendered catalytically inactive through boronate caging and is loaded into an N-acetylgalactosamine (GalNAc)-functionalized zinc metal-organic framework (Zn-MOF) for HCC-targeted delivery. The system integrates three tumor-associated stimuli, acidic pH, Zn2+ release, and reactive oxygen species (ROS) generation, as a cascaded logic gate to ensure sequential and tumor-specific activation. Acidic pH triggers Zn-MOF degradation, releasing both Zn2+ and the caged DNAzyme. Zn2+ catalyzes ROS generation, which decages the DNAzyme and enables its Zn2+-dependent cleavage of oncogenic early growth response protein 1 (EGR-1) mRNA. This logic-gated activation strategy ensures high specificity, minimal off-target effects, and synergistic antitumor efficacy by combining chemodynamic therapy and gene silencing. The proposed nanoplatform offers a robust blueprint for highly selective and safe DNAzyme-based cancer therapies.
Precise gene therapy for hepatocellular carcinoma (HCC) remains challenging due to the lack of tumor-selective activation and biosafety concerns of conventional DNAzyme systems. Herein, we report a logic-gated, triple-responsive nanoplatform that enables spatiotemporal control of DNAzyme activation exclusively within the tumor microenvironment. The DNAzyme is rendered catalytically inactive through boronate caging and is loaded into an N-acetylgalactosamine (GalNAc)-functionalized zinc metal-organic framework (Zn-MOF) for HCC-targeted delivery. The system integrates three tumor-associated stimuli, acidic pH, Zn2+ release, and reactive oxygen species (ROS) generation, as a cascaded logic gate to ensure sequential and tumor-specific activation. Acidic pH triggers Zn-MOF degradation, releasing both Zn2+ and the caged DNAzyme. Zn2+ catalyzes ROS generation, which decages the DNAzyme and enables its Zn2+-dependent cleavage of oncogenic early growth response protein 1 (EGR-1) mRNA. This logic-gated activation strategy ensures high specificity, minimal off-target effects, and synergistic antitumor efficacy by combining chemodynamic therapy and gene silencing. The proposed nanoplatform offers a robust blueprint for highly selective and safe DNAzyme-based cancer therapies.
2026, 37(10): 112094
doi: 10.1016/j.cclet.2025.112094
摘要:
Gonadotropin-releasing hormone (GnRH) analogues are widely used polypeptide therapeutics whose clinical utility is limited by pseudo-allergic reactions mediated through histamine release. This study systematically investigated the correlation between GnRH analogue-induced histamine release and the mast cell receptor Mas-related G protein-coupled receptor X2 (MRGPRX2)-a key mediator of drug-induced pseudo-allergic reactions-sing integrated, in vivo, and structural analyses. In vitro experiments demonstrated that GnRH analogues trigger MRGPRX2-dependent Ca2+ mobilization and mast cell degranulation, resulting in dose-dependent increases in β-hexosaminidase, histamine, and tumor necrosis factor α (TNF-α) release. Among the analogues tested, nafarelin exhibited the highest potency, whereas buserelin exhibited the lowest. In vivo, these analogues induced mast cell degranulation and capillary dilation in mouse paw skin, leading to localized pseudo-allergic symptoms (edema and extravasation) that were confirmed to be MRGPRX2-mediated. Molecular docking revealed that the cationic amino acid at position eight of the GnRH analogues bound complementarily to the negatively charged center within the MRGPRX2 ligand-binding pocket, suggesting a mechanistic basis for receptor activation. Functional validation via Arg8-to-Glu substitution in triptorelin significantly attenuated MRGPRX2 activation. Collectively, this work elucidates the MRGPRX2-dependent molecular mechanism underlying GnRH analogue-induced histamine release and provides a foundation for designing safer analogues with reduced adverse effects.
Gonadotropin-releasing hormone (GnRH) analogues are widely used polypeptide therapeutics whose clinical utility is limited by pseudo-allergic reactions mediated through histamine release. This study systematically investigated the correlation between GnRH analogue-induced histamine release and the mast cell receptor Mas-related G protein-coupled receptor X2 (MRGPRX2)-a key mediator of drug-induced pseudo-allergic reactions-sing integrated, in vivo, and structural analyses. In vitro experiments demonstrated that GnRH analogues trigger MRGPRX2-dependent Ca2+ mobilization and mast cell degranulation, resulting in dose-dependent increases in β-hexosaminidase, histamine, and tumor necrosis factor α (TNF-α) release. Among the analogues tested, nafarelin exhibited the highest potency, whereas buserelin exhibited the lowest. In vivo, these analogues induced mast cell degranulation and capillary dilation in mouse paw skin, leading to localized pseudo-allergic symptoms (edema and extravasation) that were confirmed to be MRGPRX2-mediated. Molecular docking revealed that the cationic amino acid at position eight of the GnRH analogues bound complementarily to the negatively charged center within the MRGPRX2 ligand-binding pocket, suggesting a mechanistic basis for receptor activation. Functional validation via Arg8-to-Glu substitution in triptorelin significantly attenuated MRGPRX2 activation. Collectively, this work elucidates the MRGPRX2-dependent molecular mechanism underlying GnRH analogue-induced histamine release and provides a foundation for designing safer analogues with reduced adverse effects.
2026, 37(10): 112097
doi: 10.1016/j.cclet.2025.112097
摘要:
Realizing biologically authentic tactile–pain sensing in flexible electronic skins (e-skins) requires materials that combine linear touch encoding with strain-gated pain signaling, while also offering spatially resolved stimulus mapping and sustainable recyclability. Here, we present a recyclable neurothreshold-mimetic eutectogel (NeuroThres-Gel) based on a strain-induced percolation threshold modulation strategy. The prepared eutectogel demonstrated shear-thinning rheology, thermoplastic reprocessability, and environmental stability in wide temperature window. Under uniaxial strain, the conductive network remains intact and reversible up to a programmable critical strain (εt) of 80%. Beyond this threshold, geometric percolation collapse occurs, resulting in a sharp, nonvolatile resistive transition that mimics neuronal action potential firing and enables strain-gated pain-like signaling. Direct-ink-writing (DIW) of NeuroThres-Gel yielded microstructured sensor arrays with volumetrically distributed receptive fields, achieving spatially resolved, vectorial pain mapping. Critically, after five melt-recycle cycles, the NeuroThres-Gel sensors retained excellent spatial nociceptive perception and stable mechanical strength, highlighting the closed-loop recyclability enabled by the dynamic cross-linked network. Collectively, NeuroThres-Gel integrated programmable tactile-to-pain conversion, directional nociceptive sensing, and sustainable recyclability into a single platform, charting a pathway toward next-generation adaptive prosthetic feedback systems and human–machine interfaces.
Realizing biologically authentic tactile–pain sensing in flexible electronic skins (e-skins) requires materials that combine linear touch encoding with strain-gated pain signaling, while also offering spatially resolved stimulus mapping and sustainable recyclability. Here, we present a recyclable neurothreshold-mimetic eutectogel (NeuroThres-Gel) based on a strain-induced percolation threshold modulation strategy. The prepared eutectogel demonstrated shear-thinning rheology, thermoplastic reprocessability, and environmental stability in wide temperature window. Under uniaxial strain, the conductive network remains intact and reversible up to a programmable critical strain (εt) of 80%. Beyond this threshold, geometric percolation collapse occurs, resulting in a sharp, nonvolatile resistive transition that mimics neuronal action potential firing and enables strain-gated pain-like signaling. Direct-ink-writing (DIW) of NeuroThres-Gel yielded microstructured sensor arrays with volumetrically distributed receptive fields, achieving spatially resolved, vectorial pain mapping. Critically, after five melt-recycle cycles, the NeuroThres-Gel sensors retained excellent spatial nociceptive perception and stable mechanical strength, highlighting the closed-loop recyclability enabled by the dynamic cross-linked network. Collectively, NeuroThres-Gel integrated programmable tactile-to-pain conversion, directional nociceptive sensing, and sustainable recyclability into a single platform, charting a pathway toward next-generation adaptive prosthetic feedback systems and human–machine interfaces.
2026, 37(10): 112100
doi: 10.1016/j.cclet.2025.112100
摘要:
Hydrogen sulfide (H2S) is a pivotal endogenous gaseous signalling molecule involved in various physiological processes. Although H2S exhibits significant anti-inflammatory effects at physiological concentrations, its clinical utility is hindered by the challenges associated with its high activity and difficulties in controlled release. We designed three photoactivatable H2S donors, HSDs (HSD1, HSD2, and HSD3), by integrating an H2S-releasing 1,4,2-dioxazole-5-thione scaffold with three fluorophores spanning the ultraviolet to red spectral range. Upon photo-irradiation, each donor induces a pronounced turn-on fluorescence (> 58-fold), accompanied by efficient H2S release (over 30%) without the formation of electrophilic by-products. Moreover, HSDs enable real-time quantitatively photo-triggered H2S-release in both live cells and murine models, and present anti-inflammatory and antioxidant effects in vivo. In a full-thickness cutaneous wound model, HSDs markedly accelerated wound healing, highlighting their potential as precision therapeutic agents for wound management. Collectively, we provide a translatable strategy to overcome the limitations of conventional H2S delivery systems and highlight the therapeutic promise of controlled H2S release in clinical application.
Hydrogen sulfide (H2S) is a pivotal endogenous gaseous signalling molecule involved in various physiological processes. Although H2S exhibits significant anti-inflammatory effects at physiological concentrations, its clinical utility is hindered by the challenges associated with its high activity and difficulties in controlled release. We designed three photoactivatable H2S donors, HSDs (HSD1, HSD2, and HSD3), by integrating an H2S-releasing 1,4,2-dioxazole-5-thione scaffold with three fluorophores spanning the ultraviolet to red spectral range. Upon photo-irradiation, each donor induces a pronounced turn-on fluorescence (> 58-fold), accompanied by efficient H2S release (over 30%) without the formation of electrophilic by-products. Moreover, HSDs enable real-time quantitatively photo-triggered H2S-release in both live cells and murine models, and present anti-inflammatory and antioxidant effects in vivo. In a full-thickness cutaneous wound model, HSDs markedly accelerated wound healing, highlighting their potential as precision therapeutic agents for wound management. Collectively, we provide a translatable strategy to overcome the limitations of conventional H2S delivery systems and highlight the therapeutic promise of controlled H2S release in clinical application.
2026, 37(10): 112103
doi: 10.1016/j.cclet.2025.112103
摘要:
Nano-carriers are crucial for photosensitizer targeted delivery to overcome the poor selectivity of conventional photosensitizers. Recently, aptamer-guided DNA tetrahedron has become a potential carrier due to its great biocompatibility and target identification ability. However, the in vivo photodynamic therapy (PDT) of DNA tetrahedron-based photosensitizer delivery system remains a charming yet challenging mission. This work aims to construct a high-targeted photosensitizer delivery system for enhanced PDT treatment, relying on the combination of aptamer-guided DNA tetrahedron, graphene-oxide and photosensitizer. Three aptamers are linked to a DNA tetrahedron to build an aptamer-guided nano-carrier for targeting liver tumor cells. Aggregation-induced emission-active photosensitizer, TTVP, was loaded into the nano-carriers through intercalation and hydrophobic interaction, leading to the improvement of their PDT effect. Subsequently, TTVP-loaded nano-carriers were adsorbed on the graphene-oxide surface via hydrogen bonds and π-stacking interactions to elevate their target identification ability. Consequently, a photosensitizer delivery system was obtained. It selectively aggregated on the liver tumor tissues and presented potent therapeutic efficacy via reactive oxygen species (ROS) generation. This system provides a fresh pathway for in vivo high-targeted and enhanced PDT treatment based on DNA nano-carriers.
Nano-carriers are crucial for photosensitizer targeted delivery to overcome the poor selectivity of conventional photosensitizers. Recently, aptamer-guided DNA tetrahedron has become a potential carrier due to its great biocompatibility and target identification ability. However, the in vivo photodynamic therapy (PDT) of DNA tetrahedron-based photosensitizer delivery system remains a charming yet challenging mission. This work aims to construct a high-targeted photosensitizer delivery system for enhanced PDT treatment, relying on the combination of aptamer-guided DNA tetrahedron, graphene-oxide and photosensitizer. Three aptamers are linked to a DNA tetrahedron to build an aptamer-guided nano-carrier for targeting liver tumor cells. Aggregation-induced emission-active photosensitizer, TTVP, was loaded into the nano-carriers through intercalation and hydrophobic interaction, leading to the improvement of their PDT effect. Subsequently, TTVP-loaded nano-carriers were adsorbed on the graphene-oxide surface via hydrogen bonds and π-stacking interactions to elevate their target identification ability. Consequently, a photosensitizer delivery system was obtained. It selectively aggregated on the liver tumor tissues and presented potent therapeutic efficacy via reactive oxygen species (ROS) generation. This system provides a fresh pathway for in vivo high-targeted and enhanced PDT treatment based on DNA nano-carriers.
2026, 37(10): 112111
doi: 10.1016/j.cclet.2025.112111
摘要:
Ulcerative colitis (UC) is a pressing clinical issue currently lacking effective therapeutic approaches. Here we conducted a screening on the natural compounds from traditional Chinese medicine to identify a potent lead, shikonin (SHK), applying a necroptosis cell model. The potency for treating UC was confirmed in a dextran sulfate sodium (DSS)-induced UC mouse model. Leveraging a photo-affinity labeling approach, heat shock protein family A member 8 (HSPA8), a key negative regulator of necroptosis, was identified as the direct target of SHK. The in vivo protection of SHK were validated through targeting HSPA8 based on necroptosis pathway. As a result, targeting HSPA8 by SHK or activate HSPA8 significantly impairs necroptosis signaling and mitigates UC. Our findings not only define HSPA8 as a novel therapeutic target for UC but also highlight SHK as a promising lead for treatment of this symptom.
Ulcerative colitis (UC) is a pressing clinical issue currently lacking effective therapeutic approaches. Here we conducted a screening on the natural compounds from traditional Chinese medicine to identify a potent lead, shikonin (SHK), applying a necroptosis cell model. The potency for treating UC was confirmed in a dextran sulfate sodium (DSS)-induced UC mouse model. Leveraging a photo-affinity labeling approach, heat shock protein family A member 8 (HSPA8), a key negative regulator of necroptosis, was identified as the direct target of SHK. The in vivo protection of SHK were validated through targeting HSPA8 based on necroptosis pathway. As a result, targeting HSPA8 by SHK or activate HSPA8 significantly impairs necroptosis signaling and mitigates UC. Our findings not only define HSPA8 as a novel therapeutic target for UC but also highlight SHK as a promising lead for treatment of this symptom.
2026, 37(10): 112122
doi: 10.1016/j.cclet.2025.112122
摘要:
Flexible wearable sensors require conductive elastomers that combine sustainability, durability, and reliable low-temperature performance. However, conventional hydrogels suffer from dehydration and freezing, while ionogels face challenges of leakage, high cost, and poor recyclability. Here, we introduce a novel polymerizable deep eutectic solvent (PDES) system based on natural lipoic acid and imidazolium derivatives, which serves as the foundation for constructing recyclable polymeric dynamic eutectic gels (PDDEGs). The PDES not only provides high ionic mobility and antifreeze capacity but also enables covalent crosslinking to form a robust yet dynamic polymeric network. Through synergistic hydrogen bonding, ionic conduction, and reversible zirconium coordination, PDDEGs achieve high stretchability, toughness, and strong adhesion. More importantly, they exhibit remarkable recyclability, efficient self-healing, and thermal remoldability, allowing solvent-free reprocessing, structural repair, and adaptive reshaping without performance loss. The gels remain flexible and conductive at −20 ℃ and function as reliable strain sensors with high sensitivity, fast response, and long-term durability in monitoring complex human motions. By combining a new class of polymerizable eutectic solvents with dynamic crosslinking, this work establishes a sustainable platform for next-generation wearable electronics capable of operating in extreme environments.
Flexible wearable sensors require conductive elastomers that combine sustainability, durability, and reliable low-temperature performance. However, conventional hydrogels suffer from dehydration and freezing, while ionogels face challenges of leakage, high cost, and poor recyclability. Here, we introduce a novel polymerizable deep eutectic solvent (PDES) system based on natural lipoic acid and imidazolium derivatives, which serves as the foundation for constructing recyclable polymeric dynamic eutectic gels (PDDEGs). The PDES not only provides high ionic mobility and antifreeze capacity but also enables covalent crosslinking to form a robust yet dynamic polymeric network. Through synergistic hydrogen bonding, ionic conduction, and reversible zirconium coordination, PDDEGs achieve high stretchability, toughness, and strong adhesion. More importantly, they exhibit remarkable recyclability, efficient self-healing, and thermal remoldability, allowing solvent-free reprocessing, structural repair, and adaptive reshaping without performance loss. The gels remain flexible and conductive at −20 ℃ and function as reliable strain sensors with high sensitivity, fast response, and long-term durability in monitoring complex human motions. By combining a new class of polymerizable eutectic solvents with dynamic crosslinking, this work establishes a sustainable platform for next-generation wearable electronics capable of operating in extreme environments.
2026, 37(10): 112123
doi: 10.1016/j.cclet.2025.112123
摘要:
Spinal cord injury (SCI) is a severe neurological disorder often leading to long-term motor dysfunction and permanent disability. Bone marrow-derived mesenchymal stem cell (BMSC) transplantation has been explored to promote SCI recovery; however, the survival and efficacy of transplanted BMSCs are severely compromised by the excessive reactive oxygen species (ROS) present at the injury site. In this study, we developed a peptide hydrogel (MnO2-Gel) with excellent ROS-scavenging capacity and good biocompatibility. In vitro experiments demonstrated that MnO2-Gel significantly enhanced BMSC survival under oxidative stress conditions. In a rat model of SCI, co-injection of MnO2-Gel and BMSCs into the lesion site markedly improved locomotor recovery, indicating the potential of this combination strategy for treating SCI.
Spinal cord injury (SCI) is a severe neurological disorder often leading to long-term motor dysfunction and permanent disability. Bone marrow-derived mesenchymal stem cell (BMSC) transplantation has been explored to promote SCI recovery; however, the survival and efficacy of transplanted BMSCs are severely compromised by the excessive reactive oxygen species (ROS) present at the injury site. In this study, we developed a peptide hydrogel (MnO2-Gel) with excellent ROS-scavenging capacity and good biocompatibility. In vitro experiments demonstrated that MnO2-Gel significantly enhanced BMSC survival under oxidative stress conditions. In a rat model of SCI, co-injection of MnO2-Gel and BMSCs into the lesion site markedly improved locomotor recovery, indicating the potential of this combination strategy for treating SCI.
2026, 37(10): 112128
doi: 10.1016/j.cclet.2025.112128
摘要:
Hydrogel-encapsulated islet cell transplantation is an effective strategy to overcome immune rejection in type 1 diabetes (T1D). However, current research primarily focuses on the immune isolation function of hydrogels about islet cell, while the influence of their mechanical properties on islet cells is often overlooked. To address this oversight, a series of alginate-gelatin (Alg-Gel) hydrogels with different mechanical strengths were prepared by adjusting the molecular weight of sodium alginate and combining it with gelatin, designated as low- (LHG, 1.98 kPa), medium- (MHG, 4.21 kPa), and high-stiffness (HHG, 22.98 kPa) hydrogels. Among them, the medium-stiffness hydrogel (MHG) exhibited stress-relaxing properties, which can mimic the mechanical properties of native islets. Furthermore, it activated the phosphatidylinositol 3-kinase (PI3K)-protein kinase B (Akt)/Wnt signaling pathway, providing a favorable three-dimensional (3D) microenvironment for insulin-producing INS-1 cells. When further loaded with platelet-rich plasma (PRP), the resulting MHG@PRP construct then leverages calcium-dependent activation of the growth factor-PI3K/Akt/mammalian target of rapamycin (mTOR) axis to enhance cellular physiological performance. It was demonstrated in vitro that MHG@PRP significantly improves islet cell viability and glucose-stimulated insulin secretion (GSIS). Furthermore, in vivo experiments using a streptozotocin (STZ)-induced diabetic mouse model confirmed that the MHG@PRP/cells construct effectively restores glycemic regulation. This hydrogel design, which synergistically combines biomechanical and biochemical cues, is expected to provide a novel and transformative paradigm for advanced islet cell therapy.
Hydrogel-encapsulated islet cell transplantation is an effective strategy to overcome immune rejection in type 1 diabetes (T1D). However, current research primarily focuses on the immune isolation function of hydrogels about islet cell, while the influence of their mechanical properties on islet cells is often overlooked. To address this oversight, a series of alginate-gelatin (Alg-Gel) hydrogels with different mechanical strengths were prepared by adjusting the molecular weight of sodium alginate and combining it with gelatin, designated as low- (LHG, 1.98 kPa), medium- (MHG, 4.21 kPa), and high-stiffness (HHG, 22.98 kPa) hydrogels. Among them, the medium-stiffness hydrogel (MHG) exhibited stress-relaxing properties, which can mimic the mechanical properties of native islets. Furthermore, it activated the phosphatidylinositol 3-kinase (PI3K)-protein kinase B (Akt)/Wnt signaling pathway, providing a favorable three-dimensional (3D) microenvironment for insulin-producing INS-1 cells. When further loaded with platelet-rich plasma (PRP), the resulting MHG@PRP construct then leverages calcium-dependent activation of the growth factor-PI3K/Akt/mammalian target of rapamycin (mTOR) axis to enhance cellular physiological performance. It was demonstrated in vitro that MHG@PRP significantly improves islet cell viability and glucose-stimulated insulin secretion (GSIS). Furthermore, in vivo experiments using a streptozotocin (STZ)-induced diabetic mouse model confirmed that the MHG@PRP/cells construct effectively restores glycemic regulation. This hydrogel design, which synergistically combines biomechanical and biochemical cues, is expected to provide a novel and transformative paradigm for advanced islet cell therapy.
2026, 37(10): 112129
doi: 10.1016/j.cclet.2025.112129
摘要:
This study aims to develop advanced phototheranostic agent to address the critical challenge of multi-modal therapy and immune microenvironment remodeling in immuno-phototherapy (IPT). Here we utilized a near infrared (NIR) o-IDTBR, and then assembled with 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[amino(polyethylene glycol)] (DSPE-PEG-NH2) to prepare o-IDTBR nanoparticles (NPs). Theoretical calculations suggest that in the aggregated state, the energy gap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), and the energy gap between the excited singlet and triplet states are reduced, as compared to the monomolecular state, leading to red-shifting absorption/emission wavelengths and enhancing the photothermal conversion and reactive oxygen species (ROS) generation, and thus improve the efficacy of photodynamic and photothermal therapies. These NIR laser-activated NPs effectively induced pyroptosis/apoptosis/necroptosis (PANoptosis) and promoted immunogenic cell death through mechanisms such as calreticulin (CRT) exposure, ATP secretion, and high mobility group box 1 (HMGB1) release. Notably, immune profiling revealed a reprogrammed tumor microenvironment in NPs and laser irradiation treated group. This phenotypic shift activated systemic antitumor immunity. Our work constructs an advanced phototheranostic agent with aggregation-induced red-shifting absorption and fluorescence wavelengths, and enhancing photothermal conversion and ROS generation capabilities, and establishes a synergistic paradigm of "imaging guidance, inducing local multi-modal cell death, systemic immune activation".
This study aims to develop advanced phototheranostic agent to address the critical challenge of multi-modal therapy and immune microenvironment remodeling in immuno-phototherapy (IPT). Here we utilized a near infrared (NIR) o-IDTBR, and then assembled with 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[amino(polyethylene glycol)] (DSPE-PEG-NH2) to prepare o-IDTBR nanoparticles (NPs). Theoretical calculations suggest that in the aggregated state, the energy gap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), and the energy gap between the excited singlet and triplet states are reduced, as compared to the monomolecular state, leading to red-shifting absorption/emission wavelengths and enhancing the photothermal conversion and reactive oxygen species (ROS) generation, and thus improve the efficacy of photodynamic and photothermal therapies. These NIR laser-activated NPs effectively induced pyroptosis/apoptosis/necroptosis (PANoptosis) and promoted immunogenic cell death through mechanisms such as calreticulin (CRT) exposure, ATP secretion, and high mobility group box 1 (HMGB1) release. Notably, immune profiling revealed a reprogrammed tumor microenvironment in NPs and laser irradiation treated group. This phenotypic shift activated systemic antitumor immunity. Our work constructs an advanced phototheranostic agent with aggregation-induced red-shifting absorption and fluorescence wavelengths, and enhancing photothermal conversion and ROS generation capabilities, and establishes a synergistic paradigm of "imaging guidance, inducing local multi-modal cell death, systemic immune activation".
2026, 37(10): 112130
doi: 10.1016/j.cclet.2025.112130
摘要:
Chronic diabetic wounds are characterized by persistent inflammation and impaired angiogenesis, presenting a major therapeutic challenge. Here, we report a three-dimensional (3D)-printed polycaprolactone (PCL) scaffold integrating shikonin (SK), a bioactive compound derived from Lithospermum erythrorhizon, to achieve controlled drug release and multifunctional wound repair. The PCL/SK scaffold exhibited a porous, breathable architecture with high mechanical integrity and biocompatibility, enabling sustained SK release over 72 h. In a diabetic mouse wound model, the PCL/SK scaffold significantly accelerated wound closure, enhanced collagen deposition, and increased the density of anti-inflammatory CD206+ macrophages compared to free SK or PCL controls. Transcriptomic and immunohistochemical analyses revealed that PCL/SK treatment upregulated angiogenesis-related genes, including vascular endothelial growth factor (Vegf), platelet endothelial cell adhesion molecule 1 (Pecam1) and TEK receptor tyrosine kinase (Tek), meanwhile elevated CD31+ and VEGF+ endothelial markers, concomitant with improved blood perfusion. Mechanistically, this effect was attributed to synergistic anti-inflammatory and pro-angiogenic modulation by sustained SK delivery and the supportive PCL microenvironment. These findings establish a bioactive drug-biomaterial hybrid platform that leverages controlled release to coordinate immune resolution and vascular regeneration, offering a promising strategy for chronic diabetic wound management and broader regenerative applications.
Chronic diabetic wounds are characterized by persistent inflammation and impaired angiogenesis, presenting a major therapeutic challenge. Here, we report a three-dimensional (3D)-printed polycaprolactone (PCL) scaffold integrating shikonin (SK), a bioactive compound derived from Lithospermum erythrorhizon, to achieve controlled drug release and multifunctional wound repair. The PCL/SK scaffold exhibited a porous, breathable architecture with high mechanical integrity and biocompatibility, enabling sustained SK release over 72 h. In a diabetic mouse wound model, the PCL/SK scaffold significantly accelerated wound closure, enhanced collagen deposition, and increased the density of anti-inflammatory CD206+ macrophages compared to free SK or PCL controls. Transcriptomic and immunohistochemical analyses revealed that PCL/SK treatment upregulated angiogenesis-related genes, including vascular endothelial growth factor (Vegf), platelet endothelial cell adhesion molecule 1 (Pecam1) and TEK receptor tyrosine kinase (Tek), meanwhile elevated CD31+ and VEGF+ endothelial markers, concomitant with improved blood perfusion. Mechanistically, this effect was attributed to synergistic anti-inflammatory and pro-angiogenic modulation by sustained SK delivery and the supportive PCL microenvironment. These findings establish a bioactive drug-biomaterial hybrid platform that leverages controlled release to coordinate immune resolution and vascular regeneration, offering a promising strategy for chronic diabetic wound management and broader regenerative applications.
2026, 37(10): 112136
doi: 10.1016/j.cclet.2025.112136
摘要:
Lanthanide complexes attract significant attention for their narrow-band emission with nearly constant wavelengths; however, developing high-efficiency lanthanide-complex organic light-emitting diode (OLED) devices and methodologies remains a primary research focus. We selected neutral ligands [1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline (TDZP) and its selenium (Se)-containing counterpart, [1,2,5]selenadiazolo[3,4-f][1,10]phenanthroline (SDZP), to form complexes with dibenzoylmethane (Hdbm). Detailed investigations combining theoretical calculations and experimental data reveal synergistic effects between excited-state lifetimes and charge carrier mobility in enhancing quantum efficiency. All the devices demonstrated characteristic lanthanide ion emission, with the Eu(dbm)3SDZP-based OLED achieving remarkable electroluminescent performance: a maximum quantum efficiency (EQEmax) of 6.7%, ranking among the highest reported values for Eu-based complex OLEDs. This integrated computational-experimental approach establishes a viable strategy for developing high-efficiency lanthanide-complex OLEDs.
Lanthanide complexes attract significant attention for their narrow-band emission with nearly constant wavelengths; however, developing high-efficiency lanthanide-complex organic light-emitting diode (OLED) devices and methodologies remains a primary research focus. We selected neutral ligands [1,2,5]thiadiazolo[3,4-f][1,10]phenanthroline (TDZP) and its selenium (Se)-containing counterpart, [1,2,5]selenadiazolo[3,4-f][1,10]phenanthroline (SDZP), to form complexes with dibenzoylmethane (Hdbm). Detailed investigations combining theoretical calculations and experimental data reveal synergistic effects between excited-state lifetimes and charge carrier mobility in enhancing quantum efficiency. All the devices demonstrated characteristic lanthanide ion emission, with the Eu(dbm)3SDZP-based OLED achieving remarkable electroluminescent performance: a maximum quantum efficiency (EQEmax) of 6.7%, ranking among the highest reported values for Eu-based complex OLEDs. This integrated computational-experimental approach establishes a viable strategy for developing high-efficiency lanthanide-complex OLEDs.
2026, 37(10): 112139
doi: 10.1016/j.cclet.2025.112139
摘要:
Inflammatory bowel disease (IBD) is a chronic condition that severely affects the gastrointestinal tract. Current treatments often have limited efficacy and significant side effects. Iron oxide nanoparticles (Fe2O3 NPs) have emerged as promising candidates for IBD therapy due to their biocompatibility and stability. This study investigates how different surface modifications influence the therapeutic efficacy of Fe2O3 NPs in IBD management. We developed four different types of modified Fe2O3 NPs, including unmodified γ-Fe2O3 NPs, amine-functionalized Fe2O3 NPs (APTS-Fe2O3 NPs), poly-L-lysine-coated Fe2O3 NPs (PLL-Fe2O3 NPs), and dimercaptosuccinic acid-coated Fe2O3 NPs (DMSA-Fe2O3 NPs). Our results demonstrate that all types of Fe2O3 NPs can adsorb proteins to form the protein corona. However, the composition of the protein corona varies, leading to different therapeutic effects of the NPs on IBD. Among them, APTS-Fe2O3 NPs showed reduced therapeutic efficacy compared to the other surface-modified NPs. This was attributed to their adsorption of higher levels of protective and translocation-related proteins, as well as enhanced permeability across intestinal epithelial cells. These findings underscore the importance of carefully tailoring nanoparticle surface properties. Overall, this study highlights the significance of understanding nanoparticle-protein interactions in designing more effective nanoparticle-based therapies for IBD.
Inflammatory bowel disease (IBD) is a chronic condition that severely affects the gastrointestinal tract. Current treatments often have limited efficacy and significant side effects. Iron oxide nanoparticles (Fe2O3 NPs) have emerged as promising candidates for IBD therapy due to their biocompatibility and stability. This study investigates how different surface modifications influence the therapeutic efficacy of Fe2O3 NPs in IBD management. We developed four different types of modified Fe2O3 NPs, including unmodified γ-Fe2O3 NPs, amine-functionalized Fe2O3 NPs (APTS-Fe2O3 NPs), poly-L-lysine-coated Fe2O3 NPs (PLL-Fe2O3 NPs), and dimercaptosuccinic acid-coated Fe2O3 NPs (DMSA-Fe2O3 NPs). Our results demonstrate that all types of Fe2O3 NPs can adsorb proteins to form the protein corona. However, the composition of the protein corona varies, leading to different therapeutic effects of the NPs on IBD. Among them, APTS-Fe2O3 NPs showed reduced therapeutic efficacy compared to the other surface-modified NPs. This was attributed to their adsorption of higher levels of protective and translocation-related proteins, as well as enhanced permeability across intestinal epithelial cells. These findings underscore the importance of carefully tailoring nanoparticle surface properties. Overall, this study highlights the significance of understanding nanoparticle-protein interactions in designing more effective nanoparticle-based therapies for IBD.
2026, 37(10): 112140
doi: 10.1016/j.cclet.2025.112140
摘要:
The Src homology 2 domain-containing phosphatase 2 (SHP2) plays a pivotal role in cellular processes and is associated with various diseases. Activation of SHP2 has been shown to be effective in inflammation-related diseases such as colitis, atherosclerosis and Parkinson's disease. Although SHP2 inhibitors have been extensively studied in recent years, especially allosteric inhibitors, only a small number of SHP2 activators exhibiting weak activation effects have been reported. Herein, we developed a facile approach to the total synthesis of plasiatine, which was extracted from the seeds of Plantago asiatica as a direct SHP2 activator. Iterative study on the structure-activity relationship identified a potent SHP2 activator, compound C8, with median effective concentration (EC50) = 0.11 µmol/L and Emax = 3.75-fold. Surface plasmon resonance experiment revealed a robust binding affinity between C8 and the SHP2 catalytic domain, with a dissociation constant (Kd) of 70.4 nmol/L. In vivo study showed that C8 significantly reduced atherosclerotic plaques and increased anti-inflammatory factors, highlighting its potential as an effective anti-atherosclerotic agent.
The Src homology 2 domain-containing phosphatase 2 (SHP2) plays a pivotal role in cellular processes and is associated with various diseases. Activation of SHP2 has been shown to be effective in inflammation-related diseases such as colitis, atherosclerosis and Parkinson's disease. Although SHP2 inhibitors have been extensively studied in recent years, especially allosteric inhibitors, only a small number of SHP2 activators exhibiting weak activation effects have been reported. Herein, we developed a facile approach to the total synthesis of plasiatine, which was extracted from the seeds of Plantago asiatica as a direct SHP2 activator. Iterative study on the structure-activity relationship identified a potent SHP2 activator, compound C8, with median effective concentration (EC50) = 0.11 µmol/L and Emax = 3.75-fold. Surface plasmon resonance experiment revealed a robust binding affinity between C8 and the SHP2 catalytic domain, with a dissociation constant (Kd) of 70.4 nmol/L. In vivo study showed that C8 significantly reduced atherosclerotic plaques and increased anti-inflammatory factors, highlighting its potential as an effective anti-atherosclerotic agent.
2026, 37(10): 112165
doi: 10.1016/j.cclet.2025.112165
摘要:
Polymer lamellar single crystals (PLSCs), the fundamental crystalline units of semicrystalline polymers, are ideal model systems to probe intrinsic structure-property relationships of polymer dielectrics. However, the reliable preparation and characterization of PLSCs remain challenging. Here, using a controlled solvent evaporation method, large-area isotactic poly(1-butene) (iPB-1) single crystals with lateral dimension spanning several hundred micrometers were directly grown on conductive substrates. This, in turn, enables straightforward fabrication of metal–insulator–metal (MIM) capacitors, and facilitates the subsequent determination of the dielectric constant for form Ⅲ iPB-1 single crystals with a remarkably low value of 1.82 ± 0.05. This low value is attributed to suppressed chain-segmental motion and low molecular packing density of form Ⅲ crystal phase. This study provides a model framework for quantifying the intrinsic dielectric performance of crystalline phase in semicrystalline polymer systems and highlighting the importance of crystal structure in determining the macroscopic behavior of polymeric dielectrics.
Polymer lamellar single crystals (PLSCs), the fundamental crystalline units of semicrystalline polymers, are ideal model systems to probe intrinsic structure-property relationships of polymer dielectrics. However, the reliable preparation and characterization of PLSCs remain challenging. Here, using a controlled solvent evaporation method, large-area isotactic poly(1-butene) (iPB-1) single crystals with lateral dimension spanning several hundred micrometers were directly grown on conductive substrates. This, in turn, enables straightforward fabrication of metal–insulator–metal (MIM) capacitors, and facilitates the subsequent determination of the dielectric constant for form Ⅲ iPB-1 single crystals with a remarkably low value of 1.82 ± 0.05. This low value is attributed to suppressed chain-segmental motion and low molecular packing density of form Ⅲ crystal phase. This study provides a model framework for quantifying the intrinsic dielectric performance of crystalline phase in semicrystalline polymer systems and highlighting the importance of crystal structure in determining the macroscopic behavior of polymeric dielectrics.
2026, 37(10): 112172
doi: 10.1016/j.cclet.2025.112172
摘要:
Three novel β-carboline alkaloid dimers, pecanthines A–C (1−3), featuring unprecedented 6/5/6/6–5/6 and 6/5/6/6/5/6 polycyclic frameworks, were isolated from the seeds of Peganum harmala. Their structures were elucidated by spectroscopic analyses and X-ray diffraction. Notably, compounds 1 and 2 represent the first heterodimeric alkaloids merging canthin-6-one and melatonin-type scaffolds, with 1 additionally displaying neuroprotective activity. In addition, a gram-scale synthesis of 3 was achieved in six steps, leveraging a key acyl-ketene imine condensation and Suzuki coupling. Biological evaluation revealed that 3 acts as a new topoisomerase Ⅰ (Topo Ⅰ) inhibitor, exhibiting remarkable antiproliferative activity. Mechanistic studies demonstrated that 3 induces DNA damage, triggering apoptosis and cell cycle arrest in cancer cells. The discovery and gram-scale synthesis of 3 provide a promising lead compound and a novel molecular scaffold for anticancer drug development.
Three novel β-carboline alkaloid dimers, pecanthines A–C (1−3), featuring unprecedented 6/5/6/6–5/6 and 6/5/6/6/5/6 polycyclic frameworks, were isolated from the seeds of Peganum harmala. Their structures were elucidated by spectroscopic analyses and X-ray diffraction. Notably, compounds 1 and 2 represent the first heterodimeric alkaloids merging canthin-6-one and melatonin-type scaffolds, with 1 additionally displaying neuroprotective activity. In addition, a gram-scale synthesis of 3 was achieved in six steps, leveraging a key acyl-ketene imine condensation and Suzuki coupling. Biological evaluation revealed that 3 acts as a new topoisomerase Ⅰ (Topo Ⅰ) inhibitor, exhibiting remarkable antiproliferative activity. Mechanistic studies demonstrated that 3 induces DNA damage, triggering apoptosis and cell cycle arrest in cancer cells. The discovery and gram-scale synthesis of 3 provide a promising lead compound and a novel molecular scaffold for anticancer drug development.
2026, 37(10): 112178
doi: 10.1016/j.cclet.2025.112178
摘要:
Aqueous zinc batteries tend to be safe, low-cost, and environmentally friendly. An aqueous cell coupling zinc metal anode and polyanion cathode provides high voltage. However, water-induced side reactions on zinc electrodes, as well as the decomposition of polyanionic cathode, limit the stability of the system. The application of water-in-salt (WiS) electrolytes offers a viable alternative. However, the solubility of conventional zinc salts with weak acidity is low. Herein, we increased the concentration of Zn(OTf)2 to 10 m (mol/kgwater) by introducing saturated betaine (BT) as a cosolvent. In the 10 m Zn(OTf)2/13 m BT electrolyte, the high salt concentration and the interactions between betaine and water effectively lower water activity. Moreover, betaine participates in the solvation structure of zinc ions, facilitating the formation of protective interphases on both the zinc anode and the Li3V2(PO4)3 cathode, thereby suppressing side reactions and cathode decomposition. As a result, the electrolyte enables reversible Zn plating/stripping over 2900 h. The Li3V2(PO4)3 cathode also maintains two pairs of redox reactions at high voltage of 1.8 V/1.7 V and 1.4 V/1.3 V, demonstrating excellent rate capability and stable cycling performance.
Aqueous zinc batteries tend to be safe, low-cost, and environmentally friendly. An aqueous cell coupling zinc metal anode and polyanion cathode provides high voltage. However, water-induced side reactions on zinc electrodes, as well as the decomposition of polyanionic cathode, limit the stability of the system. The application of water-in-salt (WiS) electrolytes offers a viable alternative. However, the solubility of conventional zinc salts with weak acidity is low. Herein, we increased the concentration of Zn(OTf)2 to 10 m (mol/kgwater) by introducing saturated betaine (BT) as a cosolvent. In the 10 m Zn(OTf)2/13 m BT electrolyte, the high salt concentration and the interactions between betaine and water effectively lower water activity. Moreover, betaine participates in the solvation structure of zinc ions, facilitating the formation of protective interphases on both the zinc anode and the Li3V2(PO4)3 cathode, thereby suppressing side reactions and cathode decomposition. As a result, the electrolyte enables reversible Zn plating/stripping over 2900 h. The Li3V2(PO4)3 cathode also maintains two pairs of redox reactions at high voltage of 1.8 V/1.7 V and 1.4 V/1.3 V, demonstrating excellent rate capability and stable cycling performance.
2026, 37(10): 112224
doi: 10.1016/j.cclet.2025.112224
摘要:
The development of unnatural α-amino esters as key building blocks for peptide drug discovery remains a significant challenge due to the inherent limitations of natural amino acids and scarcity of unnatural amino acids. By leveraging the dual reactivity of α-diazo sulfonium salts, this study reports the efficient synthesis of unnatural α-amino esters via a rhodium-catalyzed three-component tandem strategy. This method undergoes the sequential N–H insertion and nucleophilic substitution (SN1) reactions, avoiding the tedious and complex reaction operations. In addition, tandem C–H functionalization-SN1 processes for the facile construction of 1,1-di(hetero)aryl compounds were also achieved. The utility of this methodology was demonstrated by its application in the concise synthesis of the bioactive natural products Streptindole and Arsindoline B, as well as its successful scalability to gram-scale quantities. Furthermore, the mechanistic insights obtained from DFT (density functional theory) calculations provide a rational explanation of the reaction pathway, highlighting the pivotal role of rhodium-carbynoid intermediates.
The development of unnatural α-amino esters as key building blocks for peptide drug discovery remains a significant challenge due to the inherent limitations of natural amino acids and scarcity of unnatural amino acids. By leveraging the dual reactivity of α-diazo sulfonium salts, this study reports the efficient synthesis of unnatural α-amino esters via a rhodium-catalyzed three-component tandem strategy. This method undergoes the sequential N–H insertion and nucleophilic substitution (SN1) reactions, avoiding the tedious and complex reaction operations. In addition, tandem C–H functionalization-SN1 processes for the facile construction of 1,1-di(hetero)aryl compounds were also achieved. The utility of this methodology was demonstrated by its application in the concise synthesis of the bioactive natural products Streptindole and Arsindoline B, as well as its successful scalability to gram-scale quantities. Furthermore, the mechanistic insights obtained from DFT (density functional theory) calculations provide a rational explanation of the reaction pathway, highlighting the pivotal role of rhodium-carbynoid intermediates.
2026, 37(10): 112229
doi: 10.1016/j.cclet.2025.112229
摘要:
The emissive layer of stretchable optoelectronic devices currently incorporates luminescent units through physical blending or co-polymerization. However, these methods often compromise material performance due to interference from the introduced functional groups, and a significant portion of the luminescent components embedded within the material is wasted. In this work, we propose an innovative "click chemistry" strategy for integrating luminescent functional groups onto the surface of polyaniline (PANI) through a simple stirring process. After proton doping, the functionalized PANI exhibited a 29-fold increase in electrical conductivity compared to pristine PANI. This improvement originates from the extended conjugation of the anthracene moiety and enhanced proton-doping efficiency, making it promising for advanced electronic devices.
The emissive layer of stretchable optoelectronic devices currently incorporates luminescent units through physical blending or co-polymerization. However, these methods often compromise material performance due to interference from the introduced functional groups, and a significant portion of the luminescent components embedded within the material is wasted. In this work, we propose an innovative "click chemistry" strategy for integrating luminescent functional groups onto the surface of polyaniline (PANI) through a simple stirring process. After proton doping, the functionalized PANI exhibited a 29-fold increase in electrical conductivity compared to pristine PANI. This improvement originates from the extended conjugation of the anthracene moiety and enhanced proton-doping efficiency, making it promising for advanced electronic devices.
2026, 37(10): 112233
doi: 10.1016/j.cclet.2025.112233
摘要:
The integration of mechanochemistry and piezocatalysis can open new strategies for driving redox reactions used in synthetic chemistry. However, due to the complex interplay between mechanical forces and surface charges, it remains challenging to design piezocatalysts based on a clear understanding of their catalytic mechanisms. Herein, by utilizing conventional BaTiO3 as a piezoelectric material, we explore the hydroacylation of dialkyl azodicarboxylates for the synthesis of acyl hydrazides to gain insights into the piezoelectric material-mediated conversion process. Control experiments and mechanistic studies revealed that the reaction follows a pathway where mechanical activation induces polarization in the piezoelectric material, promoting benzoyl radical generation, which subsequently undergoes radical addition to acylhydrazine derivatives, leading to the formation of acylhydrazides. The collaborative contributions of piezoelectric activation and mechanical milling in the reaction between aldehydes and dialkyl azodicarboxylates enable the synthesis of a broad range of acyl hydrazides with excellent yields. This efficient and sustainable strategy provides valuable insights for theoretical guidance in designing piezocatalysis for future applications.
The integration of mechanochemistry and piezocatalysis can open new strategies for driving redox reactions used in synthetic chemistry. However, due to the complex interplay between mechanical forces and surface charges, it remains challenging to design piezocatalysts based on a clear understanding of their catalytic mechanisms. Herein, by utilizing conventional BaTiO3 as a piezoelectric material, we explore the hydroacylation of dialkyl azodicarboxylates for the synthesis of acyl hydrazides to gain insights into the piezoelectric material-mediated conversion process. Control experiments and mechanistic studies revealed that the reaction follows a pathway where mechanical activation induces polarization in the piezoelectric material, promoting benzoyl radical generation, which subsequently undergoes radical addition to acylhydrazine derivatives, leading to the formation of acylhydrazides. The collaborative contributions of piezoelectric activation and mechanical milling in the reaction between aldehydes and dialkyl azodicarboxylates enable the synthesis of a broad range of acyl hydrazides with excellent yields. This efficient and sustainable strategy provides valuable insights for theoretical guidance in designing piezocatalysis for future applications.
2026, 37(10): 112234
doi: 10.1016/j.cclet.2025.112234
摘要:
Owing to their sophisticated information-processing capabilities, multi-input DNA circuits (DCs) show great potential in spatiotemporally precise in vivo imaging of diseases. Nevertheless, engineering simple yet versatile multi-input DCs remain a big challenge. Herein, tri-input DNA circuits (tiDCs) based on a DNAzyme-driven walker system were developed via a novel double-blocking strategy, enabling high spatiotemporal-precision fluorescence imaging in vivo. A hairpin structure containing photocleavable linker was designed as the first blocking unit to lock the miRNA-complementary strand, while the miRNA-complementary strand was introduced as the second blocking unit to inhibit the Zn2+-specific DNAzyme-contained walker strand. By leveraging upconversion nanoparticles for targeted delivery and light transduction, the tiDCs generated amplified fluorescence signals exclusively upon simultaneous inputs of near-infrared (NIR) light, miRNA, and Zn2+, achieving spatiotemporally controlled imaging of arthritis. This work establishes a programmable molecular platform for visualizing complex biological systems in vivo, offering new pathways to advance diagnostic precision and therapeutic outcomes.
Owing to their sophisticated information-processing capabilities, multi-input DNA circuits (DCs) show great potential in spatiotemporally precise in vivo imaging of diseases. Nevertheless, engineering simple yet versatile multi-input DCs remain a big challenge. Herein, tri-input DNA circuits (tiDCs) based on a DNAzyme-driven walker system were developed via a novel double-blocking strategy, enabling high spatiotemporal-precision fluorescence imaging in vivo. A hairpin structure containing photocleavable linker was designed as the first blocking unit to lock the miRNA-complementary strand, while the miRNA-complementary strand was introduced as the second blocking unit to inhibit the Zn2+-specific DNAzyme-contained walker strand. By leveraging upconversion nanoparticles for targeted delivery and light transduction, the tiDCs generated amplified fluorescence signals exclusively upon simultaneous inputs of near-infrared (NIR) light, miRNA, and Zn2+, achieving spatiotemporally controlled imaging of arthritis. This work establishes a programmable molecular platform for visualizing complex biological systems in vivo, offering new pathways to advance diagnostic precision and therapeutic outcomes.
2026, 37(10): 112236
doi: 10.1016/j.cclet.2025.112236
摘要:
The simultaneous discrimination of structurally similar biological thiols in living systems remains a significant challenge. To address this, we designed a novel self-calibrating SERS probe, 2-(3,5-dinitrophenoxy)-4-(2-(4-ethynylbenzoylamino)ethyl)phenyl-2-fluoro-5-nitrobenzoate (DEP), for the simultaneous detection of hydrogen sulfide (H2S), polysulfide (H2Sn), and cysteine (Cys). This single-molecule probe incorporates three distinct binding sites, each specific to a different biothiol, enabling multiplex detection through five characteristic Raman signals (178, 264, 454, 1186, and 1600 cm-1). The Raman band at 2056 cm-1, located in the silent region, serves as an internal reference to establish a ratiometric sensing strategy, thereby improving detection accuracy. The resulting spectral variations were processed statistically using principal component analysis (PCA), allowing for the simultaneous assay of the three thiols. The DEP probe was anchored onto biocompatible gold nanorods (AuNRs), optimized for 785 nm laser excitation, to form the final SERS biosensor. The developed platform successfully identified and differentiated H2S, H2Sn, and Cys in complex biological environments, including living neurons and brain microdialysates.
The simultaneous discrimination of structurally similar biological thiols in living systems remains a significant challenge. To address this, we designed a novel self-calibrating SERS probe, 2-(3,5-dinitrophenoxy)-4-(2-(4-ethynylbenzoylamino)ethyl)phenyl-2-fluoro-5-nitrobenzoate (DEP), for the simultaneous detection of hydrogen sulfide (H2S), polysulfide (H2Sn), and cysteine (Cys). This single-molecule probe incorporates three distinct binding sites, each specific to a different biothiol, enabling multiplex detection through five characteristic Raman signals (178, 264, 454, 1186, and 1600 cm-1). The Raman band at 2056 cm-1, located in the silent region, serves as an internal reference to establish a ratiometric sensing strategy, thereby improving detection accuracy. The resulting spectral variations were processed statistically using principal component analysis (PCA), allowing for the simultaneous assay of the three thiols. The DEP probe was anchored onto biocompatible gold nanorods (AuNRs), optimized for 785 nm laser excitation, to form the final SERS biosensor. The developed platform successfully identified and differentiated H2S, H2Sn, and Cys in complex biological environments, including living neurons and brain microdialysates.
2026, 37(10): 112261
doi: 10.1016/j.cclet.2025.112261
摘要:
This study elucidates the pivotal role of hexameric capsule C in the Brønsted acid-catalyzed dimerization of styrenes to indanes. The confined environment significantly influences the reaction outcomes and requires the co-encapsulation of acid counter-anions for the effective stabilization of carbocation intermediates. These results indicate the potential to optimize the catalytic activity of hexameric capsule C through careful selection of suitable carbocation counter-anions.
This study elucidates the pivotal role of hexameric capsule C in the Brønsted acid-catalyzed dimerization of styrenes to indanes. The confined environment significantly influences the reaction outcomes and requires the co-encapsulation of acid counter-anions for the effective stabilization of carbocation intermediates. These results indicate the potential to optimize the catalytic activity of hexameric capsule C through careful selection of suitable carbocation counter-anions.
2026, 37(10): 112262
doi: 10.1016/j.cclet.2025.112262
摘要:
Aqueous fluorescence quenching poses a significant challenge for organic fluorophores in biological applications. This study demonstrates an effective supramolecular strategy to overcome this limitation through host-guest complexation with methyl-β-cyclodextrin (M-β-CD). Three naphthalimide-based dyes (1a-1c) were obtained by incorporating an azabicycloheptane auxochrome and various targeting groups. Upon M-β-CD complexation, these dyes exhibited 2.3- to 3.4-fold enhancements in fluorescence quantum yields, with binding constants (Ka) of 1.32 × 104 (1a) and 7.09 × 103 L/mol (1b), confirming stable complex formation by 1H NMR spectra. Most remarkably, cellular imaging revealed an 18.7-fold fluorescence intensity increase for dye 1a (0.40 µmol/L) when complexed with M-β-CD. This work establishes a dual design strategy of using an azabicycloheptane as the auxochrome and supramolecular complexes to enhance the aqueous performance of naphthalimide fluorophores while maintaining their targeting capabilities, offering broad potential for biological imaging applications.
Aqueous fluorescence quenching poses a significant challenge for organic fluorophores in biological applications. This study demonstrates an effective supramolecular strategy to overcome this limitation through host-guest complexation with methyl-β-cyclodextrin (M-β-CD). Three naphthalimide-based dyes (1a-1c) were obtained by incorporating an azabicycloheptane auxochrome and various targeting groups. Upon M-β-CD complexation, these dyes exhibited 2.3- to 3.4-fold enhancements in fluorescence quantum yields, with binding constants (Ka) of 1.32 × 104 (1a) and 7.09 × 103 L/mol (1b), confirming stable complex formation by 1H NMR spectra. Most remarkably, cellular imaging revealed an 18.7-fold fluorescence intensity increase for dye 1a (0.40 µmol/L) when complexed with M-β-CD. This work establishes a dual design strategy of using an azabicycloheptane as the auxochrome and supramolecular complexes to enhance the aqueous performance of naphthalimide fluorophores while maintaining their targeting capabilities, offering broad potential for biological imaging applications.
2026, 37(10): 112278
doi: 10.1016/j.cclet.2025.112278
摘要:
Axially chiral diaryl ethers are unique skeletons bearing dual-axial chirality, which have broad applications in biologically active molecules. However, the catalytic atroposelective construction of diaryl ethers is very limited. Atroposelective desymmetrization of prochiral diamines is a straightforward pathway to access C–O axially chiral diaryl ethers, but the direct use of industry feedstock chemicals as desymmetrization reagents is highly challenging. Herein, we report a chiral Brønsted acid-catalyzed desymmetrizing amidation of diamines with carboxylic acids by using ynamide as coupling reagent, enabling the efficient synthesis of C–O and C–C axially chiral anilines. The synthetic utility is demonstrated by one-pot amidation with carboxylic acids, scale-up reaction, synthesis of chiral ligand and catalyst, as well as the applications in asymmetric catalysis. Importantly, this reaction represents a rare atroposelective desymmetrization of diamines with carboxylic acids.
Axially chiral diaryl ethers are unique skeletons bearing dual-axial chirality, which have broad applications in biologically active molecules. However, the catalytic atroposelective construction of diaryl ethers is very limited. Atroposelective desymmetrization of prochiral diamines is a straightforward pathway to access C–O axially chiral diaryl ethers, but the direct use of industry feedstock chemicals as desymmetrization reagents is highly challenging. Herein, we report a chiral Brønsted acid-catalyzed desymmetrizing amidation of diamines with carboxylic acids by using ynamide as coupling reagent, enabling the efficient synthesis of C–O and C–C axially chiral anilines. The synthetic utility is demonstrated by one-pot amidation with carboxylic acids, scale-up reaction, synthesis of chiral ligand and catalyst, as well as the applications in asymmetric catalysis. Importantly, this reaction represents a rare atroposelective desymmetrization of diamines with carboxylic acids.
2026, 37(10): 112281
doi: 10.1016/j.cclet.2025.112281
摘要:
Substituted cyclopentadienyl (Cp) radicals, as well as other Cp and fluorenyl-based radicals, exhibit deviations from ideal fivefold D5h symmetric structures due to Jahn-Teller distortion. The unpaired electron is unequally distributed on the five carbons. Herein, we report the metalla-analogs of Cp radicals from one-electron reduction of antiaromatic osmacyclopentatriene complexes. The novel osmacyclopentatrienyl radicals are nonaromatic, with the single unpaired electron delocalized over the entire five-membered osmacycle. Furthermore, these osmacyclopentatrienyl radicals can be oxidized to regenerate osmacyclopentatrienes and reduced to form osmacyclopentadienes. This discovery provides new insights into radical chemistry and organometallic chemistry.
Substituted cyclopentadienyl (Cp) radicals, as well as other Cp and fluorenyl-based radicals, exhibit deviations from ideal fivefold D5h symmetric structures due to Jahn-Teller distortion. The unpaired electron is unequally distributed on the five carbons. Herein, we report the metalla-analogs of Cp radicals from one-electron reduction of antiaromatic osmacyclopentatriene complexes. The novel osmacyclopentatrienyl radicals are nonaromatic, with the single unpaired electron delocalized over the entire five-membered osmacycle. Furthermore, these osmacyclopentatrienyl radicals can be oxidized to regenerate osmacyclopentatrienes and reduced to form osmacyclopentadienes. This discovery provides new insights into radical chemistry and organometallic chemistry.
2026, 37(10): 112282
doi: 10.1016/j.cclet.2025.112282
摘要:
(-)-Veragranines A and B are two steroidal alkaloids that exhibit potent analgesic activity. Herein, we report a 5-step biomimetic synthesis of 5α,6-dihydroveragranine A form hecogenin acetate, which incorporates two well-designed cascade processes that significantly improve the synthetic efficiency. Based on synthesis, an alternative biosynthetic proposal of veragranines was proposed. Subsequently, we developed the first divergent approach enabling the synthesis of veragranines A and B in 10~12 steps from deoxycholic acid. The synthesis features a photoredox-catalyzed decarboxylative Minisci reaction that achieved good regioselective control and C20 stereochemistry inversion via a radical process. Besides, the strategic use of an A/B cis-fused starting material enabled late-stage introduction of the Δ5(6) double bond, simplifying its installation and providing a valuable strategy for the synthesis of related natural products. Notably, we evaluated a series of synthetic intermediates and derivatives of veragranines to assess their in vitro analgesic activity. We find that compound 16, which is easily accessible and features a saturated pyridine as the F-ring, emerges as a promising lead compound.
(-)-Veragranines A and B are two steroidal alkaloids that exhibit potent analgesic activity. Herein, we report a 5-step biomimetic synthesis of 5α,6-dihydroveragranine A form hecogenin acetate, which incorporates two well-designed cascade processes that significantly improve the synthetic efficiency. Based on synthesis, an alternative biosynthetic proposal of veragranines was proposed. Subsequently, we developed the first divergent approach enabling the synthesis of veragranines A and B in 10~12 steps from deoxycholic acid. The synthesis features a photoredox-catalyzed decarboxylative Minisci reaction that achieved good regioselective control and C20 stereochemistry inversion via a radical process. Besides, the strategic use of an A/B cis-fused starting material enabled late-stage introduction of the Δ5(6) double bond, simplifying its installation and providing a valuable strategy for the synthesis of related natural products. Notably, we evaluated a series of synthetic intermediates and derivatives of veragranines to assess their in vitro analgesic activity. We find that compound 16, which is easily accessible and features a saturated pyridine as the F-ring, emerges as a promising lead compound.
2026, 37(10): 112306
doi: 10.1016/j.cclet.2025.112306
摘要:
The reactivity of metal-catalyzed nitrene transfer reaction is typically governed by (2 + 1) cycloaddition reaction chemistry to forge aziridine heterocycles. Herein, we describe a strategy to overcome this classic reactivity using mixed-valency diruthenium(Ⅱ,Ⅲ) paddlewheel complexes or silver(I) catalysts. These metal complexes allow the efficient relay of the diradical nature of triplet nitrene reagents in catalytic fashion and enable (2 + 2 + 1) cycloaddition reactions of 1,6-dienes with nitrenes as an N1 unit. We have exemplified this concept in a broad substrate scope, including the functionalization of drug molecules and describe applications of the reaction products in the synthesis of drug analogues. This catalytic (2 + 2 + 1) cycloaddition now opens up new concepts and strategies in leveraging catalytic nitrene transfer reactions beyond classic aziridination chemistry.
The reactivity of metal-catalyzed nitrene transfer reaction is typically governed by (2 + 1) cycloaddition reaction chemistry to forge aziridine heterocycles. Herein, we describe a strategy to overcome this classic reactivity using mixed-valency diruthenium(Ⅱ,Ⅲ) paddlewheel complexes or silver(I) catalysts. These metal complexes allow the efficient relay of the diradical nature of triplet nitrene reagents in catalytic fashion and enable (2 + 2 + 1) cycloaddition reactions of 1,6-dienes with nitrenes as an N1 unit. We have exemplified this concept in a broad substrate scope, including the functionalization of drug molecules and describe applications of the reaction products in the synthesis of drug analogues. This catalytic (2 + 2 + 1) cycloaddition now opens up new concepts and strategies in leveraging catalytic nitrene transfer reactions beyond classic aziridination chemistry.
2026, 37(10): 112307
doi: 10.1016/j.cclet.2025.112307
摘要:
Herein, a multiphase interfacial polymerization strategy has been developed to controllably fabricate A-to-B type Janus covalent organic framework (COF) membranes with asymmetric properties. This approach allows one-pot construction of heterostructured COF membranes with opposite wettability on the upper and lower surfaces via integrating simultaneous but independent interfacial polymerizations at two interfaces of a three-phase system. Being integrated two distinct two-dimensional COF layers with the same frame structure but differing in side chains, the Janus COF membranes exhibits hydrophilic feature on one side but displays hydrophobic characteristic on the other side. Additionally, the Janus COF membranes exhibit exceptional anti-pollution performance and exclusively permits unidirectional water transport. Notably, this unique property is non-designable in the homogeneous COF membranes fabricated from the same building blocks via the conventional two-phase interfacial polymerization method. The Janus membranes were further demonstrated to be a good candidate for membrane desalination with a high rejection for MgSO4. This novel multiphase interfacial polymerization strategy offers a general way to fabricate Janus membranes with designable, predictable, and controllable asymmetric properties from a wide range of materials, holding great potential for diverse applications.
Herein, a multiphase interfacial polymerization strategy has been developed to controllably fabricate A-to-B type Janus covalent organic framework (COF) membranes with asymmetric properties. This approach allows one-pot construction of heterostructured COF membranes with opposite wettability on the upper and lower surfaces via integrating simultaneous but independent interfacial polymerizations at two interfaces of a three-phase system. Being integrated two distinct two-dimensional COF layers with the same frame structure but differing in side chains, the Janus COF membranes exhibits hydrophilic feature on one side but displays hydrophobic characteristic on the other side. Additionally, the Janus COF membranes exhibit exceptional anti-pollution performance and exclusively permits unidirectional water transport. Notably, this unique property is non-designable in the homogeneous COF membranes fabricated from the same building blocks via the conventional two-phase interfacial polymerization method. The Janus membranes were further demonstrated to be a good candidate for membrane desalination with a high rejection for MgSO4. This novel multiphase interfacial polymerization strategy offers a general way to fabricate Janus membranes with designable, predictable, and controllable asymmetric properties from a wide range of materials, holding great potential for diverse applications.
2026, 37(10): 112403
doi: 10.1016/j.cclet.2026.112403
摘要:
Herein, we report a xanthium-like multicomponent supramolecular assembly with target and effective anticancer ability, which integrates photothermal therapy (PTT), chemodynamic therapy (CDT), and chemotherapy. The ferrocene-modified iron-based metal-organic frameworks (Fc-MIL-88B) act as the core-carrier to effectively doped photothermal reagent gold nanoparticles (Au) and encapsulate the model drug emodin, then further bind with the biotin-modified cyclodextrin (Bio-PE-CD) as the targeting "thorns" for cancer cells, ultimately forming the nanoreactor Fc-MIL-88B@Au@emodin@Bio-PE-CD. Notably, the supramolecular reactor not only exhibits tumor microenvironment-responsive disassembly performance to release anticancer drugs but also provides an abundant Fe source for intracellular Fenton reaction to produce hydroxyl radicals, then cooperating with the photothermal effect of gold nanoparticles to induce apoptosis of cancer cells. Finally, the trinity supramolecule exhibits excellent therapeutic efficacy and biosafety at the cellular and in vivo levels, providing a novel strategy for the development of synergistic antitumor nanoplatforms.
Herein, we report a xanthium-like multicomponent supramolecular assembly with target and effective anticancer ability, which integrates photothermal therapy (PTT), chemodynamic therapy (CDT), and chemotherapy. The ferrocene-modified iron-based metal-organic frameworks (Fc-MIL-88B) act as the core-carrier to effectively doped photothermal reagent gold nanoparticles (Au) and encapsulate the model drug emodin, then further bind with the biotin-modified cyclodextrin (Bio-PE-CD) as the targeting "thorns" for cancer cells, ultimately forming the nanoreactor Fc-MIL-88B@Au@emodin@Bio-PE-CD. Notably, the supramolecular reactor not only exhibits tumor microenvironment-responsive disassembly performance to release anticancer drugs but also provides an abundant Fe source for intracellular Fenton reaction to produce hydroxyl radicals, then cooperating with the photothermal effect of gold nanoparticles to induce apoptosis of cancer cells. Finally, the trinity supramolecule exhibits excellent therapeutic efficacy and biosafety at the cellular and in vivo levels, providing a novel strategy for the development of synergistic antitumor nanoplatforms.
2026, 37(10): 112433
doi: 10.1016/j.cclet.2026.112433
摘要:
We report here an aerobic oxyalkylation reaction of alkenes with cyclopropanols that enables the facile synthesis of 1,5-diketones. Key to success of this reaction is utilization of a CuCl2·Phen catalyst, with the ambient air serving as both the oxidant and oxygen source. The reaction proceeds via a domino process involving a free-radical ring-opening addition of cyclopropanols to alkenes and radical capture by O2. Both intra- and intermolecular variants are feasible, providing stream-lined access to a broad range of 1,5-diketones possessing fused, spiro, bridged, and linear frameworks. The synthetic utility of this method is showcased by late-stage functionalization of bioactive molecules and synthesis of natural products (analogues).
We report here an aerobic oxyalkylation reaction of alkenes with cyclopropanols that enables the facile synthesis of 1,5-diketones. Key to success of this reaction is utilization of a CuCl2·Phen catalyst, with the ambient air serving as both the oxidant and oxygen source. The reaction proceeds via a domino process involving a free-radical ring-opening addition of cyclopropanols to alkenes and radical capture by O2. Both intra- and intermolecular variants are feasible, providing stream-lined access to a broad range of 1,5-diketones possessing fused, spiro, bridged, and linear frameworks. The synthetic utility of this method is showcased by late-stage functionalization of bioactive molecules and synthesis of natural products (analogues).
2026, 37(10): 112435
doi: 10.1016/j.cclet.2026.112435
摘要:
Organic phosphine scale inhibitors are widely used chemical additives in industrial water treatment. Due to its high stability, high solubility and anti-biodegradability, it can persist in water bodies for a long time and is a potential long-term source of phosphorus pollution. This study developed a novel Ti/IrO2–RuO2 electrode co-modified with bismuth and ionic liquid [Emim]BF4 via thermal decomposition for electrocatalytic degradation of hydroxyethylene-1,1-diphosphate (HEDP) in reverse osmosis concentrate (ROC). Analyses with scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD) revealed that adding (Bi+[Emim]BF4) to the electrode reduced the crystal grain size by 33%, enhancing compactness while maintained the typical oxide crystals rutile crystal structure. Electrochemical tests demonstrated that the Ti/IrO2-RuO2(Bi+[Emim]BF4) electrode significantly outperformed its Ti/IrO2-RuO2 counterpart and had a lifespan 1.2 times longer. Then, at optimal conditions, current density of 30 mA/cm2, initial pH of 3, 0.25 mol/L NaCl electrolyte, and a reaction time of 120 min, the removal of HEDP reached 84.22%. Mechanistic studies indicated that indirect oxidation by active chlorine dominated. Ultimately, the Ti/IrO2-RuO2(Bi+[Emim]BF4) electrode system removed 82.77% of HEDP, 83.16% of COD, and 49.73% of UV254 from actual ROC within 60 min, albeit with a limited TOC removal rate of 30.23%. Notably, it achieved a 91.55% removal rate for fluorescent substances within 10 min. This research provides valuable insights for enhancing the performance of iridium-ruthenium electrode and designing efficient electrocatalytic oxidation systems for treating phosphorus-containing wastewater.
Organic phosphine scale inhibitors are widely used chemical additives in industrial water treatment. Due to its high stability, high solubility and anti-biodegradability, it can persist in water bodies for a long time and is a potential long-term source of phosphorus pollution. This study developed a novel Ti/IrO2–RuO2 electrode co-modified with bismuth and ionic liquid [Emim]BF4 via thermal decomposition for electrocatalytic degradation of hydroxyethylene-1,1-diphosphate (HEDP) in reverse osmosis concentrate (ROC). Analyses with scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD) revealed that adding (Bi+[Emim]BF4) to the electrode reduced the crystal grain size by 33%, enhancing compactness while maintained the typical oxide crystals rutile crystal structure. Electrochemical tests demonstrated that the Ti/IrO2-RuO2(Bi+[Emim]BF4) electrode significantly outperformed its Ti/IrO2-RuO2 counterpart and had a lifespan 1.2 times longer. Then, at optimal conditions, current density of 30 mA/cm2, initial pH of 3, 0.25 mol/L NaCl electrolyte, and a reaction time of 120 min, the removal of HEDP reached 84.22%. Mechanistic studies indicated that indirect oxidation by active chlorine dominated. Ultimately, the Ti/IrO2-RuO2(Bi+[Emim]BF4) electrode system removed 82.77% of HEDP, 83.16% of COD, and 49.73% of UV254 from actual ROC within 60 min, albeit with a limited TOC removal rate of 30.23%. Notably, it achieved a 91.55% removal rate for fluorescent substances within 10 min. This research provides valuable insights for enhancing the performance of iridium-ruthenium electrode and designing efficient electrocatalytic oxidation systems for treating phosphorus-containing wastewater.
2026, 37(10): 112462
doi: 10.1016/j.cclet.2026.112462
摘要:
This study introduces a functionalized carbon nanotube (CNT) membrane electrode integrated into an electrochemical system for the efficient activation of peracetic acid (PAA) and the enhanced degradation of aniline (AN). The system achieves a remarkable 95.5% removal of AN within 120 min, significantly outperforming individual electrochemical and catalytic processes. Kinetic analysis reveals a pseudo-first-order rate constant of 2.41 × 10−2 min−1, representing 12.7-fold and 2.3-fold enhancement compared to electrochemical and catalytic systems alone. The novel approach exploits the synergistic effects of an applied electric field and the functionalized surface of CNT, with C–OH groups identified as the primary active sites for radical generation. The degradation proceeds via dual pathways: A dominant surface-mediated route involving reactive R–O• radicals, and an electron-transfer pathway, which is more prominent in the absence of an electric field. The applied voltage (2.0 V) shifts the system to favor the radical-mediated pathway, significantly improving degradation efficiency. The system also demonstrates excellent stability, maintaining over 90% efficiency across multiple cycles and robust performance in complex water matrices. Furthermore, anti-fouling tests and XDLVO theory affirmed that the H-CNT membrane possesses exceptional stability and anti-fouling properties. Life cycle assessment further highlights the reduced environmental footprint of the proposed technology. Overall, this work provides essential insights into the carbon-catalyzed PAA activation mechanism and presents a promising strategy for sustainable wastewater treatment, effectively reducing the toxicity of degradation intermediates.
This study introduces a functionalized carbon nanotube (CNT) membrane electrode integrated into an electrochemical system for the efficient activation of peracetic acid (PAA) and the enhanced degradation of aniline (AN). The system achieves a remarkable 95.5% removal of AN within 120 min, significantly outperforming individual electrochemical and catalytic processes. Kinetic analysis reveals a pseudo-first-order rate constant of 2.41 × 10−2 min−1, representing 12.7-fold and 2.3-fold enhancement compared to electrochemical and catalytic systems alone. The novel approach exploits the synergistic effects of an applied electric field and the functionalized surface of CNT, with C–OH groups identified as the primary active sites for radical generation. The degradation proceeds via dual pathways: A dominant surface-mediated route involving reactive R–O• radicals, and an electron-transfer pathway, which is more prominent in the absence of an electric field. The applied voltage (2.0 V) shifts the system to favor the radical-mediated pathway, significantly improving degradation efficiency. The system also demonstrates excellent stability, maintaining over 90% efficiency across multiple cycles and robust performance in complex water matrices. Furthermore, anti-fouling tests and XDLVO theory affirmed that the H-CNT membrane possesses exceptional stability and anti-fouling properties. Life cycle assessment further highlights the reduced environmental footprint of the proposed technology. Overall, this work provides essential insights into the carbon-catalyzed PAA activation mechanism and presents a promising strategy for sustainable wastewater treatment, effectively reducing the toxicity of degradation intermediates.
2026, 37(10): 112470
doi: 10.1016/j.cclet.2026.112470
摘要:
Gold nanoparticles (GNPs) have garnered significant attention in the biomedical field due to their exceptional antimicrobial properties. However, the precise antimicrobial mechanism of GNPs remains unclear, which greatly hinders their extensive applications. Herein, we established a bacterial metabolomic analysis platform for in-depth exploration of GNP-bacteria interactions using nano-electrospray ionization mass spectrometry (nESI-MS), which enables a direct and precise analysis of bacterial metabolites without the use of extractant. Employing nESI-MS, we analyzed the metabolites of Klebsiella pneumonia (K. p) treated by GNPs. More than 60 metabolites involving 6 major metabolic pathways, including energy metabolism, redox homeostasis, oxidative defense, membrane integrity, osmoregulation, and quorum sensing were identified. Moreover, apart from primary metabolites, we found a critical role of secondary metabolites in GNPs-bacteria interactions. Our approach provides a foundation for exploring nanomaterial-bacteria interactions and advancing knowledge of antibacterial mechanism, guiding the development of next-generation antibacterial agents.
Gold nanoparticles (GNPs) have garnered significant attention in the biomedical field due to their exceptional antimicrobial properties. However, the precise antimicrobial mechanism of GNPs remains unclear, which greatly hinders their extensive applications. Herein, we established a bacterial metabolomic analysis platform for in-depth exploration of GNP-bacteria interactions using nano-electrospray ionization mass spectrometry (nESI-MS), which enables a direct and precise analysis of bacterial metabolites without the use of extractant. Employing nESI-MS, we analyzed the metabolites of Klebsiella pneumonia (K. p) treated by GNPs. More than 60 metabolites involving 6 major metabolic pathways, including energy metabolism, redox homeostasis, oxidative defense, membrane integrity, osmoregulation, and quorum sensing were identified. Moreover, apart from primary metabolites, we found a critical role of secondary metabolites in GNPs-bacteria interactions. Our approach provides a foundation for exploring nanomaterial-bacteria interactions and advancing knowledge of antibacterial mechanism, guiding the development of next-generation antibacterial agents.
2026, 37(10): 112476
doi: 10.1016/j.cclet.2026.112476
摘要:
Membrane distillation (MD) suffers from severe fouling when treating high-salinity and high-organic shale gas produced water (SGPW). This study introduces a Fe(Ⅱ)/Fe(Ⅵ)-activated sodium sulfite (Na2SO3) pretreatment that generates sulfate radicals with high pH tolerance and strong organic degradation capacity. The process achieved total organic carbon (TOC) removals of 17.82% (Fe(Ⅱ)) and 13.83% (Fe(Ⅵ)) and maintained MD flux at 80.95%-85.70% of the initial value, while permeate conductivity decreased by 23.46% and 28.74%. Pollutant deposition decreased by 44.32% and 61.79%, with liquid entry pressure recovering to 89.20% and 90.86% of original value. Scanning electron microscope and Fourier transform infrared spectroscopy confirmed significant fouling layer reduction and maintained membrane hydrophobicity. Mechanistic studies indicate pretreatment optimizes fouling behavior by regulating organic concentration, hydrophilic/hydrophobic distribution, and coagulation efficiency. This work provides an efficient, low-cost green pretreatment for SGPW and deepens understanding of multi-mechanism fouling control by Na2SO3 oxidation.
Membrane distillation (MD) suffers from severe fouling when treating high-salinity and high-organic shale gas produced water (SGPW). This study introduces a Fe(Ⅱ)/Fe(Ⅵ)-activated sodium sulfite (Na2SO3) pretreatment that generates sulfate radicals with high pH tolerance and strong organic degradation capacity. The process achieved total organic carbon (TOC) removals of 17.82% (Fe(Ⅱ)) and 13.83% (Fe(Ⅵ)) and maintained MD flux at 80.95%-85.70% of the initial value, while permeate conductivity decreased by 23.46% and 28.74%. Pollutant deposition decreased by 44.32% and 61.79%, with liquid entry pressure recovering to 89.20% and 90.86% of original value. Scanning electron microscope and Fourier transform infrared spectroscopy confirmed significant fouling layer reduction and maintained membrane hydrophobicity. Mechanistic studies indicate pretreatment optimizes fouling behavior by regulating organic concentration, hydrophilic/hydrophobic distribution, and coagulation efficiency. This work provides an efficient, low-cost green pretreatment for SGPW and deepens understanding of multi-mechanism fouling control by Na2SO3 oxidation.
2026, 37(10): 112479
doi: 10.1016/j.cclet.2026.112479
摘要:
Photocatalytic CO2 reduction is a cutting-edge technology with significant strategic importance for mitigating climate change and advancing energy transitions. In this study, we developed a high-performance photocatalyst by constructing a tightly interfaced S-scheme heterojunction from Prussian blue analogs (PBAs). Using [Co2+(CN)6]4− as the base, we selected two PBAs with high energy-level matching and connected them via M-NC-Co-CN-M bonds. Experimental results showed that the optimized Ni/Zn-Co PBAs S-scheme photocatalyst achieved a CO2 conversion rate of ~38 µmol g-1 h-1 (94.13% CO and 5.87% CH4). This design effectively improved the utilization efficiency of photogenerated charges and enhanced redox capabilities, while the Ni site further boosted CO2 activation. This study not only offers new insights into designing efficient PBA-based photocatalysts but also demonstrates the promise of S-scheme mechanism in improving photocatalytic CO2 reduction activity.
Photocatalytic CO2 reduction is a cutting-edge technology with significant strategic importance for mitigating climate change and advancing energy transitions. In this study, we developed a high-performance photocatalyst by constructing a tightly interfaced S-scheme heterojunction from Prussian blue analogs (PBAs). Using [Co2+(CN)6]4− as the base, we selected two PBAs with high energy-level matching and connected them via M-NC-Co-CN-M bonds. Experimental results showed that the optimized Ni/Zn-Co PBAs S-scheme photocatalyst achieved a CO2 conversion rate of ~38 µmol g-1 h-1 (94.13% CO and 5.87% CH4). This design effectively improved the utilization efficiency of photogenerated charges and enhanced redox capabilities, while the Ni site further boosted CO2 activation. This study not only offers new insights into designing efficient PBA-based photocatalysts but also demonstrates the promise of S-scheme mechanism in improving photocatalytic CO2 reduction activity.
2026, 37(10): 112482
doi: 10.1016/j.cclet.2026.112482
摘要:
A highly efficient and energy-saving photothermal synergistic catalytic oxidation technology was developed to eliminate ethyl acetate (EA) and 1,2-dichloroethane (1,2-DCE) over MoOx–TiO2, derived by MIL-125(Ti), supported Ru catalysts (Ru/MoOx–TiO2). The introduction of MoOx enhanced the light absorption capacity, carrier separation capacity and redox capacity of the catalyst, thus significantly improving the photothermal synergistic catalytic performance, with Ru/MoOx–TiO2 exhibiting outstanding activity for EA and 1,2-DCE oxidation (T90% = 212 and 319 ℃, respectively). Meanwhile, the abundant Brønsted acidic sites on Ru/MoOx–TiO2 were inclined to generate more HCl and CO2, and reduce the release of chlorine-containing byproducts than that over Ru/TiO2. The characterization results by the in situ XPS, in situ PL and in situ EPR exhibited that the improvement of the photothermal synergistic catalytic oxidation performance was attributed to the coupling effect between electron migration on the catalyst surface and active oxygen species during the photothermal synergistic catalytic reaction process. This work has provided a promising path for simultaneously enhancing the removal efficiency of multi-component VOCs and the selectivity of target products.
A highly efficient and energy-saving photothermal synergistic catalytic oxidation technology was developed to eliminate ethyl acetate (EA) and 1,2-dichloroethane (1,2-DCE) over MoOx–TiO2, derived by MIL-125(Ti), supported Ru catalysts (Ru/MoOx–TiO2). The introduction of MoOx enhanced the light absorption capacity, carrier separation capacity and redox capacity of the catalyst, thus significantly improving the photothermal synergistic catalytic performance, with Ru/MoOx–TiO2 exhibiting outstanding activity for EA and 1,2-DCE oxidation (T90% = 212 and 319 ℃, respectively). Meanwhile, the abundant Brønsted acidic sites on Ru/MoOx–TiO2 were inclined to generate more HCl and CO2, and reduce the release of chlorine-containing byproducts than that over Ru/TiO2. The characterization results by the in situ XPS, in situ PL and in situ EPR exhibited that the improvement of the photothermal synergistic catalytic oxidation performance was attributed to the coupling effect between electron migration on the catalyst surface and active oxygen species during the photothermal synergistic catalytic reaction process. This work has provided a promising path for simultaneously enhancing the removal efficiency of multi-component VOCs and the selectivity of target products.
2026, 37(10): 112508
doi: 10.1016/j.cclet.2026.112508
摘要:
The worldwide utilization of antibiotics and the generation of antibiotic-resistant bacteria necessitate the development of alternative wastewater treatment strategies, in which the cycling of metallic ions and the precise modulation of Fe active sites remain critically important factors to be concerned. In this work, Mo incorporation is strategically employed to modulate Fe-O covalency through charge redistribution driven by strong Fe-Mo interactions over graphite carbon ring/CN (CCN). This design achieves an exceptional degradation rate constant, which arises from synergistic Fe/Mo catalytic-co-catalytic interactions that facilitate sustainable metal redox cycling, enhance bonding orbital overlap, and optimize surface adsorption characteristics. The Mo-modified catalyst (FeMoCCN) exhibits a greater contribution to bonding orbitals compared to the singly Fe-doped counterpart (FeCCN). The introduction of Mo enhances Fe-O covalency, thereby facilitating electron transfer for peroxymonosulfate (PMS) activation and subsequent degradation processes. Remarkably, complete electron transfer is achieved through the Fe2+/Fe3+, Mo6+/Mo4+, Fe3+/Mo4+ redox couples, further implying the robust adaptability of this Fenton-like system for antibiotic degradation while providing mechanistic insights into the synergistic effects between light irradiation, oxidant activation, and bimetallic doping modulation in advanced wastewater treatment.
The worldwide utilization of antibiotics and the generation of antibiotic-resistant bacteria necessitate the development of alternative wastewater treatment strategies, in which the cycling of metallic ions and the precise modulation of Fe active sites remain critically important factors to be concerned. In this work, Mo incorporation is strategically employed to modulate Fe-O covalency through charge redistribution driven by strong Fe-Mo interactions over graphite carbon ring/CN (CCN). This design achieves an exceptional degradation rate constant, which arises from synergistic Fe/Mo catalytic-co-catalytic interactions that facilitate sustainable metal redox cycling, enhance bonding orbital overlap, and optimize surface adsorption characteristics. The Mo-modified catalyst (FeMoCCN) exhibits a greater contribution to bonding orbitals compared to the singly Fe-doped counterpart (FeCCN). The introduction of Mo enhances Fe-O covalency, thereby facilitating electron transfer for peroxymonosulfate (PMS) activation and subsequent degradation processes. Remarkably, complete electron transfer is achieved through the Fe2+/Fe3+, Mo6+/Mo4+, Fe3+/Mo4+ redox couples, further implying the robust adaptability of this Fenton-like system for antibiotic degradation while providing mechanistic insights into the synergistic effects between light irradiation, oxidant activation, and bimetallic doping modulation in advanced wastewater treatment.
2026, 37(10): 112509
doi: 10.1016/j.cclet.2026.112509
摘要:
Triclosan (TCS) is an emerging environmental pollutant that has been widely used in personal care products and is frequently detected in the human body. As a marker on DNA and RNA, nucleic acid modifications are crucial for the versatile regulation of gene expression. However, the epigenetic mechanisms underlying TCS-induced adverse effects remain largely unclear. In this study, we systematically investigate the impact of TCS on DNA and small RNA modifications from C57BL/6 N mice at doses of 0, 50, and 200 mg kg−1 d−1, using liquid chromatography-tandem mass spectrometry (LC-MS/MS). We quantitatively quantified 23 nucleic acid modifications in seven tissues, including heart, liver, kidneys, lungs, brain, intestine, and testis. The results indicated that TCS exposure significantly suppressed body weight gain and altered organ coefficients in a dose-dependent manner. Multiple DNA and RNA modifications exhibit significant changes by TCS exposure across different tissues and display tissue-specific patterns. Notably, TCS exposure led to liver inflammation and lipid accumulation, accompanied by decreased levels of RNA N6-methyladenine (m6A) and elevated expression of fat mass and obesity-associated gene (FTO) in both mouse liver and HepG2 cells, suggesting its involvement in TCS-mediated epigenetic imbalance and hepatotoxicity. Our study provides the first comprehensive epigenetic evaluation of TCS-induced nucleic acid modification alterations across multiple organs in mammals, providing a new perspective for understanding the toxicological mechanisms of TCS from an epigenetic perspective.
Triclosan (TCS) is an emerging environmental pollutant that has been widely used in personal care products and is frequently detected in the human body. As a marker on DNA and RNA, nucleic acid modifications are crucial for the versatile regulation of gene expression. However, the epigenetic mechanisms underlying TCS-induced adverse effects remain largely unclear. In this study, we systematically investigate the impact of TCS on DNA and small RNA modifications from C57BL/6 N mice at doses of 0, 50, and 200 mg kg−1 d−1, using liquid chromatography-tandem mass spectrometry (LC-MS/MS). We quantitatively quantified 23 nucleic acid modifications in seven tissues, including heart, liver, kidneys, lungs, brain, intestine, and testis. The results indicated that TCS exposure significantly suppressed body weight gain and altered organ coefficients in a dose-dependent manner. Multiple DNA and RNA modifications exhibit significant changes by TCS exposure across different tissues and display tissue-specific patterns. Notably, TCS exposure led to liver inflammation and lipid accumulation, accompanied by decreased levels of RNA N6-methyladenine (m6A) and elevated expression of fat mass and obesity-associated gene (FTO) in both mouse liver and HepG2 cells, suggesting its involvement in TCS-mediated epigenetic imbalance and hepatotoxicity. Our study provides the first comprehensive epigenetic evaluation of TCS-induced nucleic acid modification alterations across multiple organs in mammals, providing a new perspective for understanding the toxicological mechanisms of TCS from an epigenetic perspective.
2026, 37(10): 112528
doi: 10.1016/j.cclet.2026.112528
摘要:
The determination and quantification of sugars are important for quality control and assurance of food. Here we present a gas-free electrodialytic eluent generation (EG) platform for sugar analysis by anion exchange chromatography equipped with pulsed amperometric detector. It consists of a gas-free EG for automatic production of highly pure KOH eluent with wide concentration range up to at least 210 mmol/L required for ionization and elution of sugars. The only routine reagent needed is deionized water, driven by a simple isocratic pump to realize isocratic or gradient elution. This platform overcomes many drawbacks associated with common manner of manually prepared KOH eluent driven by gradient pump, and offers an easy way for sugar profiling with improved precision and accuracy. The method was successfully applied to quantification of sugars in biscuits.
The determination and quantification of sugars are important for quality control and assurance of food. Here we present a gas-free electrodialytic eluent generation (EG) platform for sugar analysis by anion exchange chromatography equipped with pulsed amperometric detector. It consists of a gas-free EG for automatic production of highly pure KOH eluent with wide concentration range up to at least 210 mmol/L required for ionization and elution of sugars. The only routine reagent needed is deionized water, driven by a simple isocratic pump to realize isocratic or gradient elution. This platform overcomes many drawbacks associated with common manner of manually prepared KOH eluent driven by gradient pump, and offers an easy way for sugar profiling with improved precision and accuracy. The method was successfully applied to quantification of sugars in biscuits.
2026, 37(10): 112529
doi: 10.1016/j.cclet.2026.112529
摘要:
Metal-support active interfaces provide unique sites that enhance catalytic oxidation reactions. However, designing a catalyst that simultaneously promote both benzene ring cleavage and C−H bond scission remains a challenge. Herein, porous SiO2 derived from waste rice husk was used to disperse CeO2 nanoparticles, onto which Pt nanoparticles were deposited via ethylene glycol reflux reduction combined with steam redispersion to prepare a Pt/CeO2/SiO2 catalyst with abundant Pt−O−Ce active interfaces. Characterization and experimental results show that well-dispersed CeO2 and Pt nanoparticles increase oxygen vacancy concentration and Pt–O–Ce interfaces, thereby enhancing oxygen spillover from CeO2 to Pt and promoting styrene oxidation. The Pt–O–Ce interface accelerates the rate-determining C−H bond cleavage in benzaldehyde during styrene oxidation. Pt/CeO2/SiO2-H2O catalyst with abundant oxygen vacancies and Pt–O–Ce interfaces achieves excellent catalytic performance (T90 = 222 ℃, WHSV = 120,000 mL h−1 g−1). Moreover, it demonstrates superior thermal stability over 40 h and water-resistance against 10 vol% H2O, highlighting its industrial potential. This study offers a strategy for constructing supported catalysts with tailored active interfaces and high stability.
Metal-support active interfaces provide unique sites that enhance catalytic oxidation reactions. However, designing a catalyst that simultaneously promote both benzene ring cleavage and C−H bond scission remains a challenge. Herein, porous SiO2 derived from waste rice husk was used to disperse CeO2 nanoparticles, onto which Pt nanoparticles were deposited via ethylene glycol reflux reduction combined with steam redispersion to prepare a Pt/CeO2/SiO2 catalyst with abundant Pt−O−Ce active interfaces. Characterization and experimental results show that well-dispersed CeO2 and Pt nanoparticles increase oxygen vacancy concentration and Pt–O–Ce interfaces, thereby enhancing oxygen spillover from CeO2 to Pt and promoting styrene oxidation. The Pt–O–Ce interface accelerates the rate-determining C−H bond cleavage in benzaldehyde during styrene oxidation. Pt/CeO2/SiO2-H2O catalyst with abundant oxygen vacancies and Pt–O–Ce interfaces achieves excellent catalytic performance (T90 = 222 ℃, WHSV = 120,000 mL h−1 g−1). Moreover, it demonstrates superior thermal stability over 40 h and water-resistance against 10 vol% H2O, highlighting its industrial potential. This study offers a strategy for constructing supported catalysts with tailored active interfaces and high stability.
2026, 37(10): 112530
doi: 10.1016/j.cclet.2026.112530
摘要:
Protein fatty acylation encompasses S/N/O-acylation modifications that regulate diverse cellular functions, yet current methods cannot simultaneously capture all three types. Here, we present a dual-identification strategy that integrates metabolic labeling with click chemistry, hydroxylamine mediated selective hydrolysis, and cleavable bioorthogonal probes for comprehensive fatty acylation site detection. Using Alk-C16:0 and Alk-C18:0 probes in HepG2 cells, we identified 1310 and 1131 total fatty acylation sites respectively, including 588 and 674 S-acylation sites substantially exceeding single method coverage. Integration of open and closed searches revealed probe intracellular conversion induced acyl chain heterogeneity, improving identification accuracy. We discovered diagnostic ions revealing acyl chain structure and N-acylation specific cyclic immonium ions that discriminate between modification subtypes. This strategy enables unprecedented comprehensive protein fatty acylation characterization, providing a robust platform for investigating molecular mechanisms of these essential modifications.
Protein fatty acylation encompasses S/N/O-acylation modifications that regulate diverse cellular functions, yet current methods cannot simultaneously capture all three types. Here, we present a dual-identification strategy that integrates metabolic labeling with click chemistry, hydroxylamine mediated selective hydrolysis, and cleavable bioorthogonal probes for comprehensive fatty acylation site detection. Using Alk-C16:0 and Alk-C18:0 probes in HepG2 cells, we identified 1310 and 1131 total fatty acylation sites respectively, including 588 and 674 S-acylation sites substantially exceeding single method coverage. Integration of open and closed searches revealed probe intracellular conversion induced acyl chain heterogeneity, improving identification accuracy. We discovered diagnostic ions revealing acyl chain structure and N-acylation specific cyclic immonium ions that discriminate between modification subtypes. This strategy enables unprecedented comprehensive protein fatty acylation characterization, providing a robust platform for investigating molecular mechanisms of these essential modifications.
2026, 37(10): 112531
doi: 10.1016/j.cclet.2026.112531
摘要:
Pyranocoumarins are a characteristic class of pyranophenolic compounds predominantly found in plants of the Moraceae, Umbelliferae, and Rutaceae families. These pyranophenolics not only exhibit diverse physiological activities, but also have a wide range of pharmacological activities such as anti-cancer, anti-spasmatic, and anticoagulant. However, the biosynthetic mechanism of pyranocoumarins, especially the formation mechanism of the pyran core in the final step, remains unclear. It was hypothesized the pyran core is formed by dehydration of decursinol after oxidation and cyclization of demethylsuberosin. Here we characterized a berberine bridge enzyme (BBE)-like enzyme namely FcBBElike4 from Ficus carica. FcBBElike4 could catalyze direct cyclization of 6- and 8-isoprenyl coumarins into corresponding pyranocoumarins, which functionally characterized as an oxidocyclase (OC). This finding elucidated the final step in the biosynthetic pathway for pyranocoumarins. The catalytic mechanism of FcBBElike4 was investigated and a general key active site of aspartic acid residue determining the cyclization activity of BBE-like enzymes was identified. Diverse BBE-like enzymes with diene synthesis activities were mined and further engineered into rare OCs with high catalytic activity and broad substrate spectra. What is more, an enzymatic approach to synthesize pyranophenolics was constructed based on engineered OCs and applied in the synthesis of drug molecules. This study not only elucidates the key biosynthetic steps of pyranocoumarins but also offers insights into engineering common BBE-like enzymes into rare and useful OCs.
Pyranocoumarins are a characteristic class of pyranophenolic compounds predominantly found in plants of the Moraceae, Umbelliferae, and Rutaceae families. These pyranophenolics not only exhibit diverse physiological activities, but also have a wide range of pharmacological activities such as anti-cancer, anti-spasmatic, and anticoagulant. However, the biosynthetic mechanism of pyranocoumarins, especially the formation mechanism of the pyran core in the final step, remains unclear. It was hypothesized the pyran core is formed by dehydration of decursinol after oxidation and cyclization of demethylsuberosin. Here we characterized a berberine bridge enzyme (BBE)-like enzyme namely FcBBElike4 from Ficus carica. FcBBElike4 could catalyze direct cyclization of 6- and 8-isoprenyl coumarins into corresponding pyranocoumarins, which functionally characterized as an oxidocyclase (OC). This finding elucidated the final step in the biosynthetic pathway for pyranocoumarins. The catalytic mechanism of FcBBElike4 was investigated and a general key active site of aspartic acid residue determining the cyclization activity of BBE-like enzymes was identified. Diverse BBE-like enzymes with diene synthesis activities were mined and further engineered into rare OCs with high catalytic activity and broad substrate spectra. What is more, an enzymatic approach to synthesize pyranophenolics was constructed based on engineered OCs and applied in the synthesis of drug molecules. This study not only elucidates the key biosynthetic steps of pyranocoumarins but also offers insights into engineering common BBE-like enzymes into rare and useful OCs.
2026, 37(10): 112557
doi: 10.1016/j.cclet.2026.112557
摘要:
Developing S-scheme heterojunctions with a strong internal electric field (IEF) is crucial to facilitating charge separation and thereby enhancing catalytic activity. Herein, a 3D nanoflower-like oxygen vacancy (OV)-modified carbon quantum dot (CQD)/Bi2WO6 heterojunction was synthesized through a hydrothermal process followed by alkaline etching. The experimental and theoretical results demonstrate that the introduction of OVs optimizes the band structure of Bi2WO6 and increases the Fermi level difference between Bi2WO6 and the CQDs, thereby generating an enhanced interfacial IEF to boost the separation/migration of photoproduced charges. Quantitative analysis reveals that the IEF intensity of CQD/Bi2WO6-OV is 1.84 times greater than that of CQD/Bi2WO6. The S-scheme charge migration pathway between the CQDs and Bi2WO6-OV was elucidated via in situ X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR), which facilitates efficient charge separation and enhances the photocatalytic redox capability. As a result, the optimized CQD/Bi2WO6-OV S-scheme heterojunction exhibits a degradation efficiency of 95.2% for ciprofloxacin (CIP) within 40 min under visible light, and its kinetic rate constant is 3.4 and 30.8 times greater than that of Bi2WO6 and the CQDs, respectively. Furthermore, liquid chromatography-mass spectrometry (LC-MS) and Fukui function analyses elucidate the degradation mechanisms of CIP, and toxicity assessment confirms the low environmental risk of its intermediates. This work provides insights into the design of OV-engineered S-scheme heterojunctions for efficient charge separation and antibiotic photodegradation.
Developing S-scheme heterojunctions with a strong internal electric field (IEF) is crucial to facilitating charge separation and thereby enhancing catalytic activity. Herein, a 3D nanoflower-like oxygen vacancy (OV)-modified carbon quantum dot (CQD)/Bi2WO6 heterojunction was synthesized through a hydrothermal process followed by alkaline etching. The experimental and theoretical results demonstrate that the introduction of OVs optimizes the band structure of Bi2WO6 and increases the Fermi level difference between Bi2WO6 and the CQDs, thereby generating an enhanced interfacial IEF to boost the separation/migration of photoproduced charges. Quantitative analysis reveals that the IEF intensity of CQD/Bi2WO6-OV is 1.84 times greater than that of CQD/Bi2WO6. The S-scheme charge migration pathway between the CQDs and Bi2WO6-OV was elucidated via in situ X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR), which facilitates efficient charge separation and enhances the photocatalytic redox capability. As a result, the optimized CQD/Bi2WO6-OV S-scheme heterojunction exhibits a degradation efficiency of 95.2% for ciprofloxacin (CIP) within 40 min under visible light, and its kinetic rate constant is 3.4 and 30.8 times greater than that of Bi2WO6 and the CQDs, respectively. Furthermore, liquid chromatography-mass spectrometry (LC-MS) and Fukui function analyses elucidate the degradation mechanisms of CIP, and toxicity assessment confirms the low environmental risk of its intermediates. This work provides insights into the design of OV-engineered S-scheme heterojunctions for efficient charge separation and antibiotic photodegradation.
2026, 37(10): 112607
doi: 10.1016/j.cclet.2026.112607
摘要:
Electronic metal-support interaction (EMSI) offers a revolutionary strategy for designing high-performance electrocatalysts by precisely modulating interfacial electron transfer dynamics. Herein, we construct a Ru-loaded tungsten-molybdenum bimetallic phosphide heterostructure (Ru/WP-MoP) through EMSI engineering, which demonstrates exceptional hydrogen evolution reaction (HER) performance across pH-universal electrolytes. The optimized catalyst presents a remarkably low overpotential of 40 mV at 10 mA/cm2 in alkaline media, outperforming Ru/C (η10 = 52 mV). Remarkably, it retains significant activity even under acidic conditions (η10 = 55 mV) and alkaline seawater (η10 = 42 mV). In alkaline media, it operates continuously at 200 mA/cm2 for 55 h with current density decay of less than 2%. Combined X-ray photoelectron spectroscopy analysis reveals that the strong EMSI effect induces electron transfer from WP-MoP to Ru, optimizing the d-band center position and reducing the water dissociation energy barrier compared with monometallic counterparts. This work establishes a general paradigm for developing robust transition metal phosphide catalysts via interfacial electronic structure manipulation, particularly for industrial-scale seawater electrolysis applications.
Electronic metal-support interaction (EMSI) offers a revolutionary strategy for designing high-performance electrocatalysts by precisely modulating interfacial electron transfer dynamics. Herein, we construct a Ru-loaded tungsten-molybdenum bimetallic phosphide heterostructure (Ru/WP-MoP) through EMSI engineering, which demonstrates exceptional hydrogen evolution reaction (HER) performance across pH-universal electrolytes. The optimized catalyst presents a remarkably low overpotential of 40 mV at 10 mA/cm2 in alkaline media, outperforming Ru/C (η10 = 52 mV). Remarkably, it retains significant activity even under acidic conditions (η10 = 55 mV) and alkaline seawater (η10 = 42 mV). In alkaline media, it operates continuously at 200 mA/cm2 for 55 h with current density decay of less than 2%. Combined X-ray photoelectron spectroscopy analysis reveals that the strong EMSI effect induces electron transfer from WP-MoP to Ru, optimizing the d-band center position and reducing the water dissociation energy barrier compared with monometallic counterparts. This work establishes a general paradigm for developing robust transition metal phosphide catalysts via interfacial electronic structure manipulation, particularly for industrial-scale seawater electrolysis applications.
Dual-guest co–intercalation engineering enables high-energy and long-life aqueous zinc-ion batteries
2026, 37(10): 112787
doi: 10.1016/j.cclet.2026.112787
摘要:
Ammonium vanadate (NVO) is an attractive cathode material for aqueous zinc-ion batteries (AZIBs) owing to its tunable layered structure. However, its practical use is limited by structural instability and irreversible NH4+ extraction during cycling. To overcome these challenges, we employed a dual-guest pillar strategy for NVO, utilising a one-pot hydrothermal co-intercalation technique to insert Al3+ and benzyltrimethylammonium ions (BTMA+) into its interlayer spacing. The synergistic intercalation of Al3+ and BTMA+ not only expanded the interlayer spacing to 10.9 Å but also further modulated the electronic structure. Simulations reveal a narrowed band gap and enhanced Zn2+ adsorption capability, which synergistically boost rapid Zn2+ migration and enhance structural stability. Consequently, the resultant cathode delivers a high specific capacity of 432.8 mAh/g at 1.0 A/g, alongside excellent rate capability and cycling stability (92.07% capacity retention after 2000 cycles at 6.0 A/g). This work demonstrates that dual-guest co-intercalation-enabled molecular pillaring and electronic modulation is an effective strategy for fabricating high-performance vanadium-based cathodes for advanced AZIBs.
Ammonium vanadate (NVO) is an attractive cathode material for aqueous zinc-ion batteries (AZIBs) owing to its tunable layered structure. However, its practical use is limited by structural instability and irreversible NH4+ extraction during cycling. To overcome these challenges, we employed a dual-guest pillar strategy for NVO, utilising a one-pot hydrothermal co-intercalation technique to insert Al3+ and benzyltrimethylammonium ions (BTMA+) into its interlayer spacing. The synergistic intercalation of Al3+ and BTMA+ not only expanded the interlayer spacing to 10.9 Å but also further modulated the electronic structure. Simulations reveal a narrowed band gap and enhanced Zn2+ adsorption capability, which synergistically boost rapid Zn2+ migration and enhance structural stability. Consequently, the resultant cathode delivers a high specific capacity of 432.8 mAh/g at 1.0 A/g, alongside excellent rate capability and cycling stability (92.07% capacity retention after 2000 cycles at 6.0 A/g). This work demonstrates that dual-guest co-intercalation-enabled molecular pillaring and electronic modulation is an effective strategy for fabricating high-performance vanadium-based cathodes for advanced AZIBs.
2026, 37(10): 112794
doi: 10.1016/j.cclet.2026.112794
摘要:
Niobium pentoxide (Nb2O5) is a promising yet inefficient photocatalyst due to its wide bandgap, rapid charge recombination, and limited active sites. Herein, we propose a predictive doping paradigm guided by multi-dimensional atomic mismatch (in ionic radius, valence state, and element nature) to direct boron into interstitial sites within a three-dimensional (3D) cross-linked ultrathin Nb2O5 architecture. This atomic-mismatch-guided interstitial doping effectively engineers the electronic structure, substantially reducing the exciton binding energy and creating long-lived shallow traps for charge carriers. The deliberately constructed 3D porous network provides abundant exposed active sites, high adsorption capacity, and enhanced mass transport. Synergistically, the tailored electronic structure enables highly efficient visible-light photocatalysis. In the optimized catalyst (BNO-2), this synergistic mechanism leads to exceptional doxorubicin (DOX) degradation (96.9% within 30 min) under visible light, along with effective detoxification and progressive mineralization. Mechanistic studies identify the superoxide radical as the predominant reactive species. This work not only establishes a novel predictive doping paradigm based on atomic mismatch but also demonstrates the capability of concurrently engineering nanoarchitecture and electronic structure to design high-performance environmental remediation materials.
Niobium pentoxide (Nb2O5) is a promising yet inefficient photocatalyst due to its wide bandgap, rapid charge recombination, and limited active sites. Herein, we propose a predictive doping paradigm guided by multi-dimensional atomic mismatch (in ionic radius, valence state, and element nature) to direct boron into interstitial sites within a three-dimensional (3D) cross-linked ultrathin Nb2O5 architecture. This atomic-mismatch-guided interstitial doping effectively engineers the electronic structure, substantially reducing the exciton binding energy and creating long-lived shallow traps for charge carriers. The deliberately constructed 3D porous network provides abundant exposed active sites, high adsorption capacity, and enhanced mass transport. Synergistically, the tailored electronic structure enables highly efficient visible-light photocatalysis. In the optimized catalyst (BNO-2), this synergistic mechanism leads to exceptional doxorubicin (DOX) degradation (96.9% within 30 min) under visible light, along with effective detoxification and progressive mineralization. Mechanistic studies identify the superoxide radical as the predominant reactive species. This work not only establishes a novel predictive doping paradigm based on atomic mismatch but also demonstrates the capability of concurrently engineering nanoarchitecture and electronic structure to design high-performance environmental remediation materials.
2026, 37(10): 112843
doi: 10.1016/j.cclet.2026.112843
摘要:
Achieving precise control over product selectivity in electrochemical alkene oxidation requires catalysts that can be programmed to favor specific bond-forming pathways. Here, we demonstrate that carbon dots (CDs) serve as programmable interfacial mediators to direct propylene electro oxidation exclusively toward the epoxy bond formation on Ag-graphene hybrids. The engineered Ag-6CDs/G catalyst exhibits a remarkable propylene oxide (PO) Faradaic efficiency of 39.71% and a production rate of 218.85 mmol g‒1 h‒1. We deconvolute the triple role of CDs in programming this selectivity: (1) As a structural mediator that dictates Ag nanoparticle size and spatial distribution, maximizing active site density; (2) as an electronic mediator that fine tunes the Ag d band center, thereby optimizing the adsorption strength ratio between propylene (C=C) and the crucial *OH intermediate to a value ideal for C–O coupling; and (3) as a local microenvironment mediator whose oxygenated surface facilitates water activation, ensuring an efficient supply of oxygen species. This multifunctional mediation is rigorously verified through in situ spectroscopy, electrochemical diagnostics, and density functional theory (DFT) calculations, which collectively map the reaction coordinate and identify the CD induced shifts in adsorption energetics as the origin of the selective pathway. Our work provides a generalizable blueprint for programming bond forming selectivity in electrocatalysis through rational interfacial design.
Achieving precise control over product selectivity in electrochemical alkene oxidation requires catalysts that can be programmed to favor specific bond-forming pathways. Here, we demonstrate that carbon dots (CDs) serve as programmable interfacial mediators to direct propylene electro oxidation exclusively toward the epoxy bond formation on Ag-graphene hybrids. The engineered Ag-6CDs/G catalyst exhibits a remarkable propylene oxide (PO) Faradaic efficiency of 39.71% and a production rate of 218.85 mmol g‒1 h‒1. We deconvolute the triple role of CDs in programming this selectivity: (1) As a structural mediator that dictates Ag nanoparticle size and spatial distribution, maximizing active site density; (2) as an electronic mediator that fine tunes the Ag d band center, thereby optimizing the adsorption strength ratio between propylene (C=C) and the crucial *OH intermediate to a value ideal for C–O coupling; and (3) as a local microenvironment mediator whose oxygenated surface facilitates water activation, ensuring an efficient supply of oxygen species. This multifunctional mediation is rigorously verified through in situ spectroscopy, electrochemical diagnostics, and density functional theory (DFT) calculations, which collectively map the reaction coordinate and identify the CD induced shifts in adsorption energetics as the origin of the selective pathway. Our work provides a generalizable blueprint for programming bond forming selectivity in electrocatalysis through rational interfacial design.
2026, 37(10): 112870
doi: 10.1016/j.cclet.2026.112870
摘要:
The copper-catalyzed enantioselective [4 + 1] annulation of yne-thienyl esters with 1,3-dicarbonyl compounds was realized through an elegant remote stereocontrol strategy. Greatly diverse spirocycles were obtained in moderate to good yields with excellent stereochemical control. Moreover, preliminary mechanistic studies suggest an remote substitution and Conia-ene cascade pathway on the remote stereochemical induction progress.
The copper-catalyzed enantioselective [4 + 1] annulation of yne-thienyl esters with 1,3-dicarbonyl compounds was realized through an elegant remote stereocontrol strategy. Greatly diverse spirocycles were obtained in moderate to good yields with excellent stereochemical control. Moreover, preliminary mechanistic studies suggest an remote substitution and Conia-ene cascade pathway on the remote stereochemical induction progress.
2026, 37(10): 112890
doi: 10.1016/j.cclet.2026.112890
摘要:
Bilayer nanographenes represent an emerging class of molecular carbon architectures that provide unique opportunities to explore interlayer electronic communication and chiroptical phenomena in confined π-systems. However, the development of well-defined chiral bilayer nanographenes capable of transferring chirality across extended π-surfaces and supramolecular assemblies remains challenging. Herein, we report the synthesis and structural characterization of a chiral bilayer spironanographene (spiro-NG) composed of two nanographene subunits connected through a rigid spirobifluorene core. Single-crystal X-ray diffraction reveals a folded bilayer geometry that enforces significant interlayer π-overlap while simultaneously generating intrinsic molecular chirality. Enantiomeric resolution affords configurationally stable P- and M-spiro-NG, which display pronounced circular dichroism (CD) and circularly polarized luminescence (CPL). Furthermore, the exposed π-surfaces of the bilayer scaffold enable π-surface recognition with coronene, leading to hetero-π stacked co-crystals that highlight the supramolecular adaptability of the nanographene framework. Notably, supramolecular co-assembly of spiro-NG with achiral fluorophores enables chirality transfer through Förster resonance energy transfer, resulting in induced CPL emission with tunable wavelengths. These findings establish bilayer spironanographene as a versatile chiral nanographene platform that integrates structural chirality, supramolecular recognition, and chiroptical functionality, offering new opportunities for the development of chiral carbon-based photonic materials.
Bilayer nanographenes represent an emerging class of molecular carbon architectures that provide unique opportunities to explore interlayer electronic communication and chiroptical phenomena in confined π-systems. However, the development of well-defined chiral bilayer nanographenes capable of transferring chirality across extended π-surfaces and supramolecular assemblies remains challenging. Herein, we report the synthesis and structural characterization of a chiral bilayer spironanographene (spiro-NG) composed of two nanographene subunits connected through a rigid spirobifluorene core. Single-crystal X-ray diffraction reveals a folded bilayer geometry that enforces significant interlayer π-overlap while simultaneously generating intrinsic molecular chirality. Enantiomeric resolution affords configurationally stable P- and M-spiro-NG, which display pronounced circular dichroism (CD) and circularly polarized luminescence (CPL). Furthermore, the exposed π-surfaces of the bilayer scaffold enable π-surface recognition with coronene, leading to hetero-π stacked co-crystals that highlight the supramolecular adaptability of the nanographene framework. Notably, supramolecular co-assembly of spiro-NG with achiral fluorophores enables chirality transfer through Förster resonance energy transfer, resulting in induced CPL emission with tunable wavelengths. These findings establish bilayer spironanographene as a versatile chiral nanographene platform that integrates structural chirality, supramolecular recognition, and chiroptical functionality, offering new opportunities for the development of chiral carbon-based photonic materials.
2026, 37(10): 112941
doi: 10.1016/j.cclet.2026.112941
摘要:
Amphipathic TAP-dU and TAP-dC were designed with a distinctive donor-π-acceptor (D-π-A) electronic architecture, which the nucleoside function and TAP-moiety act as the electron donor and electron acceptor, respectively. The base-triggered charge transfer is influenced by protonation/deprotonation states and conformational twisting. Hydrogen-bonding interactions between the pyrimidine and ribose were thoroughly examined by nuclear magnetic resonance (1H NMR) spectroscopy, single-crystal X-ray crystallography, and density functional theory (DFT) calculations. Importantly, TAP-dU exhibits pH-dependent self-assembly and π-π stacking interactions, leading to an aggregated fluorescence multicolor shift from blue to green to yellow, with emission wavelengths reaching up to 545 nm. Unlike our previously reported nucleus-targeted TPE-dU/TPE-dC and mitochondria-targeted TPE-FdU, this study demonstrates that both nontoxic TAP-dC and TAP-dU effectively achieve endoplasmic reticulum (ER)-specific imaging in NIH-3T3 and HeLa cells. Additionally, due to its biocompatibility, TAP-dC also serves as a promising candidate for in vivo Ag+ detection in NIH-3T3 and zebrafish via bioimaging.
Amphipathic TAP-dU and TAP-dC were designed with a distinctive donor-π-acceptor (D-π-A) electronic architecture, which the nucleoside function and TAP-moiety act as the electron donor and electron acceptor, respectively. The base-triggered charge transfer is influenced by protonation/deprotonation states and conformational twisting. Hydrogen-bonding interactions between the pyrimidine and ribose were thoroughly examined by nuclear magnetic resonance (1H NMR) spectroscopy, single-crystal X-ray crystallography, and density functional theory (DFT) calculations. Importantly, TAP-dU exhibits pH-dependent self-assembly and π-π stacking interactions, leading to an aggregated fluorescence multicolor shift from blue to green to yellow, with emission wavelengths reaching up to 545 nm. Unlike our previously reported nucleus-targeted TPE-dU/TPE-dC and mitochondria-targeted TPE-FdU, this study demonstrates that both nontoxic TAP-dC and TAP-dU effectively achieve endoplasmic reticulum (ER)-specific imaging in NIH-3T3 and HeLa cells. Additionally, due to its biocompatibility, TAP-dC also serves as a promising candidate for in vivo Ag+ detection in NIH-3T3 and zebrafish via bioimaging.
2026, 37(10): 112980
doi: 10.1016/j.cclet.2026.112980
摘要:
Zwitterionic hydrogels as a new generation of functional materials are widely used in many frontier fields. However, zwitterionic hydrogels usually contain a large amount of active water and are inevitably frozen at low temperatures, thus sacrificing their mechanical properties and conductivity, which greatly limits their application. Herein, a novel strategy, namely the unique anti-polyelectrolyte effect (APE) of zwitterions is proposed to reduce the freezing point of zwitterionic hydrogels. The regulation mechanism of this strategy is that the electrostatic associated zwitterionic groups are exposed, thus increasing hydration by allowing these groups to establish strong hydrogen bonding with water molecules during the volume expansion process of zwitterionic polymer in salt. The overall water activity is decreased in the hydrogels, thus reducing the freezing point of the hydrogels. Sulfonic-based 2-(methacryloyloxy)ethyl dimethyl(3-sulfopropyl)-ammonium hydroxide (SBMA) and carboxylic-based 2-carboxy-N,N-dimethyl-N-(2′-methacryloyloxyethyl)ethanaminium inner salt (CBMA) zwitterionic monomers are selected as a proof of concept. SBMA based hydrogels with strong APE have a higher bound water content and a lower free water content than CBMA based hydrogels with almost no APE. Benefitting from the strong APE, the freezing point of SBMA based hydrogel (−20.9 ℃) is significantly lower than that of CBMA based hydrogel (−12.4 ℃). This work offers a practical and meaningful guidance for the design of anti-freezing zwitterionic hydrogels and further promotes the application of zwitterionic hydrogels in low temperature environments.
Zwitterionic hydrogels as a new generation of functional materials are widely used in many frontier fields. However, zwitterionic hydrogels usually contain a large amount of active water and are inevitably frozen at low temperatures, thus sacrificing their mechanical properties and conductivity, which greatly limits their application. Herein, a novel strategy, namely the unique anti-polyelectrolyte effect (APE) of zwitterions is proposed to reduce the freezing point of zwitterionic hydrogels. The regulation mechanism of this strategy is that the electrostatic associated zwitterionic groups are exposed, thus increasing hydration by allowing these groups to establish strong hydrogen bonding with water molecules during the volume expansion process of zwitterionic polymer in salt. The overall water activity is decreased in the hydrogels, thus reducing the freezing point of the hydrogels. Sulfonic-based 2-(methacryloyloxy)ethyl dimethyl(3-sulfopropyl)-ammonium hydroxide (SBMA) and carboxylic-based 2-carboxy-N,N-dimethyl-N-(2′-methacryloyloxyethyl)ethanaminium inner salt (CBMA) zwitterionic monomers are selected as a proof of concept. SBMA based hydrogels with strong APE have a higher bound water content and a lower free water content than CBMA based hydrogels with almost no APE. Benefitting from the strong APE, the freezing point of SBMA based hydrogel (−20.9 ℃) is significantly lower than that of CBMA based hydrogel (−12.4 ℃). This work offers a practical and meaningful guidance for the design of anti-freezing zwitterionic hydrogels and further promotes the application of zwitterionic hydrogels in low temperature environments.
2026, 37(10): 113018
doi: 10.1016/j.cclet.2026.113018
摘要:
How to break through the oxidation energy barrier of C(sp3)-H bonds with high dissociation energy and prevent excessive oxidation is a significant challenge. This study presents the atomic-level regulation of POMOF dimensions by inducing structural differentiation through hydroxide end-capping. Two homologous isomers, named as Co-W10 and OH-Co-W10 respectively, have formed three-dimensional (3D) and two-dimensional (2D) structures through varied metal coordination modes. The 2D structure of OH-Co-W10 demonstrates excellent electron delocalization and transfer channels over the 3D structure of Co-W10. OH-Co-W10 exhibits enhanced oxygen activation capacity compared to Co-W10. In the catalytic oxidation of toluene, OH-Co-W10 achieves an impressive conversion rate of 98.1%, and the selectivity of benzaldehyde is as high as 97.3% (6720.2 µmol/g), which is cleaner and more efficient than that of the latest photocatalysts and Co-W10 (4713.1 µmol/g). In this study, the hydroxide capping strategy is proposed for generation of homologous isomers, offering a new direction for catalytic oxidation of C(sp3)-H bonds by expounding differences in active sites through distinct structural features.
How to break through the oxidation energy barrier of C(sp3)-H bonds with high dissociation energy and prevent excessive oxidation is a significant challenge. This study presents the atomic-level regulation of POMOF dimensions by inducing structural differentiation through hydroxide end-capping. Two homologous isomers, named as Co-W10 and OH-Co-W10 respectively, have formed three-dimensional (3D) and two-dimensional (2D) structures through varied metal coordination modes. The 2D structure of OH-Co-W10 demonstrates excellent electron delocalization and transfer channels over the 3D structure of Co-W10. OH-Co-W10 exhibits enhanced oxygen activation capacity compared to Co-W10. In the catalytic oxidation of toluene, OH-Co-W10 achieves an impressive conversion rate of 98.1%, and the selectivity of benzaldehyde is as high as 97.3% (6720.2 µmol/g), which is cleaner and more efficient than that of the latest photocatalysts and Co-W10 (4713.1 µmol/g). In this study, the hydroxide capping strategy is proposed for generation of homologous isomers, offering a new direction for catalytic oxidation of C(sp3)-H bonds by expounding differences in active sites through distinct structural features.
2026, 37(10): 112875
doi: 10.1016/j.cclet.2026.112875
摘要:
2026, 37(10): 112887
doi: 10.1016/j.cclet.2026.112887
摘要:
2026, 37(10): 112961
doi: 10.1016/j.cclet.2026.112961
摘要:
2026, 37(5): 110827
doi: 10.1016/j.cclet.2025.110827
摘要:
Oxidation-coupled clusters of [E9]4– are rarely synthesised, and the investigation of their reactivity is profoundly hindered by their high charge and limited yield. In this study, we successfully synthesized two Nb-containing clusters [(Ge9–Ge9)(NbCp2)2]4– (1a) and [(Ge9=Ge9=Ge9)NbCp2]5– (2a), by reacting [Ge9–Ge9]6– and [Ge9=Ge9=Ge9]6– with NbCp4. Theoretical calculations indicate that the formation of 1a and 2a from dimer and trimer is thermodynamically favorable. Furthermore, a Au-containing cluster incorporating the dimeric [Sn9–Sn9]6– cluster, [Au(Sn9–Sn9)]5– (3a), was successfully synthesized, despite the inability to independently synthesize [Sn9–Sn9]6–. A systematic bonding analysis was conducted on these newly synthesized clusters and their parent structures to investigate their bonding patterns.
Oxidation-coupled clusters of [E9]4– are rarely synthesised, and the investigation of their reactivity is profoundly hindered by their high charge and limited yield. In this study, we successfully synthesized two Nb-containing clusters [(Ge9–Ge9)(NbCp2)2]4– (1a) and [(Ge9=Ge9=Ge9)NbCp2]5– (2a), by reacting [Ge9–Ge9]6– and [Ge9=Ge9=Ge9]6– with NbCp4. Theoretical calculations indicate that the formation of 1a and 2a from dimer and trimer is thermodynamically favorable. Furthermore, a Au-containing cluster incorporating the dimeric [Sn9–Sn9]6– cluster, [Au(Sn9–Sn9)]5– (3a), was successfully synthesized, despite the inability to independently synthesize [Sn9–Sn9]6–. A systematic bonding analysis was conducted on these newly synthesized clusters and their parent structures to investigate their bonding patterns.
2026, 37(5): 110829
doi: 10.1016/j.cclet.2025.110829
摘要:
The rise of antibiotic-resistant bacteria and the formation of biofilms are significant challenges in surgical practice, posing a serious threat to public health due to postoperative wound infections. A promising approach to tackle this issue is the combination of photothermal therapy (PTT) and chemodynamic therapy (CDT), which has shown remarkable effectiveness in treating both cancer and wound infections. In our study, we developed an innovative artificial nanoplatform called Ni-2@F127 by encapsulating Ni-2 in a biocompatible Pluronic. When exposed to 880 nm laser irradiation, Ni-2@F127 exhibited exceptional photothermal performance, achieving a photothermal conversion efficiency of 60.4%, along with significant photocatalytic capabilities. This platform activates a Fenton-like reaction that catalyzes hydrogen peroxide (H₂O₂), producing toxic hydroxyl radicals (•OH) effectively. The synergistic effects of hyperthermia and •OH not only destroy tumor cells but also demonstrate powerful antimicrobial activity, significantly inhibiting the growth of Escherichia coli and Staphylococcus aureus (S. aureus) in vitro under near-infrared (NIR) irradiation. Importantly, in animal models, Ni-2@F127 effectively eliminates S. aureus from deep tissues in cases of subcutaneous abscesses and knife injuries, significantly accelerating abscess resolution and promoting wound healing. The compelling evidence suggests that Ni-based metal complexes could serve as transformative antibacterial agents in phototherapy, unlocking vast potential for their application in wound healing and the treatment of bacterial infections.
The rise of antibiotic-resistant bacteria and the formation of biofilms are significant challenges in surgical practice, posing a serious threat to public health due to postoperative wound infections. A promising approach to tackle this issue is the combination of photothermal therapy (PTT) and chemodynamic therapy (CDT), which has shown remarkable effectiveness in treating both cancer and wound infections. In our study, we developed an innovative artificial nanoplatform called Ni-2@F127 by encapsulating Ni-2 in a biocompatible Pluronic. When exposed to 880 nm laser irradiation, Ni-2@F127 exhibited exceptional photothermal performance, achieving a photothermal conversion efficiency of 60.4%, along with significant photocatalytic capabilities. This platform activates a Fenton-like reaction that catalyzes hydrogen peroxide (H₂O₂), producing toxic hydroxyl radicals (•OH) effectively. The synergistic effects of hyperthermia and •OH not only destroy tumor cells but also demonstrate powerful antimicrobial activity, significantly inhibiting the growth of Escherichia coli and Staphylococcus aureus (S. aureus) in vitro under near-infrared (NIR) irradiation. Importantly, in animal models, Ni-2@F127 effectively eliminates S. aureus from deep tissues in cases of subcutaneous abscesses and knife injuries, significantly accelerating abscess resolution and promoting wound healing. The compelling evidence suggests that Ni-based metal complexes could serve as transformative antibacterial agents in phototherapy, unlocking vast potential for their application in wound healing and the treatment of bacterial infections.
2026, 37(5): 110851
doi: 10.1016/j.cclet.2025.110851
摘要:
Solid-state lithium (Li) metal batteries have attracted significant attention due to their high energy density and improved safety performance. However, sluggish Li-ion transport and rapid anion migration in solid-state electrolytes often result in heterogeneous Li-ion flux distribution and thus Li dendrite growth. Herein, we developed a highly conductive composite solid electrolyte with an elevated Li-ion transference number through incorporating Gd-doped CeO2 (GDC) nanofillers with abundant surface oxygen defects into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrices. The defect concentrations were effectively controlled by regulating the Gd doping ratio in CeO2. As a result, the highest oxygen concentration of 12.2% is achieved for the GDC with 10% Gd doping (GDC-10). The GDC-10 electrolyte demonstrated a high Li-ion transference number of 0.59 and an improved ionic conductivity of 0.40 mS/cm at room temperature, attributed to anion immobilization and enhanced Li-salt dissociation. This was due to the strong interactions between positively charged oxygen vacancies and anions, which effectively reduces surface concentration polarization and homogenizes Li-ion flux. Therefore, LiLi symmetric cells exhibited exceptional cycling stability of 1500 h without noticeable Li dendrite growth at 1 mA/cm2 and 1 mAh/cm2. Furthermore, LiLiFePO4 full cell also stably cycles for 500 cycles with a capacity retention of 90.44% at 1 C. This work provides new insights into the design of composite solid electrolytes through the defect regulation of fillers.
Solid-state lithium (Li) metal batteries have attracted significant attention due to their high energy density and improved safety performance. However, sluggish Li-ion transport and rapid anion migration in solid-state electrolytes often result in heterogeneous Li-ion flux distribution and thus Li dendrite growth. Herein, we developed a highly conductive composite solid electrolyte with an elevated Li-ion transference number through incorporating Gd-doped CeO2 (GDC) nanofillers with abundant surface oxygen defects into poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrices. The defect concentrations were effectively controlled by regulating the Gd doping ratio in CeO2. As a result, the highest oxygen concentration of 12.2% is achieved for the GDC with 10% Gd doping (GDC-10). The GDC-10 electrolyte demonstrated a high Li-ion transference number of 0.59 and an improved ionic conductivity of 0.40 mS/cm at room temperature, attributed to anion immobilization and enhanced Li-salt dissociation. This was due to the strong interactions between positively charged oxygen vacancies and anions, which effectively reduces surface concentration polarization and homogenizes Li-ion flux. Therefore, LiLi symmetric cells exhibited exceptional cycling stability of 1500 h without noticeable Li dendrite growth at 1 mA/cm2 and 1 mAh/cm2. Furthermore, LiLiFePO4 full cell also stably cycles for 500 cycles with a capacity retention of 90.44% at 1 C. This work provides new insights into the design of composite solid electrolytes through the defect regulation of fillers.
2026, 37(5): 110852
doi: 10.1016/j.cclet.2025.110852
摘要:
High-entropy alloys (HEAs) have emerged as promising electrocatalysts due to their unique compositional complexity and tunable electronic structures. However, achieving rapid and efficient synthesis of HEA nanoparticles (NPs) with high electrocatalytic activity and understanding their structural and electronic characteristics remains challenging. Here, we report the synthesis of FeCoNiCuCr HEA NPs via an ultrafast carbon thermal shock (CTS) method. Local structural investigations combining synchrotron pair distribution function (PDF) and X-ray absorption fine structure (XAFS) reveal that incorporating Cr introduces local tetragonal distortions, resulting in residual strain that enhances catalytic performance. This local distortion could be attributed to atomic-scale elemental segregation between Cr and Cu, further stabilizing the structure and improving activity. These synergistic effects, combined with uniform carbon-loaded NPs morphology achieved by the CTS process, enable superior OER performance. This study highlights the role of structural and electronic modulation in HEA catalysts, offering valuable insights for the design of next-generation electrocatalysts.
High-entropy alloys (HEAs) have emerged as promising electrocatalysts due to their unique compositional complexity and tunable electronic structures. However, achieving rapid and efficient synthesis of HEA nanoparticles (NPs) with high electrocatalytic activity and understanding their structural and electronic characteristics remains challenging. Here, we report the synthesis of FeCoNiCuCr HEA NPs via an ultrafast carbon thermal shock (CTS) method. Local structural investigations combining synchrotron pair distribution function (PDF) and X-ray absorption fine structure (XAFS) reveal that incorporating Cr introduces local tetragonal distortions, resulting in residual strain that enhances catalytic performance. This local distortion could be attributed to atomic-scale elemental segregation between Cr and Cu, further stabilizing the structure and improving activity. These synergistic effects, combined with uniform carbon-loaded NPs morphology achieved by the CTS process, enable superior OER performance. This study highlights the role of structural and electronic modulation in HEA catalysts, offering valuable insights for the design of next-generation electrocatalysts.
2026, 37(5): 110858
doi: 10.1016/j.cclet.2025.110858
摘要:
Zero-dimensional (0D) hybrid copper halides have attracted significant attention owing to their unique photophysical properties and remarkable structural diversity. In this work, two 0D self-assemblies compounds of copper iodide dimers were synthesized, namely, (4-MBTP)2(Cu2I4)0.5I (1) and (4-MBTP)(Cu2I4)0.5 (2) (4-MBTP = (4-methylbenzyl)triphenylphosphonium chloride). Compound 1 exhibits blue emission centered at 474 nm, while compound 2 shows yellow emission centered at 559 nm at room temperature. The results combined with crystal structure, spectroscopy analysis, characterization, and theoretical studies reveal that the blue light of compound 1 stems from multiple defect states caused by the presence of I vacancies, while the yellow emission of compound 2 is attributed to through-space charge-transfer (TSCT) and cluster-centered (CC) excited state. Strikingly, the crystal structure can transform from compound 1 into compound 2 with luminescence color change from blue to yellow through treating with methanol. This work provides a structural transformation strategy of hybrid copper halides, as well as realizes the regulation of light emission from defect states to non-defect states, making them feasible candidates for information encryption and optical data storage.
Zero-dimensional (0D) hybrid copper halides have attracted significant attention owing to their unique photophysical properties and remarkable structural diversity. In this work, two 0D self-assemblies compounds of copper iodide dimers were synthesized, namely, (4-MBTP)2(Cu2I4)0.5I (1) and (4-MBTP)(Cu2I4)0.5 (2) (4-MBTP = (4-methylbenzyl)triphenylphosphonium chloride). Compound 1 exhibits blue emission centered at 474 nm, while compound 2 shows yellow emission centered at 559 nm at room temperature. The results combined with crystal structure, spectroscopy analysis, characterization, and theoretical studies reveal that the blue light of compound 1 stems from multiple defect states caused by the presence of I vacancies, while the yellow emission of compound 2 is attributed to through-space charge-transfer (TSCT) and cluster-centered (CC) excited state. Strikingly, the crystal structure can transform from compound 1 into compound 2 with luminescence color change from blue to yellow through treating with methanol. This work provides a structural transformation strategy of hybrid copper halides, as well as realizes the regulation of light emission from defect states to non-defect states, making them feasible candidates for information encryption and optical data storage.
2026, 37(5): 110859
doi: 10.1016/j.cclet.2025.110859
摘要:
Rechargeable aqueous zinc-ion batteries (RAZIBs) have been considered as viable alternatives to lithium-ion batteries in electrochemical energy storage due to their intrinsic safety, low cost, and environmental friendliness. However, the further practical application of RAZIBs is restricted by the growth of zinc dendrites and severe side reactions during cycling. To address these issues, we proposed a new lysine (Lys) additive to the ZnSO4 electrolyte, the hydrolyzed Lys+ cations can be adsorbed on the Zn anode's surface to modify the interface between the zinc electrode and the ZnSO4 electrolyte. This modification helps weaken the "tip effect" and guides the uniform zinc deposition, effectively alleviating the formation of zinc dendrites. Additionally, introducing alkaline Lys can regulate the pH value of the ZnSO4 electrolyte and suppress side reactions, thereby decreasing the production of by-products. Consequently, the Zn||Zn symmetric cell with Lys additive stably cycled for 4500 h at 1 mA/cm2, and the Zn||NH4V4O10 full cell with Lys additive exhibited improved performance (with a capacity retention of 72% after 1000 cycles) at 5 A/g. This strategy provides valuable insights for developing stable Zn anode toward high-performance RAZIBs.
Rechargeable aqueous zinc-ion batteries (RAZIBs) have been considered as viable alternatives to lithium-ion batteries in electrochemical energy storage due to their intrinsic safety, low cost, and environmental friendliness. However, the further practical application of RAZIBs is restricted by the growth of zinc dendrites and severe side reactions during cycling. To address these issues, we proposed a new lysine (Lys) additive to the ZnSO4 electrolyte, the hydrolyzed Lys+ cations can be adsorbed on the Zn anode's surface to modify the interface between the zinc electrode and the ZnSO4 electrolyte. This modification helps weaken the "tip effect" and guides the uniform zinc deposition, effectively alleviating the formation of zinc dendrites. Additionally, introducing alkaline Lys can regulate the pH value of the ZnSO4 electrolyte and suppress side reactions, thereby decreasing the production of by-products. Consequently, the Zn||Zn symmetric cell with Lys additive stably cycled for 4500 h at 1 mA/cm2, and the Zn||NH4V4O10 full cell with Lys additive exhibited improved performance (with a capacity retention of 72% after 1000 cycles) at 5 A/g. This strategy provides valuable insights for developing stable Zn anode toward high-performance RAZIBs.
2026, 37(5): 110862
doi: 10.1016/j.cclet.2025.110862
摘要:
The dissolution of lithium polysulfides (Li2Sx, 4 ≤ x ≤ 8, LiPSs) intermediates and slow redox kinetics are the main factors leading to the rapid capacity degradation of lithium-sulfur batteries (LSBs), significantly limits the practical development of LSBs. To overcome challenges, NbN embedded in nitrogen-doped carbon nanotubes (NbN@NCNT) composites were synthesized here as sulfur hosts by taking advantage of the superior electrical conductivity and excellent catalytic activity of the metal nitride NbN. The incorporation of NbN enhanced the polysulfides conversion efficiency and suppressed the shuttling effect, thereby enhancing cycling stability in LSBs. XPS results revealed the formation of Li2S, indicating that Li2S8 was sufficiently effectively reduced and catalytically converted to the Li2S. Consequently, after 100 cycles, the capacity retention rate of LSBs using the S/NbN@NCNT electrode reached 71.5% at a current density of 2 mA/cm2 with a high sulfur loading of 3 mg/cm2. More importantly, even at high current density of 8 mA/cm2, the battery assembled with NbN@NCNT was still able to reach the high capacity of 878.14 mAh/g, demonstrating outstanding rate capability. This study offered novel insights into the potential for enhancing the sulfur reaction kinetics in LSBs.
The dissolution of lithium polysulfides (Li2Sx, 4 ≤ x ≤ 8, LiPSs) intermediates and slow redox kinetics are the main factors leading to the rapid capacity degradation of lithium-sulfur batteries (LSBs), significantly limits the practical development of LSBs. To overcome challenges, NbN embedded in nitrogen-doped carbon nanotubes (NbN@NCNT) composites were synthesized here as sulfur hosts by taking advantage of the superior electrical conductivity and excellent catalytic activity of the metal nitride NbN. The incorporation of NbN enhanced the polysulfides conversion efficiency and suppressed the shuttling effect, thereby enhancing cycling stability in LSBs. XPS results revealed the formation of Li2S, indicating that Li2S8 was sufficiently effectively reduced and catalytically converted to the Li2S. Consequently, after 100 cycles, the capacity retention rate of LSBs using the S/NbN@NCNT electrode reached 71.5% at a current density of 2 mA/cm2 with a high sulfur loading of 3 mg/cm2. More importantly, even at high current density of 8 mA/cm2, the battery assembled with NbN@NCNT was still able to reach the high capacity of 878.14 mAh/g, demonstrating outstanding rate capability. This study offered novel insights into the potential for enhancing the sulfur reaction kinetics in LSBs.
2026, 37(5): 110863
doi: 10.1016/j.cclet.2025.110863
摘要:
Semiconducting metal oxide based gas sensors exhibit great promise for convenient detection of acetone, a biomarker gas in the exhaled breath of type-Ⅰ diabetes patients. However, the detection usually suffers the interference from exhaled moisture. To overcome this challenge, in this work, a novel hierarchical heterojunction structure consisting of SnO2 nanofiber core and Co3O4 nanosheet shell (denoted as SnO2@Co3O4 core-shell composite) was proposed for fabricating acetone sensor with excellent humidity resistance. Compared with SnO2 nanofibers and Co3O4 nanosheets, the SnO2@Co3O4 showed the highest sensing response, with a response value (Rg/Ra) of 11.27-50 ppm acetone at 110 ℃. In addition, the hierarchical SnO2@Co3O4 core-shell structure shows fast response/recovery speed (19/43 s), lower detection limit (125 ppb), excellent selectivity and stability in a humidity environment (relative humidity 30%-90%) with a relative change of only 3%. The enhanced gas sensing performance toward acetone is attributed to the synergistic effect between the two components, the unique core-shell hierarchical structure and the rich oxygen vacancy density. Density functional theory calculations reveal that the SnO2@Co3O4 has higher acetone adsorption energy than the two components. In addition, a novel SnO2@Co3O4 gas sensing module and smart portable sensor device enable efficient real-time monitoring of acetone concentrations on a smartphone via Bluetooth communication.
Semiconducting metal oxide based gas sensors exhibit great promise for convenient detection of acetone, a biomarker gas in the exhaled breath of type-Ⅰ diabetes patients. However, the detection usually suffers the interference from exhaled moisture. To overcome this challenge, in this work, a novel hierarchical heterojunction structure consisting of SnO2 nanofiber core and Co3O4 nanosheet shell (denoted as SnO2@Co3O4 core-shell composite) was proposed for fabricating acetone sensor with excellent humidity resistance. Compared with SnO2 nanofibers and Co3O4 nanosheets, the SnO2@Co3O4 showed the highest sensing response, with a response value (Rg/Ra) of 11.27-50 ppm acetone at 110 ℃. In addition, the hierarchical SnO2@Co3O4 core-shell structure shows fast response/recovery speed (19/43 s), lower detection limit (125 ppb), excellent selectivity and stability in a humidity environment (relative humidity 30%-90%) with a relative change of only 3%. The enhanced gas sensing performance toward acetone is attributed to the synergistic effect between the two components, the unique core-shell hierarchical structure and the rich oxygen vacancy density. Density functional theory calculations reveal that the SnO2@Co3O4 has higher acetone adsorption energy than the two components. In addition, a novel SnO2@Co3O4 gas sensing module and smart portable sensor device enable efficient real-time monitoring of acetone concentrations on a smartphone via Bluetooth communication.
2026, 37(5): 110864
doi: 10.1016/j.cclet.2025.110864
摘要:
Metal-organic framework [Zn2(tz)2(ox)] (CALF-20) has attracted great attention due to its excellent ability to capture carbon dioxide. There are great interests to develop similar adsorbents for gas adsorption and separation. To develop more efficient porous adsorbent, it is essential to study the relationship between these structures and properties. Neutron diffraction has been proved to be an excellent tool for determining both the structural details of MOF host and the precise locations of adsorbed gas within the pore, offering unique opportunities for understanding the structure-properties relationship. Herein, we report the synthesis and structure characterization of MOF [Zn2(mtz)2(ox)], which exhibits high CO2 adsorption capacity. Neutron powder diffraction experiment on the solvated, the activated and CO2 loaded samples unveils the preferred binding sites of CO2 within the MOFs, where CO2 locates toward the center of the pore and interacts with methyl group or triazole via CH···O hydrogen bonding. The adsorption process of CO2 in [Zn2(mtz)2(ox)] is accompanied by the cell volume expansion, so [Zn2(mtz)2(ox)] with more compact structure can show a better adsorption performance. The structure-properties relationship in [Zn2(mtz)2(ox)] elucidated by present study offer a path to develop more advanced porous physisorbent materials.
Metal-organic framework [Zn2(tz)2(ox)] (CALF-20) has attracted great attention due to its excellent ability to capture carbon dioxide. There are great interests to develop similar adsorbents for gas adsorption and separation. To develop more efficient porous adsorbent, it is essential to study the relationship between these structures and properties. Neutron diffraction has been proved to be an excellent tool for determining both the structural details of MOF host and the precise locations of adsorbed gas within the pore, offering unique opportunities for understanding the structure-properties relationship. Herein, we report the synthesis and structure characterization of MOF [Zn2(mtz)2(ox)], which exhibits high CO2 adsorption capacity. Neutron powder diffraction experiment on the solvated, the activated and CO2 loaded samples unveils the preferred binding sites of CO2 within the MOFs, where CO2 locates toward the center of the pore and interacts with methyl group or triazole via CH···O hydrogen bonding. The adsorption process of CO2 in [Zn2(mtz)2(ox)] is accompanied by the cell volume expansion, so [Zn2(mtz)2(ox)] with more compact structure can show a better adsorption performance. The structure-properties relationship in [Zn2(mtz)2(ox)] elucidated by present study offer a path to develop more advanced porous physisorbent materials.
2026, 37(5): 110889
doi: 10.1016/j.cclet.2025.110889
摘要:
The replacement of Pt/C catalysts with Pt-based alloy catalysts was considered a promising strategy to reduce platinum-group-metal (PGM) content in proton exchange membrane fuel cell. However, inexpensive transition metal atoms in Pt-based alloy catalysts are subject to metal dissolution issues, leading to stability issues of oxygen reduction reaction (ORR) catalysts. In this work, a PtCuNi/C-WO3-x catalyst is designed employing non-stoichiometric WO3-x with abundant oxygen vacancies (Ovac). The WO3-x can dramatically improve the stability of PtCuNi without sacrificing the activity. Theoretical calculation suggests a decreased vacancy formation energy of W in WO3-x at the presence of Ovac, as well as increased vacancy formation energies of Pt/Cu/Ni in PtCuNi alloy particles with the existence of surface W dopant. Combined with the experimental discovery of slower dissolution rates of metals in PtCuNi/C-WO3-x catalyst, a dissolution-induced stability enhancement mechanism is proposed, whereby facilitated dissolution of W atoms from WO3-x bulk could re-deposit on Pt-alloy surface and inhibit the dissolution of catalytically active metal atoms, revealing a dynamic process that enhances the stability. The PtCuNi/C-WO3-x also shows great potential to be used as cathode catalyst in membrane electrode assembly for high-temperature proton exchange membrane fuel cells.
The replacement of Pt/C catalysts with Pt-based alloy catalysts was considered a promising strategy to reduce platinum-group-metal (PGM) content in proton exchange membrane fuel cell. However, inexpensive transition metal atoms in Pt-based alloy catalysts are subject to metal dissolution issues, leading to stability issues of oxygen reduction reaction (ORR) catalysts. In this work, a PtCuNi/C-WO3-x catalyst is designed employing non-stoichiometric WO3-x with abundant oxygen vacancies (Ovac). The WO3-x can dramatically improve the stability of PtCuNi without sacrificing the activity. Theoretical calculation suggests a decreased vacancy formation energy of W in WO3-x at the presence of Ovac, as well as increased vacancy formation energies of Pt/Cu/Ni in PtCuNi alloy particles with the existence of surface W dopant. Combined with the experimental discovery of slower dissolution rates of metals in PtCuNi/C-WO3-x catalyst, a dissolution-induced stability enhancement mechanism is proposed, whereby facilitated dissolution of W atoms from WO3-x bulk could re-deposit on Pt-alloy surface and inhibit the dissolution of catalytically active metal atoms, revealing a dynamic process that enhances the stability. The PtCuNi/C-WO3-x also shows great potential to be used as cathode catalyst in membrane electrode assembly for high-temperature proton exchange membrane fuel cells.
2026, 37(5): 110891
doi: 10.1016/j.cclet.2025.110891
摘要:
Structural design is an effective way to realize the functional construction of hole transporting materials (HTMs). In order to have an insight into the relationship between molecular structure and function of HTMs, three isomeric HTMs (RQ1, RQ2 and RQ3) are constructed with functional group of dibenzothiophene which is connected to different positions on the side chains of carbazole-aromatic derivatives. In combination with computational simulation and experimental study, although the isomeric RQ1–RQ3 with the same molecular formula exhibit similar frontier molecular orbital energy levels and optical absorption, their hole transporting ability and interaction at perovskite/HTMs interface in perovskite solar cells (PSCs) are completely different. In comparison with the RQ2 (18.69%) and RQ3 (22.56%), the results indicate that the molecule RQ1 in PSCs application can yield higher power conversion efficiency (23.50%) because of its higher hole mobility and effective charge transfer at perovskite/HTMs interface. Moreover, the mutually corroborating between the computational simulation and the experimental results demonstrate the reliability of the theoretical model for molecular design of isomeric HTMs. This strategy of obtaining high-performance HTMs through simple structural design is expected to inspire researchers to further optimize the efficiency of PSCs.
Structural design is an effective way to realize the functional construction of hole transporting materials (HTMs). In order to have an insight into the relationship between molecular structure and function of HTMs, three isomeric HTMs (RQ1, RQ2 and RQ3) are constructed with functional group of dibenzothiophene which is connected to different positions on the side chains of carbazole-aromatic derivatives. In combination with computational simulation and experimental study, although the isomeric RQ1–RQ3 with the same molecular formula exhibit similar frontier molecular orbital energy levels and optical absorption, their hole transporting ability and interaction at perovskite/HTMs interface in perovskite solar cells (PSCs) are completely different. In comparison with the RQ2 (18.69%) and RQ3 (22.56%), the results indicate that the molecule RQ1 in PSCs application can yield higher power conversion efficiency (23.50%) because of its higher hole mobility and effective charge transfer at perovskite/HTMs interface. Moreover, the mutually corroborating between the computational simulation and the experimental results demonstrate the reliability of the theoretical model for molecular design of isomeric HTMs. This strategy of obtaining high-performance HTMs through simple structural design is expected to inspire researchers to further optimize the efficiency of PSCs.
2026, 37(5): 110892
doi: 10.1016/j.cclet.2025.110892
摘要:
Traditional polycrystalline P2 layered oxides face challenges such as irreversible phase transitions, poor air stability, and structural distortion, which negatively impact their electrochemical performance. In this study, a single-crystal material, P2-Na2/3Ni1/4Mn2/3Mg1/12O2 (SC-NMM), was synthesized using co-precipitation coupled with the molten salt method. Owing to the strong integrity and high thermal stability of the main {001} planes of the large-sized single crystal, SC-NMM exhibits a high reversible specific capacity (173.5 mAh/g at 20 mA/g) and stable cycle performance (93.38% capacity retention after 100 cycles at 100 mA/g) at high voltage. Additionally, the Na-ion full cell constructed with the SC-NMM cathode and hard carbon anode demonstrates a cathode energy density of 397.4 Wh/kg. The excellent electrochemical performance of SC-NMM originates from the reversible anion redox and single-phase solid solution reaction mechanism. This work provides a reference for synthesizing single-crystal layered transition metal oxides with high electrochemical performance by eliminating irreversible phase transitions through crystal orientation modulation.
Traditional polycrystalline P2 layered oxides face challenges such as irreversible phase transitions, poor air stability, and structural distortion, which negatively impact their electrochemical performance. In this study, a single-crystal material, P2-Na2/3Ni1/4Mn2/3Mg1/12O2 (SC-NMM), was synthesized using co-precipitation coupled with the molten salt method. Owing to the strong integrity and high thermal stability of the main {001} planes of the large-sized single crystal, SC-NMM exhibits a high reversible specific capacity (173.5 mAh/g at 20 mA/g) and stable cycle performance (93.38% capacity retention after 100 cycles at 100 mA/g) at high voltage. Additionally, the Na-ion full cell constructed with the SC-NMM cathode and hard carbon anode demonstrates a cathode energy density of 397.4 Wh/kg. The excellent electrochemical performance of SC-NMM originates from the reversible anion redox and single-phase solid solution reaction mechanism. This work provides a reference for synthesizing single-crystal layered transition metal oxides with high electrochemical performance by eliminating irreversible phase transitions through crystal orientation modulation.
2026, 37(5): 110893
doi: 10.1016/j.cclet.2025.110893
摘要:
Aqueous zinc-ion batteries (AZIBs) have emerged as strong contenders for large-scale energy storage solutions, attributed to their cost-effectiveness and enhanced safety profiles. Nevertheless, their widespread adoption is currently hindered by their poor performance in low-temperature conditions. Herein, an electrolyte is developed by utilizing weakly solvated and film-forming molecule dimethyl sulfite (DMS) to achieve smooth de-solvation and high ionic conductivity at low temperature. The DMS disrupts the hydrogen bonding network of water and lowers the freezing point of the electrolyte to -40.9 ℃. The designed electrolyte achieves ionic conductivity up to 10.75 mS/cm at -30 ℃. Due to the chemical reactivity of DMS and trifluoromethanesulfonate anions in the Zn2+-solvation shell, a ZnF2-ZnS hybrid solid electrolyte interphase (SEI) is successively generated on Zn metal surface. Mechanistic studies reveal that such robust hybrid interphase can promote Zn2+ desolvation and rapid Zn2+ transport. In addition, the addition of DMS effectively suppresses the dendritic growth, hydrogen evolution reaction (HER), and corrosion-induced passivation on the anode surface, facilitating long-term cycling at subzero temperatures. At -40 ℃, the Zn//Zn symmetrical cell cycles for 1200 h at 0.5 mA/cm2 and 0.5 mAh/cm2, and the Zn//NVO cell achieves an ultra-long cycle life of 1000 cycles with a high capacity retention of 82.89% at 1 A/g.
Aqueous zinc-ion batteries (AZIBs) have emerged as strong contenders for large-scale energy storage solutions, attributed to their cost-effectiveness and enhanced safety profiles. Nevertheless, their widespread adoption is currently hindered by their poor performance in low-temperature conditions. Herein, an electrolyte is developed by utilizing weakly solvated and film-forming molecule dimethyl sulfite (DMS) to achieve smooth de-solvation and high ionic conductivity at low temperature. The DMS disrupts the hydrogen bonding network of water and lowers the freezing point of the electrolyte to -40.9 ℃. The designed electrolyte achieves ionic conductivity up to 10.75 mS/cm at -30 ℃. Due to the chemical reactivity of DMS and trifluoromethanesulfonate anions in the Zn2+-solvation shell, a ZnF2-ZnS hybrid solid electrolyte interphase (SEI) is successively generated on Zn metal surface. Mechanistic studies reveal that such robust hybrid interphase can promote Zn2+ desolvation and rapid Zn2+ transport. In addition, the addition of DMS effectively suppresses the dendritic growth, hydrogen evolution reaction (HER), and corrosion-induced passivation on the anode surface, facilitating long-term cycling at subzero temperatures. At -40 ℃, the Zn//Zn symmetrical cell cycles for 1200 h at 0.5 mA/cm2 and 0.5 mAh/cm2, and the Zn//NVO cell achieves an ultra-long cycle life of 1000 cycles with a high capacity retention of 82.89% at 1 A/g.
2026, 37(5): 110952
doi: 10.1016/j.cclet.2025.110952
摘要:
Aqueous zinc-ion batteries (AZIBs) are the low-cost and safe secondary battery technology with great application prospects, but remain hindered by the severe Zn-electrolyte interface compatibility, especially in extreme environmental temperature. Innovative electrolyte design is the key to solving the above problems. Here, we introduce an electrolyte additive of Poloxamer 407 (P407) as a solvation restructuring agent and H2O cluster modulator, effectively stabilizing H2O molecules and suppressing parasitic reactions. Meanwhile, P407 facilitates the formation of a stable solid electrolyte interphase (SEI) composed of organic-inorganic composite, thereby improving the interfacial chemistry. More importantly, the thermoreversible gelation property of P407 enhances the system’s high-temperature stability by forming micelle network structures that effectively retains H2O molecules, while at low temperature, it maintains the fluidity of the electrolyte, ensuring efficient ion transport. By using P407-containing electrolyte, the Zn anode achieves long cycling life of 4000, 850, and 1000 h at 30, 60 and −30 ℃, respectively. Moreover, the modified electrolyte enables the Zn-V2O5 full cells to achieve excellent rate performance and cycling stability in a wide temperature range from −30 ℃ to 60 ℃. This study highlights a simple yet effective strategy for electrolyte modification using P407, providing a pathway toward the development of high-performance AZIBs with broad temperature adaptability.
Aqueous zinc-ion batteries (AZIBs) are the low-cost and safe secondary battery technology with great application prospects, but remain hindered by the severe Zn-electrolyte interface compatibility, especially in extreme environmental temperature. Innovative electrolyte design is the key to solving the above problems. Here, we introduce an electrolyte additive of Poloxamer 407 (P407) as a solvation restructuring agent and H2O cluster modulator, effectively stabilizing H2O molecules and suppressing parasitic reactions. Meanwhile, P407 facilitates the formation of a stable solid electrolyte interphase (SEI) composed of organic-inorganic composite, thereby improving the interfacial chemistry. More importantly, the thermoreversible gelation property of P407 enhances the system’s high-temperature stability by forming micelle network structures that effectively retains H2O molecules, while at low temperature, it maintains the fluidity of the electrolyte, ensuring efficient ion transport. By using P407-containing electrolyte, the Zn anode achieves long cycling life of 4000, 850, and 1000 h at 30, 60 and −30 ℃, respectively. Moreover, the modified electrolyte enables the Zn-V2O5 full cells to achieve excellent rate performance and cycling stability in a wide temperature range from −30 ℃ to 60 ℃. This study highlights a simple yet effective strategy for electrolyte modification using P407, providing a pathway toward the development of high-performance AZIBs with broad temperature adaptability.
2026, 37(5): 110953
doi: 10.1016/j.cclet.2025.110953
摘要:
Solvated-ion co-intercalation mechanism with high-rate capability properties makes graphite anode reconsider as optional anode for sodium-ion batteries and capacitors. The size effect has been widely investigated for various transition metal oxide materials, but such influences on the co-intercalation mechanism remain largely unexplored. In this study, natural graphite anodes with different particle sizes ranging from 25 µm to 1.7 µm for [Na(diglyme)x]+ co-interaction are systematically investigated through detailed kinetics analysis and in-situ X-ray diffraction characterization. Importantly, we find that the reaction pathways of the co-intercalation and co-extraction are quite different. The reduced graphite size results in the loss of phase transitions during the co-extraction process and then the disappearance of the sharp anodic redox peak. The small-sized graphite anodes display boosted capacitor-like responses and provide additional surface adsorption with a slightly increased capacity. Finally, a hybrid sodium-ion capacitor (SIC), using graphite anode and activated carbon cathode, is assembled without complex presodiation treatments. Such optimized hybrid SICs deliver high energy densities of 60 Wh/kg at 240 W/kg and high power density of ~16,000 W/kg with 32 Wh/kg, and ultralong 30,000 stable cycles. This work provides fundamental insights into the Na+-solvent co-intercalation mechanism with tunable capacitor-like kinetics, representing a promising direction for high-power sodium-ion storage.
Solvated-ion co-intercalation mechanism with high-rate capability properties makes graphite anode reconsider as optional anode for sodium-ion batteries and capacitors. The size effect has been widely investigated for various transition metal oxide materials, but such influences on the co-intercalation mechanism remain largely unexplored. In this study, natural graphite anodes with different particle sizes ranging from 25 µm to 1.7 µm for [Na(diglyme)x]+ co-interaction are systematically investigated through detailed kinetics analysis and in-situ X-ray diffraction characterization. Importantly, we find that the reaction pathways of the co-intercalation and co-extraction are quite different. The reduced graphite size results in the loss of phase transitions during the co-extraction process and then the disappearance of the sharp anodic redox peak. The small-sized graphite anodes display boosted capacitor-like responses and provide additional surface adsorption with a slightly increased capacity. Finally, a hybrid sodium-ion capacitor (SIC), using graphite anode and activated carbon cathode, is assembled without complex presodiation treatments. Such optimized hybrid SICs deliver high energy densities of 60 Wh/kg at 240 W/kg and high power density of ~16,000 W/kg with 32 Wh/kg, and ultralong 30,000 stable cycles. This work provides fundamental insights into the Na+-solvent co-intercalation mechanism with tunable capacitor-like kinetics, representing a promising direction for high-power sodium-ion storage.
2026, 37(5): 110954
doi: 10.1016/j.cclet.2025.110954
摘要:
High-performance electrode materials are of paramount significance for practical applications in energy storage devices, and the design of hollow-structured active electrode materials is a simple effective strategy. Herin, a three-dimensional nickel cobalt cadmium ternary sulfide hollow nanoprism material (NiCoCd-S) was successfully synthesized by combination of refluxing, hydrothermal and calcination methods. The co-existence and synergism of Ni, Co and Cd endow the material surface with abundant catalytic active sites, facilitating the progress of the reaction, enabling it to exhibit better performance than single-metal or bimetallic compounds. The unique hollow structure facilitates increased contact between the electrolyte and more electroactive sites, while the shorter diffusion pathways enable rapid ion/electron transfer rates within the material, synergistically generating enhanced supercapacitive activity. The synthesized NiCoCd-S shows a high specific capacitance (Cg) of 1643.7 F/g@1 A/g, along with a prolonged cycling life (81.6% capacitance retention after 10,000 cycles). When assembling the NiCoCd-S//AC asymmetric supercapacitor, it demonstrates an impressive energy/power density of 105.9 Wh/kg and 919.2 W/kg, respectively. After 10,000 charging-discharging cycles, the initial capacitance can still be maintained at 88.5%. The present work offers a strategy for the rational design of hollow nanostructured polymetallic sulfides with high electrochemical performance and stability.
High-performance electrode materials are of paramount significance for practical applications in energy storage devices, and the design of hollow-structured active electrode materials is a simple effective strategy. Herin, a three-dimensional nickel cobalt cadmium ternary sulfide hollow nanoprism material (NiCoCd-S) was successfully synthesized by combination of refluxing, hydrothermal and calcination methods. The co-existence and synergism of Ni, Co and Cd endow the material surface with abundant catalytic active sites, facilitating the progress of the reaction, enabling it to exhibit better performance than single-metal or bimetallic compounds. The unique hollow structure facilitates increased contact between the electrolyte and more electroactive sites, while the shorter diffusion pathways enable rapid ion/electron transfer rates within the material, synergistically generating enhanced supercapacitive activity. The synthesized NiCoCd-S shows a high specific capacitance (Cg) of 1643.7 F/g@1 A/g, along with a prolonged cycling life (81.6% capacitance retention after 10,000 cycles). When assembling the NiCoCd-S//AC asymmetric supercapacitor, it demonstrates an impressive energy/power density of 105.9 Wh/kg and 919.2 W/kg, respectively. After 10,000 charging-discharging cycles, the initial capacitance can still be maintained at 88.5%. The present work offers a strategy for the rational design of hollow nanostructured polymetallic sulfides with high electrochemical performance and stability.
2026, 37(5): 110974
doi: 10.1016/j.cclet.2025.110974
摘要:
Electrochemical NO reduction reaction (NORR) has gained extensive attention as a promising approach to achieve both harmful NO removal and ambient NH3 production. Main-group metal-based single-atom catalysts (SACs) hold great promise for electrocatalysis but still lack adequate investigation. Herein, by means of the first-principles calculations, we systematically explore the potential of main-group metal-embedded BC3 monolayer (denoted as M@VB and M@VC, M = Mg, Ca, Al, Ga, In, Ge, Sn, Sb, and Bi) as highly efficient SACs for the NORR toward NH3 synthesis. After examining the structural stability, NO adsorbability, NORR catalytic performance, and NH3 selectivity, we screen Al@VB, Ga@VB, and Ge@VC out of 18 candidate systems. Remarkably, NO can be adsorbed and activated on them with moderate ΔG*NO of -1.27~-1.90 eV, and spontaneously reduced into NH3 without any limiting potential. Moreover, the three screened candidates can effectively inhibit the production of N2O/N2 byproducts under high NO converge, as well as the competing hydrogen evolution reaction (HER). Our work not only offers several high-efficiency NORR electrocatalysts, but also guides the rational design of potential main-group metal-based SACs.
Electrochemical NO reduction reaction (NORR) has gained extensive attention as a promising approach to achieve both harmful NO removal and ambient NH3 production. Main-group metal-based single-atom catalysts (SACs) hold great promise for electrocatalysis but still lack adequate investigation. Herein, by means of the first-principles calculations, we systematically explore the potential of main-group metal-embedded BC3 monolayer (denoted as M@VB and M@VC, M = Mg, Ca, Al, Ga, In, Ge, Sn, Sb, and Bi) as highly efficient SACs for the NORR toward NH3 synthesis. After examining the structural stability, NO adsorbability, NORR catalytic performance, and NH3 selectivity, we screen Al@VB, Ga@VB, and Ge@VC out of 18 candidate systems. Remarkably, NO can be adsorbed and activated on them with moderate ΔG*NO of -1.27~-1.90 eV, and spontaneously reduced into NH3 without any limiting potential. Moreover, the three screened candidates can effectively inhibit the production of N2O/N2 byproducts under high NO converge, as well as the competing hydrogen evolution reaction (HER). Our work not only offers several high-efficiency NORR electrocatalysts, but also guides the rational design of potential main-group metal-based SACs.
2026, 37(5): 111158
doi: 10.1016/j.cclet.2025.111158
摘要:
Phenylphosphonate functionalized fully-reduced hourglass-shaped organophosphomolybdate(V) hybrid (H2bib){Ni[Mo6(PO3C6H5)4O15H6]2}·9H2O (bib = 4,4′-bis(imidazolyl)bibpheny) was synthesized as a photoelectrochemical (PEC) sensor. Benefiting from the electron transfer interaction between organic phenyl groups and inorganic {P4Mo6} skeleton, compound achieved a low detection limit of 4.61 nmol/L and high sensitivity of 264.02 µA L/µmol toward the PEC detection of levofloxacin in aqueous solution, together with excellent practicality in milk sample.
Phenylphosphonate functionalized fully-reduced hourglass-shaped organophosphomolybdate(V) hybrid (H2bib){Ni[Mo6(PO3C6H5)4O15H6]2}·9H2O (bib = 4,4′-bis(imidazolyl)bibpheny) was synthesized as a photoelectrochemical (PEC) sensor. Benefiting from the electron transfer interaction between organic phenyl groups and inorganic {P4Mo6} skeleton, compound achieved a low detection limit of 4.61 nmol/L and high sensitivity of 264.02 µA L/µmol toward the PEC detection of levofloxacin in aqueous solution, together with excellent practicality in milk sample.
2026, 37(5): 111236
doi: 10.1016/j.cclet.2025.111236
摘要:
In drug discovery, it is extremely important to identify highly potent leads with desirable drug-like profiles. Almost all the marketed phosphodiesterase 5 (PDE5) inhibitors such as sildenafil, vardenafil, and tadalafil have poor selectivity over PDE6 or PDE11 and leading to several side effects. Herein, a metabolites-based scaffold hopping strategy was performed to discover selective PDE5 inhibitors with remarkable metabolic stability. The Eu(OTf)3-catalyzed Mannich-type reaction followed by l-selectride catalyzed reduction was used to prepare chiral 2,3,3a,4,5,6-hexahydro-1H-benzo[b]pyrido[2,3,4-de][1,6] naphthyridines as novel PDE5 inhibitors with high enantioselectivity (> 99% ee and > 30:1 dr). Lead L9 exhibited a half maximal inhibitory concentration (IC50) of 1.03 nmol/L with higher selectivity (> 898-fold) over PDE6 or PDE11 than sildenafil and tadalafil, implying the potential relief from side effects. Especially, the co-crystal binding pattern of L9 with PDE5 is revealed to be different from that of sildenafil, which possibly explain the former's high selectivity. And oral administration of L9·HCl (5.0 mg/kg) exhibited better therapeutic effects than pirfenidone (150 mg/kg) in a bleomycin-induced idiopathic pulmonary fibrosis (IPF) rat model, highlighting the potential of L9·HCl for the treatment of IPF.
In drug discovery, it is extremely important to identify highly potent leads with desirable drug-like profiles. Almost all the marketed phosphodiesterase 5 (PDE5) inhibitors such as sildenafil, vardenafil, and tadalafil have poor selectivity over PDE6 or PDE11 and leading to several side effects. Herein, a metabolites-based scaffold hopping strategy was performed to discover selective PDE5 inhibitors with remarkable metabolic stability. The Eu(OTf)3-catalyzed Mannich-type reaction followed by l-selectride catalyzed reduction was used to prepare chiral 2,3,3a,4,5,6-hexahydro-1H-benzo[b]pyrido[2,3,4-de][1,6] naphthyridines as novel PDE5 inhibitors with high enantioselectivity (> 99% ee and > 30:1 dr). Lead L9 exhibited a half maximal inhibitory concentration (IC50) of 1.03 nmol/L with higher selectivity (> 898-fold) over PDE6 or PDE11 than sildenafil and tadalafil, implying the potential relief from side effects. Especially, the co-crystal binding pattern of L9 with PDE5 is revealed to be different from that of sildenafil, which possibly explain the former's high selectivity. And oral administration of L9·HCl (5.0 mg/kg) exhibited better therapeutic effects than pirfenidone (150 mg/kg) in a bleomycin-induced idiopathic pulmonary fibrosis (IPF) rat model, highlighting the potential of L9·HCl for the treatment of IPF.
2026, 37(5): 111248
doi: 10.1016/j.cclet.2025.111248
摘要:
Intracerebral hemorrhage (ICH) is a devastating subtype of stroke with high mortality and poor prognosis among survivors. Neuroinflammation after ICH plays a critical role in both secondary brain injury and repair. In the early stages of ICH, excessive activation of microglia triggers pro-inflammation, leading to the release of various pro-inflammatory cytokines that exacerbate neuronal damage and worsen neurological deficits. Pterostilbene (PTE), a natural polyphenol with potent anti-inflammatory and antioxidant properties, is an ideal neuroprotective agent. However, its clinical application is limited by poor bioavailability and low blood-brain barrier (BBB) penetrability following oral administration. Here, we developed PTE-loaded methoxy poly(ethylene glycol)-poly(ε-caprolactone) (mPEG-PCL) nanoparticles (PTE-NPs) to enhance the bioavailability of PTE and performed an intranasal delivery strategy for non-invasive and efficient transport to the ICH lesion. PTE-NPs significantly suppressed pro-inflammatory microglia activation and cytokine release, thereby reducing inflammation-mediated neuronal damage in the peri–hematomal region. In the two ICH mouse models, PTE-NPs demonstrated significant therapeutic efficacy in improving neurological function with good biosafety. This study provides a potential therapeutic strategy for the treatment of ICH and its future clinical translation.
Intracerebral hemorrhage (ICH) is a devastating subtype of stroke with high mortality and poor prognosis among survivors. Neuroinflammation after ICH plays a critical role in both secondary brain injury and repair. In the early stages of ICH, excessive activation of microglia triggers pro-inflammation, leading to the release of various pro-inflammatory cytokines that exacerbate neuronal damage and worsen neurological deficits. Pterostilbene (PTE), a natural polyphenol with potent anti-inflammatory and antioxidant properties, is an ideal neuroprotective agent. However, its clinical application is limited by poor bioavailability and low blood-brain barrier (BBB) penetrability following oral administration. Here, we developed PTE-loaded methoxy poly(ethylene glycol)-poly(ε-caprolactone) (mPEG-PCL) nanoparticles (PTE-NPs) to enhance the bioavailability of PTE and performed an intranasal delivery strategy for non-invasive and efficient transport to the ICH lesion. PTE-NPs significantly suppressed pro-inflammatory microglia activation and cytokine release, thereby reducing inflammation-mediated neuronal damage in the peri–hematomal region. In the two ICH mouse models, PTE-NPs demonstrated significant therapeutic efficacy in improving neurological function with good biosafety. This study provides a potential therapeutic strategy for the treatment of ICH and its future clinical translation.
2026, 37(5): 111257
doi: 10.1016/j.cclet.2025.111257
摘要:
Target therapy represents a paradigm shift to a precise and personalized approach. Unlike the great success of antibody-drug conjugate (ADC) in clinical practice, peptide-drug conjugate (PDC) with good tissue penetration and drug loading capacity exhibits poor stability, quick blood clearance and cellular internalization that limit their translation. In this study, a feasible approach for constructing an in vivo self-assembling peptide-drug conjugate (sPDC) was proposed by rationally designing the combination of tumor-specific targeting peptide module, responsive self-assembling peptide module, and therapeutic drug. Two optimized sPDCs (sPDC1 and sPDC2) capable of specifically targeting human epidermal growth factor receptor 2 (HER2) on the surface of tumors were reported. sPDCs could selectively target HER2-positive tumors and effectively kill HER2 overexpressing tumor cells. In addition, weak but significant efficacy of sPDCs was also observed in HER2-negative tumors, which was likely by-stander effect due to the release of monomethyl auristatin E (MMAE) in the tumor microenvironment. Finally, in HER2-positive xenograft mouse models, sPDC1 showed superior therapeutic efficacy over the clinical HER2-targeted therapeutic agents trastuzumab and lapatinib, and roughly equivalent therapeutic efficacy compared with RC48 even in large tumor-bearing mouse models. Therefore, sPDC1 was promising to serve as a lead compound for further clinical development for oncology therapy.
Target therapy represents a paradigm shift to a precise and personalized approach. Unlike the great success of antibody-drug conjugate (ADC) in clinical practice, peptide-drug conjugate (PDC) with good tissue penetration and drug loading capacity exhibits poor stability, quick blood clearance and cellular internalization that limit their translation. In this study, a feasible approach for constructing an in vivo self-assembling peptide-drug conjugate (sPDC) was proposed by rationally designing the combination of tumor-specific targeting peptide module, responsive self-assembling peptide module, and therapeutic drug. Two optimized sPDCs (sPDC1 and sPDC2) capable of specifically targeting human epidermal growth factor receptor 2 (HER2) on the surface of tumors were reported. sPDCs could selectively target HER2-positive tumors and effectively kill HER2 overexpressing tumor cells. In addition, weak but significant efficacy of sPDCs was also observed in HER2-negative tumors, which was likely by-stander effect due to the release of monomethyl auristatin E (MMAE) in the tumor microenvironment. Finally, in HER2-positive xenograft mouse models, sPDC1 showed superior therapeutic efficacy over the clinical HER2-targeted therapeutic agents trastuzumab and lapatinib, and roughly equivalent therapeutic efficacy compared with RC48 even in large tumor-bearing mouse models. Therefore, sPDC1 was promising to serve as a lead compound for further clinical development for oncology therapy.
2026, 37(5): 111274
doi: 10.1016/j.cclet.2025.111274
摘要:
The poor biofilm colonization, charge transfer, and storage at the anode have long been major obstacles to achieving high power generation in bioelectrochemical systems (BES). To overcome this challenge, we developed electrospun carbon nanofiber-interpenetrated reduced graphene oxide aerogels (CNF/rGO-x, where x denotes the mass ratio of CNF to rGO, with x = 2, 4, 6) to modify the surface of carbon cloth (CC), significantly enhancing its electrochemical performance. The CNF/rGO-6 aerogel featured a porous, interconnected conductive scaffold, endowing the CC electrode with a larger electrochemically active area, higher specific capacitance, and a rougher surface. These properties significantly improved biofilm adhesion, extracellular electron transfer, and charge storage capabilities. As a result, the BES equipped with a CNF/rGO-6 electrode achieved an impressive power density of 3080.3 mW/m2, significantly higher than those of BES with CNF/rGO-4 (2426.3 mW/m2), CNF/rGO-2 (2717 mW/m2), rGO (1978.3 mW/m2), and pure CC (1050.4 mW/m2) electrodes. Furthermore, the CNF/rGO-6 electrode supported a high abundance of electroactive bacteria and enhanced their viability. With its simple fabrication, low weight, and exceptional electrochemical performance, the CNF/rGO-6 aerogel demonstrates significant potential as an electrode material for high-performance and cost-effective BES.
The poor biofilm colonization, charge transfer, and storage at the anode have long been major obstacles to achieving high power generation in bioelectrochemical systems (BES). To overcome this challenge, we developed electrospun carbon nanofiber-interpenetrated reduced graphene oxide aerogels (CNF/rGO-x, where x denotes the mass ratio of CNF to rGO, with x = 2, 4, 6) to modify the surface of carbon cloth (CC), significantly enhancing its electrochemical performance. The CNF/rGO-6 aerogel featured a porous, interconnected conductive scaffold, endowing the CC electrode with a larger electrochemically active area, higher specific capacitance, and a rougher surface. These properties significantly improved biofilm adhesion, extracellular electron transfer, and charge storage capabilities. As a result, the BES equipped with a CNF/rGO-6 electrode achieved an impressive power density of 3080.3 mW/m2, significantly higher than those of BES with CNF/rGO-4 (2426.3 mW/m2), CNF/rGO-2 (2717 mW/m2), rGO (1978.3 mW/m2), and pure CC (1050.4 mW/m2) electrodes. Furthermore, the CNF/rGO-6 electrode supported a high abundance of electroactive bacteria and enhanced their viability. With its simple fabrication, low weight, and exceptional electrochemical performance, the CNF/rGO-6 aerogel demonstrates significant potential as an electrode material for high-performance and cost-effective BES.
2026, 37(5): 111282
doi: 10.1016/j.cclet.2025.111282
摘要:
Oral leukoplakia (OLK) is a common and representative malignant disease of oral mucosa, and possess a higher risk of cancer. Compared with traditional surgical treatment, photodynamic therapy (PDT) has great potential in OLK treatment, due to its advantages of minimally invasiveness and low toxic side effects. However, traditional photosensitizer administration suffers from short retention time due to the fluid environment of saliva and extensive tongue movement, leading to poor drug (photosensitizer) utilization and limited therapeutic outcome. To address such issue, here a photosensitive guanosine (G)-based hydrogel system (G@GQD) was constructed, in which graphene quantum dots (GQDs) featuring high photosensitization activity was loaded through three dimensional (3D) fiber network physical encapsulation. The favorable adhesion of the G@GQD hydrogel on the tongue, together with sustained GQDs release, significantly enhanced the retention of GQDs within the oral cavity. As a result, G@GQD hydrogel could continuously generate high levels of reactive oxygen species (ROS) under irradiation, demonstrating a sustained therapeutic efficiency in vitro. Compared with free GQDs, G@GQD exhibited significantly improved PDT efficiency in treating 4-nitroquinoline 1-oxide (4-NQO)-induced OLK animals. This study presented a promising strategy in overcoming the drug retention barrier that caused by saliva and tongue movement, which has far-reaching significance for the future PDT therapies.
Oral leukoplakia (OLK) is a common and representative malignant disease of oral mucosa, and possess a higher risk of cancer. Compared with traditional surgical treatment, photodynamic therapy (PDT) has great potential in OLK treatment, due to its advantages of minimally invasiveness and low toxic side effects. However, traditional photosensitizer administration suffers from short retention time due to the fluid environment of saliva and extensive tongue movement, leading to poor drug (photosensitizer) utilization and limited therapeutic outcome. To address such issue, here a photosensitive guanosine (G)-based hydrogel system (G@GQD) was constructed, in which graphene quantum dots (GQDs) featuring high photosensitization activity was loaded through three dimensional (3D) fiber network physical encapsulation. The favorable adhesion of the G@GQD hydrogel on the tongue, together with sustained GQDs release, significantly enhanced the retention of GQDs within the oral cavity. As a result, G@GQD hydrogel could continuously generate high levels of reactive oxygen species (ROS) under irradiation, demonstrating a sustained therapeutic efficiency in vitro. Compared with free GQDs, G@GQD exhibited significantly improved PDT efficiency in treating 4-nitroquinoline 1-oxide (4-NQO)-induced OLK animals. This study presented a promising strategy in overcoming the drug retention barrier that caused by saliva and tongue movement, which has far-reaching significance for the future PDT therapies.
2026, 37(5): 111284
doi: 10.1016/j.cclet.2025.111284
摘要:
Light is a powerful tool for controlling hydrogel formation and drug release, which are essential in tissue engineering and drug delivery. Achieving orthogonal control over hydrogelation and drug release using different wavelengths of light offers precise spatiotemporal regulation but is challenged by limited penetration depth and spectral crosstalk of commonly used visible light. Herein, this work develops an orthogonal light-responsive hydrogel based on dual-wavelength upconversion nanoparticles (UCNPs) for controlled hydrogelation and drug release. Upon 808 nm excitation, these UCNPs emit green light, triggering the photopolymerization of hyaluronic acid-2-aminoethyl methacrylate hydrogels. While 980 nm induces ultraviolet emission, enabling controlled and sustained drug release. Through structural design, the emissions under dual-wavelength excitation exhibit no spectral crosstalk, enabling orthogonal light control of both processes. In vitro and in vivo experiments show that both hydrogel formation and drug release processes can be finely tuned by controlling the power density and excitation durations, significantly enhancing the spatiotemporal precision of drug delivery. This orthogonal light-responsive hydrogel holds significant potential for precise, spatiotemporally controlled drug delivery.
Light is a powerful tool for controlling hydrogel formation and drug release, which are essential in tissue engineering and drug delivery. Achieving orthogonal control over hydrogelation and drug release using different wavelengths of light offers precise spatiotemporal regulation but is challenged by limited penetration depth and spectral crosstalk of commonly used visible light. Herein, this work develops an orthogonal light-responsive hydrogel based on dual-wavelength upconversion nanoparticles (UCNPs) for controlled hydrogelation and drug release. Upon 808 nm excitation, these UCNPs emit green light, triggering the photopolymerization of hyaluronic acid-2-aminoethyl methacrylate hydrogels. While 980 nm induces ultraviolet emission, enabling controlled and sustained drug release. Through structural design, the emissions under dual-wavelength excitation exhibit no spectral crosstalk, enabling orthogonal light control of both processes. In vitro and in vivo experiments show that both hydrogel formation and drug release processes can be finely tuned by controlling the power density and excitation durations, significantly enhancing the spatiotemporal precision of drug delivery. This orthogonal light-responsive hydrogel holds significant potential for precise, spatiotemporally controlled drug delivery.
PROTAC degraders of FSP1 act as potent GPX4 sensitizers to induce ferroptosis for hepatoma treatment
2026, 37(5): 111285
doi: 10.1016/j.cclet.2025.111285
摘要:
Induction of ferroptosis is a promising strategy for tumor treatment. In light of the fact that the inhibition of ferroptosis suppressor protein 1 (FSP1) can enhance the susceptibility of hepatoma cells to glutathione peroxidase 4 (GPX4) inhibitors, we hypothesized that FSP1 degraders may conspicuously improve the therapeutic efficacy of GPX4 inhibitors against hepatoma. Here, we developed a strategy using an iFSP1 analog (FSP1 inhibitor) and the pomalidomide (E3 ligase ligand) to construct proteolysis targeting chimeras (PROTACs) for degrading FSP1. Among these, C7, the first-in-class PROTAC degrader of FSP1, induced FSP1 degradation with a half-maximal degradation concentration (DC50) value of 0.66 µmol/L. The synergistic application of C7 (1 µmol/L) and the GPX4 inhibitor ML162 (100 nmol/L) markedly induced ferroptosis and effectively inhibited hepatoma cells viability. Further mechanism studies revealed that C7 targets FSP1 and down-regulates it through the ubiquitin-proteasome pathway. In vivo experiments demonstrated that the therapeutic alliance of C7 and ML162 markedly surpassed the efficacy of iFSP1 (FSP1 inhibitor) and ML162 in suppressing tumor proliferation. Collectively, these findings indicated that PROTAC degraders of FSP1 function as potent sensitizers of GPX4 inhibitors to induce ferroptosis, thus representing a promising strategy for hepatoma treatment.
Induction of ferroptosis is a promising strategy for tumor treatment. In light of the fact that the inhibition of ferroptosis suppressor protein 1 (FSP1) can enhance the susceptibility of hepatoma cells to glutathione peroxidase 4 (GPX4) inhibitors, we hypothesized that FSP1 degraders may conspicuously improve the therapeutic efficacy of GPX4 inhibitors against hepatoma. Here, we developed a strategy using an iFSP1 analog (FSP1 inhibitor) and the pomalidomide (E3 ligase ligand) to construct proteolysis targeting chimeras (PROTACs) for degrading FSP1. Among these, C7, the first-in-class PROTAC degrader of FSP1, induced FSP1 degradation with a half-maximal degradation concentration (DC50) value of 0.66 µmol/L. The synergistic application of C7 (1 µmol/L) and the GPX4 inhibitor ML162 (100 nmol/L) markedly induced ferroptosis and effectively inhibited hepatoma cells viability. Further mechanism studies revealed that C7 targets FSP1 and down-regulates it through the ubiquitin-proteasome pathway. In vivo experiments demonstrated that the therapeutic alliance of C7 and ML162 markedly surpassed the efficacy of iFSP1 (FSP1 inhibitor) and ML162 in suppressing tumor proliferation. Collectively, these findings indicated that PROTAC degraders of FSP1 function as potent sensitizers of GPX4 inhibitors to induce ferroptosis, thus representing a promising strategy for hepatoma treatment.
2026, 37(5): 111291
doi: 10.1016/j.cclet.2025.111291
摘要:
Decellularized amniotic membrane (dAM) holds significant potential in tissue engineering; however, its inherent mechanical limitations and rapid degradation hinder its clinical translation. This study integrates dAM with high molecular weight polymer polycaprolactone (PCL) and natural gelatin (Gel) nanofibers using electrospinning technology and a 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) covalent crosslinking system to produce two composite biomaterials. Both PCL-dAM and Gel-dAM composites demonstrate enhanced strain, tensile strength, and elasticity compared to pure dAM, showcasing improved mechanical properties and significantly reduced degradation rates, with Gel-dAM exhibiting superior overall performance. Gel-dAM also shows considerably better compatibility with fibroblasts, macrophages, and tendon stem cells than PCL-dAM, suggesting that it more effectively supports cell adhesion, proliferation, and differentiation, thus providing a more favorable microenvironment for tissue repair. In macrophage immune modulation, Gel-dAM significantly promotes the polarization of macrophages toward the M2 phenotype, exhibiting potential anti-inflammatory and repair-enhancing effects, thereby offering new insights into the use of dAM in tissue regeneration. These advancements open new possibilities for the clinical application of dAM, particularly in tissue repair and wound dressing.
Decellularized amniotic membrane (dAM) holds significant potential in tissue engineering; however, its inherent mechanical limitations and rapid degradation hinder its clinical translation. This study integrates dAM with high molecular weight polymer polycaprolactone (PCL) and natural gelatin (Gel) nanofibers using electrospinning technology and a 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) covalent crosslinking system to produce two composite biomaterials. Both PCL-dAM and Gel-dAM composites demonstrate enhanced strain, tensile strength, and elasticity compared to pure dAM, showcasing improved mechanical properties and significantly reduced degradation rates, with Gel-dAM exhibiting superior overall performance. Gel-dAM also shows considerably better compatibility with fibroblasts, macrophages, and tendon stem cells than PCL-dAM, suggesting that it more effectively supports cell adhesion, proliferation, and differentiation, thus providing a more favorable microenvironment for tissue repair. In macrophage immune modulation, Gel-dAM significantly promotes the polarization of macrophages toward the M2 phenotype, exhibiting potential anti-inflammatory and repair-enhancing effects, thereby offering new insights into the use of dAM in tissue regeneration. These advancements open new possibilities for the clinical application of dAM, particularly in tissue repair and wound dressing.
2026, 37(5): 111292
doi: 10.1016/j.cclet.2025.111292
摘要:
Patchouli oil (PAO), a traditional herbal remedy with notable anti-inflammatory properties, has demonstrated significant therapeutic potential in gastrointestinal diseases. However, its instability in acidic environments and low bioavailability hinder PAO's clinical application. In this study, we developed a pharmaceutical solid-state form of PAO using a β-cyclodextrin (βCD)-based inclusion cocrystal technology, thus obtaining PAO-βCD cocrystals. PAO-βCD cocrystals exhibited enhanced dissolution and stability. We further encapsulated them in pH-sensitive Eudragit-coated pellets (PAO-βCD@pellet) to achieve site-specific delivery of PAO to the inflamed colon. In vivo results from the dextran sulfate sodium salt (DSS)-induced colitis mouse model showed that PAO-βCD@pellet significantly improved the colonic release of PAO, as evidenced by fluorescence tracking and quantitative analysis of patchouli alcohol, the main active compound of PAO. Furthermore, PAO-βCD@pellet demonstrated superior therapeutic efficacy, reducing disease activity index, preventing intestinal barrier damage, and modulating the gut microbiome. Histological examination confirmed alleviating intestinal epithelial cell damage caused by oxidative stress and inflammation. These findings suggest that PAO-βCD@pellet offers a promising targeted treatment strategy for inflammatory bowel disease (IBD) with enhanced stability, bioavailability, and therapeutic outcomes.
Patchouli oil (PAO), a traditional herbal remedy with notable anti-inflammatory properties, has demonstrated significant therapeutic potential in gastrointestinal diseases. However, its instability in acidic environments and low bioavailability hinder PAO's clinical application. In this study, we developed a pharmaceutical solid-state form of PAO using a β-cyclodextrin (βCD)-based inclusion cocrystal technology, thus obtaining PAO-βCD cocrystals. PAO-βCD cocrystals exhibited enhanced dissolution and stability. We further encapsulated them in pH-sensitive Eudragit-coated pellets (PAO-βCD@pellet) to achieve site-specific delivery of PAO to the inflamed colon. In vivo results from the dextran sulfate sodium salt (DSS)-induced colitis mouse model showed that PAO-βCD@pellet significantly improved the colonic release of PAO, as evidenced by fluorescence tracking and quantitative analysis of patchouli alcohol, the main active compound of PAO. Furthermore, PAO-βCD@pellet demonstrated superior therapeutic efficacy, reducing disease activity index, preventing intestinal barrier damage, and modulating the gut microbiome. Histological examination confirmed alleviating intestinal epithelial cell damage caused by oxidative stress and inflammation. These findings suggest that PAO-βCD@pellet offers a promising targeted treatment strategy for inflammatory bowel disease (IBD) with enhanced stability, bioavailability, and therapeutic outcomes.
2026, 37(5): 111318
doi: 10.1016/j.cclet.2025.111318
摘要:
Alzheimer's disease (AD) is a chronic, progressive neurodegenerative disorder with no effective therapeutic agents currently available. Inhibiting phosphodiesterase 4 (PDE4) has emerged as a promising strategy for AD treatment. In this study, we employed a synergistic approach combining generative recurrent neural network (RNN)-driven combinatorial compound design, virtual screening, and structure-activity relationship (SAR) analysis to discover novel PDE4 inhibitors. Utilizing α-mangostin as a hit compound (half maximal inhibitory concentration (IC50) = 1.31 µmol/L), we identified a novel PDE4 inhibitor, 13d (IC50 = 72.8 nmol/L) with moderate liver microsomal stability (rat liver microsomes (RLM), t1/2 = 32.4 min). In vitro activity results indicated that 13d exhibited favorable anti-inflammatory effects and promising neuroprotective activity. In vivo experiments demonstrated that 13d significantly improved AlCl3-induced zebrafish AD model by inhibiting PDE4 and reducing inflammatory cytokine. Further, 13d significantly alleviated AlCl3/d-galactose-induced AD mouse model. These findings highlight the potent PDE4 inhibitor 13d with promising anti-AD activity, underscoring the potential of artificial intelligence-driven drug discovery for novel therapeutic agents for AD.
Alzheimer's disease (AD) is a chronic, progressive neurodegenerative disorder with no effective therapeutic agents currently available. Inhibiting phosphodiesterase 4 (PDE4) has emerged as a promising strategy for AD treatment. In this study, we employed a synergistic approach combining generative recurrent neural network (RNN)-driven combinatorial compound design, virtual screening, and structure-activity relationship (SAR) analysis to discover novel PDE4 inhibitors. Utilizing α-mangostin as a hit compound (half maximal inhibitory concentration (IC50) = 1.31 µmol/L), we identified a novel PDE4 inhibitor, 13d (IC50 = 72.8 nmol/L) with moderate liver microsomal stability (rat liver microsomes (RLM), t1/2 = 32.4 min). In vitro activity results indicated that 13d exhibited favorable anti-inflammatory effects and promising neuroprotective activity. In vivo experiments demonstrated that 13d significantly improved AlCl3-induced zebrafish AD model by inhibiting PDE4 and reducing inflammatory cytokine. Further, 13d significantly alleviated AlCl3/d-galactose-induced AD mouse model. These findings highlight the potent PDE4 inhibitor 13d with promising anti-AD activity, underscoring the potential of artificial intelligence-driven drug discovery for novel therapeutic agents for AD.
2026, 37(5): 111324
doi: 10.1016/j.cclet.2025.111324
摘要:
Tumor-associated carbohydrate antigen (TACA)-based cancer vaccines face clinical challenges due to heterogeneous TACA expression, which compromises antibody-mediated tumor recognition and leads to suboptimal therapeutic outcomes. To address this limitation, we report a combined strategy that integrates vaccination with TACA-based antibody-recruiting molecules. This approach simultaneously redirects anti-TACA antibodies to tumor cells expressing a secondary target, thereby enhancing the efficacy of TACA-based vaccines. Using sialyl-Tn (sTn) as a model TACA and epidermal growth factor receptor (EGFR) and human epidermal growth factor receptor 2 (HER2) as model protein targets, we designed two nanobody (Nb)-sTn conjugates as TACA-based antibody-recruiting molecules: EGFR-targeting 7D12-sTn and HER2-targeting C7b-sTn. These conjugates were synthesized via sortase A-mediated ligation and demonstrated strong binding profiles. Importantly, they effectively redirected anti-sTn antibodies, generated by the Theratope vaccine, to target cells in situ, significantly improving the recognition of tumor cells by anti-sTn antibodies. The synergistic potential of these conjugates in amplifying the therapeutic effect of the sTn-KLH vaccine was further validated through complement-dependent cytotoxicity assays. This innovative strategy represents a highly promising approach to overcome the clinical challenges posed by TACA heterogeneity in cancer vaccine development.
Tumor-associated carbohydrate antigen (TACA)-based cancer vaccines face clinical challenges due to heterogeneous TACA expression, which compromises antibody-mediated tumor recognition and leads to suboptimal therapeutic outcomes. To address this limitation, we report a combined strategy that integrates vaccination with TACA-based antibody-recruiting molecules. This approach simultaneously redirects anti-TACA antibodies to tumor cells expressing a secondary target, thereby enhancing the efficacy of TACA-based vaccines. Using sialyl-Tn (sTn) as a model TACA and epidermal growth factor receptor (EGFR) and human epidermal growth factor receptor 2 (HER2) as model protein targets, we designed two nanobody (Nb)-sTn conjugates as TACA-based antibody-recruiting molecules: EGFR-targeting 7D12-sTn and HER2-targeting C7b-sTn. These conjugates were synthesized via sortase A-mediated ligation and demonstrated strong binding profiles. Importantly, they effectively redirected anti-sTn antibodies, generated by the Theratope vaccine, to target cells in situ, significantly improving the recognition of tumor cells by anti-sTn antibodies. The synergistic potential of these conjugates in amplifying the therapeutic effect of the sTn-KLH vaccine was further validated through complement-dependent cytotoxicity assays. This innovative strategy represents a highly promising approach to overcome the clinical challenges posed by TACA heterogeneity in cancer vaccine development.
2026, 37(5): 111334
doi: 10.1016/j.cclet.2025.111334
摘要:
The rapid proliferation of tumor cells is driven by metabolic reprogramming and redox regulation. Real-time monitoring of glutathione (GSH)/adenosine-5′-triphosphate (ATP) provides a dynamic perspective for tumor metabolism and is crucial for guiding precision treatment. We report a dual-site activatable fluorescent probe M901 for simultaneously detecting GSH and ATP without spectral overlap, and the detection range (GSH: 0–7 mmol/L, ATP: 0–6.5 mmol/L) matching the physiological concentration range. Based on this, M901 visualizes a bidirectional regulatory relationship between ATP synthesis↓ (energy imbalance) ↔ electron transport chain dysfunction ↔ reactive oxygen species (ROS)↑ ↔ GSH↓ (oxidative stress). Additionally, M901 reveals for the first time the dynamic compensatory mechanism between GSH and ATP in cellular oxidative stress induced by the inhibition of solute carrier family 7 member 11 (SLC7A11) or glutathione peroxidase 4 (GPX4). In vivo imaging further confirms oxidative stress and mitochondrial dysfunction are core pathological mechanisms leading to liver injury, with treatment efficacy positively correlated with GSH/ATP levels. Importantly, the dynamic visualization of GSH/ATP by M901 enables real-time evaluation of the anti-tumor effects of ferroptosis inducers and cisplatin, guiding successful precision resection of invasive malignant tumors (negative margins <0.2 mm). This study confirms the potential of M901 as a clinical visualization tool for diagnosing, treating and monitoring a variety of diseases.
The rapid proliferation of tumor cells is driven by metabolic reprogramming and redox regulation. Real-time monitoring of glutathione (GSH)/adenosine-5′-triphosphate (ATP) provides a dynamic perspective for tumor metabolism and is crucial for guiding precision treatment. We report a dual-site activatable fluorescent probe M901 for simultaneously detecting GSH and ATP without spectral overlap, and the detection range (GSH: 0–7 mmol/L, ATP: 0–6.5 mmol/L) matching the physiological concentration range. Based on this, M901 visualizes a bidirectional regulatory relationship between ATP synthesis↓ (energy imbalance) ↔ electron transport chain dysfunction ↔ reactive oxygen species (ROS)↑ ↔ GSH↓ (oxidative stress). Additionally, M901 reveals for the first time the dynamic compensatory mechanism between GSH and ATP in cellular oxidative stress induced by the inhibition of solute carrier family 7 member 11 (SLC7A11) or glutathione peroxidase 4 (GPX4). In vivo imaging further confirms oxidative stress and mitochondrial dysfunction are core pathological mechanisms leading to liver injury, with treatment efficacy positively correlated with GSH/ATP levels. Importantly, the dynamic visualization of GSH/ATP by M901 enables real-time evaluation of the anti-tumor effects of ferroptosis inducers and cisplatin, guiding successful precision resection of invasive malignant tumors (negative margins <0.2 mm). This study confirms the potential of M901 as a clinical visualization tool for diagnosing, treating and monitoring a variety of diseases.
2026, 37(5): 111336
doi: 10.1016/j.cclet.2025.111336
摘要:
Molecular networking-guided chemical investigation of the Euphorbia endophyte Malbranchea umbrina D16 led to the isolation of 14 novel unusually cyclized triterpenoids (UCT) involving three different skeletal types. Compounds 1–10 are tricyclic triterpenoids featuring a 1-cyclohexyloctahydro-1H-indene core, in which 1 incoporates an unusual 7,7-dimethyl-6,8-dioxabicyclo[3.1.2]octane motif. Compounds 11–13 represent a rare class of bicyclic triterpenes (6/5 ring system) containing various O-heterocycles at the side chain. Compound 14 is an acyclic triterpenoid with O-heterocycles at both ends. Their structures were assigned by spectroscopic, chemical, computational, and crystallographic means, which also allowed the stereochemical revisions of three previously reported analogues. Compound 1 significantly inhibited the adipogenesis in 3T3-L1 adipocytes via activating the AMP-activated protein kinase (AMPK) signalling.
Molecular networking-guided chemical investigation of the Euphorbia endophyte Malbranchea umbrina D16 led to the isolation of 14 novel unusually cyclized triterpenoids (UCT) involving three different skeletal types. Compounds 1–10 are tricyclic triterpenoids featuring a 1-cyclohexyloctahydro-1H-indene core, in which 1 incoporates an unusual 7,7-dimethyl-6,8-dioxabicyclo[3.1.2]octane motif. Compounds 11–13 represent a rare class of bicyclic triterpenes (6/5 ring system) containing various O-heterocycles at the side chain. Compound 14 is an acyclic triterpenoid with O-heterocycles at both ends. Their structures were assigned by spectroscopic, chemical, computational, and crystallographic means, which also allowed the stereochemical revisions of three previously reported analogues. Compound 1 significantly inhibited the adipogenesis in 3T3-L1 adipocytes via activating the AMP-activated protein kinase (AMPK) signalling.
2026, 37(5): 111337
doi: 10.1016/j.cclet.2025.111337
摘要:
Ferroptosis is a cell death pathway that plays a crucial role in numerous biological processes. Although closely related to ferrous ion, the execution of ferroptosis was found to be impacted by zinc ion (Zn2+) in recent years. However, most of the related researches focused on the effects of exogenously added Zn2+, while the fundamental understanding of endogenous Zn2+ during ferroptosis still needs further exploration. Herein, a ratiometric fluorescent probe based on pyridine-substituted boron dipyrromethene (BODIPY) fluorophore (BDP-p) was designed to track the endogenous Zn2+ in cells during ferroptosis process. Zn2+ coordination induced an enhancement on the intramolecular charge transfer (ICT), leading to an obvious red shift from 563 nm to 594 nm. In A549 cells, we found fluorescence ratio of the probe elevated in some discrete regions during erastin induced ferroptosis, and this change followed the same trend as the reactive oxygen species (ROS) level. The results suggested that the Zn2+ would be localized in some discrete areas in A549 cells during ferroptosis. This work not only provided a reliable design strategy for developing ratiometric probes of Zn2+, but also supplemented the current understanding of the non-negligible role of Zn2+ in ferroptosis.
Ferroptosis is a cell death pathway that plays a crucial role in numerous biological processes. Although closely related to ferrous ion, the execution of ferroptosis was found to be impacted by zinc ion (Zn2+) in recent years. However, most of the related researches focused on the effects of exogenously added Zn2+, while the fundamental understanding of endogenous Zn2+ during ferroptosis still needs further exploration. Herein, a ratiometric fluorescent probe based on pyridine-substituted boron dipyrromethene (BODIPY) fluorophore (BDP-p) was designed to track the endogenous Zn2+ in cells during ferroptosis process. Zn2+ coordination induced an enhancement on the intramolecular charge transfer (ICT), leading to an obvious red shift from 563 nm to 594 nm. In A549 cells, we found fluorescence ratio of the probe elevated in some discrete regions during erastin induced ferroptosis, and this change followed the same trend as the reactive oxygen species (ROS) level. The results suggested that the Zn2+ would be localized in some discrete areas in A549 cells during ferroptosis. This work not only provided a reliable design strategy for developing ratiometric probes of Zn2+, but also supplemented the current understanding of the non-negligible role of Zn2+ in ferroptosis.
2026, 37(5): 111338
doi: 10.1016/j.cclet.2025.111338
摘要:
Bacteria and stains on tooth and various dental materials severely harm dental health and beauty and require feasible solutions. In this study, a simple strategy was developed to produce nano-coating on different substrates for persistent antibacterial and whitening. The coating is formed by the lysozyme (Lys), hemoglobin (Hb), and glucose oxidase (GOD) via co-assembly, in which the phase transition of Lys initiated the co-assembly to anchor other two proteins. During therapy, the GOD continuously oxidizes glucose in the oral environment to cut off the nutrition of bacteria meanwhile generating H2O2, which would be further catalyzed by the ferrous ions in Hb to produce reactive oxygen species (ROS) for effective decomposition of surrounding bacteria and stains. Moreover, the Hb can perform persistent release of oxygen, which not only enhances the efficiency of glucose oxidation to produce more ROS but directly suppresses anaerobic bacteria via reversing the local hypoxia environment in the mouth. The experimental results indicated that our strategy is able to form nano-film of proteins both on the surface of dental orthosis and human tooth, which further causes obvious reduction of the bacteria not only on the coated substrate but in the surrounding tissue with up to 100% of the bacteriostatic rate. In addition, both the dental orthosis and human tooth were also rapidly cleaned due to the local ROS generation, leading to a sustained anti-staining property in the long term.
Bacteria and stains on tooth and various dental materials severely harm dental health and beauty and require feasible solutions. In this study, a simple strategy was developed to produce nano-coating on different substrates for persistent antibacterial and whitening. The coating is formed by the lysozyme (Lys), hemoglobin (Hb), and glucose oxidase (GOD) via co-assembly, in which the phase transition of Lys initiated the co-assembly to anchor other two proteins. During therapy, the GOD continuously oxidizes glucose in the oral environment to cut off the nutrition of bacteria meanwhile generating H2O2, which would be further catalyzed by the ferrous ions in Hb to produce reactive oxygen species (ROS) for effective decomposition of surrounding bacteria and stains. Moreover, the Hb can perform persistent release of oxygen, which not only enhances the efficiency of glucose oxidation to produce more ROS but directly suppresses anaerobic bacteria via reversing the local hypoxia environment in the mouth. The experimental results indicated that our strategy is able to form nano-film of proteins both on the surface of dental orthosis and human tooth, which further causes obvious reduction of the bacteria not only on the coated substrate but in the surrounding tissue with up to 100% of the bacteriostatic rate. In addition, both the dental orthosis and human tooth were also rapidly cleaned due to the local ROS generation, leading to a sustained anti-staining property in the long term.
2026, 37(5): 111343
doi: 10.1016/j.cclet.2025.111343
摘要:
Molecular glass refers to amorphous rigid small molecules with certain polymer-like properties. Herein, spirobixanthene is first adopted as the backbone to develop negative photoresist X4Ep with four epoxy moieties. F4Ep based on classical spirobifluorene is also synthesized as a benchmark against X4Ep. Both exhibit good thermostability and similar sensitivity. However, in e-beam lithography, performances of X4Ep completely surpass F4Ep. F4Ep lithography shows inevitably minor bridges no matter how we optimize process conditions. The relatively poor performances of F4Ep may be probably ascribed to its partial crystallization tendency inducing uneven photoacid generator (PAG) distribution and uneven acid diffusion, which thus promotes nonuniform epoxy crosslink to form rough patterns. X4Ep readily achieves dense lines without any defects. The superiority of X4Ep to F4Ep can be ascribed to the exceptional yet apparent structural distortion and asymmetry of spirobixanthene, which guarantees a perfect amorphous state and uniform crosslink. Finally, the optimal line/space (L/S) pattern with half pitch (HP) of 25 nm and line edge roughness (LER) of 2.7 nm is achieved. Therefore, spirobixanthene is a valuable molecular glass backbone for high-performance photoresists in the future.
Molecular glass refers to amorphous rigid small molecules with certain polymer-like properties. Herein, spirobixanthene is first adopted as the backbone to develop negative photoresist X4Ep with four epoxy moieties. F4Ep based on classical spirobifluorene is also synthesized as a benchmark against X4Ep. Both exhibit good thermostability and similar sensitivity. However, in e-beam lithography, performances of X4Ep completely surpass F4Ep. F4Ep lithography shows inevitably minor bridges no matter how we optimize process conditions. The relatively poor performances of F4Ep may be probably ascribed to its partial crystallization tendency inducing uneven photoacid generator (PAG) distribution and uneven acid diffusion, which thus promotes nonuniform epoxy crosslink to form rough patterns. X4Ep readily achieves dense lines without any defects. The superiority of X4Ep to F4Ep can be ascribed to the exceptional yet apparent structural distortion and asymmetry of spirobixanthene, which guarantees a perfect amorphous state and uniform crosslink. Finally, the optimal line/space (L/S) pattern with half pitch (HP) of 25 nm and line edge roughness (LER) of 2.7 nm is achieved. Therefore, spirobixanthene is a valuable molecular glass backbone for high-performance photoresists in the future.
2026, 37(5): 111347
doi: 10.1016/j.cclet.2025.111347
摘要:
Layered double hydroxides (LDHs) hold great promise for flexible solid-state supercapacitors owing to their high theoretical capacitance and distinctive architecture. However, their proneness to agglomeration and poor electrical conductivity have long hindered the manifestation of outstanding electrochemical performance. In a groundbreaking approach, we have engineered a hierarchical carbon nanofiber-based NiCo2S4/NiCo-LDH/C nanostructure array. The meticulously crafted hierarchical structure not only imparts remarkable stability to the electrode but also ingeniously harnesses the synergistic interplay among materials. Through density functional theory calculations, we have precisely identified and verified the active sites for charge transfer, unveiling a new understanding of the underlying mechanisms. This unique structure significantly facilitates ion transfer in the vicinity of NiCo-LDH, substantially elevates electrical conductivity, and notably increases the adsorption capacity of OH-. Moreover, it gives a substantial boost to the quantum capacitance. As a result, the electrode showcases a high specific capacitance of 1838.3 F/g. This research pioneers an effective and versatile strategy that can be readily applied to the majority of LDHs, opening up new avenues for enhancing their efficiency of supercapacitor materials.
Layered double hydroxides (LDHs) hold great promise for flexible solid-state supercapacitors owing to their high theoretical capacitance and distinctive architecture. However, their proneness to agglomeration and poor electrical conductivity have long hindered the manifestation of outstanding electrochemical performance. In a groundbreaking approach, we have engineered a hierarchical carbon nanofiber-based NiCo2S4/NiCo-LDH/C nanostructure array. The meticulously crafted hierarchical structure not only imparts remarkable stability to the electrode but also ingeniously harnesses the synergistic interplay among materials. Through density functional theory calculations, we have precisely identified and verified the active sites for charge transfer, unveiling a new understanding of the underlying mechanisms. This unique structure significantly facilitates ion transfer in the vicinity of NiCo-LDH, substantially elevates electrical conductivity, and notably increases the adsorption capacity of OH-. Moreover, it gives a substantial boost to the quantum capacitance. As a result, the electrode showcases a high specific capacitance of 1838.3 F/g. This research pioneers an effective and versatile strategy that can be readily applied to the majority of LDHs, opening up new avenues for enhancing their efficiency of supercapacitor materials.
2026, 37(5): 111350
doi: 10.1016/j.cclet.2025.111350
摘要:
The advent of the most representative commercially available formulations of paclitaxel, Taxol and Abraxane®, resolved the intravenous challenge of paclitaxel by increasing the water solubility. However, the severe excipient-related toxicity and poor stability of Taxol, along with the low drug loading (10%), complex preparation processes, and poor tumor selectivity of Abraxane®, present significant clinical dilemma. To overcome the challenges, 16-methylheptadecanoic acid (16-MH), with excellent biocompatibility was selected as the assembly module. The paclitaxel-16-MH prodrug nanoassemblies (PSSMH NPs) were constructed by conjugating 16-MH with redox-sensitive disulfide bonds and paclitaxel through an ethylene glycol. PSSMH NPs featured the advantages of easy preparation, high drug loading (> 50%) and superior stability (stable storage for 60 days at 25 ℃). Notably, the area under the concentration−time curve (AUC0–24 h) of PSSMH NPs was 14.95-fold compared with Taxol, indicating a significant improvement in the in vivo fate of paclitaxel. Moreover, the existence of redox-sensitive disulfide bonds endowed PSSMH NPs with increased tumor selectivity, resulting in exceptional tolerance and antitumor efficacy. Overall, the redox-triggered prodrug nano-system with high tumor selectivity and biocompatibility exhibits substantial potential for clinical translation.
The advent of the most representative commercially available formulations of paclitaxel, Taxol and Abraxane®, resolved the intravenous challenge of paclitaxel by increasing the water solubility. However, the severe excipient-related toxicity and poor stability of Taxol, along with the low drug loading (10%), complex preparation processes, and poor tumor selectivity of Abraxane®, present significant clinical dilemma. To overcome the challenges, 16-methylheptadecanoic acid (16-MH), with excellent biocompatibility was selected as the assembly module. The paclitaxel-16-MH prodrug nanoassemblies (PSSMH NPs) were constructed by conjugating 16-MH with redox-sensitive disulfide bonds and paclitaxel through an ethylene glycol. PSSMH NPs featured the advantages of easy preparation, high drug loading (> 50%) and superior stability (stable storage for 60 days at 25 ℃). Notably, the area under the concentration−time curve (AUC0–24 h) of PSSMH NPs was 14.95-fold compared with Taxol, indicating a significant improvement in the in vivo fate of paclitaxel. Moreover, the existence of redox-sensitive disulfide bonds endowed PSSMH NPs with increased tumor selectivity, resulting in exceptional tolerance and antitumor efficacy. Overall, the redox-triggered prodrug nano-system with high tumor selectivity and biocompatibility exhibits substantial potential for clinical translation.
2026, 37(5): 111356
doi: 10.1016/j.cclet.2025.111356
摘要:
The escalating threat of antimicrobial resistance necessitates advanced tools for rapid and selective antibiotic detection in environmental systems. Herein, we report polyphenol-derived carbon dots (P-CDs) synthesized via a one-step solvothermal method using polyphenols and citric acid, enabling dual-mode detection of tetracyclines and quinolones through pH-tunable fluorescence. The P-CDs exhibit distinct fluorescence quenching for tetracyclines (e.g., oxytetracycline (OTC)) and enhancement for quinolones (e.g., norfloxacin (NOR)), driven by synergistic multiple molecular interactions facilitated by surface phenolic groups. With detection limits of 8.19 µmol/L (OTC) and 5.27 µmol/L (NOR), P-CDs achieve 6-fold higher sensitivity compared to conventional carbon dots. Their pH adaptability (pH 2–12), specificity (> 90% selectivity against seven antibiotic classes), and robust performance in real water matrices (e.g., river water and wastewater) underscore their potential as eco-friendly sensors for on-site environmental monitoring. This work highlights a versatile platform to address antibiotic contamination and advance public health safety.
The escalating threat of antimicrobial resistance necessitates advanced tools for rapid and selective antibiotic detection in environmental systems. Herein, we report polyphenol-derived carbon dots (P-CDs) synthesized via a one-step solvothermal method using polyphenols and citric acid, enabling dual-mode detection of tetracyclines and quinolones through pH-tunable fluorescence. The P-CDs exhibit distinct fluorescence quenching for tetracyclines (e.g., oxytetracycline (OTC)) and enhancement for quinolones (e.g., norfloxacin (NOR)), driven by synergistic multiple molecular interactions facilitated by surface phenolic groups. With detection limits of 8.19 µmol/L (OTC) and 5.27 µmol/L (NOR), P-CDs achieve 6-fold higher sensitivity compared to conventional carbon dots. Their pH adaptability (pH 2–12), specificity (> 90% selectivity against seven antibiotic classes), and robust performance in real water matrices (e.g., river water and wastewater) underscore their potential as eco-friendly sensors for on-site environmental monitoring. This work highlights a versatile platform to address antibiotic contamination and advance public health safety.
2026, 37(5): 111381
doi: 10.1016/j.cclet.2025.111381
摘要:
Natural products bearing a bicyclo[3.2.2]nonane motif pose a considerable challenge to chemical synthesis. We developed a europium-promoted inverse-electron-demand Diels–Alder reaction of benzo[2,3]tropone derivatives with electron-rich olefins, which offers an expeditious approach to densely substituted bicyclo[3.2.2]nonanes. This method enabled the concise synthesis of a tetracyclic amine, subsequently identified as a downstream suppressor of autophagy.
Natural products bearing a bicyclo[3.2.2]nonane motif pose a considerable challenge to chemical synthesis. We developed a europium-promoted inverse-electron-demand Diels–Alder reaction of benzo[2,3]tropone derivatives with electron-rich olefins, which offers an expeditious approach to densely substituted bicyclo[3.2.2]nonanes. This method enabled the concise synthesis of a tetracyclic amine, subsequently identified as a downstream suppressor of autophagy.
2026, 37(5): 111399
doi: 10.1016/j.cclet.2025.111399
摘要:
Immunotherapy has emerged as a promising strategy for combating tumor metastasis and recurrence, however, its efficacy is often hampered by the immunosuppressive tumor microenvironment (TME). The integration of nanomedicine-based photothermal therapy (PTT) with immunotherapy offers great potential to reshape the immune landscape, thereby enhancing immune responses and therapeutic outcomes. Nevertheless, conventional hyperthermia may induce heat-related damage and excessive inflammation in normal tissues. To address this challenge, we developed a novel therapeutic platform that combines tumor-specific delivery of melittin (MLT) with mild PTT using two-dimensional palladium nanosheets (Pd NSs). This approach allows for selective accumulation of MLT at tumor sites via the enhanced permeability and retention (EPR) effect and TME-responsive release, thereby maximizing antitumor efficacy while minimizing off-target toxicity. The resulting nanocomposite, MLT@Pd@PEG, exhibits excellent biocompatibility and efficient photothermal conversion under 808 nm laser irradiation. The acidic pH and localized heat in the TME synergistically trigger the controlled release of MLT, which disrupts cancer cell membranes and promotes tumor cell apoptosis. Moreover, this treatment facilitates the release of tumor-associated antigens and danger-associated molecular patterns (DAMPs), thereby activating cytotoxic T lymphocytes and natural killer (NK) cells. In vivo studies demonstrate that the combination of immune checkpoint blockade and MLT@Pd@PEG not only eradicates primary and distant tumors in bilateral tumor-bearing mouse models but also prevents tumor recurrence and metastasis by inducing durable immune memory. This comprehensive strategy integrating precise MLT delivery with mild PTT holds significant promise for advancing next-generation cancer immunotherapy.
Immunotherapy has emerged as a promising strategy for combating tumor metastasis and recurrence, however, its efficacy is often hampered by the immunosuppressive tumor microenvironment (TME). The integration of nanomedicine-based photothermal therapy (PTT) with immunotherapy offers great potential to reshape the immune landscape, thereby enhancing immune responses and therapeutic outcomes. Nevertheless, conventional hyperthermia may induce heat-related damage and excessive inflammation in normal tissues. To address this challenge, we developed a novel therapeutic platform that combines tumor-specific delivery of melittin (MLT) with mild PTT using two-dimensional palladium nanosheets (Pd NSs). This approach allows for selective accumulation of MLT at tumor sites via the enhanced permeability and retention (EPR) effect and TME-responsive release, thereby maximizing antitumor efficacy while minimizing off-target toxicity. The resulting nanocomposite, MLT@Pd@PEG, exhibits excellent biocompatibility and efficient photothermal conversion under 808 nm laser irradiation. The acidic pH and localized heat in the TME synergistically trigger the controlled release of MLT, which disrupts cancer cell membranes and promotes tumor cell apoptosis. Moreover, this treatment facilitates the release of tumor-associated antigens and danger-associated molecular patterns (DAMPs), thereby activating cytotoxic T lymphocytes and natural killer (NK) cells. In vivo studies demonstrate that the combination of immune checkpoint blockade and MLT@Pd@PEG not only eradicates primary and distant tumors in bilateral tumor-bearing mouse models but also prevents tumor recurrence and metastasis by inducing durable immune memory. This comprehensive strategy integrating precise MLT delivery with mild PTT holds significant promise for advancing next-generation cancer immunotherapy.
2026, 37(5): 111401
doi: 10.1016/j.cclet.2025.111401
摘要:
In the treatment of B-cell lymphoma, chemotherapy as a monotherapy encounters significant challenges like drug resistance, side effects, and limited cytotoxicity. A novel strategy combining chemotherapy and photothermal therapy uses nanomaterials to convert light into heat, locally heating tumor tissues to induce thermal ablation while enhancing the effectiveness of chemotherapeutic agents and reducing toxic side effects on normal cells. Here, we developed a multifunctional black phosphorus nanosheets (BP NSs) for chemo-photothermal synergistic therapy of lymphoma. BP NSs were synthesized from bulk black phosphorus crystal powders utilizing a modified liquid exfoliation technique and functionalized with polyethylene glycol (PEG) to improve stability. The PEGylated BP NSs were loaded with two chemotherapeutic agents, gemcitabine (Gem) and doxorubicin (DOX), forming GD-BP@PEG NSs. The nanosheets exhibit excellent physical stability, efficient photothermal conversion, and pH/near-infrared (NIR) dual-responsive drug release. In vitro cell experiments demonstrated that GD-BP@PEG NSs significantly increased cytotoxicity and apoptosis, especially with NIR laser irradiation. Furthermore, in vivo studies in A20 lymphoma-bearing BALB/c nude mice revealed GD-BP@PEG NSs passively accumulated with high concentrations at the tumor site, efficiently inhibiting lymphoma growth with minimal systemic toxicity, demonstrating significant advantages over single treatments of chemotherapy or photothermal therapy alone. In summary, this pH/NIR dual-triggered BP NSs system could serve as a promising nanoplatform for chemo-photothermal synergistic treatment of B-cell lymphoma.
In the treatment of B-cell lymphoma, chemotherapy as a monotherapy encounters significant challenges like drug resistance, side effects, and limited cytotoxicity. A novel strategy combining chemotherapy and photothermal therapy uses nanomaterials to convert light into heat, locally heating tumor tissues to induce thermal ablation while enhancing the effectiveness of chemotherapeutic agents and reducing toxic side effects on normal cells. Here, we developed a multifunctional black phosphorus nanosheets (BP NSs) for chemo-photothermal synergistic therapy of lymphoma. BP NSs were synthesized from bulk black phosphorus crystal powders utilizing a modified liquid exfoliation technique and functionalized with polyethylene glycol (PEG) to improve stability. The PEGylated BP NSs were loaded with two chemotherapeutic agents, gemcitabine (Gem) and doxorubicin (DOX), forming GD-BP@PEG NSs. The nanosheets exhibit excellent physical stability, efficient photothermal conversion, and pH/near-infrared (NIR) dual-responsive drug release. In vitro cell experiments demonstrated that GD-BP@PEG NSs significantly increased cytotoxicity and apoptosis, especially with NIR laser irradiation. Furthermore, in vivo studies in A20 lymphoma-bearing BALB/c nude mice revealed GD-BP@PEG NSs passively accumulated with high concentrations at the tumor site, efficiently inhibiting lymphoma growth with minimal systemic toxicity, demonstrating significant advantages over single treatments of chemotherapy or photothermal therapy alone. In summary, this pH/NIR dual-triggered BP NSs system could serve as a promising nanoplatform for chemo-photothermal synergistic treatment of B-cell lymphoma.
2026, 37(5): 111403
doi: 10.1016/j.cclet.2025.111403
摘要:
The low tumor immunogenicity, high immunosuppressive microenvironment, and off-target toxicity severely limit the efficiency of the cyclic guanosine monophosphate-adenosine monophosphate synthase-stimulator of interferon genes (cGAS-STING) pathway that plays an important role in tumor immunotherapy. We herein develop a multifunctional nano-assembly with tumor targeting, double-stranded DNA (dsDNA) releasing, Mn2+ sensitizing and immune microenvironment reprogramming capabilities for improving cGAS-STING to bridge innate and adaptive immunity. The drug-free nano-assembly composed of organic AIE-type photosensitizer and MnO2 can improve the tumor immune microenvironment by consuming glutathione and producing oxygen in the presence of H2O2, concurrently enhancing the release of damaged dsDNA and sensitizing the cGAS by controlled release of Mn2+ to magnify cGAS-STING immunity. In vivo experiments reveal that the multi-mode synergistic activation of STING pathway at the headstream can not only damage the primary tumors to amplify innate immunity, but also facilitate the maturation of dendritic cells, infiltration of cytotoxic T lymphocytes and expansion of adaptive immunity to inhibit primary tumor metastasis and recurrence in the long term.
The low tumor immunogenicity, high immunosuppressive microenvironment, and off-target toxicity severely limit the efficiency of the cyclic guanosine monophosphate-adenosine monophosphate synthase-stimulator of interferon genes (cGAS-STING) pathway that plays an important role in tumor immunotherapy. We herein develop a multifunctional nano-assembly with tumor targeting, double-stranded DNA (dsDNA) releasing, Mn2+ sensitizing and immune microenvironment reprogramming capabilities for improving cGAS-STING to bridge innate and adaptive immunity. The drug-free nano-assembly composed of organic AIE-type photosensitizer and MnO2 can improve the tumor immune microenvironment by consuming glutathione and producing oxygen in the presence of H2O2, concurrently enhancing the release of damaged dsDNA and sensitizing the cGAS by controlled release of Mn2+ to magnify cGAS-STING immunity. In vivo experiments reveal that the multi-mode synergistic activation of STING pathway at the headstream can not only damage the primary tumors to amplify innate immunity, but also facilitate the maturation of dendritic cells, infiltration of cytotoxic T lymphocytes and expansion of adaptive immunity to inhibit primary tumor metastasis and recurrence in the long term.
2026, 37(5): 111405
doi: 10.1016/j.cclet.2025.111405
摘要:
Chiral phthalides are present in numerous natural products and bioactive molecules. Synthesizing phthalides from alkenes is an effective strategy. However, the challenges of facial-selectivity in the addition to Z/E mixed alkenes and diastereoselectivity at vicinal stereogenic centers have prevented the achievement of a highly selective stereoconvergent synthesis of chiral sulfonyl phthalides from Z/E alkene mixtures. Therefore, we have developed an efficient methodology for the stereoconvergent synthesis of chiral sulfonyl phthalides, using the Cu/PyBim catalytic system. This method enables the asymmetric construction of sulfonyl phthalides with multiple stereocenters for the first time. It exhibits broad applicability across various terminal and internal alkene substrates, and accommodates a diverse array of aryl, alkyl, and nitrogen radical precursors, all under exceptionally mild reaction conditions. The experimental results indicate that the reaction utilizes a Curtin-Hammett kinetic control strategy, leading to the stereoconvergent synthesis of Z/E internal alkene substrates with significant enantioselectivity and diastereoselectivity in the asymmetric construction of chiral sulfonyl phthalides.
Chiral phthalides are present in numerous natural products and bioactive molecules. Synthesizing phthalides from alkenes is an effective strategy. However, the challenges of facial-selectivity in the addition to Z/E mixed alkenes and diastereoselectivity at vicinal stereogenic centers have prevented the achievement of a highly selective stereoconvergent synthesis of chiral sulfonyl phthalides from Z/E alkene mixtures. Therefore, we have developed an efficient methodology for the stereoconvergent synthesis of chiral sulfonyl phthalides, using the Cu/PyBim catalytic system. This method enables the asymmetric construction of sulfonyl phthalides with multiple stereocenters for the first time. It exhibits broad applicability across various terminal and internal alkene substrates, and accommodates a diverse array of aryl, alkyl, and nitrogen radical precursors, all under exceptionally mild reaction conditions. The experimental results indicate that the reaction utilizes a Curtin-Hammett kinetic control strategy, leading to the stereoconvergent synthesis of Z/E internal alkene substrates with significant enantioselectivity and diastereoselectivity in the asymmetric construction of chiral sulfonyl phthalides.
2026, 37(5): 111407
doi: 10.1016/j.cclet.2025.111407
摘要:
Fluoroorganic chemistry is one of the most hectic areas of current chemical research, exerting a profound effect on the most vital industries such as medicine, pesticide, and material science. Synthesis of fluorine-containing organic molecules, particularly those that bear C(sp3)−F bonds, remains a great challenge in modern chemical synthesis. Herein, we disclose a new strategy for the construction of a carbon−fluorine quaternary center, which was accomplished with the silver(Ⅰ)-catalyzed intramolecular Wagner−Meerwein rearrangement fluorination of allylic gem-disubstituted alkene derivatives by using a hypervalent monofluoroiodine(Ⅲ) reagent 1 (AFBI). Interestingly, the tunable five/six-membered heterocycle selectivity is achieved by the intramolecular Wagner−Meerwein rearrangement fluorination via a judicious choice of the group R1 attached to the C−C double bond. This versatile strategy features simple starting materials, mild reaction conditions, good functional-group compatibility, high bond-forming efficiency (e.g., one C−F and one C−O bond), and excellent chemoselectivity. The proposed reaction mechanisms and the roles of the catalyst AgBF4 were understood by control experiments and density functional theory calculations.
Fluoroorganic chemistry is one of the most hectic areas of current chemical research, exerting a profound effect on the most vital industries such as medicine, pesticide, and material science. Synthesis of fluorine-containing organic molecules, particularly those that bear C(sp3)−F bonds, remains a great challenge in modern chemical synthesis. Herein, we disclose a new strategy for the construction of a carbon−fluorine quaternary center, which was accomplished with the silver(Ⅰ)-catalyzed intramolecular Wagner−Meerwein rearrangement fluorination of allylic gem-disubstituted alkene derivatives by using a hypervalent monofluoroiodine(Ⅲ) reagent 1 (AFBI). Interestingly, the tunable five/six-membered heterocycle selectivity is achieved by the intramolecular Wagner−Meerwein rearrangement fluorination via a judicious choice of the group R1 attached to the C−C double bond. This versatile strategy features simple starting materials, mild reaction conditions, good functional-group compatibility, high bond-forming efficiency (e.g., one C−F and one C−O bond), and excellent chemoselectivity. The proposed reaction mechanisms and the roles of the catalyst AgBF4 were understood by control experiments and density functional theory calculations.
2026, 37(5): 111419
doi: 10.1016/j.cclet.2025.111419
摘要:
Macrocyclic cascade supramolecular assembly could significantly enhance the fluorescence/phosphorescence resonance energy transfer (F/PRET) efficiency through macrocyclic and spatial dual confinement effect. Herein, we reported a cascade supramolecular assembly containing 6-bromoisoquinolinium-modified permethylated cyclodextrin (BQ-PCD), cucurbit[7]uril (CB[7]), and tetra(4-sulfonatophenyl)porphyrin (TPPS), in which the enhanced PRET from 6-bromoisoquinolinium (BQ) to TPPS could be achieved through the dual macrocyclic confinement for multicolor delayed luminescence and information encryption. In TPPS$\subset$BQ-PCD$\subset$CB[7], pure organic room temperature phosphorescence of BQ-PCD at 530 nm is induced by CB[7] macrocyclic confinement, which further transferred to TPPS via spatial confinement, achieving delayed fluorescence at 645 and 715 nm with high PRET efficiency and quantum yield (17.9%). Meanwhile, reversible TPPS concentration-dependent multicolor luminescence was achieved in presence of competitive guest (methionine peptide), followed by porphyrin-photosensitization process, being applied in information encryption. This research presents a facile strategy for efficient PRET through macrocyclic cascade confinement assembly.
Macrocyclic cascade supramolecular assembly could significantly enhance the fluorescence/phosphorescence resonance energy transfer (F/PRET) efficiency through macrocyclic and spatial dual confinement effect. Herein, we reported a cascade supramolecular assembly containing 6-bromoisoquinolinium-modified permethylated cyclodextrin (BQ-PCD), cucurbit[7]uril (CB[7]), and tetra(4-sulfonatophenyl)porphyrin (TPPS), in which the enhanced PRET from 6-bromoisoquinolinium (BQ) to TPPS could be achieved through the dual macrocyclic confinement for multicolor delayed luminescence and information encryption. In TPPS$\subset$BQ-PCD$\subset$CB[7], pure organic room temperature phosphorescence of BQ-PCD at 530 nm is induced by CB[7] macrocyclic confinement, which further transferred to TPPS via spatial confinement, achieving delayed fluorescence at 645 and 715 nm with high PRET efficiency and quantum yield (17.9%). Meanwhile, reversible TPPS concentration-dependent multicolor luminescence was achieved in presence of competitive guest (methionine peptide), followed by porphyrin-photosensitization process, being applied in information encryption. This research presents a facile strategy for efficient PRET through macrocyclic cascade confinement assembly.
2026, 37(5): 111426
doi: 10.1016/j.cclet.2025.111426
摘要:
The fabrication of three-component supramolecular organic frameworks (SOFs) is a considerable difficulty owing to the intricate noncovalent interactions and the constraints of current synthesis techniques. In this study, we designed and synthesized two photosensitive modules: a naphthalene-modified triphenylamine derivative (NA-TPA) as the donor unit, and a trimethylated viologen-modified triphenylamine (MV-TPA) as the acceptor unit. These modules can self-assemble into a novel two-dimensional SOF via encapsulation-enhanced donor-acceptor interactions with cucurbit[8]uril (CB[8]) in the aqueous solution. The resulting donor-acceptor SOF forms stable two-dimensional nanosheet structures in water. Compared to the individual monomers NA-TPA and MV-TPA, the SOF enhances electron transfer and significantly improves the generation of superoxide anion radicals (O2•−), which in turn effectively promotes the photocatalytic cyclization reaction between o-phenylenediamine and benzaldehyde in water, achieving a yield of up to 94%. This work offers valuable insights into the design and construction of three-component SOFs based on encapsulation-enhanced donor-acceptor interactions for photocatalytic applications.
The fabrication of three-component supramolecular organic frameworks (SOFs) is a considerable difficulty owing to the intricate noncovalent interactions and the constraints of current synthesis techniques. In this study, we designed and synthesized two photosensitive modules: a naphthalene-modified triphenylamine derivative (NA-TPA) as the donor unit, and a trimethylated viologen-modified triphenylamine (MV-TPA) as the acceptor unit. These modules can self-assemble into a novel two-dimensional SOF via encapsulation-enhanced donor-acceptor interactions with cucurbit[8]uril (CB[8]) in the aqueous solution. The resulting donor-acceptor SOF forms stable two-dimensional nanosheet structures in water. Compared to the individual monomers NA-TPA and MV-TPA, the SOF enhances electron transfer and significantly improves the generation of superoxide anion radicals (O2•−), which in turn effectively promotes the photocatalytic cyclization reaction between o-phenylenediamine and benzaldehyde in water, achieving a yield of up to 94%. This work offers valuable insights into the design and construction of three-component SOFs based on encapsulation-enhanced donor-acceptor interactions for photocatalytic applications.
2026, 37(5): 111429
doi: 10.1016/j.cclet.2025.111429
摘要:
The generation of transient radical species via carbon–metal bond homolysis is extremely useful, which can be harnessed to promote useful and selective radical-type transformations by the combination of transition metal catalysis. We herein establish a carbon–metal bond homolysis/recombination model for the formation of enantiomerically enriched carbon-metal species, which accounts for the Ni-catalyzed enantioconvergent carboxylation of racemic benzyl ammonium salts with CO2. Theoretical studies suggest a distinct pathway involving a stereoinvertive nucleophilic substitution-type oxidative addition of racemic benzyl ammonium salts to Ni(0), forming a racemic benzyl Ni(Ⅱ) intermediate. Subsequent C–Ni bond homolysis of one enantiomer enables the formation of a transient radical, followed by a dynamic rotation along C–C· bond and radical recombination forming another more thermodynamically favored enantiomer. Geometry analysis suggests less H–H repulsion between the benzyl group and chiral ligand in the more stable isomer. After the reduction and stereoretentive inner-sphere nucleophilic attack on CO2 process, the desired enantiomerically enriched carboxylic acid product is generated. ETS-NOCV analysis reveals a significant back-donation interaction between the dx2-y2 orbital of Ni atom and the unoccupied π* orbital of CO2 in inner-sphere transition state, thus effectively stabilizing the Ni–CO2 complex and facilitating subsequent C–C bond formation. The theoretical calculations provide critical insights into the systematic development of transition metal-catalyzed asymmetric carboxylation, highlighting significant potential for broad applications in synthetic organic chemistry.
The generation of transient radical species via carbon–metal bond homolysis is extremely useful, which can be harnessed to promote useful and selective radical-type transformations by the combination of transition metal catalysis. We herein establish a carbon–metal bond homolysis/recombination model for the formation of enantiomerically enriched carbon-metal species, which accounts for the Ni-catalyzed enantioconvergent carboxylation of racemic benzyl ammonium salts with CO2. Theoretical studies suggest a distinct pathway involving a stereoinvertive nucleophilic substitution-type oxidative addition of racemic benzyl ammonium salts to Ni(0), forming a racemic benzyl Ni(Ⅱ) intermediate. Subsequent C–Ni bond homolysis of one enantiomer enables the formation of a transient radical, followed by a dynamic rotation along C–C· bond and radical recombination forming another more thermodynamically favored enantiomer. Geometry analysis suggests less H–H repulsion between the benzyl group and chiral ligand in the more stable isomer. After the reduction and stereoretentive inner-sphere nucleophilic attack on CO2 process, the desired enantiomerically enriched carboxylic acid product is generated. ETS-NOCV analysis reveals a significant back-donation interaction between the dx2-y2 orbital of Ni atom and the unoccupied π* orbital of CO2 in inner-sphere transition state, thus effectively stabilizing the Ni–CO2 complex and facilitating subsequent C–C bond formation. The theoretical calculations provide critical insights into the systematic development of transition metal-catalyzed asymmetric carboxylation, highlighting significant potential for broad applications in synthetic organic chemistry.
2026, 37(5): 111430
doi: 10.1016/j.cclet.2025.111430
摘要:
Although C2-symmetric C–C atropisomeric diphosphines such as BINAP and SEGPHOS, have achieved tremendous success in enantioselective catalysis in recent centuries, developing diphosphines based on new structural scaffolds is still highly desirable. Here, C2-symmetric N–N atropisomeric diphosphines have been synthesized and comprehensively analyzed. These diphosphines exhibit excellent substituent-dependent tunable dihedral angles comparable to other useful electron-enriched diphosphines. With the aid of these newly developed diphosphines, the transition-metal catalyzed enantioselective dearomatization of heteroaryls is carried out to yield final products with excellent enantioselectivities, indicating their exceptional stereoinduction abilities.
Although C2-symmetric C–C atropisomeric diphosphines such as BINAP and SEGPHOS, have achieved tremendous success in enantioselective catalysis in recent centuries, developing diphosphines based on new structural scaffolds is still highly desirable. Here, C2-symmetric N–N atropisomeric diphosphines have been synthesized and comprehensively analyzed. These diphosphines exhibit excellent substituent-dependent tunable dihedral angles comparable to other useful electron-enriched diphosphines. With the aid of these newly developed diphosphines, the transition-metal catalyzed enantioselective dearomatization of heteroaryls is carried out to yield final products with excellent enantioselectivities, indicating their exceptional stereoinduction abilities.
2026, 37(5): 111442
doi: 10.1016/j.cclet.2025.111442
摘要:
Chiral 1,2,3,4-tetrahydro-1,5-naphthyridines are frequently encountered in many bioactive compounds. However, the methods for their asymmetric synthesis are quite limited. Herein, we developed a straightforward and efficient route to enantioenriched tetrahydro-1,5-naphthyridines from pyridine derivatives tethered with alkene moieties (34 examples, up to 99% yield, 93% ee). The reaction proceeded via Csp2–H activation pathway initiated by site-selective deprotonation with the assistance of La[N(SiMe3)2]3/PyBox, followed by alkene insertion into the resulting La-aryl bond. The potential utility of the current method in organic synthesis was highlighted by scale-up synthesis of chiral product and its further transformations. Moreover, some of the products show a pronounced inhibitory effect on A549 cell activity. In addition, experimental studies and DFT calculations were carried out to elucidate the origin of enantiocontrol.
Chiral 1,2,3,4-tetrahydro-1,5-naphthyridines are frequently encountered in many bioactive compounds. However, the methods for their asymmetric synthesis are quite limited. Herein, we developed a straightforward and efficient route to enantioenriched tetrahydro-1,5-naphthyridines from pyridine derivatives tethered with alkene moieties (34 examples, up to 99% yield, 93% ee). The reaction proceeded via Csp2–H activation pathway initiated by site-selective deprotonation with the assistance of La[N(SiMe3)2]3/PyBox, followed by alkene insertion into the resulting La-aryl bond. The potential utility of the current method in organic synthesis was highlighted by scale-up synthesis of chiral product and its further transformations. Moreover, some of the products show a pronounced inhibitory effect on A549 cell activity. In addition, experimental studies and DFT calculations were carried out to elucidate the origin of enantiocontrol.
2026, 37(5): 111443
doi: 10.1016/j.cclet.2025.111443
摘要:
A kind of inherently chiral molecular barrels were efficiently constructed by a directional cascade hooping strategy. This strategy involves the anchoring of three nonsymmetric connecting arms onto a cap-dissymmetric bis(tetraoxacalix[2]arene[2]triazine) cage core, followed by hooping via imine condensation and reduction to afford the target molecular barrels with well-defined connectivity. The precise and high-yielding synthesis stems from both the bidirectional Ctriazine-N bond flipping dynamics and the reversible nature of imine formation. The molecular barrels comprise a bis(tetraoxacalix[2]arene[2]triazine) core encircled by a 72-membered loop, forming three fan-shaped cavities with inherent chirality and multiple endo-functionalized sites. The existence of multiple diastereoisomeric conformers due to the restricted Ctriazine-N bond flipping by the constrained loop structure was revealed by variable-temperature NMR studies and DFT calculations.
A kind of inherently chiral molecular barrels were efficiently constructed by a directional cascade hooping strategy. This strategy involves the anchoring of three nonsymmetric connecting arms onto a cap-dissymmetric bis(tetraoxacalix[2]arene[2]triazine) cage core, followed by hooping via imine condensation and reduction to afford the target molecular barrels with well-defined connectivity. The precise and high-yielding synthesis stems from both the bidirectional Ctriazine-N bond flipping dynamics and the reversible nature of imine formation. The molecular barrels comprise a bis(tetraoxacalix[2]arene[2]triazine) core encircled by a 72-membered loop, forming three fan-shaped cavities with inherent chirality and multiple endo-functionalized sites. The existence of multiple diastereoisomeric conformers due to the restricted Ctriazine-N bond flipping by the constrained loop structure was revealed by variable-temperature NMR studies and DFT calculations.
2026, 37(5): 111454
doi: 10.1016/j.cclet.2025.111454
摘要:
The typical organic perylenetetracarboxylate (PTC) luminophore suffers from limited bio-application due to its aggregation-caused quenching (ACQ) induced undesirable electrochemiluminescence (ECL) efficiency in aqueous solution. Herein, the ECL emission of PTC was highly improved through the ingenious coordination of PTC (ligand) with Tb3+ (metal ion) to prepare the Tb-PTC metal-organic framework (Tb-PTC MOF), which prevented the π-π stacking and the aggregation of PTC molecules in a homogeneous phase. Moreover, we found that the ECL emission of Tb-PTC MOF was further enhanced by regulating its morphology, pore size and electron transfer ability using different solvents during its synthesis procedure. Notably, under the mixture of DMF, EtOH, and H2O (v/v/v, 1:1:1), a mesoporous Tb-PTC MOF exhibited an outstanding ECL intensity, which may be attributed to two reasons. Firstly, the mesopore and rough surface of Tb-PTC MOF (luminophore) provided abundant active sites and enlarged contact surfaces for S2O82– (coreactant). Secondly, Tb-PTC MOF with higher electron transfer ability could accelerate electron/hole recombination to enhance its ECL emission. Additionally, Tb-PTC MOF with excellent ECL performance was applied as a luminophore to fabricate an ultrasensitive ECL immunosensor for cardiac troponin Ⅰ (cTnI) detection, related to acute myocardial infarction. The constructed ECL immunosensor exhibited a satisfactory linear range (1 fg/mL − 20 ng/mL) and a low detection limit of 0.48 fg/mL. This study provides a new trend for the preparation of PTC-based nanomaterials with highly efficient ECL performance, broadening the scope for sensitive immunoassay in disease diagnosis.
The typical organic perylenetetracarboxylate (PTC) luminophore suffers from limited bio-application due to its aggregation-caused quenching (ACQ) induced undesirable electrochemiluminescence (ECL) efficiency in aqueous solution. Herein, the ECL emission of PTC was highly improved through the ingenious coordination of PTC (ligand) with Tb3+ (metal ion) to prepare the Tb-PTC metal-organic framework (Tb-PTC MOF), which prevented the π-π stacking and the aggregation of PTC molecules in a homogeneous phase. Moreover, we found that the ECL emission of Tb-PTC MOF was further enhanced by regulating its morphology, pore size and electron transfer ability using different solvents during its synthesis procedure. Notably, under the mixture of DMF, EtOH, and H2O (v/v/v, 1:1:1), a mesoporous Tb-PTC MOF exhibited an outstanding ECL intensity, which may be attributed to two reasons. Firstly, the mesopore and rough surface of Tb-PTC MOF (luminophore) provided abundant active sites and enlarged contact surfaces for S2O82– (coreactant). Secondly, Tb-PTC MOF with higher electron transfer ability could accelerate electron/hole recombination to enhance its ECL emission. Additionally, Tb-PTC MOF with excellent ECL performance was applied as a luminophore to fabricate an ultrasensitive ECL immunosensor for cardiac troponin Ⅰ (cTnI) detection, related to acute myocardial infarction. The constructed ECL immunosensor exhibited a satisfactory linear range (1 fg/mL − 20 ng/mL) and a low detection limit of 0.48 fg/mL. This study provides a new trend for the preparation of PTC-based nanomaterials with highly efficient ECL performance, broadening the scope for sensitive immunoassay in disease diagnosis.
2026, 37(5): 111461
doi: 10.1016/j.cclet.2025.111461
摘要:
Tertiary N–CF3 compounds have attracted intensive attention due to their great significance in discovery of new lead compounds, however, the synthesis of tertiary diaryl N–CF3 derivatives is still challenging. Herein, we successfully edit diaryl N–H into thiocarbamoyl fluorides with trifluoromethanesulfonyl chloride by use of a PⅢ/PⅤ redox catalyst, leading to the formation of series of diaryl N–CF3 with silver fluoride. In addition, this process is also highly efficient to dialkyl and alkylaryl secondary amines. The mechanism investigation illustrated that the use of hydrosilane is crucial to the success of this transformation. It acts as both terminal reductants to cycle the PⅢ/PⅤ couple and fluoride acceptor to promote the reaction between less reactive amine and thiocarbonyl difluoride intermediate.
Tertiary N–CF3 compounds have attracted intensive attention due to their great significance in discovery of new lead compounds, however, the synthesis of tertiary diaryl N–CF3 derivatives is still challenging. Herein, we successfully edit diaryl N–H into thiocarbamoyl fluorides with trifluoromethanesulfonyl chloride by use of a PⅢ/PⅤ redox catalyst, leading to the formation of series of diaryl N–CF3 with silver fluoride. In addition, this process is also highly efficient to dialkyl and alkylaryl secondary amines. The mechanism investigation illustrated that the use of hydrosilane is crucial to the success of this transformation. It acts as both terminal reductants to cycle the PⅢ/PⅤ couple and fluoride acceptor to promote the reaction between less reactive amine and thiocarbonyl difluoride intermediate.
2026, 37(5): 111484
doi: 10.1016/j.cclet.2025.111484
摘要:
The site-selective C(sp3)-H functionalization is of great importance in synthetic chemistry. However, γ-amino C(sp3)-H functionalization of aliphatic amines remains challenging. Herein, we develop an efficient γ-C(sp3)-H acylation of aliphatic amines by cooperative photoredox NHC/Pd catalysis. The process entails the following key steps: (ⅰ) photoinduced palladium-promoted formation of aryl radical, (ⅰ) generation of transient γ-amino alkyl radical through aryl radical-mediated 1,7-HAT, (ⅲ) single-electron oxidation of Breslow enolate intermediate to persistent ketyl radical, and (ⅳ) radical/radical coupling of γ-amino alkyl radical with ketyl radical. The synthetic utility of this γ-amino C(sp3)-H acylation is illustrated by the conversion of readily available aliphatic amines to a diverse collection of γ-aminoketones, which serve as versatile building blocks to enable the synthesis of pyrrolines of interest in medicinal chemistry. The radical mechanism is supported by the results of various control experiments, in situ EPR analysis, radical trapping experiment, and isotopic labeling studies.
The site-selective C(sp3)-H functionalization is of great importance in synthetic chemistry. However, γ-amino C(sp3)-H functionalization of aliphatic amines remains challenging. Herein, we develop an efficient γ-C(sp3)-H acylation of aliphatic amines by cooperative photoredox NHC/Pd catalysis. The process entails the following key steps: (ⅰ) photoinduced palladium-promoted formation of aryl radical, (ⅰ) generation of transient γ-amino alkyl radical through aryl radical-mediated 1,7-HAT, (ⅲ) single-electron oxidation of Breslow enolate intermediate to persistent ketyl radical, and (ⅳ) radical/radical coupling of γ-amino alkyl radical with ketyl radical. The synthetic utility of this γ-amino C(sp3)-H acylation is illustrated by the conversion of readily available aliphatic amines to a diverse collection of γ-aminoketones, which serve as versatile building blocks to enable the synthesis of pyrrolines of interest in medicinal chemistry. The radical mechanism is supported by the results of various control experiments, in situ EPR analysis, radical trapping experiment, and isotopic labeling studies.
2026, 37(5): 111499
doi: 10.1016/j.cclet.2025.111499
摘要:
Nanobelts have attracted significant attention in both synthetic and supramolecular chemistry due to their distinctive structures and promising applications. However, their synthesis remains challenging due to the high strain inherent in their ribbon-like configurations. A promising approach to mitigate this strain involves incorporating heteroatoms, such as sulfur and oxygen, which not only alleviate strain but also introduce new functionalities. In this study, we report the synthesis of a novel C2-symmetric nanobelt, [7]cyclophenoxathiin ([7]CP), through a multi-step process. The structure of [7]CP was confirmed using NMR, mass spectrometry, and single-crystal X-ray diffraction, revealing a heptagonal frustum-shaped geometry. Host-guest interactions between [7]CP and selected fullerenes were investigated using UV–vis absorption, 1H NMR, and X-ray crystallography. Our findings demonstrate that [7]CP forms 1:1 complexes with fullerenes, exhibiting moderate binding through π−π interactions, with binding constants of 1638, 2534, and 3682 L/mol for C60, C70, and PC61BM, respectively. The reduced cavity size of [7]CP prevents the formation of dimeric complexes observed with [7]cyclophenoxathiin, while still allowing it to function effectively as a molecular container.
Nanobelts have attracted significant attention in both synthetic and supramolecular chemistry due to their distinctive structures and promising applications. However, their synthesis remains challenging due to the high strain inherent in their ribbon-like configurations. A promising approach to mitigate this strain involves incorporating heteroatoms, such as sulfur and oxygen, which not only alleviate strain but also introduce new functionalities. In this study, we report the synthesis of a novel C2-symmetric nanobelt, [7]cyclophenoxathiin ([7]CP), through a multi-step process. The structure of [7]CP was confirmed using NMR, mass spectrometry, and single-crystal X-ray diffraction, revealing a heptagonal frustum-shaped geometry. Host-guest interactions between [7]CP and selected fullerenes were investigated using UV–vis absorption, 1H NMR, and X-ray crystallography. Our findings demonstrate that [7]CP forms 1:1 complexes with fullerenes, exhibiting moderate binding through π−π interactions, with binding constants of 1638, 2534, and 3682 L/mol for C60, C70, and PC61BM, respectively. The reduced cavity size of [7]CP prevents the formation of dimeric complexes observed with [7]cyclophenoxathiin, while still allowing it to function effectively as a molecular container.
2026, 37(5): 111501
doi: 10.1016/j.cclet.2025.111501
摘要:
Metal-free nanoparticles capable of executing synergistic photothermal therapy (PTT) and photodynamic therapy (PDT) under the action of a single-wavelength laser have garnered considerable attention. Here, a novel type of nitrogen-sulfur co-doped carbon nanoparticles (TG-CNPs) was synthesized from taurine and genipin using a solvothermal method in dimethylformamide. The TG-CNPs, with an average size of approximately 25 nm, demonstrated red and near-infrared absorption/emission in aqueous solution. TG-CNPs exhibited negligible dark cytotoxicity, excellent biocompatibility, and remarkable lysosomal localization ability. Upon 655-nm laser irradiation, TG-CNPs exhibited strong photothermal performance with a photothermal conversion efficiency of 30% along with the efficient generation of superoxide radicals (•O2−). Leveraging the enhanced permeability and retention (EPR) effect, TG-CNPs facilitated passive targeting and accumulation at the tumor site. Notably, following a single round of 655-nm laser treatment, the tumors in the mice were completely eradicated, with no evidence of recurrence observed over the subsequent five months. This study introduces a promising metal-free, heteroatom-doped carbon nanoparticle platform for effective synergistic PTT/PDT in tumor treatment.
Metal-free nanoparticles capable of executing synergistic photothermal therapy (PTT) and photodynamic therapy (PDT) under the action of a single-wavelength laser have garnered considerable attention. Here, a novel type of nitrogen-sulfur co-doped carbon nanoparticles (TG-CNPs) was synthesized from taurine and genipin using a solvothermal method in dimethylformamide. The TG-CNPs, with an average size of approximately 25 nm, demonstrated red and near-infrared absorption/emission in aqueous solution. TG-CNPs exhibited negligible dark cytotoxicity, excellent biocompatibility, and remarkable lysosomal localization ability. Upon 655-nm laser irradiation, TG-CNPs exhibited strong photothermal performance with a photothermal conversion efficiency of 30% along with the efficient generation of superoxide radicals (•O2−). Leveraging the enhanced permeability and retention (EPR) effect, TG-CNPs facilitated passive targeting and accumulation at the tumor site. Notably, following a single round of 655-nm laser treatment, the tumors in the mice were completely eradicated, with no evidence of recurrence observed over the subsequent five months. This study introduces a promising metal-free, heteroatom-doped carbon nanoparticle platform for effective synergistic PTT/PDT in tumor treatment.
2026, 37(5): 111544
doi: 10.1016/j.cclet.2025.111544
摘要:
Although the incorporation of deuterium has been widely researched, controlled deuterium labelling at precise sites is still very challenging. Herein, efficient catalytic synthesis of deuterated pyrroles is focused, the radical cyclizations of N-propargyl enamines were achieved from photoredox-mediated deuterated water splitting, giving deuterated pyrroles with deuterations at the C(sp2) and C(sp3) precisely. One or two-sites-deuterium incorporation as well as the controllable deuteration label at multi-H/D-exchange-sites, such as a methyl group, have been realized in high selectivity and efficiency via the solvent-controlled divergent deuterations. A halogen effect between solvents and substrates was proposed to initiate different catalytic cycles for the deuterations. The broad tolerance to substrates, the gram scale synthesis under natural sunlight irradiation and its applications in the synthesis of drug analogues further verified their practicality.
Although the incorporation of deuterium has been widely researched, controlled deuterium labelling at precise sites is still very challenging. Herein, efficient catalytic synthesis of deuterated pyrroles is focused, the radical cyclizations of N-propargyl enamines were achieved from photoredox-mediated deuterated water splitting, giving deuterated pyrroles with deuterations at the C(sp2) and C(sp3) precisely. One or two-sites-deuterium incorporation as well as the controllable deuteration label at multi-H/D-exchange-sites, such as a methyl group, have been realized in high selectivity and efficiency via the solvent-controlled divergent deuterations. A halogen effect between solvents and substrates was proposed to initiate different catalytic cycles for the deuterations. The broad tolerance to substrates, the gram scale synthesis under natural sunlight irradiation and its applications in the synthesis of drug analogues further verified their practicality.
2026, 37(5): 111555
doi: 10.1016/j.cclet.2025.111555
摘要:
A concise asymmetric synthesis of the anti-influenza drug (–)-oseltamivir phosphate (1) has been accomplished in 9 steps with an overall yield of 24%, starting from ethyl propiolate. The key features in this synthesis include an efficient biphasic Pd-catalyzed regioselectively intramolecular Heck-type cyclization to provide access to the highly valued chiral six-membered carbocyclic architecture, a regioselective and diastereoselective nitroso hetero-Diels-Alder reaction to construct the bicyclic oxazine 4 as well as a Cu(OTf)2-mediated regioselective and diastereoselective nucleophilic substitution reaction of bicyclic oxazine 4 with 3-pentanol to yield the trans-1,2-substituted diamino cyclohexyl amyl ether 16 with the correct three contiguous stereocenters. This rapid functionalization of the advanced molecular framework would offer an effective strategy for the asymmetric synthesis of other oseltamivir phosphate analogues.
A concise asymmetric synthesis of the anti-influenza drug (–)-oseltamivir phosphate (1) has been accomplished in 9 steps with an overall yield of 24%, starting from ethyl propiolate. The key features in this synthesis include an efficient biphasic Pd-catalyzed regioselectively intramolecular Heck-type cyclization to provide access to the highly valued chiral six-membered carbocyclic architecture, a regioselective and diastereoselective nitroso hetero-Diels-Alder reaction to construct the bicyclic oxazine 4 as well as a Cu(OTf)2-mediated regioselective and diastereoselective nucleophilic substitution reaction of bicyclic oxazine 4 with 3-pentanol to yield the trans-1,2-substituted diamino cyclohexyl amyl ether 16 with the correct three contiguous stereocenters. This rapid functionalization of the advanced molecular framework would offer an effective strategy for the asymmetric synthesis of other oseltamivir phosphate analogues.
2026, 37(5): 111614
doi: 10.1016/j.cclet.2025.111614
摘要:
The intrinsic scintillation property of uranium has recently endowed this heaviest naturally occurring element with new opportunities for X-ray radiation detection and visualization. However, the low radiation stability of most uranium compounds hinders their practical application, particularly in X-ray imaging. Here, we presented a flexible two-dimensional uranium-organic framework (UOF, SCU-334) as an air-stable scintillating material for X-ray detection and, for the first time, a systematic investigation of X-ray imaging in UOFs. Following continuous high dose rate X-ray irradiation exceeding 50 Gy, which equals thousands of chest X-ray diagnoses, SCU-334 retains over 90% of its initial performance, representing a significant improvement over previously reported scintillating UOFs. The upgraded radiation resistance of SCU-334 is attributed to its flexible structure that dissipates energy more efficiently under high-energy particle bombardment through conformation fluctuation and relaxation. This work offers a promising approach to improve the radiation resistance of uranium-based scintillators.
The intrinsic scintillation property of uranium has recently endowed this heaviest naturally occurring element with new opportunities for X-ray radiation detection and visualization. However, the low radiation stability of most uranium compounds hinders their practical application, particularly in X-ray imaging. Here, we presented a flexible two-dimensional uranium-organic framework (UOF, SCU-334) as an air-stable scintillating material for X-ray detection and, for the first time, a systematic investigation of X-ray imaging in UOFs. Following continuous high dose rate X-ray irradiation exceeding 50 Gy, which equals thousands of chest X-ray diagnoses, SCU-334 retains over 90% of its initial performance, representing a significant improvement over previously reported scintillating UOFs. The upgraded radiation resistance of SCU-334 is attributed to its flexible structure that dissipates energy more efficiently under high-energy particle bombardment through conformation fluctuation and relaxation. This work offers a promising approach to improve the radiation resistance of uranium-based scintillators.
2026, 37(5): 111615
doi: 10.1016/j.cclet.2025.111615
摘要:
Synthesizing 2-deoxyglycosides, prevalent motifs in bioactive molecules, presents significant challenges in stereocontrol and functional group tolerance. We report a metal-free, photo-induced O-glycosylation of glycals using acridinium salts under visible light. This method effectively couples diverse glycals with both carboxylic acids and alcohols, providing facile access to α-2-deoxyglycosides under mild conditions with broad substrate scope and functional group compatibility. The protocol exhibits high α-stereoselectivity with carboxylic acids and moderate α-selectivity with alcohols, enabling late-stage functionalization of complex molecules, including amino acids, peptides, and drugs. Mechanistic experiments implicate the possible involvement of radical intermediates, potentially operating via a chain reaction. Notably, 2-deoxyglycosylation of NSAIDs using this method enhanced their neuroprotective properties in vitro. This photo-induced strategy offers a practical and versatile platform for accessing complex 2-deoxyglycans relevant to medicinal chemistry and chemical biology.
Synthesizing 2-deoxyglycosides, prevalent motifs in bioactive molecules, presents significant challenges in stereocontrol and functional group tolerance. We report a metal-free, photo-induced O-glycosylation of glycals using acridinium salts under visible light. This method effectively couples diverse glycals with both carboxylic acids and alcohols, providing facile access to α-2-deoxyglycosides under mild conditions with broad substrate scope and functional group compatibility. The protocol exhibits high α-stereoselectivity with carboxylic acids and moderate α-selectivity with alcohols, enabling late-stage functionalization of complex molecules, including amino acids, peptides, and drugs. Mechanistic experiments implicate the possible involvement of radical intermediates, potentially operating via a chain reaction. Notably, 2-deoxyglycosylation of NSAIDs using this method enhanced their neuroprotective properties in vitro. This photo-induced strategy offers a practical and versatile platform for accessing complex 2-deoxyglycans relevant to medicinal chemistry and chemical biology.
2026, 37(5): 111616
doi: 10.1016/j.cclet.2025.111616
摘要:
Glial fibrillary acidic protein (GFAP) can serve as a promising early blood biomarker for Alzheimer's disease (AD). Existing assays mostly rely on antibody-based detection technologies, the preparation of antibodies is relatively complex, costly, and requires high storage conditions. In this study, we screened an aptamer specifically targeting GFAP (KD = 0.621 µmol/L) through systematic evolution of ligands by exponential enrichment (SELEX) technique for the first time and then applied which to develop a simple but sensitive fluorescent sensor by combining isothermal exponential amplification reaction (EXPAR) with hybridization chain reaction (HCR). The platform achieved a broad linear detection range (10 pg/mL to 10 µg/mL) and a low detection limit (0.24 pg/mL). The results detected by the proposed sensor were highly correlated with that detected by ELISA method (R = 0.9989, P < 0.0001). The work overcomes the limitations of antibody-based technologies and provides a promising solution for early diagnosis of AD.
Glial fibrillary acidic protein (GFAP) can serve as a promising early blood biomarker for Alzheimer's disease (AD). Existing assays mostly rely on antibody-based detection technologies, the preparation of antibodies is relatively complex, costly, and requires high storage conditions. In this study, we screened an aptamer specifically targeting GFAP (KD = 0.621 µmol/L) through systematic evolution of ligands by exponential enrichment (SELEX) technique for the first time and then applied which to develop a simple but sensitive fluorescent sensor by combining isothermal exponential amplification reaction (EXPAR) with hybridization chain reaction (HCR). The platform achieved a broad linear detection range (10 pg/mL to 10 µg/mL) and a low detection limit (0.24 pg/mL). The results detected by the proposed sensor were highly correlated with that detected by ELISA method (R = 0.9989, P < 0.0001). The work overcomes the limitations of antibody-based technologies and provides a promising solution for early diagnosis of AD.
2026, 37(5): 111617
doi: 10.1016/j.cclet.2025.111617
摘要:
The development of innovative strategies for inert B–H bond functionalization of carboranes and exploration of their potential applications represents a central task in organic chemistry. Here, we demonstrate the facile B–H bond functionalization in carboranes through a cage···Ⅰ(Ⅲ) interaction between a nido-carborane cluster and a hypervalent iodine(Ⅲ) unit. Both experimental and theoretical investigations reveal that the cage···Ⅰ(Ⅲ) interaction induces a charge transfer from the boron cage to the iodine moiety, which leads to a significant decrease of the negative charge at the B(9)–H site of nido-carborane. This facilitates the activation of the B–H bond and subsequent chemical transformations. The unprecedented cage···Ⅰ(Ⅲ) interaction offers a similar B–H bond activation mode as metal mediation. Furthermore, the treatment of nido-carboranes with the iodide(Ⅲ) reagent of PhI(OAc)2 affords nido-carborane-phenyl iodonium zwitterions as versatile synthons, which enable the modular construction of exopolyhedral B–O, B–N, B–P, and B–S bonds of carborane derivatives. This approach provides an efficient and scalable synthetic platform for metal-free and site-selective B–H bond functionalization of nido-carboranes under mild conditions. Notably, the developed 2D-3D fused structures can be used as ligands for the facile construction of novel boron cluster-fused hetero-polycyclic metal complexes in one step. These compounds demonstrate intriguing photophysical properties including aggregation-induced emission, tunable emission wavelength, and oxygen sensing.
The development of innovative strategies for inert B–H bond functionalization of carboranes and exploration of their potential applications represents a central task in organic chemistry. Here, we demonstrate the facile B–H bond functionalization in carboranes through a cage···Ⅰ(Ⅲ) interaction between a nido-carborane cluster and a hypervalent iodine(Ⅲ) unit. Both experimental and theoretical investigations reveal that the cage···Ⅰ(Ⅲ) interaction induces a charge transfer from the boron cage to the iodine moiety, which leads to a significant decrease of the negative charge at the B(9)–H site of nido-carborane. This facilitates the activation of the B–H bond and subsequent chemical transformations. The unprecedented cage···Ⅰ(Ⅲ) interaction offers a similar B–H bond activation mode as metal mediation. Furthermore, the treatment of nido-carboranes with the iodide(Ⅲ) reagent of PhI(OAc)2 affords nido-carborane-phenyl iodonium zwitterions as versatile synthons, which enable the modular construction of exopolyhedral B–O, B–N, B–P, and B–S bonds of carborane derivatives. This approach provides an efficient and scalable synthetic platform for metal-free and site-selective B–H bond functionalization of nido-carboranes under mild conditions. Notably, the developed 2D-3D fused structures can be used as ligands for the facile construction of novel boron cluster-fused hetero-polycyclic metal complexes in one step. These compounds demonstrate intriguing photophysical properties including aggregation-induced emission, tunable emission wavelength, and oxygen sensing.
2026, 37(5): 111649
doi: 10.1016/j.cclet.2025.111649
摘要:
Metal-organic frameworks (MOFs) with tunable structures provide a versatile platform for exploring active sites and show great potential in enzyme-like catalysis. In this study, arginine was employed as a modulator to synthesize an arginine-copper metal-organic framework (Arg-Cu-MOF), which demonstrated superior peroxidase-like activity and stability in comparison to unmodified Cu-MOF. The improved activity resulted from an increased density of Cu+ active sites, facilitating efficient •OH generation through H2O2 decomposition. Glyphosate interacts with the copper sites in a way that affects •OH generation and chromogenic substrate oxidation, leading to detectable colorimetric changes. By integrating Arg-Cu-MOF into a needle sensor, we allowed sample handling, reagent mixing, and signal readout, enabling both precise instrumental measurements and semi-quantitative visual detection of glyphosate. This sensor offers a detection range of 0.05–200 µg/mL with a detection limit of 0.049 µg/mL. This work highlights the potential of MOF modulation strategies and integrated detection platforms to enhance analytical performance, improve user-friendliness, and expand the application scope of biomimetic nanomaterials.
Metal-organic frameworks (MOFs) with tunable structures provide a versatile platform for exploring active sites and show great potential in enzyme-like catalysis. In this study, arginine was employed as a modulator to synthesize an arginine-copper metal-organic framework (Arg-Cu-MOF), which demonstrated superior peroxidase-like activity and stability in comparison to unmodified Cu-MOF. The improved activity resulted from an increased density of Cu+ active sites, facilitating efficient •OH generation through H2O2 decomposition. Glyphosate interacts with the copper sites in a way that affects •OH generation and chromogenic substrate oxidation, leading to detectable colorimetric changes. By integrating Arg-Cu-MOF into a needle sensor, we allowed sample handling, reagent mixing, and signal readout, enabling both precise instrumental measurements and semi-quantitative visual detection of glyphosate. This sensor offers a detection range of 0.05–200 µg/mL with a detection limit of 0.049 µg/mL. This work highlights the potential of MOF modulation strategies and integrated detection platforms to enhance analytical performance, improve user-friendliness, and expand the application scope of biomimetic nanomaterials.
2026, 37(5): 111706
doi: 10.1016/j.cclet.2025.111706
摘要:
The host-guest doped strategy has become the main method for constructing organic phosphorescence materials. In the doped system, guest molecules emit phosphorescence, therefore, improving the luminescence performance of guests is the key to optimizing the phosphorescence property of the doped materials. Herein, we designed to introduce the carbonyl group on the guest molecules. Carbonyl group can effectively promote n-π* transitions, thereby increasing the spin-orbit coupling (SOC) constant of the guests, ultimately improving the phosphorescence performance of the doped materials. Using the indazole derivative (IZ) as the initial guest, two other guests containing carboxyl group (IZ-CG) or ethoxycarbonyl group (IZ-EG) were successfully obtained. Further selected two small molecules and two polymers as the hosts to construct four doped systems. Among these doped systems, the phosphorescence performance of doped materials with IZ-CG or IZ-EG as the guest is significantly better than that of doped materials with IZ as the guest. The phosphorescence lifetime has increased by 2.3-5.0 times, and the phosphorescence quantum yield has increased by 3.0-5.7 times. Theoretical calculations and single crystal structures indicated that carbonyl groups can not only increase the SOC constant, but also enhance the intermolecular interactions of the guests. In addition, doped material can be effectively used for imaging subcutaneous and lymph nodes in mice, achieving a high signal-to-noise ratio.
The host-guest doped strategy has become the main method for constructing organic phosphorescence materials. In the doped system, guest molecules emit phosphorescence, therefore, improving the luminescence performance of guests is the key to optimizing the phosphorescence property of the doped materials. Herein, we designed to introduce the carbonyl group on the guest molecules. Carbonyl group can effectively promote n-π* transitions, thereby increasing the spin-orbit coupling (SOC) constant of the guests, ultimately improving the phosphorescence performance of the doped materials. Using the indazole derivative (IZ) as the initial guest, two other guests containing carboxyl group (IZ-CG) or ethoxycarbonyl group (IZ-EG) were successfully obtained. Further selected two small molecules and two polymers as the hosts to construct four doped systems. Among these doped systems, the phosphorescence performance of doped materials with IZ-CG or IZ-EG as the guest is significantly better than that of doped materials with IZ as the guest. The phosphorescence lifetime has increased by 2.3-5.0 times, and the phosphorescence quantum yield has increased by 3.0-5.7 times. Theoretical calculations and single crystal structures indicated that carbonyl groups can not only increase the SOC constant, but also enhance the intermolecular interactions of the guests. In addition, doped material can be effectively used for imaging subcutaneous and lymph nodes in mice, achieving a high signal-to-noise ratio.
2026, 37(5): 111717
doi: 10.1016/j.cclet.2025.111717
摘要:
Coupling photocatalytic H2 generation with antibiotic degradation offers a promising strategy for addressing energy and environmental challenges, leveraging the synergistic benefits of these processes. Herein, a novel heterojunction photocatalyst consisting of ultrafine CeO2 nanoparticles anchored onto CdS nanosheets was prepared using a simple one-pot in-situ hydrothermal method, enabling the simultaneous photocatalytic H2 generation and tetracycline (TC) degradation. The H2 generation efficiency of the optimal CeO2/CdS (CC-0.10) is 3544 µmol g-1 h-1, which surpasses pure CdS by 29.3 times. Additionally, TC is degraded by CC-0.10 at a rate constant (k value) of 0.0352 min-1, 2.73 times faster than CdS (0.0129 min-1). The free radical quenching and electron spin resonance experiments revealed the active involvement of •OH and •O2- radicals in the TC degradation process. Moreover, the unique CeO2/CdS heterojunction photocatalyst was also effective in degrading TC wastewater with an H2 yield of 1374 µmol g-1 h-1, displaying its dual performance in simultaneously degrading antibiotic wastewater and producing H2. The CeO2/CdS type Ⅱ charge transfer mechanism is confirmed by XPS, EPR, KPFM, fs-TAS, and DFT calculations. This work introduces a promising approach to constructing rare-earth oxide/metal sulfide nanocomposites for addressing the interconnected challenges of energy production and environmental pollution.
Coupling photocatalytic H2 generation with antibiotic degradation offers a promising strategy for addressing energy and environmental challenges, leveraging the synergistic benefits of these processes. Herein, a novel heterojunction photocatalyst consisting of ultrafine CeO2 nanoparticles anchored onto CdS nanosheets was prepared using a simple one-pot in-situ hydrothermal method, enabling the simultaneous photocatalytic H2 generation and tetracycline (TC) degradation. The H2 generation efficiency of the optimal CeO2/CdS (CC-0.10) is 3544 µmol g-1 h-1, which surpasses pure CdS by 29.3 times. Additionally, TC is degraded by CC-0.10 at a rate constant (k value) of 0.0352 min-1, 2.73 times faster than CdS (0.0129 min-1). The free radical quenching and electron spin resonance experiments revealed the active involvement of •OH and •O2- radicals in the TC degradation process. Moreover, the unique CeO2/CdS heterojunction photocatalyst was also effective in degrading TC wastewater with an H2 yield of 1374 µmol g-1 h-1, displaying its dual performance in simultaneously degrading antibiotic wastewater and producing H2. The CeO2/CdS type Ⅱ charge transfer mechanism is confirmed by XPS, EPR, KPFM, fs-TAS, and DFT calculations. This work introduces a promising approach to constructing rare-earth oxide/metal sulfide nanocomposites for addressing the interconnected challenges of energy production and environmental pollution.
2026, 37(5): 111720
doi: 10.1016/j.cclet.2025.111720
摘要:
Regulating gas diffusion is essential for a range of natural and industrial processes, including underwater breathing, aeration reactor and energy device. Natural organisms, e.g., water boatman, utilize their superaerophilic (SAL) abdomen to create a plastron underwater, enabling efficient gas exchange with dissolved oxygen. Herein, inspired by nature, we have developed a superaerophilic stripe that can form an air film underwater to enhance gas diffusion. Increasing the width (w) of the superaerophilic stripe and height (h) of water, along with decreasing the distance between the bubble and the stripe (d), can improve gas diffusion. Due to the improved dissolved gas diffusion, an efficient hydrogen evolution reaction driven by enhanced H2 diffusion was successfully achieved, resulting in an electrode potential decrease ~13 mV at the same current density of 1 mA/cm2 compared to that without the SAL stripe. This research offers important theoretical insights into the dynamics of gas diffusion and presents practical methods for enhancing gas mass transfer.
Regulating gas diffusion is essential for a range of natural and industrial processes, including underwater breathing, aeration reactor and energy device. Natural organisms, e.g., water boatman, utilize their superaerophilic (SAL) abdomen to create a plastron underwater, enabling efficient gas exchange with dissolved oxygen. Herein, inspired by nature, we have developed a superaerophilic stripe that can form an air film underwater to enhance gas diffusion. Increasing the width (w) of the superaerophilic stripe and height (h) of water, along with decreasing the distance between the bubble and the stripe (d), can improve gas diffusion. Due to the improved dissolved gas diffusion, an efficient hydrogen evolution reaction driven by enhanced H2 diffusion was successfully achieved, resulting in an electrode potential decrease ~13 mV at the same current density of 1 mA/cm2 compared to that without the SAL stripe. This research offers important theoretical insights into the dynamics of gas diffusion and presents practical methods for enhancing gas mass transfer.
2026, 37(5): 111789
doi: 10.1016/j.cclet.2025.111789
摘要:
Exposure to different neonicotinoid insecticides (NNIs) can cause varying degrees of harm to mammals and may even be carcinogenic. Due to their similar molecular structures, it is not only difficult to distinguish NNIs in analysis, but also cross-reactions can also occur. These cross-reactions cause the calibration curves to exhibit strong nonlinearities that cannot be fitted by usual mathematical models. Here, we present an electrochemical sensor array comprising three sensing units for the simultaneous determination of imidacloprid, thiamethoxam, and nitenpyram. The method eliminates cross-reaction with the aid of machine learning. The machine learning model comprises three components: the Douglas-Peucker algorithm for data compression, principal component analysis for classification, and an artificial neural network for quantification. The randomly assigned validation set showed a classification accuracy of 96.3% for the model. The prediction accuracy was 98.77%. The limit of detection was < 0.037 µmol/L, with a detection range from 0.1 µmol/L to 200 µmol/L. Finally, the spiked tea samples were tested, and a satisfactory agreement was obtained between the expected and predicted values.
Exposure to different neonicotinoid insecticides (NNIs) can cause varying degrees of harm to mammals and may even be carcinogenic. Due to their similar molecular structures, it is not only difficult to distinguish NNIs in analysis, but also cross-reactions can also occur. These cross-reactions cause the calibration curves to exhibit strong nonlinearities that cannot be fitted by usual mathematical models. Here, we present an electrochemical sensor array comprising three sensing units for the simultaneous determination of imidacloprid, thiamethoxam, and nitenpyram. The method eliminates cross-reaction with the aid of machine learning. The machine learning model comprises three components: the Douglas-Peucker algorithm for data compression, principal component analysis for classification, and an artificial neural network for quantification. The randomly assigned validation set showed a classification accuracy of 96.3% for the model. The prediction accuracy was 98.77%. The limit of detection was < 0.037 µmol/L, with a detection range from 0.1 µmol/L to 200 µmol/L. Finally, the spiked tea samples were tested, and a satisfactory agreement was obtained between the expected and predicted values.
2026, 37(5): 111790
doi: 10.1016/j.cclet.2025.111790
摘要:
In this work, bis-trimethylammonium pillar[5]arene (TP5) was synthesized for ionic pair assembly with 4,4′-biphenyldisulfonic acid (BA) to prepare a new kind of ionic single crystals (TP5-BA). The single crystal structure revealed that TP5-BA adopted an ordered cross-stacked arrangement under the combined influence of electrostatic interactions and π-π stacking forces. It is worth noting that TP5-BA exhibited exceptional performance in the adsorption of iodine vapor, with an adsorption capacity as high as 3.27 g/g. After 6 days, its retention rate remained at a high level of 99.71%. This finding may open up a new direction in supramolecular chemistry with ionic pair self-assembly, not only for the development of novel iodine adsorbent materials but also for many other potential applications such as catalysis and energy.
In this work, bis-trimethylammonium pillar[5]arene (TP5) was synthesized for ionic pair assembly with 4,4′-biphenyldisulfonic acid (BA) to prepare a new kind of ionic single crystals (TP5-BA). The single crystal structure revealed that TP5-BA adopted an ordered cross-stacked arrangement under the combined influence of electrostatic interactions and π-π stacking forces. It is worth noting that TP5-BA exhibited exceptional performance in the adsorption of iodine vapor, with an adsorption capacity as high as 3.27 g/g. After 6 days, its retention rate remained at a high level of 99.71%. This finding may open up a new direction in supramolecular chemistry with ionic pair self-assembly, not only for the development of novel iodine adsorbent materials but also for many other potential applications such as catalysis and energy.
2026, 37(5): 111791
doi: 10.1016/j.cclet.2025.111791
摘要:
Benzohydroxamic acid (BHA) occurs as recalcitrant organic pollutant discharged from mining industry. While Fenton-like oxidation based on peroxymonosulfate (PMS) has been extensively applied for organic contamination mitigation, its conventional reaction pathway dependent on free radicals needs high energy input with elevated carbon emission. Here, we meticulously developed a novel single-atom catalyst featuring Co-N4 coordination (Cox@NC) to initiate a non-radical Fenton-like oxidation for BHA treatment. Results showed single-atom Co-N4 with the considerable Co content (>2 wt%) and quantitative N coordination displayed exceptional reactivity to activate PMS for BHA degradation with a turnover frequency > 16 min−1. Such single-atom Co-N4 formed a surface-reactive complexes with mild oxidation potential by coordinating with PMS to mediate electron transfer for oxidation of BHA. The mediated ETP further triggered polymerization transformation pathway of BHA through formation and coupling of phenoxy-like radicals, resulting in a considerable recovery yield of BHA polymers (~43%) and superior utilization efficiency of PMS (~434%). Combined with ultrahigh-resolution mass analysis, the identified polymerized products illustrated the related polymerization mechanisms of BHA including hydroxylation, monomer radical generation, dimerization, and chain extension. Such Fenton-like catalysis of single-atom Co-N4 exhibited more remarkable application potentials in mineral processing wastewater treatment compared to traditional Fenton reaction, reducing oxidant consumption and increasing organic carbon recovery. This study enhances development of resource-efficient Fenton-like oxidation technologies for mineral processing wastewater treatment.
Benzohydroxamic acid (BHA) occurs as recalcitrant organic pollutant discharged from mining industry. While Fenton-like oxidation based on peroxymonosulfate (PMS) has been extensively applied for organic contamination mitigation, its conventional reaction pathway dependent on free radicals needs high energy input with elevated carbon emission. Here, we meticulously developed a novel single-atom catalyst featuring Co-N4 coordination (Cox@NC) to initiate a non-radical Fenton-like oxidation for BHA treatment. Results showed single-atom Co-N4 with the considerable Co content (>2 wt%) and quantitative N coordination displayed exceptional reactivity to activate PMS for BHA degradation with a turnover frequency > 16 min−1. Such single-atom Co-N4 formed a surface-reactive complexes with mild oxidation potential by coordinating with PMS to mediate electron transfer for oxidation of BHA. The mediated ETP further triggered polymerization transformation pathway of BHA through formation and coupling of phenoxy-like radicals, resulting in a considerable recovery yield of BHA polymers (~43%) and superior utilization efficiency of PMS (~434%). Combined with ultrahigh-resolution mass analysis, the identified polymerized products illustrated the related polymerization mechanisms of BHA including hydroxylation, monomer radical generation, dimerization, and chain extension. Such Fenton-like catalysis of single-atom Co-N4 exhibited more remarkable application potentials in mineral processing wastewater treatment compared to traditional Fenton reaction, reducing oxidant consumption and increasing organic carbon recovery. This study enhances development of resource-efficient Fenton-like oxidation technologies for mineral processing wastewater treatment.
2026, 37(5): 111811
doi: 10.1016/j.cclet.2025.111811
摘要:
Metallocenes are a wide family of organometallic compounds, in which two cyclopentadienyl ligands "sandwich" a metal ion, M(η5-C5R5)2, and have considerable potential for use as components in molecular electronics applications. Here we have studied the electronic transport properties of the matallocenes MCp2 (M = V, Cr, Mn, Fe, Co, Ni, Ru; Cp = η5-C5H5) and MCp*2 (M = Mn, Fe, Co; Cp* = η5-C5Me5). Molecular junctions have been fabricated using either two gold, or one gold and one graphene electrode(s), giving rise to single-molecule conductance values of the order of -4 to -3 log(G/G0)) depending on both the nature of the metallocene and the electrode materials. Calculations on model junctions at the density functional theory level of theory reveal significant charge transfer from the metallocene to the junction electrodes and changes in the nature of the primary charge transport pathways in response to the nature of the metal, supporting ligands, molecular oxidation state and electrode composition.
Metallocenes are a wide family of organometallic compounds, in which two cyclopentadienyl ligands "sandwich" a metal ion, M(η5-C5R5)2, and have considerable potential for use as components in molecular electronics applications. Here we have studied the electronic transport properties of the matallocenes MCp2 (M = V, Cr, Mn, Fe, Co, Ni, Ru; Cp = η5-C5H5) and MCp*2 (M = Mn, Fe, Co; Cp* = η5-C5Me5). Molecular junctions have been fabricated using either two gold, or one gold and one graphene electrode(s), giving rise to single-molecule conductance values of the order of -4 to -3 log(G/G0)) depending on both the nature of the metallocene and the electrode materials. Calculations on model junctions at the density functional theory level of theory reveal significant charge transfer from the metallocene to the junction electrodes and changes in the nature of the primary charge transport pathways in response to the nature of the metal, supporting ligands, molecular oxidation state and electrode composition.
2026, 37(5): 111825
doi: 10.1016/j.cclet.2025.111825
摘要:
Nickel-iron double hydroxides are corroded by Cl− during seawater electrolysis, which reduces their catalytic activity and stability. Here, a high-performance bifunctional electrocatalyst (NiFe-LDH/MoNi4) with enhanced chloride corrosion resistance was synthesized. In the OER process, Mo element in the catalyst was reconstructed to form MoO42−, which repelled Cl− to prevent the catalyst from being corroded. Besides, the heterostructure of NiFe-LDH/MoNi4 decreased the reduction of HER active site during HER process (Mo element dissolves easily in alkaline media due to thermodynamic instability). Therefore, based on in-situ self-reconstruction of Mo element and heterostructure in alkaline seawater, NiFe-LDH/MoNi4 delivered a current density of 10 mA/cm2 for the HER (OER) at industrial temperatures (80 ℃) with an overpotential of merely 32 mV (139 mV). Additionally, when NiFe-LDH/MoNi4 is employed as both the anode and cathode, a battery voltage of just 1.39 V (3.13 V) is sufficient to attain a current density of 10 mA/cm2 (1 A/cm2). The system is also capable of sustained operation at a high current density of 500 mA/cm2 for a period of 50 h.
Nickel-iron double hydroxides are corroded by Cl− during seawater electrolysis, which reduces their catalytic activity and stability. Here, a high-performance bifunctional electrocatalyst (NiFe-LDH/MoNi4) with enhanced chloride corrosion resistance was synthesized. In the OER process, Mo element in the catalyst was reconstructed to form MoO42−, which repelled Cl− to prevent the catalyst from being corroded. Besides, the heterostructure of NiFe-LDH/MoNi4 decreased the reduction of HER active site during HER process (Mo element dissolves easily in alkaline media due to thermodynamic instability). Therefore, based on in-situ self-reconstruction of Mo element and heterostructure in alkaline seawater, NiFe-LDH/MoNi4 delivered a current density of 10 mA/cm2 for the HER (OER) at industrial temperatures (80 ℃) with an overpotential of merely 32 mV (139 mV). Additionally, when NiFe-LDH/MoNi4 is employed as both the anode and cathode, a battery voltage of just 1.39 V (3.13 V) is sufficient to attain a current density of 10 mA/cm2 (1 A/cm2). The system is also capable of sustained operation at a high current density of 500 mA/cm2 for a period of 50 h.
2026, 37(5): 111838
doi: 10.1016/j.cclet.2025.111838
摘要:
Although periodate (PI) activation via iron-based Fenton-like reactions effectively generates reactive oxygen species (ROS) for pollutant degradation, Fe(Ⅲ) accumulation poses a major challenge to sustained ROS generation. Here, amorphous-boron (AB) was employed as a co-catalyst for boosting Fenton-like activation of PI (primarily Fe(Ⅲ)/PI) towards water decontamination, and the AB/Fe(Ⅲ)/PI process can promptly and steadily oxidize sulfamethoxazole (SMX) during 5 cycling tests. Through integrated qualitative and semi-quantitative analyses of ROS, including EPR, quenching, and chemical probes, AB can directly activate PI to produce hydroxyl radical and indirectly accelerate Fenton-like activation of PI to produce Fe(Ⅳ) by reducing Fe(Ⅲ). The synergetic routes of radical (hydroxyl radical) and non-radical (Fe(Ⅳ)) ensure the high capability of AB/Fe(Ⅲ)/PI for degrading a wide variety of contaminants with diversiform molecular structures. Moreover, characterizations (XPS, EPR, HAADF-STEM, HRTEM, Raman, and XRD) reveals the stepwise boron oxidation via B-B bond cleavage can sustainably donate electron for direct and indirect activation of PI. The self-cleaning surface caused by the synergetic stepwise oxidation of boron and dissolution of boron oxide maintains the high stability of AB for co-catalyzing Fenton-like activation of PI during long-term operation. Therefore, this study proposes a novel Fenton-like technique for eliminating organic contaminants with low iron sludge output and long-term stability.
Although periodate (PI) activation via iron-based Fenton-like reactions effectively generates reactive oxygen species (ROS) for pollutant degradation, Fe(Ⅲ) accumulation poses a major challenge to sustained ROS generation. Here, amorphous-boron (AB) was employed as a co-catalyst for boosting Fenton-like activation of PI (primarily Fe(Ⅲ)/PI) towards water decontamination, and the AB/Fe(Ⅲ)/PI process can promptly and steadily oxidize sulfamethoxazole (SMX) during 5 cycling tests. Through integrated qualitative and semi-quantitative analyses of ROS, including EPR, quenching, and chemical probes, AB can directly activate PI to produce hydroxyl radical and indirectly accelerate Fenton-like activation of PI to produce Fe(Ⅳ) by reducing Fe(Ⅲ). The synergetic routes of radical (hydroxyl radical) and non-radical (Fe(Ⅳ)) ensure the high capability of AB/Fe(Ⅲ)/PI for degrading a wide variety of contaminants with diversiform molecular structures. Moreover, characterizations (XPS, EPR, HAADF-STEM, HRTEM, Raman, and XRD) reveals the stepwise boron oxidation via B-B bond cleavage can sustainably donate electron for direct and indirect activation of PI. The self-cleaning surface caused by the synergetic stepwise oxidation of boron and dissolution of boron oxide maintains the high stability of AB for co-catalyzing Fenton-like activation of PI during long-term operation. Therefore, this study proposes a novel Fenton-like technique for eliminating organic contaminants with low iron sludge output and long-term stability.
2026, 37(5): 111839
doi: 10.1016/j.cclet.2025.111839
摘要:
The utilization of photoelectrocatalytic (PEC) technology for water pollution treatment and value-added chemical production is important in sustainable development strategies. A system combining Ag3PO4/g-C3N4 S-scheme heterojunction photoanodic oxidation with natural air diffusion electrode (NADE) reduction was designed. The PEC system could remove 94.5% of tetracycline (TC) with the first-order kinetic rate constant of 0.148 min-1, while the H2O2 yield in the cathodic chamber reached 4.3 µmol-1 h-1 cm-2 under 2.0 V cell voltage. The rate constant of TC degradation by the Ag3PO4/g-C3N4 coupled NADE PEC system was 4.4 times that of Ag3PO4/g-C3N4 coupled Pt PEC system (0.034 min-1). This was attributed to the synergistic effect between accelerated photoanode carrier transfer and increased H2O2 yield. The production of H2O2 in the cathode chamber of the PEC system with the presence of TC was 2.3 times that of absence of TC (1.9 µmol-1 h-1 cm-2). The active substances playing a major role in this PEC system were mainly h+ followed by •OH. Significantly, the efficient operation of the PEC system under actual sunlight will be conducive to the exploration of practical applications in the future. This study provides new insights for constructing efficient cathode-anode coupled PEC systems for water purification and simultaneous H2O2 production.
The utilization of photoelectrocatalytic (PEC) technology for water pollution treatment and value-added chemical production is important in sustainable development strategies. A system combining Ag3PO4/g-C3N4 S-scheme heterojunction photoanodic oxidation with natural air diffusion electrode (NADE) reduction was designed. The PEC system could remove 94.5% of tetracycline (TC) with the first-order kinetic rate constant of 0.148 min-1, while the H2O2 yield in the cathodic chamber reached 4.3 µmol-1 h-1 cm-2 under 2.0 V cell voltage. The rate constant of TC degradation by the Ag3PO4/g-C3N4 coupled NADE PEC system was 4.4 times that of Ag3PO4/g-C3N4 coupled Pt PEC system (0.034 min-1). This was attributed to the synergistic effect between accelerated photoanode carrier transfer and increased H2O2 yield. The production of H2O2 in the cathode chamber of the PEC system with the presence of TC was 2.3 times that of absence of TC (1.9 µmol-1 h-1 cm-2). The active substances playing a major role in this PEC system were mainly h+ followed by •OH. Significantly, the efficient operation of the PEC system under actual sunlight will be conducive to the exploration of practical applications in the future. This study provides new insights for constructing efficient cathode-anode coupled PEC systems for water purification and simultaneous H2O2 production.
2026, 37(5): 111840
doi: 10.1016/j.cclet.2025.111840
摘要:
Improving the reactivity of Fe(Ⅲ) is the bottleneck in the catalytic activity of persulfate-based Fenton-like chemistry. In this study, the Fe(Ⅲ)-PA catalyst was prepared for the activation of persulfate (PMS) by co-precipitation of phytate with iron ions. In particular, the Fe(Ⅲ)-PA/PMS system achieved efficient degradation of the target pollutant TCH under a wide range of pH conditions from 3.0 to 9.0. In the Fe(Ⅲ) PA/PMS/TCH system, the oxidative degradation of TCH was mainly via the direct electron transfer pathway. Density functional theory (DFT) calculations revealed the mechanism of PMS activation potentiation, that is, phytate reduced the adsorption energy of the catalyst for PMS from -0.43 eV to -2.72 eV by coordination with the ferrihydrite. Moreover, Fe(Ⅲ)-PA functions as an electron shuttle and accelerates the electron transfer process between TCH and PMS. The removal of TCH under the electron transfer process (ETP) mediated by Fe(Ⅲ)-PA was selective, thereby demonstrating less sensitivity to the presence of co-existing ions and natural organic matter (NOMs). This work provides a viable case for ligand-enhanced Fe(Ⅲ) activation of PMS and reveals the critical role of direct electron transfer in pollutant elimination.
Improving the reactivity of Fe(Ⅲ) is the bottleneck in the catalytic activity of persulfate-based Fenton-like chemistry. In this study, the Fe(Ⅲ)-PA catalyst was prepared for the activation of persulfate (PMS) by co-precipitation of phytate with iron ions. In particular, the Fe(Ⅲ)-PA/PMS system achieved efficient degradation of the target pollutant TCH under a wide range of pH conditions from 3.0 to 9.0. In the Fe(Ⅲ) PA/PMS/TCH system, the oxidative degradation of TCH was mainly via the direct electron transfer pathway. Density functional theory (DFT) calculations revealed the mechanism of PMS activation potentiation, that is, phytate reduced the adsorption energy of the catalyst for PMS from -0.43 eV to -2.72 eV by coordination with the ferrihydrite. Moreover, Fe(Ⅲ)-PA functions as an electron shuttle and accelerates the electron transfer process between TCH and PMS. The removal of TCH under the electron transfer process (ETP) mediated by Fe(Ⅲ)-PA was selective, thereby demonstrating less sensitivity to the presence of co-existing ions and natural organic matter (NOMs). This work provides a viable case for ligand-enhanced Fe(Ⅲ) activation of PMS and reveals the critical role of direct electron transfer in pollutant elimination.
2026, 37(5): 111844
doi: 10.1016/j.cclet.2025.111844
摘要:
Aqueously dispersed nanomaterials exhibiting circularly polarized luminescence (CPL) hold great potentials in biological fields due to the inherent chirality of biological systems and its excellent biocompatibility. However, the limited availability of biodegradable CPL nanoparticles in aqueous media has severely constrained the development of biomedical CPL. Here, we present a facile strategy for achieving tunable CPL of aqueously dispersed nanotoroids through the co-assembly of a homopolypeptide with three achiral triphenylamine derivatives, showing a CPL performance depending on the architecture and doping content of small molecules. Remarkably, a deep-red CPL can be achieved with a record luminescence dissymmetry factor (glum = 1.1 × 10−2) among aqueously polypeptide-based nanoparticles. Furthermore, the densely packed nanostructure completely suppressed the intrinsic reactive oxygen species generation of the chromophores by restricting oxygen diffusion and quenching exciton-energy transfer, thereby eliminating phototoxic risks while preserving imaging fidelity. Overall, this work not only provides a facile method for achieving aqueous CPL from achiral molecules but also establishes a structure-property relationship between chromophore geometry and supramolecular CPL performance, advancing their potential in biological fields.
Aqueously dispersed nanomaterials exhibiting circularly polarized luminescence (CPL) hold great potentials in biological fields due to the inherent chirality of biological systems and its excellent biocompatibility. However, the limited availability of biodegradable CPL nanoparticles in aqueous media has severely constrained the development of biomedical CPL. Here, we present a facile strategy for achieving tunable CPL of aqueously dispersed nanotoroids through the co-assembly of a homopolypeptide with three achiral triphenylamine derivatives, showing a CPL performance depending on the architecture and doping content of small molecules. Remarkably, a deep-red CPL can be achieved with a record luminescence dissymmetry factor (glum = 1.1 × 10−2) among aqueously polypeptide-based nanoparticles. Furthermore, the densely packed nanostructure completely suppressed the intrinsic reactive oxygen species generation of the chromophores by restricting oxygen diffusion and quenching exciton-energy transfer, thereby eliminating phototoxic risks while preserving imaging fidelity. Overall, this work not only provides a facile method for achieving aqueous CPL from achiral molecules but also establishes a structure-property relationship between chromophore geometry and supramolecular CPL performance, advancing their potential in biological fields.
2026, 37(5): 111851
doi: 10.1016/j.cclet.2025.111851
摘要:
Lactate (LA) is now recognized as a critical carbon source for tumor metabolism, making its transport blockade a promising anticancer therapeutic strategy. In this study, we incorporated α-cyano-4-hydroxycinnamate (CHC) into hollow-structured CuS@PCN nanoparticles to inhibit LA influx by suppressing the expression of the monocarboxylate transporter 1 (MCT1) in tumor cells. This intervention shifted tumor cell metabolism from LA-fueled oxidative phosphorylation towards anaerobic glycolysis, consequently elevating intratumoral oxygen (O2) levels. The photosensitizer-based metal-organic framework (PCN) component was then able to efficiently convert this elevated O2 into abundant reactive oxygen species (ROS), thereby enhancing photodynamic therapy (PDT) efficacy. Notably, the hollow mesoporous CuS nanoparticle core functioned dually as a high-capacity CHC carrier and a photothermal agent that enables CHC release under near-infrared (NIR) irradiation. Further surface conjugation with folic acid-polyethylene glycol (FA-PEG) imparted tumor-targeting specificity via folate receptor recognition and prolonged systemic circulation. Both in vitro and in vivo evaluations demonstrated the excellent biocompatibility and significantly improved PDT performance of the synthesized CHC-CuS@PCN-FA (CHC-CP-FA) nanoplatform. These findings underscore the considerable potential of CHC-CP-FA for future cancer treatment applications.
Lactate (LA) is now recognized as a critical carbon source for tumor metabolism, making its transport blockade a promising anticancer therapeutic strategy. In this study, we incorporated α-cyano-4-hydroxycinnamate (CHC) into hollow-structured CuS@PCN nanoparticles to inhibit LA influx by suppressing the expression of the monocarboxylate transporter 1 (MCT1) in tumor cells. This intervention shifted tumor cell metabolism from LA-fueled oxidative phosphorylation towards anaerobic glycolysis, consequently elevating intratumoral oxygen (O2) levels. The photosensitizer-based metal-organic framework (PCN) component was then able to efficiently convert this elevated O2 into abundant reactive oxygen species (ROS), thereby enhancing photodynamic therapy (PDT) efficacy. Notably, the hollow mesoporous CuS nanoparticle core functioned dually as a high-capacity CHC carrier and a photothermal agent that enables CHC release under near-infrared (NIR) irradiation. Further surface conjugation with folic acid-polyethylene glycol (FA-PEG) imparted tumor-targeting specificity via folate receptor recognition and prolonged systemic circulation. Both in vitro and in vivo evaluations demonstrated the excellent biocompatibility and significantly improved PDT performance of the synthesized CHC-CuS@PCN-FA (CHC-CP-FA) nanoplatform. These findings underscore the considerable potential of CHC-CP-FA for future cancer treatment applications.
2026, 37(5): 111853
doi: 10.1016/j.cclet.2025.111853
摘要:
Chemical scavengers are frequently used to quantify the contribution of target radicals to contaminant removal in natural and engineered waters. While favored for their ease of use and versatility across systems, improper selection can lead to significant kinetic and mechanistic misinterpretations. This study presents a critical evaluation of chemical scavengers in radical-induced reactions across various environmental scenarios. Specifically, we demonstrate that in systems containing both target and coexisting radicals, commonly used scavengers can react with both species, complicating the measurement of reaction kinetics and leading to misinterpretation of target radical contributions. In addition, we discuss the challenges associated with applying scavengers in heterogeneous systems, where the distribution of scavengers and target compounds across interfaces significantly impacts the evaluation of radical contributions. Further, our insights from non-steady-state systems into radicals' dynamic behavior and transient phenomena are often overlooked in other steady-state conditions. We address interactions between scavengers and triplet excited-state compounds in photochemical systems, emphasizing the importance of selecting appropriate scavengers to ensure accurate kinetic profiling and radical quantification. These findings hold significant implications for advancing scavenger research across a broad range of chemical research and practical applications.
Chemical scavengers are frequently used to quantify the contribution of target radicals to contaminant removal in natural and engineered waters. While favored for their ease of use and versatility across systems, improper selection can lead to significant kinetic and mechanistic misinterpretations. This study presents a critical evaluation of chemical scavengers in radical-induced reactions across various environmental scenarios. Specifically, we demonstrate that in systems containing both target and coexisting radicals, commonly used scavengers can react with both species, complicating the measurement of reaction kinetics and leading to misinterpretation of target radical contributions. In addition, we discuss the challenges associated with applying scavengers in heterogeneous systems, where the distribution of scavengers and target compounds across interfaces significantly impacts the evaluation of radical contributions. Further, our insights from non-steady-state systems into radicals' dynamic behavior and transient phenomena are often overlooked in other steady-state conditions. We address interactions between scavengers and triplet excited-state compounds in photochemical systems, emphasizing the importance of selecting appropriate scavengers to ensure accurate kinetic profiling and radical quantification. These findings hold significant implications for advancing scavenger research across a broad range of chemical research and practical applications.
2026, 37(5): 111857
doi: 10.1016/j.cclet.2025.111857
摘要:
Chlorine is not only widely used as an important basic chemical, but also shows promising in-situ electrochemical remediation. Unfortunately, its electrochemical production usually relies on expensive noble-metal dimensionally stable anode (DSA). Herein, a high-performance non-noble metal Co3O4/Ti anode was developed by a simple electrodeposition-calcination method, demonstrating a high efficiency in producing active chlorine in a wide pH range (3–11) and at relatively low Cl- concentration close to different real environmental requirements due to its abundant surface area and active sites provided by the interlaced nanosheet structure anode. Compared with commercial DSA, the Co3O4/Ti anode offered significant advantages in terms of Faraday efficiency, electric energy consumption and economic cost, achieving the rate of active chlorine production of 14.97 mg L-1 min-1 in 0.5 mol/L NaCl electrolyte solution (pH 6) with a Faraday efficiency of 96.8% and low energy consumption of 2.49 kWh/kg. Moreover, the robust backbone structure of the anode enabled the Faraday efficiency to be maintained at about 92.2% without deactivation after ten cycles of reaction. In addition, this Co3O4/Ti electrode demonstrated effectiveness in treating organic pollutants and mariculture wastewater and seawater rapid sterilization. This study provides new inspirations for the construction of highly efficient, low-cost, and low energy consumption non-noble metal cobalt-based anode for the in-situ environmental remediation application.
Chlorine is not only widely used as an important basic chemical, but also shows promising in-situ electrochemical remediation. Unfortunately, its electrochemical production usually relies on expensive noble-metal dimensionally stable anode (DSA). Herein, a high-performance non-noble metal Co3O4/Ti anode was developed by a simple electrodeposition-calcination method, demonstrating a high efficiency in producing active chlorine in a wide pH range (3–11) and at relatively low Cl- concentration close to different real environmental requirements due to its abundant surface area and active sites provided by the interlaced nanosheet structure anode. Compared with commercial DSA, the Co3O4/Ti anode offered significant advantages in terms of Faraday efficiency, electric energy consumption and economic cost, achieving the rate of active chlorine production of 14.97 mg L-1 min-1 in 0.5 mol/L NaCl electrolyte solution (pH 6) with a Faraday efficiency of 96.8% and low energy consumption of 2.49 kWh/kg. Moreover, the robust backbone structure of the anode enabled the Faraday efficiency to be maintained at about 92.2% without deactivation after ten cycles of reaction. In addition, this Co3O4/Ti electrode demonstrated effectiveness in treating organic pollutants and mariculture wastewater and seawater rapid sterilization. This study provides new inspirations for the construction of highly efficient, low-cost, and low energy consumption non-noble metal cobalt-based anode for the in-situ environmental remediation application.
2026, 37(5): 111858
doi: 10.1016/j.cclet.2025.111858
摘要:
Per- and polyfluoroalkyl substances (PFASs), especially perfluorooctanoic acid (PFOA), pose a significant threat to ecosystems and human health due to their extreme persistence and bioaccumulative properties. Although metal-organic frameworks (MOFs) show potential for adsorption, their efficiency is limited by insufficient active sites and the inability to control the design of adsorption centers, which is a key bottleneck for practical application. In this study, defect engineering was employed to synthesize NH2-UiO-66 derivatives with gradient defect densities (NH2-UiO-66, -LD, -HD), exposing unsaturated Zr sites to enhance PFOA capture. The optimized NH2-UiO-66-HD exhibited ultrafast kinetics, achieving 95% removal within 30 min and a theoretical adsorption capacity of up to 739.31 mg/g, surpassing most MOFs and traditional adsorbents. Mechanistic studies revealed that defect-induced unsaturated Zr sites act as high-affinity anchors, strongly coordinating with the -COO- group of PFOA, while forming a triple interaction mechanism with N–H···F hydrogen bonds and electrostatic interactions (-NH3+), a synergy not previously reported. The material maintained over 90% efficiency through seven cycles, addressing long-standing regenerability challenges in PFAS remediation. This research pioneers a programmable defect-control approach to create hierarchical active sites in MOFs and first demonstrates the synergy of Zr coordination, hydrogen bonding, and electrostatic attraction for ultra-efficient PFAS removal.
Per- and polyfluoroalkyl substances (PFASs), especially perfluorooctanoic acid (PFOA), pose a significant threat to ecosystems and human health due to their extreme persistence and bioaccumulative properties. Although metal-organic frameworks (MOFs) show potential for adsorption, their efficiency is limited by insufficient active sites and the inability to control the design of adsorption centers, which is a key bottleneck for practical application. In this study, defect engineering was employed to synthesize NH2-UiO-66 derivatives with gradient defect densities (NH2-UiO-66, -LD, -HD), exposing unsaturated Zr sites to enhance PFOA capture. The optimized NH2-UiO-66-HD exhibited ultrafast kinetics, achieving 95% removal within 30 min and a theoretical adsorption capacity of up to 739.31 mg/g, surpassing most MOFs and traditional adsorbents. Mechanistic studies revealed that defect-induced unsaturated Zr sites act as high-affinity anchors, strongly coordinating with the -COO- group of PFOA, while forming a triple interaction mechanism with N–H···F hydrogen bonds and electrostatic interactions (-NH3+), a synergy not previously reported. The material maintained over 90% efficiency through seven cycles, addressing long-standing regenerability challenges in PFAS remediation. This research pioneers a programmable defect-control approach to create hierarchical active sites in MOFs and first demonstrates the synergy of Zr coordination, hydrogen bonding, and electrostatic attraction for ultra-efficient PFAS removal.
2026, 37(5): 111860
doi: 10.1016/j.cclet.2025.111860
摘要:
The high sensitivity of platinum (Pt)-based catalysts to CO during the hydrogen oxidation reaction (HOR) at the anode is one of the key issues for the long-term stable development of proton exchange membrane fuel cells (PEMFCs). Modulating the electronic structure of Pt is considered an effective approach to enhancing HOR activity and improving CO tolerance. Herein, we utilized the synergistic effect between the transition metal interstitial compounds (TMICs) of VN and Pt to develop a Pt-VN heterojunction-loaded carbon nanofiber catalyst (Pt-VN/NCNF) for CO tolerance in HOR. The introduction of VN causes electronic orbitals rearrangement of Pt, thereby optimizing the adsorption of H on the Pt surface. Meanwhile, the overlap of the d-band of the electron-deficient Pt with the 1π and 5σ bonding orbitals of CO was significantly reduced, which suppresses the strong CO adsorption on Pt surfaces and leave more active sites for H2 adsorption and oxidation. As a result, Pt-VN/NCNF exhibits a mass activity of 1.26 mA/µgPt, 41 times higher than that of commercial Pt/C. Encouragingly, Pt-VN/NCNF maintains 96.7% of its original activity even in the presence of 1000 ppm CO. As anticipated, Pt-VN/NCNF-based PEMFCs demonstrate superior CO tolerance to Pt/C in H2/CO mixtures with CO concentrations ranging from 10 ppm to 1000 ppm.
The high sensitivity of platinum (Pt)-based catalysts to CO during the hydrogen oxidation reaction (HOR) at the anode is one of the key issues for the long-term stable development of proton exchange membrane fuel cells (PEMFCs). Modulating the electronic structure of Pt is considered an effective approach to enhancing HOR activity and improving CO tolerance. Herein, we utilized the synergistic effect between the transition metal interstitial compounds (TMICs) of VN and Pt to develop a Pt-VN heterojunction-loaded carbon nanofiber catalyst (Pt-VN/NCNF) for CO tolerance in HOR. The introduction of VN causes electronic orbitals rearrangement of Pt, thereby optimizing the adsorption of H on the Pt surface. Meanwhile, the overlap of the d-band of the electron-deficient Pt with the 1π and 5σ bonding orbitals of CO was significantly reduced, which suppresses the strong CO adsorption on Pt surfaces and leave more active sites for H2 adsorption and oxidation. As a result, Pt-VN/NCNF exhibits a mass activity of 1.26 mA/µgPt, 41 times higher than that of commercial Pt/C. Encouragingly, Pt-VN/NCNF maintains 96.7% of its original activity even in the presence of 1000 ppm CO. As anticipated, Pt-VN/NCNF-based PEMFCs demonstrate superior CO tolerance to Pt/C in H2/CO mixtures with CO concentrations ranging from 10 ppm to 1000 ppm.
2026, 37(5): 111862
doi: 10.1016/j.cclet.2025.111862
摘要:
To elucidate the regulatory mechanisms of interlayers on interfacial polymerization (IP) dynamics and thin-film composite (TFC) membrane performance, UiO-66 and its derivatives with tailored properties were synthesized and employed as interlayers to fabricate TFC membranes. The influence of interlayer's charge and porosity on IP reaction was systematically investigated based on the forward osmosis (FO) system. Results showed that the introduction of the UiO-66 interlayer promoted the diffusion of the reactive monomer during the initial stage of the IP reaction, resulting in a wrinkled and thin polyamide (PA) layer. Compared to the pristine TFC membrane, the UiO-66–0% interlayered TFC membrane exhibited 2.7-fold enhanced water permeability (21.67 L m−2 h−1 (LMH)) but reduced salt rejection (3.69 g m−2 h−1 (gMH)). Incorporation of amino-functionalized UiO-66–30% with enhanced positive charge induced a double-layer PA structure, reducing water flux to 15.13 LMH. Engineering hierarchically porous UiO-66 (HP-UiO-66–30%) achieved balanced performance, maintaining high flux (21.04 LMH) while significantly improving rejection (1.39 gMH). This study demonstrates that strategic modulation of nanomaterial functionality and porosity enables precise PA layer engineering for high-performance TFC membranes with simultaneously enhanced permeability and selectivity.
To elucidate the regulatory mechanisms of interlayers on interfacial polymerization (IP) dynamics and thin-film composite (TFC) membrane performance, UiO-66 and its derivatives with tailored properties were synthesized and employed as interlayers to fabricate TFC membranes. The influence of interlayer's charge and porosity on IP reaction was systematically investigated based on the forward osmosis (FO) system. Results showed that the introduction of the UiO-66 interlayer promoted the diffusion of the reactive monomer during the initial stage of the IP reaction, resulting in a wrinkled and thin polyamide (PA) layer. Compared to the pristine TFC membrane, the UiO-66–0% interlayered TFC membrane exhibited 2.7-fold enhanced water permeability (21.67 L m−2 h−1 (LMH)) but reduced salt rejection (3.69 g m−2 h−1 (gMH)). Incorporation of amino-functionalized UiO-66–30% with enhanced positive charge induced a double-layer PA structure, reducing water flux to 15.13 LMH. Engineering hierarchically porous UiO-66 (HP-UiO-66–30%) achieved balanced performance, maintaining high flux (21.04 LMH) while significantly improving rejection (1.39 gMH). This study demonstrates that strategic modulation of nanomaterial functionality and porosity enables precise PA layer engineering for high-performance TFC membranes with simultaneously enhanced permeability and selectivity.
2026, 37(5): 111864
doi: 10.1016/j.cclet.2025.111864
摘要:
Porous liquids (PLs), as a new class of porous materials with permanent porosity and liquid fluidity, have attracted extensive research interest due to their excellent physical and chemical properties. Herein, we synthesized a chiral porous liquid D-his-ZIF-8-[Bpy][NTf2] based on a metal-organic framework (MOF) and used it as a new stationary phase to investigate its separation performance by high-resolution gas chromatography. The porosity of this porous liquid system was verified through Brunauer-Emmett-Teller (BET) and positron (e+) annihilation lifetime spectroscopy (PALS). The results showed that the D-his-ZIF-8-[Bpy][NTf2] coated capillary column (column A) exhibited excellent separation performance for n-alkanes, n-alcohols, alkylbenzens, isomers, and racemic compounds. Among them, fifteen pairs of enantiomers including alcohols, esters, epoxides, ketones, haloalkanes, and amino acid derivatives were well separated on column A with good reproducibility and stability. The relative standard deviations (RSDs) of the retention time and peak area of two analytes (3-butyne-2-ol and dichlorobenzene) were <1.80% and 0.80%, respectively. By comparing the chiral recognition ability of D-his-ZIF-8-[Bpy][NTf2] coated column A with D-his-ZIF-8 coated column B, the column A has better separation efficiency for chiral compounds than column B. In addition, the chiral recognition ability of column A is complementary to that of commercially available β-DEX 120 column (column C). Compared with the commercial HP-35 column and the previously reported P5A-C10–2NH2 column for the separation of organic mixtures and/or isomers, column A exhibits similar separation performance and has a good separation complementarity to these two columns. Hence, this work opens up a new way for the practical application of porous framework solid materials in gas chromatography.
Porous liquids (PLs), as a new class of porous materials with permanent porosity and liquid fluidity, have attracted extensive research interest due to their excellent physical and chemical properties. Herein, we synthesized a chiral porous liquid D-his-ZIF-8-[Bpy][NTf2] based on a metal-organic framework (MOF) and used it as a new stationary phase to investigate its separation performance by high-resolution gas chromatography. The porosity of this porous liquid system was verified through Brunauer-Emmett-Teller (BET) and positron (e+) annihilation lifetime spectroscopy (PALS). The results showed that the D-his-ZIF-8-[Bpy][NTf2] coated capillary column (column A) exhibited excellent separation performance for n-alkanes, n-alcohols, alkylbenzens, isomers, and racemic compounds. Among them, fifteen pairs of enantiomers including alcohols, esters, epoxides, ketones, haloalkanes, and amino acid derivatives were well separated on column A with good reproducibility and stability. The relative standard deviations (RSDs) of the retention time and peak area of two analytes (3-butyne-2-ol and dichlorobenzene) were <1.80% and 0.80%, respectively. By comparing the chiral recognition ability of D-his-ZIF-8-[Bpy][NTf2] coated column A with D-his-ZIF-8 coated column B, the column A has better separation efficiency for chiral compounds than column B. In addition, the chiral recognition ability of column A is complementary to that of commercially available β-DEX 120 column (column C). Compared with the commercial HP-35 column and the previously reported P5A-C10–2NH2 column for the separation of organic mixtures and/or isomers, column A exhibits similar separation performance and has a good separation complementarity to these two columns. Hence, this work opens up a new way for the practical application of porous framework solid materials in gas chromatography.
2026, 37(5): 111874
doi: 10.1016/j.cclet.2025.111874
摘要:
Geometrical configurations at the nanometer scale are inherently linked to electronic properties, offering exciting opportunity to engineer the latter through precise structural control. The honeycomb structure, a prominent geometry in two-dimensional materials like graphene, has become a versatile platform for advancing energy technologies, quantum computing, and nanoscale sensing. Achieving a perfect honeycomb network at large scale remains challenging but desired, especially when atomic defects and disorder can severely impact materials' properties and performances. Intrinsic topological defects often persist due to the conformational flexibility of the precursor skeletons, which allows precursor monomers to deform despite variations in preparation parameters. To address this challenge, we employ a tripod molecular precursor, pTBPT, combined with ultrahigh vacuum on-surface synthesis. Networks comprising rings of different edges are initially formed after deposition of pTBPT on Cu (111) at room temperature to 420 K. At low coverage (~0.015 monolayer) selenium doping, we achieve the fabrication of ordered honeycomb networks with much improved structural homogeneity. Selenium doping facilitated the formation of ordered two-dimensional metal-organic nanostructure from 360 K to 480 K. The disorder−order transition of molecular networks through selenium doping on Cu (111) is explored through high-resolution scanning tunneling microscopy (STM). A persistent homology method is resorted to quantify the degree of order of our patterns. The regulation of energy diagrams in the absence or presence of the selenium atom is revealed by density functional theory (DFT) calculations. These findings can enrich the on-surface synthesis toolbox of conformationally flexible precursors, for the design of ordered nanoarchitectures, and for future development of engineered honeycomb nanomaterials.
Geometrical configurations at the nanometer scale are inherently linked to electronic properties, offering exciting opportunity to engineer the latter through precise structural control. The honeycomb structure, a prominent geometry in two-dimensional materials like graphene, has become a versatile platform for advancing energy technologies, quantum computing, and nanoscale sensing. Achieving a perfect honeycomb network at large scale remains challenging but desired, especially when atomic defects and disorder can severely impact materials' properties and performances. Intrinsic topological defects often persist due to the conformational flexibility of the precursor skeletons, which allows precursor monomers to deform despite variations in preparation parameters. To address this challenge, we employ a tripod molecular precursor, pTBPT, combined with ultrahigh vacuum on-surface synthesis. Networks comprising rings of different edges are initially formed after deposition of pTBPT on Cu (111) at room temperature to 420 K. At low coverage (~0.015 monolayer) selenium doping, we achieve the fabrication of ordered honeycomb networks with much improved structural homogeneity. Selenium doping facilitated the formation of ordered two-dimensional metal-organic nanostructure from 360 K to 480 K. The disorder−order transition of molecular networks through selenium doping on Cu (111) is explored through high-resolution scanning tunneling microscopy (STM). A persistent homology method is resorted to quantify the degree of order of our patterns. The regulation of energy diagrams in the absence or presence of the selenium atom is revealed by density functional theory (DFT) calculations. These findings can enrich the on-surface synthesis toolbox of conformationally flexible precursors, for the design of ordered nanoarchitectures, and for future development of engineered honeycomb nanomaterials.
2026, 37(5): 111903
doi: 10.1016/j.cclet.2025.111903
摘要:
In light of the prevalent issues associated with metal ion dissolution, secondary pollution, and poor stability in traditional metal-based Fenton catalysts, this study innovatively developed a metal-free carbon-based catalyst co-doped with Si-O bonds and graphitic nitrogen using natural diatomite as the precursor. By leveraging the synergistic effects of Si-O bonds and graphitic nitrogen, the electronic structure of the carbon matrix was effectively modulated, establishing an efficient electron transport channel for peroxymonosulfate (PMS) activation. Results showed that the Fenton-like performance of the resulting catalysts was far superior to those of traditional metal catalysts and can be comparable to various single-atom catalysts. Both the radical and 1O2 pathways exhibited a negligible role in the metal-free Si-O/N@DM/PMS systems. In contrast, electron transfer process (ETP) was the predominate oxidation pathway for acetaminophen (PCM) degradation in the Si-O/N@DM/PMS systems. To facilitate engineering applications, we further designed a proton membrane reactor integrated with a four-channel PMS system, which could introduce an enlarged ETP pathway for pollutant degradation; this addresses the key issues of both sulfate pollution and metal leaching in water caused by traditional metal-based Fenton systems.
In light of the prevalent issues associated with metal ion dissolution, secondary pollution, and poor stability in traditional metal-based Fenton catalysts, this study innovatively developed a metal-free carbon-based catalyst co-doped with Si-O bonds and graphitic nitrogen using natural diatomite as the precursor. By leveraging the synergistic effects of Si-O bonds and graphitic nitrogen, the electronic structure of the carbon matrix was effectively modulated, establishing an efficient electron transport channel for peroxymonosulfate (PMS) activation. Results showed that the Fenton-like performance of the resulting catalysts was far superior to those of traditional metal catalysts and can be comparable to various single-atom catalysts. Both the radical and 1O2 pathways exhibited a negligible role in the metal-free Si-O/N@DM/PMS systems. In contrast, electron transfer process (ETP) was the predominate oxidation pathway for acetaminophen (PCM) degradation in the Si-O/N@DM/PMS systems. To facilitate engineering applications, we further designed a proton membrane reactor integrated with a four-channel PMS system, which could introduce an enlarged ETP pathway for pollutant degradation; this addresses the key issues of both sulfate pollution and metal leaching in water caused by traditional metal-based Fenton systems.
2026, 37(5): 111914
doi: 10.1016/j.cclet.2025.111914
摘要:
Eliminating heavy metals from industrial high-salinity wastewater is imperative for sustainable industrial development and environmental protection. Herein, a citrate-modified biochar that demonstrated robust anti-salt interference was developed. The sorbent achieved an adsorption capacity of 252.14 mg/g in 4.1 mol/L NaCl solution and 232.55 mg/g in 1.4 mol/L Na2SO4 solution, maintaining efficient Cu(Ⅱ) adsorption over four cycles. It retained an adsorption capacity of 236.89 mg/g in real waste salt-derived brine. Adsorption followed pseudo-first-order kinetics (k = 0.0901 min-1) and conformed to the Langmuir isotherm (qmax = 251.21 mg/g) model, indicating that physical adsorption on a homogeneous surface primarily governs the adsorption mechanisms. Thermodynamic analysis revealed that the adsorption is spontaneous and endothermic, with enhanced affinity for Cu(Ⅱ) at higher temperatures. Oxygen-containing groups, especially the hydroxyl group, drove adsorption via surface precipitation/complexation, ultimately generating posnjakite (Cu4(SO4)(OH)6·2H2O). Cost analysis showed that the total expenditure for treating 1000 L of wastewater (300 mgCu/L) was ＄28.89 (＄0.0963/gCu(Ⅱ)) and the treatment capacity using fixed-bed columns was 120 L/kg. These findings offer a viable and cost-effective strategy for Cu(Ⅱ) elimination from high-salinity wastewater.
Eliminating heavy metals from industrial high-salinity wastewater is imperative for sustainable industrial development and environmental protection. Herein, a citrate-modified biochar that demonstrated robust anti-salt interference was developed. The sorbent achieved an adsorption capacity of 252.14 mg/g in 4.1 mol/L NaCl solution and 232.55 mg/g in 1.4 mol/L Na2SO4 solution, maintaining efficient Cu(Ⅱ) adsorption over four cycles. It retained an adsorption capacity of 236.89 mg/g in real waste salt-derived brine. Adsorption followed pseudo-first-order kinetics (k = 0.0901 min-1) and conformed to the Langmuir isotherm (qmax = 251.21 mg/g) model, indicating that physical adsorption on a homogeneous surface primarily governs the adsorption mechanisms. Thermodynamic analysis revealed that the adsorption is spontaneous and endothermic, with enhanced affinity for Cu(Ⅱ) at higher temperatures. Oxygen-containing groups, especially the hydroxyl group, drove adsorption via surface precipitation/complexation, ultimately generating posnjakite (Cu4(SO4)(OH)6·2H2O). Cost analysis showed that the total expenditure for treating 1000 L of wastewater (300 mgCu/L) was ＄28.89 (＄0.0963/gCu(Ⅱ)) and the treatment capacity using fixed-bed columns was 120 L/kg. These findings offer a viable and cost-effective strategy for Cu(Ⅱ) elimination from high-salinity wastewater.
2026, 37(5): 111923
doi: 10.1016/j.cclet.2025.111923
摘要:
Non-noble metal catalysts have garnered significant attention as sustainable alternatives to precious metal catalysts for the abatement of hydrocarbon emissions and mitigating environmental pollution. In this study, we employed an in-situ exsolution strategy coupled with oxidation stabilization to engineer the surface of cobalt-doped LaFeO3-δ catalysts, successfully extending their application in an oxygen-rich scenario. The formed unique socket-like structure facilitates the exposure of highly reactive CoOx particles with superior homogeneity in both size and distribution. The optimized catalyst, CoOx@LFCO-3, achieved 90% toluene conversion at a notably lower temperature of 237 ℃ with a space velocity of 20,000 mL g−1 h−1. Mechanistic studies revealed that the enhanced interaction between exsolved cobalt oxides and the perovskite support, along with abundant active sites, significantly improved the catalyst's performance in low-temperature toluene oxidation. This work presents a scalable approach for developing cost-effective, high-performance perovskite oxide catalysts for environmental applications.
Non-noble metal catalysts have garnered significant attention as sustainable alternatives to precious metal catalysts for the abatement of hydrocarbon emissions and mitigating environmental pollution. In this study, we employed an in-situ exsolution strategy coupled with oxidation stabilization to engineer the surface of cobalt-doped LaFeO3-δ catalysts, successfully extending their application in an oxygen-rich scenario. The formed unique socket-like structure facilitates the exposure of highly reactive CoOx particles with superior homogeneity in both size and distribution. The optimized catalyst, CoOx@LFCO-3, achieved 90% toluene conversion at a notably lower temperature of 237 ℃ with a space velocity of 20,000 mL g−1 h−1. Mechanistic studies revealed that the enhanced interaction between exsolved cobalt oxides and the perovskite support, along with abundant active sites, significantly improved the catalyst's performance in low-temperature toluene oxidation. This work presents a scalable approach for developing cost-effective, high-performance perovskite oxide catalysts for environmental applications.
2026, 37(5): 111927
doi: 10.1016/j.cclet.2025.111927
摘要:
The preparation of porous molecularly imprinted polymers (MIPs) from starch, a natural product, presents significant challenges. In this study, we developed a straightforward method for preparing porous MIPs (DFP-MIPs) by crosslinking short amylose as a functional monomer with decafluorobiphenyl (DFP) as a cross-linker. Experimental results indicated that DFP-MIPs exhibited a larger specific surface area (14.06 m2/g) and adsorption capacity (26.3 mg/g), and a high imprinting factor of 3.14 for estradiol (E2), compared to MIPs prepared using tetrafluorobenzenediamine with a single benzene ring as the cross-linker. A method for detecting E2 in milk and meat samples was also established using DFP-MIPs as the adsorbent in conjunction with high-performance liquid chromatography. Under optimal conditions, this method demonstrated a linear range of 0.0200–0.400 µg/g, a detection limit of 0.00300 µg/g, and a recovery rate of 85.2% to 101.4%. The proposed method for preparing DFP-MIPs is expected to provide a new pathway for the development of porous and highly selective MIPs using amylose.
The preparation of porous molecularly imprinted polymers (MIPs) from starch, a natural product, presents significant challenges. In this study, we developed a straightforward method for preparing porous MIPs (DFP-MIPs) by crosslinking short amylose as a functional monomer with decafluorobiphenyl (DFP) as a cross-linker. Experimental results indicated that DFP-MIPs exhibited a larger specific surface area (14.06 m2/g) and adsorption capacity (26.3 mg/g), and a high imprinting factor of 3.14 for estradiol (E2), compared to MIPs prepared using tetrafluorobenzenediamine with a single benzene ring as the cross-linker. A method for detecting E2 in milk and meat samples was also established using DFP-MIPs as the adsorbent in conjunction with high-performance liquid chromatography. Under optimal conditions, this method demonstrated a linear range of 0.0200–0.400 µg/g, a detection limit of 0.00300 µg/g, and a recovery rate of 85.2% to 101.4%. The proposed method for preparing DFP-MIPs is expected to provide a new pathway for the development of porous and highly selective MIPs using amylose.
2026, 37(5): 111931
doi: 10.1016/j.cclet.2025.111931
摘要:
Developing a supramolecular polymer gel based on carbonized polymer dots with highly efficient lubrication properties is very challenging. Here, we obtained a kind of carbonized polymer dots (CPDs) by thermal reflux of long-chain aliphatic amines in halogenated benzene solvents. The CPDs nano-gel achieved high lubrication performance due to entangling effect of long chain and reversible thixotropic behavior after gel formation. Two-dimensional correlation synchronous (2D-COS) showed the CPDs connect small carbon dots into large hydrophobic structures through their own dense chain entanglement, thus trapping oil to form gel. Chain entanglement, as a non-permanent crosslinking, can slide under stress, and this flexible and dynamic characteristic allows it to maintain efficient and long-lasting lubrication without hysteresis during friction. The tribological test results showed a significant reduction of 38.14% in the coefficient of friction and 93.71% in wear scar diameter after lubrication with CPDs nano-gel. Moreover, the serial analysis for the friction interface and computational methodologies revealed that the formation of tribochemical film between friction pairs is the key to reduce wear. This study underscored the possibility of utilizing carbonized polymer dots for self-assembly applications, and we anticipate that supramolecular carbonized polymer dots gels have great potential in lubrication and emission reduction, ultimately contributing to the development of a sustainable society.
Developing a supramolecular polymer gel based on carbonized polymer dots with highly efficient lubrication properties is very challenging. Here, we obtained a kind of carbonized polymer dots (CPDs) by thermal reflux of long-chain aliphatic amines in halogenated benzene solvents. The CPDs nano-gel achieved high lubrication performance due to entangling effect of long chain and reversible thixotropic behavior after gel formation. Two-dimensional correlation synchronous (2D-COS) showed the CPDs connect small carbon dots into large hydrophobic structures through their own dense chain entanglement, thus trapping oil to form gel. Chain entanglement, as a non-permanent crosslinking, can slide under stress, and this flexible and dynamic characteristic allows it to maintain efficient and long-lasting lubrication without hysteresis during friction. The tribological test results showed a significant reduction of 38.14% in the coefficient of friction and 93.71% in wear scar diameter after lubrication with CPDs nano-gel. Moreover, the serial analysis for the friction interface and computational methodologies revealed that the formation of tribochemical film between friction pairs is the key to reduce wear. This study underscored the possibility of utilizing carbonized polymer dots for self-assembly applications, and we anticipate that supramolecular carbonized polymer dots gels have great potential in lubrication and emission reduction, ultimately contributing to the development of a sustainable society.
2026, 37(5): 111935
doi: 10.1016/j.cclet.2025.111935
摘要:
Rational design of nonmetallic heteroatom-doped biochar catalysts for peroxymonosulfate (PMS) activation faces dual challenges in regulating electronic structures and clarifying non-radical pathways. This study addressed this through a nitrogen-oxygen co-doped biochar (NOBCBM) synthesized via mechanochemical ball milling and chemical doping. Co-doping of C=O, pyridinic N, and graphitic N synergistically enhanced electron transfer and PMS activation efficiency compared to single N-doped biochar systems. The optimized NOBCBM removed 94% oxytetracycline (OTC) (20 mg/L) in 30 min, with a kinetic constant (kobs = 0.1523 min−1) over twice that of NSBCBM (0.0664 min−1). Radical quenching and electron paramagnetic resonance identified singlet oxygen (1O2) and electron transfer as dominant non-radical pathways. Density functional theory (DFT) calculations revealed oxygen doping elevates local electrostatic potential and redistributes electron density at N-active sites, amplifying catalytic activity. The system demonstrated robust catalytic performance across pH 3–11, high salinity, and complex water matrices, maintaining > 80% OTC removal over 72 h. Plant growth assays and life cycle assessment (LCA) confirmed minimal ecological impacts, with purified water supporting normal seedling development. This work elucidates the critical role of N/O co-doping in steering PMS activation toward non-radical mechanisms while establishing a sustainable paradigm for metal-free biochar catalysis in water remediation.
Rational design of nonmetallic heteroatom-doped biochar catalysts for peroxymonosulfate (PMS) activation faces dual challenges in regulating electronic structures and clarifying non-radical pathways. This study addressed this through a nitrogen-oxygen co-doped biochar (NOBCBM) synthesized via mechanochemical ball milling and chemical doping. Co-doping of C=O, pyridinic N, and graphitic N synergistically enhanced electron transfer and PMS activation efficiency compared to single N-doped biochar systems. The optimized NOBCBM removed 94% oxytetracycline (OTC) (20 mg/L) in 30 min, with a kinetic constant (kobs = 0.1523 min−1) over twice that of NSBCBM (0.0664 min−1). Radical quenching and electron paramagnetic resonance identified singlet oxygen (1O2) and electron transfer as dominant non-radical pathways. Density functional theory (DFT) calculations revealed oxygen doping elevates local electrostatic potential and redistributes electron density at N-active sites, amplifying catalytic activity. The system demonstrated robust catalytic performance across pH 3–11, high salinity, and complex water matrices, maintaining > 80% OTC removal over 72 h. Plant growth assays and life cycle assessment (LCA) confirmed minimal ecological impacts, with purified water supporting normal seedling development. This work elucidates the critical role of N/O co-doping in steering PMS activation toward non-radical mechanisms while establishing a sustainable paradigm for metal-free biochar catalysis in water remediation.
2026, 37(5): 111975
doi: 10.1016/j.cclet.2025.111975
摘要:
Spontaneous resolution is a way for constructing chiral compounds from achiral modules, but the products are usually stochastic, which is unsuitable for enantioselective applications. Herein, a pair of chiral hydrogen-bonded frameworks assembled from achiral modules was reported. By introducing reusable chiral inducers, enantiomerically enriched NKU-777-xD/xL were obtained and exhibited superior enantioselective sensing performance. Notably, the amount of chiral inducer shows a positive correlation with the enantioselective sensing function, reflecting the degree of enantiomeric excess of NKU-777-xD/xL. Molecular-level mechanism studies reveal that competitive absorption governs the sensing functions of NKU-777-xD/xL, and the enantioselectivity is due to the enantioselective interactions of the hydrogen-bonded frameworks with targeting chiral molecules. This work not only provides a facile way to synthesize enantiomerically enriched chiral hydrogen-bonded frameworks from achiral modules using reusable chiral inducer but also gains insights into the inducer-controlled enantiomerically enriched chiral compounds for enantioselective applications.
Spontaneous resolution is a way for constructing chiral compounds from achiral modules, but the products are usually stochastic, which is unsuitable for enantioselective applications. Herein, a pair of chiral hydrogen-bonded frameworks assembled from achiral modules was reported. By introducing reusable chiral inducers, enantiomerically enriched NKU-777-xD/xL were obtained and exhibited superior enantioselective sensing performance. Notably, the amount of chiral inducer shows a positive correlation with the enantioselective sensing function, reflecting the degree of enantiomeric excess of NKU-777-xD/xL. Molecular-level mechanism studies reveal that competitive absorption governs the sensing functions of NKU-777-xD/xL, and the enantioselectivity is due to the enantioselective interactions of the hydrogen-bonded frameworks with targeting chiral molecules. This work not only provides a facile way to synthesize enantiomerically enriched chiral hydrogen-bonded frameworks from achiral modules using reusable chiral inducer but also gains insights into the inducer-controlled enantiomerically enriched chiral compounds for enantioselective applications.
2026, 37(5): 112064
doi: 10.1016/j.cclet.2025.112064
摘要:
Molecular glues (MGs) represent a promising approach in protein regulation, especially for "undruggable" targets. Despite the advantages over traditional protein inhibitors and proteolysis-targeting chimeras (PROTACs), MGs show various off-target effects, inducing general toxicities in patients. Herein, we describe a structure-guided design of visible-light photocaged MGs (vc-MGs), which precisely and spatiotemporally control the G1 to S phase transition 1 (GSPT1) protein level and Burkitt's lymphoma through visible-light irradiation in vitro and in vivo. Notably, activated VL-MG-9 showed a potent antitumor effect in the RAMOS xenograft mouse model, while VL-MG-9 alone has no GSPT1 degradation activity or general toxicity in various organs even at high dose. Furthermore, proteomics assay and apoptosis analysis confirmed the selectivity and safety of VL-MG-9. Significantly, pharmacokinetic results demonstrated the enhanced permeability and bioavailability (F%) of VL-MG-9. These data clearly reveal the practicality and importance of vc-MGs as preliminary tool for the targeted therapy of malignancies with reduced systemic toxicity and improved druggability.
Molecular glues (MGs) represent a promising approach in protein regulation, especially for "undruggable" targets. Despite the advantages over traditional protein inhibitors and proteolysis-targeting chimeras (PROTACs), MGs show various off-target effects, inducing general toxicities in patients. Herein, we describe a structure-guided design of visible-light photocaged MGs (vc-MGs), which precisely and spatiotemporally control the G1 to S phase transition 1 (GSPT1) protein level and Burkitt's lymphoma through visible-light irradiation in vitro and in vivo. Notably, activated VL-MG-9 showed a potent antitumor effect in the RAMOS xenograft mouse model, while VL-MG-9 alone has no GSPT1 degradation activity or general toxicity in various organs even at high dose. Furthermore, proteomics assay and apoptosis analysis confirmed the selectivity and safety of VL-MG-9. Significantly, pharmacokinetic results demonstrated the enhanced permeability and bioavailability (F%) of VL-MG-9. These data clearly reveal the practicality and importance of vc-MGs as preliminary tool for the targeted therapy of malignancies with reduced systemic toxicity and improved druggability.
2026, 37(5): 112202
doi: 10.1016/j.cclet.2025.112202
摘要:
The visible light photocatalytic gem‑carboamination reactions of α-diazo esters by using o-hydroxyaryl enaminones and amines as reaction partners have been realized, leading to the straightforward synthesis of chromone derived α-amino esters which could be easily hydrolyzed to functionalized α-amino acids. The reactions mediated by molecular iodine proceed via free radical pathway under metal-free conditions. Unlike the conventional carbene-based functionalization of diazo compounds involving nucleophilic/electrophilic or two electron neutral groups, the current protocol allows the installation of two nucleophilic functional structures to the carbon center, providing practical new tool for the synthesis of amino acids.
The visible light photocatalytic gem‑carboamination reactions of α-diazo esters by using o-hydroxyaryl enaminones and amines as reaction partners have been realized, leading to the straightforward synthesis of chromone derived α-amino esters which could be easily hydrolyzed to functionalized α-amino acids. The reactions mediated by molecular iodine proceed via free radical pathway under metal-free conditions. Unlike the conventional carbene-based functionalization of diazo compounds involving nucleophilic/electrophilic or two electron neutral groups, the current protocol allows the installation of two nucleophilic functional structures to the carbon center, providing practical new tool for the synthesis of amino acids.
2026, 37(5): 112348
doi: 10.1016/j.cclet.2025.112348
摘要:
The unstable solid electrolyte interphase (SEI) characterized by sluggish ion transport kinetics and consecutive side reactions poses a major challenge to the commercialization of sodium-ion batteries (SIBs). Here, ethoxy (pentafluoro) cyclotriphosphazene (PFPN) as a multifunctional electrolyte additive is reported to construct stable and highly ion-conductive SEI. PFPN decomposes preferentially to form the NaF, Na3N-rich SEI with fast Na+ migration kinetics due to its low lowest unoccupied molecular orbital energy and strong adsorption on hard carbon (HC) anode. Meanwhile, the incorporation of PFPN effectively suppresses exothermic reactions at the electrode/electrolyte interface, thereby reducing the risk of thermal runaway. As expected, the HCNa cell with PFPN additive demonstrates homogeneous sodium deposition on HC anode and delivers a high reversible capacity of 248.5 mAh/g with negligible capacity decay after 1000 cycles at 0.1 A/g. The NaNi0.33Fe0.33Mn0.33O2 (NFM)HC full cell also yields enhanced cycling stability under -20 ℃. This study proposes a simple and effective SEI regulation strategy for high-performance and safe SIBs.
The unstable solid electrolyte interphase (SEI) characterized by sluggish ion transport kinetics and consecutive side reactions poses a major challenge to the commercialization of sodium-ion batteries (SIBs). Here, ethoxy (pentafluoro) cyclotriphosphazene (PFPN) as a multifunctional electrolyte additive is reported to construct stable and highly ion-conductive SEI. PFPN decomposes preferentially to form the NaF, Na3N-rich SEI with fast Na+ migration kinetics due to its low lowest unoccupied molecular orbital energy and strong adsorption on hard carbon (HC) anode. Meanwhile, the incorporation of PFPN effectively suppresses exothermic reactions at the electrode/electrolyte interface, thereby reducing the risk of thermal runaway. As expected, the HCNa cell with PFPN additive demonstrates homogeneous sodium deposition on HC anode and delivers a high reversible capacity of 248.5 mAh/g with negligible capacity decay after 1000 cycles at 0.1 A/g. The NaNi0.33Fe0.33Mn0.33O2 (NFM)HC full cell also yields enhanced cycling stability under -20 ℃. This study proposes a simple and effective SEI regulation strategy for high-performance and safe SIBs.
2026, 37(5): 112373
doi: 10.1016/j.cclet.2026.112373
摘要:
A homogeneous dual catalytic system that synergistically merges photochemical and halogen-bond catalysis has been developed for the radical sulfonylation-annulation of (hetero)arene-tethered alkynes and alkenes with RSO2Cl. This protocol efficiently constructs a variety of sulfonylated fused-(hetero)arenes with good functional group compatibility under mild and eco-friendly conditions. The process is initiated by halogen-bond activation of RSO2Cl, which facilitates subsequent photocatalyzed heterolytic S-Cl cleavage via a SET pathway to generate RSO2 radicals; an alternative EnT pathway for radical generation was also identified.
A homogeneous dual catalytic system that synergistically merges photochemical and halogen-bond catalysis has been developed for the radical sulfonylation-annulation of (hetero)arene-tethered alkynes and alkenes with RSO2Cl. This protocol efficiently constructs a variety of sulfonylated fused-(hetero)arenes with good functional group compatibility under mild and eco-friendly conditions. The process is initiated by halogen-bond activation of RSO2Cl, which facilitates subsequent photocatalyzed heterolytic S-Cl cleavage via a SET pathway to generate RSO2 radicals; an alternative EnT pathway for radical generation was also identified.
2026, 37(5): 112417
doi: 10.1016/j.cclet.2026.112417
摘要:
Despite the enormous potential of heteroatom-doped carbon materials for sodium storage applications, direct doping strategies still face two critical unresolved challenges: Elucidating the modulation mechanism of heteroatom doping on the hybrid energy storage behavior of sodium-ion hybrid capacitors (SIHCs), and maintaining structural integrity while achieving high sulfur-nitrogen (S, N) co-doping levels. Herein, we report a facile and controllable synthetic approach for preparing highly S, N co-doped porous carbon (denoted as SNGN-1), using sodium gallate, pre-synthesized via the neutralization reaction of gallic acid with sodium hydroxide, as the precursor. The as-fabricated SNGN-1 possesses a high nitrogen content of 4.02 at% and a sulfur content of 1.31 at%, coupled with abundant structural defects, a large specific surface area, superior electronic conductivity, exceptional sodium storage capability and robust cycling stability. Computational results demonstrate that the Na+ adsorption energy (Ead) of SNGN-1 is -1.936 eV, corresponding to a substantial increase in the absolute value relative to its undoped counterpart; additionally, the incorporation of heteroatoms leads to a marked intensification of the valence and conduction band peaks near the Fermi level. When employed as the anode for sodium-ion half-cells, SNGN-1 delivers a high reversible capacity of 585 mAh/g at a current density of 0.1 A/g, and retains stable cycling performance even after 1000 cycles at 2 A/g. More impressively, the SIHC device assembled with SNGN-1 as the anode achieves remarkable energy/power density metrics, delivering a high energy density of 165.2 Wh/kg at a power density of 218.6 W/kg. These findings highlight the great potential of SNGN-1 as a high-performance anode material for advanced sodium-ion batteries and SIHCs, thereby paving the way for the development of next-generation low-cost energy storage systems.
Despite the enormous potential of heteroatom-doped carbon materials for sodium storage applications, direct doping strategies still face two critical unresolved challenges: Elucidating the modulation mechanism of heteroatom doping on the hybrid energy storage behavior of sodium-ion hybrid capacitors (SIHCs), and maintaining structural integrity while achieving high sulfur-nitrogen (S, N) co-doping levels. Herein, we report a facile and controllable synthetic approach for preparing highly S, N co-doped porous carbon (denoted as SNGN-1), using sodium gallate, pre-synthesized via the neutralization reaction of gallic acid with sodium hydroxide, as the precursor. The as-fabricated SNGN-1 possesses a high nitrogen content of 4.02 at% and a sulfur content of 1.31 at%, coupled with abundant structural defects, a large specific surface area, superior electronic conductivity, exceptional sodium storage capability and robust cycling stability. Computational results demonstrate that the Na+ adsorption energy (Ead) of SNGN-1 is -1.936 eV, corresponding to a substantial increase in the absolute value relative to its undoped counterpart; additionally, the incorporation of heteroatoms leads to a marked intensification of the valence and conduction band peaks near the Fermi level. When employed as the anode for sodium-ion half-cells, SNGN-1 delivers a high reversible capacity of 585 mAh/g at a current density of 0.1 A/g, and retains stable cycling performance even after 1000 cycles at 2 A/g. More impressively, the SIHC device assembled with SNGN-1 as the anode achieves remarkable energy/power density metrics, delivering a high energy density of 165.2 Wh/kg at a power density of 218.6 W/kg. These findings highlight the great potential of SNGN-1 as a high-performance anode material for advanced sodium-ion batteries and SIHCs, thereby paving the way for the development of next-generation low-cost energy storage systems.
2026, 37(5): 110860
doi: 10.1016/j.cclet.2025.110860
摘要:
In the context of the continuously increasing energy demand, the ongoing advancement of innovative energy storage technologies is regarded as an important strategy to alleviate the energy crisis. Among various energy storage technologies, supercapacitors (SCs) demonstrate significant potential in the future energy storage sector due to their exceptional high-power density and long cycle life. As the core component of SCs, the choice of electrode materials is crucial to their performance, with carbon materials being favored for their excellent electrical conductivity and large specific surface area. In particular, porous carbon materials derived from biomass-based polymers have become a research hotspot due to their unique advantages. Through chemical modification and high-temperature carbonization, these materials can form more stable and optimized porous structures, significantly enhancing their electrochemical performance while meeting environmental protection requirements, thereby highlighting their superiority as electrode materials. This article aims to review the sources, production, and applications of carbon materials derived from biomass-based polymers. We have deeply summarized the preparation and activation methods of carbon from different biomass-based polymer sources. In addition, a comprehensive analysis and systematic comparison of novel modification techniques, such as heteroatom doping, copolymerization, and the incorporation of nanomaterials, were performed to enhance the performance of SCs. Finally, according to the technical challenges to be solved, the goal of large-scale development of biomass-based polymer-derived porous carbon in the field of energy storage is proposed, which is crucial for coping with the global energy crisis and reducing environmental impact.
In the context of the continuously increasing energy demand, the ongoing advancement of innovative energy storage technologies is regarded as an important strategy to alleviate the energy crisis. Among various energy storage technologies, supercapacitors (SCs) demonstrate significant potential in the future energy storage sector due to their exceptional high-power density and long cycle life. As the core component of SCs, the choice of electrode materials is crucial to their performance, with carbon materials being favored for their excellent electrical conductivity and large specific surface area. In particular, porous carbon materials derived from biomass-based polymers have become a research hotspot due to their unique advantages. Through chemical modification and high-temperature carbonization, these materials can form more stable and optimized porous structures, significantly enhancing their electrochemical performance while meeting environmental protection requirements, thereby highlighting their superiority as electrode materials. This article aims to review the sources, production, and applications of carbon materials derived from biomass-based polymers. We have deeply summarized the preparation and activation methods of carbon from different biomass-based polymer sources. In addition, a comprehensive analysis and systematic comparison of novel modification techniques, such as heteroatom doping, copolymerization, and the incorporation of nanomaterials, were performed to enhance the performance of SCs. Finally, according to the technical challenges to be solved, the goal of large-scale development of biomass-based polymer-derived porous carbon in the field of energy storage is proposed, which is crucial for coping with the global energy crisis and reducing environmental impact.
2026, 37(5): 110973
doi: 10.1016/j.cclet.2025.110973
摘要:
Solid-state batteries that present lower risk factors and higher energy density are promising for advanced energy storage and applications. In particular, solid-state electrolytes (SSEs) are the critical components that responsible for ionic transport between negative electrodes and positive electrodes. It is crucial to fundamentally understand the ionic transport models and behaviors in the SSEs, with purpose of enhancing ion transport rate and stability of SSEs. To rationally improve the solid-state ion transport behavior of electrolytes, this review summarizes recent progresses on the transport principles and multiscale characterization methods of ion transport in SSEs, including traditional electrochemical methods, frequency-dependent spectroscopy, two-dimensional morphological imaging and three-dimensional morphological imaging. It is emphasized that combination of multiscale and multiple methods would be a developing trend for fundamentally understanding the mechanism of ion transport in SSEs. According to comprehensive transport principle and behaviors, hierarchical fillers are designed for composite electrolytes with fast ionic transport abilities. The remaining challenges for establishing advanced multiscale characterization methods are also discussed.
Solid-state batteries that present lower risk factors and higher energy density are promising for advanced energy storage and applications. In particular, solid-state electrolytes (SSEs) are the critical components that responsible for ionic transport between negative electrodes and positive electrodes. It is crucial to fundamentally understand the ionic transport models and behaviors in the SSEs, with purpose of enhancing ion transport rate and stability of SSEs. To rationally improve the solid-state ion transport behavior of electrolytes, this review summarizes recent progresses on the transport principles and multiscale characterization methods of ion transport in SSEs, including traditional electrochemical methods, frequency-dependent spectroscopy, two-dimensional morphological imaging and three-dimensional morphological imaging. It is emphasized that combination of multiscale and multiple methods would be a developing trend for fundamentally understanding the mechanism of ion transport in SSEs. According to comprehensive transport principle and behaviors, hierarchical fillers are designed for composite electrolytes with fast ionic transport abilities. The remaining challenges for establishing advanced multiscale characterization methods are also discussed.
2026, 37(5): 111262
doi: 10.1016/j.cclet.2025.111262
摘要:
Inflammatory bowel disease (IBD), which includes Crohn’s disease and ulcerative colitis, represents a significant health challenge due to its intricate interplay of genetic, environmental, and immunological factors. While current treatments are effective at managing symptoms, they are not without drawbacks, such as potential side effects, the financial strain on patients, and the risk of complications. Nanotechnology presents an innovative solution to these challenges, offering the potential to improve the bioavailability, stability, and precise delivery of natural compounds with potent anti-inflammatory properties. This review examines the array of nanoparticle (NP) delivery systems that are revolutionizing IBD treatment, including lipid-based NPs, polymeric NPs, metallic NPs, plant-derived exosomes, and mesoporous silica NPs. Furthermore, the review explores the various responsive mechanisms of NPs, including pH-responsive, reactive oxygen species (ROS)-responsive, enzyme-responsive, charge-mediated, ligand-receptor targeted, and multi-responsive systems. The therapeutic potential of nanomedicines derived from natural products is highlighted, with a focus on their roles in immunomodulation, reducing inflammation, repairing the intestinal barrier, and modulating the gut microbiota. Nanotechnology boosts IBD treatment with novel natural NPs. NPs delivery systems offer notable benefits, such as improving drug solubility, increasing the efficiency of absorption, alongside providing a controlled and sustained release of therapeutic agents directly at the inflammation site. Despite the promising capabilities of nanotechnology in IBD treatment, obstacles remain. These include the necessity for comprehensive toxicological assessments, formulating strategies to guarantee the safety and effectiveness of these innovative treatments. Therefore, this review provides a systematic analysis that provides guidance for the research and development of NPs based natural products.
Inflammatory bowel disease (IBD), which includes Crohn’s disease and ulcerative colitis, represents a significant health challenge due to its intricate interplay of genetic, environmental, and immunological factors. While current treatments are effective at managing symptoms, they are not without drawbacks, such as potential side effects, the financial strain on patients, and the risk of complications. Nanotechnology presents an innovative solution to these challenges, offering the potential to improve the bioavailability, stability, and precise delivery of natural compounds with potent anti-inflammatory properties. This review examines the array of nanoparticle (NP) delivery systems that are revolutionizing IBD treatment, including lipid-based NPs, polymeric NPs, metallic NPs, plant-derived exosomes, and mesoporous silica NPs. Furthermore, the review explores the various responsive mechanisms of NPs, including pH-responsive, reactive oxygen species (ROS)-responsive, enzyme-responsive, charge-mediated, ligand-receptor targeted, and multi-responsive systems. The therapeutic potential of nanomedicines derived from natural products is highlighted, with a focus on their roles in immunomodulation, reducing inflammation, repairing the intestinal barrier, and modulating the gut microbiota. Nanotechnology boosts IBD treatment with novel natural NPs. NPs delivery systems offer notable benefits, such as improving drug solubility, increasing the efficiency of absorption, alongside providing a controlled and sustained release of therapeutic agents directly at the inflammation site. Despite the promising capabilities of nanotechnology in IBD treatment, obstacles remain. These include the necessity for comprehensive toxicological assessments, formulating strategies to guarantee the safety and effectiveness of these innovative treatments. Therefore, this review provides a systematic analysis that provides guidance for the research and development of NPs based natural products.
2026, 37(5): 111319
doi: 10.1016/j.cclet.2025.111319
摘要:
Infected bone defects (IBD) are intricate and formidable conditions characterized by elevated rates of infection recurrence and delayed healing, resulting from dysregulation of the bone immune microenvironment (IME) mediated by microbes. The conventional approaches including surgical intervention and antibiotic therapy encounter challenges such as antibiotic resistance and susceptibility to postoperative infections. Considering the diverse impacts of various immune cells (ICs) and cytokines, the investigations into the IME have been conducted to offer potential strategies for treating IBD by addressing the requirements of infection eradication and bone regeneration (BREG). However, there is still a lack of review discussing the impacts of IME on IBD in light of its diverse components. Hydrogels, as promising materials in the treatment of IBD, can mimic the extracellular matrix of natural tissues, providing an optimal environment for cell growth and tissue regeneration. Recent studies have focused on investigating immune modulation through hydrogel delivery for treating IBD. This review aims to discuss the effects of different types of ICs and cytokines on the IME in IBD while summarizing current progress and strategies targeting this microenvironment using hydrogels. The insights gained from this review will aid the development of future immunomodulatory approaches for IBD treatment.
Infected bone defects (IBD) are intricate and formidable conditions characterized by elevated rates of infection recurrence and delayed healing, resulting from dysregulation of the bone immune microenvironment (IME) mediated by microbes. The conventional approaches including surgical intervention and antibiotic therapy encounter challenges such as antibiotic resistance and susceptibility to postoperative infections. Considering the diverse impacts of various immune cells (ICs) and cytokines, the investigations into the IME have been conducted to offer potential strategies for treating IBD by addressing the requirements of infection eradication and bone regeneration (BREG). However, there is still a lack of review discussing the impacts of IME on IBD in light of its diverse components. Hydrogels, as promising materials in the treatment of IBD, can mimic the extracellular matrix of natural tissues, providing an optimal environment for cell growth and tissue regeneration. Recent studies have focused on investigating immune modulation through hydrogel delivery for treating IBD. This review aims to discuss the effects of different types of ICs and cytokines on the IME in IBD while summarizing current progress and strategies targeting this microenvironment using hydrogels. The insights gained from this review will aid the development of future immunomodulatory approaches for IBD treatment.
2026, 37(5): 111390
doi: 10.1016/j.cclet.2025.111390
摘要:
Hepatocellular carcinoma (HCC) is the most common type of primary liver cancer and is among the leading causes of cancer-related mortality. Immunotherapy strategies targeting HCC are widely used in clinical practice. However, the pronounced immunosuppressive characteristics of the tumor microenvironment in HCC significantly hinder the efficacy of immunotherapy, often leading to suboptimal therapeutic outcomes. Innovative immunomodulatory delivery systems offer a promising path for HCC therapy by enabling precise targeting of tumor sites and significantly reducing the chances of systemic toxicity and side effects. This study describes the immune microenvironment of HCC and the mechanisms leading to immune evasion. This study then explores the issues and restrictions of current mainstream immunotherapies, highlighting the breakthroughs achieved through drug delivery systems crafted with innovative micro-nanomaterials for HCC immunotherapy. Besides, the application scenarios and challenges encountered by micro-nanomaterials in clinical translational applications were also discussed, and future development trends in this field were prospected, offering a theoretical foundation for the design of efficient HCC treatment strategies.
Hepatocellular carcinoma (HCC) is the most common type of primary liver cancer and is among the leading causes of cancer-related mortality. Immunotherapy strategies targeting HCC are widely used in clinical practice. However, the pronounced immunosuppressive characteristics of the tumor microenvironment in HCC significantly hinder the efficacy of immunotherapy, often leading to suboptimal therapeutic outcomes. Innovative immunomodulatory delivery systems offer a promising path for HCC therapy by enabling precise targeting of tumor sites and significantly reducing the chances of systemic toxicity and side effects. This study describes the immune microenvironment of HCC and the mechanisms leading to immune evasion. This study then explores the issues and restrictions of current mainstream immunotherapies, highlighting the breakthroughs achieved through drug delivery systems crafted with innovative micro-nanomaterials for HCC immunotherapy. Besides, the application scenarios and challenges encountered by micro-nanomaterials in clinical translational applications were also discussed, and future development trends in this field were prospected, offering a theoretical foundation for the design of efficient HCC treatment strategies.
2026, 37(5): 111392
doi: 10.1016/j.cclet.2025.111392
摘要:
Ocular posterior segment diseases (OPSDs), including uveitis, glaucoma, retinitis pigmentosa (RP), fundus neovascular diseases (FNDs), and age-related macular degeneration (AMD), are major causes of global blindness. The eye's biological barriers often prevent conventional drugs from reaching the posterior segment effectively, while potentially causing adverse effects. Nanocarrier-based drug delivery systems (DDS) offer promising solutions, with their small size, tunable properties, and high biocompatibility enhancing drug permeability, stability, and targeted delivery. These systems may reduce administration frequency, prolong therapeutic effects, minimize side effects, and improve patient compliance. Unlike previous reviews, this article comprehensively examines novel nanocarriers for OPSD treatment. We first analyze small molecules, their nanocarriers, and administration methods based on recent two-decade research. Next, we compare nanocarrier stability, biocompatibility, ocular penetration, drug release kinetics, and formulation ease, emphasizing recent advances in design, preparation, and functional modification. Finally, by evaluating clinical applications and challenges, we discuss translational hurdles and future prospects for OPSD nanotherapeutics. Greater research efforts are needed to realize nanocarriers' full potential in OPSD treatment.
Ocular posterior segment diseases (OPSDs), including uveitis, glaucoma, retinitis pigmentosa (RP), fundus neovascular diseases (FNDs), and age-related macular degeneration (AMD), are major causes of global blindness. The eye's biological barriers often prevent conventional drugs from reaching the posterior segment effectively, while potentially causing adverse effects. Nanocarrier-based drug delivery systems (DDS) offer promising solutions, with their small size, tunable properties, and high biocompatibility enhancing drug permeability, stability, and targeted delivery. These systems may reduce administration frequency, prolong therapeutic effects, minimize side effects, and improve patient compliance. Unlike previous reviews, this article comprehensively examines novel nanocarriers for OPSD treatment. We first analyze small molecules, their nanocarriers, and administration methods based on recent two-decade research. Next, we compare nanocarrier stability, biocompatibility, ocular penetration, drug release kinetics, and formulation ease, emphasizing recent advances in design, preparation, and functional modification. Finally, by evaluating clinical applications and challenges, we discuss translational hurdles and future prospects for OPSD nanotherapeutics. Greater research efforts are needed to realize nanocarriers' full potential in OPSD treatment.
2026, 37(5): 111396
doi: 10.1016/j.cclet.2025.111396
摘要:
Tetrahedral framework nucleic acids (tFNAs), a novel class of nanodelivery carriers, demonstrate significant potential due to their well-defined topological structure, programmable molecular recognition capabilities, and exceptional biocompatibility. This article systematically reviews the dynamic behavior of tFNAs across multi-scale delivery processes. At the macroscale, it elucidates the organ accumulation and metabolism of tFNAs following various routes of administration. At the microscale, it delves into the transmembrane transport mechanisms and subcellular localization characteristics of tFNAs. Furthermore, this review discusses the current research status of strategies aimed at improving the delivery efficiency of tFNAs through active targeted modifications and proposes cutting-edge approaches to developing precision delivery systems leveraging engineering modifications and intelligent response designs.
Tetrahedral framework nucleic acids (tFNAs), a novel class of nanodelivery carriers, demonstrate significant potential due to their well-defined topological structure, programmable molecular recognition capabilities, and exceptional biocompatibility. This article systematically reviews the dynamic behavior of tFNAs across multi-scale delivery processes. At the macroscale, it elucidates the organ accumulation and metabolism of tFNAs following various routes of administration. At the microscale, it delves into the transmembrane transport mechanisms and subcellular localization characteristics of tFNAs. Furthermore, this review discusses the current research status of strategies aimed at improving the delivery efficiency of tFNAs through active targeted modifications and proposes cutting-edge approaches to developing precision delivery systems leveraging engineering modifications and intelligent response designs.
2026, 37(5): 111707
doi: 10.1016/j.cclet.2025.111707
摘要:
Hydrogels, soft materials made from polymer networks capable of absorbing water, demonstrate remarkable compatibility in diverse hybridizations. When the fillers that can undergo reversible crystallization are used for incorporation, the materials’ mechanical properties and functions would be significantly improved. Therefore, these hydrogels, named crystal hydrogels, are emerging as a class of new advanced functional materials. This review offers a comprehensive examination of these materials from five distinct angles. We first discuss their fundamental characteristics and then elaborate on the synthesis methods of crystal hydrogels, categorizing them into three types based on their crystal formation mechanisms. The third section is dedicated to describing the properties of crystal hydrogels. Furthermore, we explore the diverse and remarkable applications that have emerged with the advancement of crystal hydrogels. The review concludes by summarizing the core concepts and assessing the recent opportunities and challenges faced by crystal hydrogels.
Hydrogels, soft materials made from polymer networks capable of absorbing water, demonstrate remarkable compatibility in diverse hybridizations. When the fillers that can undergo reversible crystallization are used for incorporation, the materials’ mechanical properties and functions would be significantly improved. Therefore, these hydrogels, named crystal hydrogels, are emerging as a class of new advanced functional materials. This review offers a comprehensive examination of these materials from five distinct angles. We first discuss their fundamental characteristics and then elaborate on the synthesis methods of crystal hydrogels, categorizing them into three types based on their crystal formation mechanisms. The third section is dedicated to describing the properties of crystal hydrogels. Furthermore, we explore the diverse and remarkable applications that have emerged with the advancement of crystal hydrogels. The review concludes by summarizing the core concepts and assessing the recent opportunities and challenges faced by crystal hydrogels.
2026, 37(5): 111843
doi: 10.1016/j.cclet.2025.111843
摘要:
Myocardial infarction (MI) is a disease with a very high mortality rate among cardiovascular diseases. It causes extensive damage to myocardial cells due to prolonged and repeated ischemia and hypoxia. Early coronary revascularization is the best method for treating MI. However, the reperfusion process in MI can produce reactive oxygen species, further damaging myocardial tissue, and triggering MI-reperfusion injury (MI/RI). Although various traditional treatment strategies exist, the treatment of myocardial ischemia including MI and MI/RI remain a significant challenge. Mitochondrial dysfunction plays an important role in the emergence and development of myocardial ischemia. In recent years, with the advancement of nanobiomedicine, therapeutic strategies for targeting mitochondria have gained increasing attentions in diseases' therapy. Thus, nanobiomedicine targeting mitochondria has shown great promise in the treatment of myocardial ischemia. This review first comprehensively elaborates on the mechanisms of mitochondrial homeostasis in MI and MI/RI, and then focuses on the application progress of nanomaterials targeting mitochondrial homeostasis (oxidative stress, mitophagy, mitochondrial fusion and fission, etc.) in improving myocardial ischemia. Ultimately, this article looks forward to the prospects of nanomaterials in the targeting treatment of MI and MI/RI, aiming to provide more effective and innovative ideas for clinical treatments.
Myocardial infarction (MI) is a disease with a very high mortality rate among cardiovascular diseases. It causes extensive damage to myocardial cells due to prolonged and repeated ischemia and hypoxia. Early coronary revascularization is the best method for treating MI. However, the reperfusion process in MI can produce reactive oxygen species, further damaging myocardial tissue, and triggering MI-reperfusion injury (MI/RI). Although various traditional treatment strategies exist, the treatment of myocardial ischemia including MI and MI/RI remain a significant challenge. Mitochondrial dysfunction plays an important role in the emergence and development of myocardial ischemia. In recent years, with the advancement of nanobiomedicine, therapeutic strategies for targeting mitochondria have gained increasing attentions in diseases' therapy. Thus, nanobiomedicine targeting mitochondria has shown great promise in the treatment of myocardial ischemia. This review first comprehensively elaborates on the mechanisms of mitochondrial homeostasis in MI and MI/RI, and then focuses on the application progress of nanomaterials targeting mitochondrial homeostasis (oxidative stress, mitophagy, mitochondrial fusion and fission, etc.) in improving myocardial ischemia. Ultimately, this article looks forward to the prospects of nanomaterials in the targeting treatment of MI and MI/RI, aiming to provide more effective and innovative ideas for clinical treatments.
2026, 37(5): 111861
doi: 10.1016/j.cclet.2025.111861
摘要:
The electrochemical CO2 reduction (CO2R) holds the potential to manufacture carbon-based chemicals and fuels while advancing toward carbon neutrality. On the path to achieving practical CO2R, a significant challenge lies in the formation of carbonate salts due to the interplay between CO2, local alkalinity and metal cations. The carbonate issue leads to the wastage of CO2 reactant, thus resulting in low carbon utilization efficiency and high costs for carbonate regeneration. Additionally, such salt formation can threaten the operation stability of the CO2R in electrolyzers equipped with gas diffusion electrodes (GDE). These challenges motivate us to conduct the present review, aiming to provide a comprehensive understanding and propose solution strategies for the carbonate problem. We start from the mechanism insights into carbonate formation with specific analysis on the kinetics of carbonate formation, mass transfer process, and the influence of interfacial pH, followed by the exposition of advanced techniques to monitor the carbonate accumulation. Next, the design strategies to solve the carbonate problem including the optimization of electrolyte, electrode, membranes and operation conditions, are presented, with a highlight on acidic CO2 electrolysis system without introducing metal cations into electrolyte systems. We finally end up by offering future opportunities in this evolving field. These timely and inspiring perspectives can guide researchers in addressing carbonate-related issues and advance CO2R toward practical feasibility.
The electrochemical CO2 reduction (CO2R) holds the potential to manufacture carbon-based chemicals and fuels while advancing toward carbon neutrality. On the path to achieving practical CO2R, a significant challenge lies in the formation of carbonate salts due to the interplay between CO2, local alkalinity and metal cations. The carbonate issue leads to the wastage of CO2 reactant, thus resulting in low carbon utilization efficiency and high costs for carbonate regeneration. Additionally, such salt formation can threaten the operation stability of the CO2R in electrolyzers equipped with gas diffusion electrodes (GDE). These challenges motivate us to conduct the present review, aiming to provide a comprehensive understanding and propose solution strategies for the carbonate problem. We start from the mechanism insights into carbonate formation with specific analysis on the kinetics of carbonate formation, mass transfer process, and the influence of interfacial pH, followed by the exposition of advanced techniques to monitor the carbonate accumulation. Next, the design strategies to solve the carbonate problem including the optimization of electrolyte, electrode, membranes and operation conditions, are presented, with a highlight on acidic CO2 electrolysis system without introducing metal cations into electrolyte systems. We finally end up by offering future opportunities in this evolving field. These timely and inspiring perspectives can guide researchers in addressing carbonate-related issues and advance CO2R toward practical feasibility.
2026, 37(5): 111902
doi: 10.1016/j.cclet.2025.111902
摘要:
Organophosphorus (OPs) compounds are extensively utilized in pesticides, chemical warfare agents, pharmaceuticals, and industrial applications due to their distinctive chemical properties, including biological activity, persistence, and hydrophobicity. However, their excessive use has led to significant environmental toxicity and pollution concerns, underscoring the urgent need for sustainable methods to monitor OPs pollutants. Traditional detection relies on bulky instruments, whereas organic fluorescent probes present advantages such as high selectivity, sensitivity, and portability. This review summarizes recent advancements in these probes for OPs detection, outlines characterization strategies based on underlying mechanisms, discusses challenges and future directions, and introduces OPs’ features, probe mechanisms, and design guidelines, providing theoretical insights and technical references for the development of novel organic fluorescent probes.
Organophosphorus (OPs) compounds are extensively utilized in pesticides, chemical warfare agents, pharmaceuticals, and industrial applications due to their distinctive chemical properties, including biological activity, persistence, and hydrophobicity. However, their excessive use has led to significant environmental toxicity and pollution concerns, underscoring the urgent need for sustainable methods to monitor OPs pollutants. Traditional detection relies on bulky instruments, whereas organic fluorescent probes present advantages such as high selectivity, sensitivity, and portability. This review summarizes recent advancements in these probes for OPs detection, outlines characterization strategies based on underlying mechanisms, discusses challenges and future directions, and introduces OPs’ features, probe mechanisms, and design guidelines, providing theoretical insights and technical references for the development of novel organic fluorescent probes.
2026, 37(5): 111904
doi: 10.1016/j.cclet.2025.111904
摘要:
Electrocatalytic CO2 reduction to formate using renewable energy offers a promising route for sustainable chemical production and carbon utilization. Bismuth-based catalysts stand out for their exceptional selectivity towards formate, combining intrinsic advantages with practical viability. This review critically examines recent advances in strategically tailoring bismuth-based catalysts for selective CO2-to-formate conversion. Moving beyond conventional material classifications, we emphasize mechanistic understanding of the reaction pathways and active sites governing formate generation. Crucially, we dissect the synthesis strategies enabling precise control over catalyst properties—ranging from metallic bismuth nanostructures and single atoms to tailored compounds, heterostructures, and alloys—and link these design principles to performance optimization. In addition, we incorporate operando characterization and computational insights within catalyst-specific case studies to examine selected dynamic reaction mechanisms and key enhancement mechanisms under operational conditions. Finally, we outline forward-looking research trajectories, addressing critical challenges like achieving industrially relevant performance and stability, and proposing innovative pathways focused on advanced catalyst architectures, microenvironment engineering, and predictive frameworks for scalable implementation.
Electrocatalytic CO2 reduction to formate using renewable energy offers a promising route for sustainable chemical production and carbon utilization. Bismuth-based catalysts stand out for their exceptional selectivity towards formate, combining intrinsic advantages with practical viability. This review critically examines recent advances in strategically tailoring bismuth-based catalysts for selective CO2-to-formate conversion. Moving beyond conventional material classifications, we emphasize mechanistic understanding of the reaction pathways and active sites governing formate generation. Crucially, we dissect the synthesis strategies enabling precise control over catalyst properties—ranging from metallic bismuth nanostructures and single atoms to tailored compounds, heterostructures, and alloys—and link these design principles to performance optimization. In addition, we incorporate operando characterization and computational insights within catalyst-specific case studies to examine selected dynamic reaction mechanisms and key enhancement mechanisms under operational conditions. Finally, we outline forward-looking research trajectories, addressing critical challenges like achieving industrially relevant performance and stability, and proposing innovative pathways focused on advanced catalyst architectures, microenvironment engineering, and predictive frameworks for scalable implementation.
2026, 37(5): 111915
doi: 10.1016/j.cclet.2025.111915
摘要:
Electrocatalytic oxygen reduction reaction (ORR) is a key sustainable energy process, but its efficiency and durability are severely affected by reactive oxygen species (ROS) such as hydroxyl radicals and superoxide anions. Understanding the kinetics of these transient intermediates is crucial for revealing the ORR mechanism and designing novel electrocatalysts. Many new in situ and operando characterization techniques have emerged in ROS detection. This article reviews recent progress in the detection and quantification methods for ROS during the electrocatalytic ORR, including fluorescence spectroscopy, UV–vis absorption spectroscopy, electron paramagnetic spectroscopy, scanning electrochemical microscopy, and electrochemiluminescence related technologies. The aim is to provide latest references for researchers in this field and promote further development of electrocatalytic ORR related research.
Electrocatalytic oxygen reduction reaction (ORR) is a key sustainable energy process, but its efficiency and durability are severely affected by reactive oxygen species (ROS) such as hydroxyl radicals and superoxide anions. Understanding the kinetics of these transient intermediates is crucial for revealing the ORR mechanism and designing novel electrocatalysts. Many new in situ and operando characterization techniques have emerged in ROS detection. This article reviews recent progress in the detection and quantification methods for ROS during the electrocatalytic ORR, including fluorescence spectroscopy, UV–vis absorption spectroscopy, electron paramagnetic spectroscopy, scanning electrochemical microscopy, and electrochemiluminescence related technologies. The aim is to provide latest references for researchers in this field and promote further development of electrocatalytic ORR related research.
2026, 37(5): 111929
doi: 10.1016/j.cclet.2025.111929
摘要:
Asymmetric reduction of unsaturated compounds via dynamic kinetic resolution (DKR) has significantly enhanced the efficiency and selectivity of synthesizing enantiomerically pure compounds from racemic substrates. This approach combines the simultaneous racemization of substrates with enantioselective reduction, enabling quantitative yields and high enantiomeric excess. In the past several years, remarkable advances in this field have been achieved, ranging from the development of innovative catalytic systems, novel synthetic strategies, expansion of substrate scope, deeper mechanistic understanding, and their applications. These advancements offer alternative and efficient methods in the asymmetric synthesis of chiral molecules bearing multiple consecutive stereogenic centers, particularly beneficial for the synthesis of natural products or chiral intermediates in pharmaceuticals and fine chemicals. In this review, we summarize the recent advances during the last several years according to the substrate types in this powerful and productive field, with an emphasis on the development of new catalytic systems and the insight into the DKR process.
Asymmetric reduction of unsaturated compounds via dynamic kinetic resolution (DKR) has significantly enhanced the efficiency and selectivity of synthesizing enantiomerically pure compounds from racemic substrates. This approach combines the simultaneous racemization of substrates with enantioselective reduction, enabling quantitative yields and high enantiomeric excess. In the past several years, remarkable advances in this field have been achieved, ranging from the development of innovative catalytic systems, novel synthetic strategies, expansion of substrate scope, deeper mechanistic understanding, and their applications. These advancements offer alternative and efficient methods in the asymmetric synthesis of chiral molecules bearing multiple consecutive stereogenic centers, particularly beneficial for the synthesis of natural products or chiral intermediates in pharmaceuticals and fine chemicals. In this review, we summarize the recent advances during the last several years according to the substrate types in this powerful and productive field, with an emphasis on the development of new catalytic systems and the insight into the DKR process.
2026, 37(5): 111960
doi: 10.1016/j.cclet.2025.111960
摘要:
The growing global demand for sustainable energy makes biodiesel an important renewable alternative to alleviate the energy crisis and reduce greenhouse gas emissions. Therefore, there is an urgent need to develop efficient, environmentally friendly and economically viable biodiesel production methods. Hypercrosslinked polymers (HCPs), as aromatic porous organic polymers, are solid frameworks that can be used as heterogeneous catalyst, and they are a promising platform for biodiesel catalytic conversion due to their low cost, highly accessible active site, tunable catalytic site types. In addition, innovative green synthesis strategies make environmentally begin production of HCPs possible. In recent years, HCPs has developed rapidly in the field of biomass catalysis. Unfortunately, to the best of our knowledge, there are no publications focusing on the green synthesis and application of HCPs-based materials for biodiesel production. This review provides an update on the synthesis and utilisation of green and efficient HCPs for catalytic biodiesel production. Initially, the green routes for HCPs synthesis are described, followed by a comprehensive summary of the various approaches to biodiesel production. The primary focus is on the utilisation of HCPs as carriers of active sites in the catalytic conversion of biodiesel, with particular emphasis on catalyst design, morphology control, and intelligent management in terms of application extension. Ultimately, thought-provoking recommendations are proposed to utilize improved green HCPs in combination with advanced production processes to achieve more efficient and sustainable development.
The growing global demand for sustainable energy makes biodiesel an important renewable alternative to alleviate the energy crisis and reduce greenhouse gas emissions. Therefore, there is an urgent need to develop efficient, environmentally friendly and economically viable biodiesel production methods. Hypercrosslinked polymers (HCPs), as aromatic porous organic polymers, are solid frameworks that can be used as heterogeneous catalyst, and they are a promising platform for biodiesel catalytic conversion due to their low cost, highly accessible active site, tunable catalytic site types. In addition, innovative green synthesis strategies make environmentally begin production of HCPs possible. In recent years, HCPs has developed rapidly in the field of biomass catalysis. Unfortunately, to the best of our knowledge, there are no publications focusing on the green synthesis and application of HCPs-based materials for biodiesel production. This review provides an update on the synthesis and utilisation of green and efficient HCPs for catalytic biodiesel production. Initially, the green routes for HCPs synthesis are described, followed by a comprehensive summary of the various approaches to biodiesel production. The primary focus is on the utilisation of HCPs as carriers of active sites in the catalytic conversion of biodiesel, with particular emphasis on catalyst design, morphology control, and intelligent management in terms of application extension. Ultimately, thought-provoking recommendations are proposed to utilize improved green HCPs in combination with advanced production processes to achieve more efficient and sustainable development.
2026, 37(5): 112142
doi: 10.1016/j.cclet.2025.112142
摘要:
Hydrogen-bonded frameworks (HOFs) are attracting interest for industrial and environmental applications. This review emphasizes recent developments in HOFs, concentrating on their structural characteristics, types of hydrogen bonding, and the connections that affect their mechanical properties and environmental responsiveness. It highlights hinge-like flexibility, rigidity, and framework retention, which enhance adaptability and structural integrity while trapping gases. A proposed mechanism for the selective adsorption of noble gases and light hydrocarbons emphasizes their potential in gas storage and environmental remediation. Overall, HOFs are presented as versatile materials ready to tackle emerging industrial challenges.
Hydrogen-bonded frameworks (HOFs) are attracting interest for industrial and environmental applications. This review emphasizes recent developments in HOFs, concentrating on their structural characteristics, types of hydrogen bonding, and the connections that affect their mechanical properties and environmental responsiveness. It highlights hinge-like flexibility, rigidity, and framework retention, which enhance adaptability and structural integrity while trapping gases. A proposed mechanism for the selective adsorption of noble gases and light hydrocarbons emphasizes their potential in gas storage and environmental remediation. Overall, HOFs are presented as versatile materials ready to tackle emerging industrial challenges.
2026, 37(5): 112235
doi: 10.1016/j.cclet.2025.112235
摘要:
The stereoselective synthesis of 1,2-cis-galacturonic acid and 2-amino-2-deoxy-galacturonic acid glycosides remains a critical challenge in carbohydrate chemistry owing to the electronic and steric effects imposed by the C5-carboxyl group and C2 substituents. The available synthetic strategies can be divided into two divergent pathways: the construction of the glycan backbone before introducing the carboxyl group and the use of pre-formed uronic acid donors during glycosylation. Key advances include the use of remotely participating acyl groups, conformational control via 3,6-lactone intermediates, chelation-directed anomerisation and steric shielding by bulky protecting groups such as 4,6-O-di-tert-butylsilylene and 4,6-O-benzylidene. This review comprehensively overviews the current strategies that overcome stereo-chemical challenges in the synthesis of 1,2-cis-galacturonic and aminogalacturonic acid–containing glycans. In addition, the application of these methodologies to the synthesis of biologically relevant carbohydrates is examined.
The stereoselective synthesis of 1,2-cis-galacturonic acid and 2-amino-2-deoxy-galacturonic acid glycosides remains a critical challenge in carbohydrate chemistry owing to the electronic and steric effects imposed by the C5-carboxyl group and C2 substituents. The available synthetic strategies can be divided into two divergent pathways: the construction of the glycan backbone before introducing the carboxyl group and the use of pre-formed uronic acid donors during glycosylation. Key advances include the use of remotely participating acyl groups, conformational control via 3,6-lactone intermediates, chelation-directed anomerisation and steric shielding by bulky protecting groups such as 4,6-O-di-tert-butylsilylene and 4,6-O-benzylidene. This review comprehensively overviews the current strategies that overcome stereo-chemical challenges in the synthesis of 1,2-cis-galacturonic and aminogalacturonic acid–containing glycans. In addition, the application of these methodologies to the synthesis of biologically relevant carbohydrates is examined.
2026, 37(5): 111876
doi: 10.1016/j.cclet.2025.111876
摘要:
2026, 37(5): 112260
doi: 10.1016/j.cclet.2025.112260
摘要:
