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2026 Volume 37 Issue 10
2026, 37(10): 111432
doi: 10.1016/j.cclet.2025.111432
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
(-)-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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
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
Abstract:
2026, 37(10): 112887
doi: 10.1016/j.cclet.2026.112887
Abstract:
