Diamond-like (DL) compounds constitute a pivotal class of materials for advanced optoelectronic applications, particularly as infrared (IR) nonlinear optical (NLO) crystals, owing to their intrinsically high proportion of non-centrosymmetric structures and oriented tetrahedral units that synergistically enhance second-order NLO responses. Over the past decades, more than 300 DL compounds have been rationally designed and synthesized, with over 90 demonstrating significant NLO activity. However, performance-driven DL structural design remains highly challenging in this field. To advance the targeted design of high-performance IR NLO materials, this review provides a systematic and updated summary of DL IR NLO compounds, with a particular emphasis on emerging and promising alkaline earth metal tetrahedral and mixed anionic NLO-active tetrahedral units, chemical and structural diversity, structural evolution, and property modifications in DL chalcogenide, pnictide, and halide systems. Finally, future opportunities and challenges in DL functional material discovery are discussed, with the aim of providing a clear chemical perspective to stimulate the discovery of new DL IR NLO materials with desired properties.
类金刚石（DL）化合物是先进光电应用的关键材料，特别是红外非线性光学（NLO）晶体，因为它们具有高比例的非中心对称结构和定向四面体单元，可以协同增强二阶NLO响应。在过去的几十年里，人们合理设计和合成了300多种DL化合物，其中90多种具有显著的NLO活性。然而，性能驱动的深度学习结构设计在该领域仍然具有很高的挑战性。为了促进高性能红外NLO材料的有针对性的设计，本文对DL - IR NLO化合物进行了系统的和最新的总结，特别强调了新兴的和有前途的碱土金属四面体和混合阴离子NLO活性四面体单元，DL -硫族化合物、pnictide和卤化物体系的化学和结构多样性、结构演变和性质修饰。最后，讨论了DL功能材料发现的未来机遇和挑战，目的是提供一个清晰的化学视角，以刺激发现具有理想性能的新型DL IR NLO材料。
{"title":"Harnessing tetrahedral diversity: The path to superior diamond-like IR NLO crystals","authors":"Ailijiang Abudurusuli, Linan Wang, Junben Huang, Xueling Hou, Miriding Mutailipu, Shilie Pan, Junjie Li","doi":"10.1016/j.ccr.2026.217642","DOIUrl":"https://doi.org/10.1016/j.ccr.2026.217642","url":null,"abstract":"Diamond-like (DL) compounds constitute a pivotal class of materials for advanced optoelectronic applications, particularly as infrared (IR) nonlinear optical (NLO) crystals, owing to their intrinsically high proportion of non-centrosymmetric structures and oriented tetrahedral units that synergistically enhance second-order NLO responses. Over the past decades, more than 300 DL compounds have been rationally designed and synthesized, with over 90 demonstrating significant NLO activity. However, performance-driven DL structural design remains highly challenging in this field. To advance the targeted design of high-performance IR NLO materials, this review provides a systematic and updated summary of DL IR NLO compounds, with a particular emphasis on emerging and promising alkaline earth metal tetrahedral and mixed anionic NLO-active tetrahedral units, chemical and structural diversity, structural evolution, and property modifications in DL chalcogenide, pnictide, and halide systems. Finally, future opportunities and challenges in DL functional material discovery are discussed, with the aim of providing a clear chemical perspective to stimulate the discovery of new DL IR NLO materials with desired properties.","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"285 1","pages":""},"PeriodicalIF":20.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098424","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-01DOI: 10.1016/j.ccr.2026.217656
Yuhao Liu, Xinjie Chen, Gai Li, Minghui Wang, Miaomiao Yang, Jing Li, Xiaodong Shi, Yonghao Xiao, Fengyun Su, Xinlong Tian
The efficient solar-to-energy (STE) technique, relying on the advanced semiconductor materials, is critically important for addressing the global energy crisis. The ideal semiconductors for efficient STE conversion should exhibit high electronic dimensionality guided by the advanced concept. Herein, electronic dimensionality refers to the connectivity of atomic orbitals in the frontier electronic bands, which directly influence the charge transport anisotropy and carrier effective masses. The advanced three-dimensional (3D) electronic dimensionality enables the isotropic and efficient charge carrier transport, a feature of high-STE-performance semiconductors. Bournonite CuPbSbS3, a recently emerging metal sulfide (MS) material, features the 3D electronic dimensionality, direct bandgap of approximately 1.3 eV, and defect-tolerant feature, rendering it a highly promising candidate for high-performance STE systems. This review begins by outlining the design principles and fundamental semiconductor characteristics of CuPbSbS3, and then offers a comprehensive survey of its exploration process and applications across the STE spectrum, from photovoltaics to photocatalysis. Finally, perspective on the challenges and opportunities for future research on bournonite CuPbSbS3 are provided.
{"title":"Design concept and solar-to-energy applications of CuPbSbS3 from photovoltaics to photocatalysis","authors":"Yuhao Liu, Xinjie Chen, Gai Li, Minghui Wang, Miaomiao Yang, Jing Li, Xiaodong Shi, Yonghao Xiao, Fengyun Su, Xinlong Tian","doi":"10.1016/j.ccr.2026.217656","DOIUrl":"https://doi.org/10.1016/j.ccr.2026.217656","url":null,"abstract":"The efficient solar-to-energy (STE) technique, relying on the advanced semiconductor materials, is critically important for addressing the global energy crisis. The ideal semiconductors for efficient STE conversion should exhibit high electronic dimensionality guided by the advanced concept. Herein, electronic dimensionality refers to the connectivity of atomic orbitals in the frontier electronic bands, which directly influence the charge transport anisotropy and carrier effective masses. The advanced three-dimensional (3D) electronic dimensionality enables the isotropic and efficient charge carrier transport, a feature of high-STE-performance semiconductors. Bournonite CuPbSbS<ce:inf loc=\"post\">3</ce:inf>, a recently emerging metal sulfide (MS) material, features the 3D electronic dimensionality, direct bandgap of approximately 1.3 eV, and defect-tolerant feature, rendering it a highly promising candidate for high-performance STE systems. This review begins by outlining the design principles and fundamental semiconductor characteristics of CuPbSbS<ce:inf loc=\"post\">3</ce:inf>, and then offers a comprehensive survey of its exploration process and applications across the STE spectrum, from photovoltaics to photocatalysis. Finally, perspective on the challenges and opportunities for future research on bournonite CuPbSbS<ce:inf loc=\"post\">3</ce:inf> are provided.","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"67 1","pages":""},"PeriodicalIF":20.6,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098425","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-31DOI: 10.1016/j.ccr.2026.217638
Ming-Yue Wang , Jing Zeng , Yue-Fan Lai , Lei-Jiao Peng , Dan-Dan Wang , Min-Min Wang , Mei-ling Yang , Yue Lan , Jia-Qi Hu , Feng-Qing Yang , Die Gao
Covalent organic frameworks (COFs), characterized by high specific surface area, tunable pore structures, and excellent stability, provide an ideal platform for developing high-performance ratiometric fluorescence sensors. By measuring the intensity ratio of two emission signals, these sensors offer built-in self-calibration, overcoming the limitations of single-signal probes affected by environmental interference, and thus improving sensitivity, selectivity, and reliability in detecting trace analytes in complex samples. This review systematically outlines construction strategies for dual-emission COF-based ratiometric sensors, such as intrinsic backbone dual-emission, doping-induced dual-emission, and hybrid/heterostructure-induced dual-emission. For each approach, advantages, limitations, and development directions are discussed. Key structural factors (e.g. topology, π–π stacking, donor–acceptor motifs, pore environment, and crystallinity) and their roles in integrating luminescent units are discussed to explain how they collectively influence dual-emission performance and stability. Common construction challenges and corresponding mitigation strategies are also summarized to enhance sensor reliability and efficiency. The review further elaborates on relevant sensing mechanisms, including excited-state intramolecular proton transfer (ESIPT) and Förster resonance energy transfer (FRET), as well as summarizes the interrelationships of construction strategy-response mode-sensing mechanism. Performance advantages and recent applications in environmental monitoring, food safety, and biomedical analysis are highlighted. Despite their promise, practical use of these sensors still faces challenges in signal controllability and environmental adaptability. Based on current limitations, this review suggests future directions: precise control and mechanistic study of dual-emission behavior, enhancing signal reliability in real samples and enabling device integration, and data-driven material design for performance optimization. Through collaborative advances, dual-emission COF-based sensors are expected to evolve into versatile detection platforms for environmental, clinical, and food safety applications, promoting the practical adoption of next-generation sensing technologies.
{"title":"Covalent organic frameworks based dual-emission materials for ratiometric fluorescence sensing: A review on design strategies, mechanisms, and applications","authors":"Ming-Yue Wang , Jing Zeng , Yue-Fan Lai , Lei-Jiao Peng , Dan-Dan Wang , Min-Min Wang , Mei-ling Yang , Yue Lan , Jia-Qi Hu , Feng-Qing Yang , Die Gao","doi":"10.1016/j.ccr.2026.217638","DOIUrl":"10.1016/j.ccr.2026.217638","url":null,"abstract":"<div><div>Covalent organic frameworks (COFs), characterized by high specific surface area, tunable pore structures, and excellent stability, provide an ideal platform for developing high-performance ratiometric fluorescence sensors. By measuring the intensity ratio of two emission signals, these sensors offer built-in self-calibration, overcoming the limitations of single-signal probes affected by environmental interference, and thus improving sensitivity, selectivity, and reliability in detecting trace analytes in complex samples. This review systematically outlines construction strategies for dual-emission COF-based ratiometric sensors, such as intrinsic backbone dual-emission, doping-induced dual-emission, and hybrid/heterostructure-induced dual-emission. For each approach, advantages, limitations, and development directions are discussed. Key structural factors (e.g. topology, π–π stacking, donor–acceptor motifs, pore environment, and crystallinity) and their roles in integrating luminescent units are discussed to explain how they collectively influence dual-emission performance and stability. Common construction challenges and corresponding mitigation strategies are also summarized to enhance sensor reliability and efficiency. The review further elaborates on relevant sensing mechanisms, including excited-state intramolecular proton transfer (ESIPT) and Förster resonance energy transfer (FRET), as well as summarizes the interrelationships of construction strategy-response mode-sensing mechanism. Performance advantages and recent applications in environmental monitoring, food safety, and biomedical analysis are highlighted. Despite their promise, practical use of these sensors still faces challenges in signal controllability and environmental adaptability. Based on current limitations, this review suggests future directions: precise control and mechanistic study of dual-emission behavior, enhancing signal reliability in real samples and enabling device integration, and data-driven material design for performance optimization. Through collaborative advances, dual-emission COF-based sensors are expected to evolve into versatile detection platforms for environmental, clinical, and food safety applications, promoting the practical adoption of next-generation sensing technologies.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"555 ","pages":"Article 217638"},"PeriodicalIF":23.5,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076409","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-31DOI: 10.1016/j.ccr.2026.217604
Evelin Gruden, Gašper Tavčar
N-Heterocyclic carbenes (NHCs) have become cornerstone ligands in modern coordination and main-group chemistry, yet their interactions with metal and non-metal fluorides have long remained underexplored because many fluorides are poorly soluble and often difficult to handle. This review surveys the synthesis, structures, and reactivity of all structurally characterized NHC complexes and adducts containing the NHC-M-F fragment reported from the advent of isolable NHCs (1991) through mid-2025. Across 33 elements spanning the s-, p-, d-, and f-blocks, we compile 458 reported compounds, including 277 crystallographically authenticated species, and organize the field by element group and oxidation state. Emphasis is placed on practical synthetic entry points: direct coordination to soluble fluoride sources, transmetalation and synthon strategies, dehydrofluorination routes from fluoride salts, fluorination of pre-formed halide, hydride, or organo precursors, and redox-driven fluoride formation. We highlight how ligand sterics and electronics (including CAAC and related carbenes) govern stability and speciation. Comparative analysis of NHC–M and M–F metrics, typical geometries, and 19F NMR ranges reveals periodic trends and recurring structural motifs, providing a unified reference framework for designing new NHC-stabilized fluoride compounds and leveraging their distinctive reactivity.
n-杂环碳烯（NHCs）已成为现代配位和主基团化学的基础配体，但由于许多氟化物难溶且难以处理，它们与金属和非金属氟化物的相互作用长期以来一直未得到充分研究。本文综述了自1991年可分离NHCs出现到2025年中期，所有结构表征的含NHC- m - f片段的NHC配合物和加合物的合成、结构和反应性。在横跨s-， p-， d-和f-块的33个元素中，我们编译了458个已报道的化合物，其中包括277个晶体学鉴定的物种，并按元素族和氧化态组织该领域。重点放在实际的合成切入点：与可溶性氟化物来源的直接协调、金属转化和合成策略、氟化物盐的脱氢氟化途径、预形成的卤化物、氢化物或有机前体的氟化以及氧化还原驱动的氟化物形成。我们强调配体的立体和电子学（包括CAAC和相关的碳烯）如何控制稳定性和物种形成。NHC-M和M-F指标、典型几何形状和19F NMR范围的对比分析揭示了周期性趋势和反复出现的结构基元，为设计新的nhc稳定氟化物化合物和利用其独特的反应性提供了统一的参考框架。
{"title":"Unveiling the versatility and reactivity of N-heterocyclic carbene complexes with metal and non-metal fluorides: a comprehensive review","authors":"Evelin Gruden, Gašper Tavčar","doi":"10.1016/j.ccr.2026.217604","DOIUrl":"10.1016/j.ccr.2026.217604","url":null,"abstract":"<div><div>N-Heterocyclic carbenes (NHCs) have become cornerstone ligands in modern coordination and main-group chemistry, yet their interactions with metal and non-metal fluorides have long remained underexplored because many fluorides are poorly soluble and often difficult to handle. This review surveys the synthesis, structures, and reactivity of all structurally characterized NHC complexes and adducts containing the NHC-M-F fragment reported from the advent of isolable NHCs (1991) through mid-2025. Across 33 elements spanning the s-, p-, d-, and f-blocks, we compile 458 reported compounds, including 277 crystallographically authenticated species, and organize the field by element group and oxidation state. Emphasis is placed on practical synthetic entry points: direct coordination to soluble fluoride sources, transmetalation and synthon strategies, dehydrofluorination routes from fluoride salts, fluorination of pre-formed halide, hydride, or organo precursors, and redox-driven fluoride formation. We highlight how ligand sterics and electronics (including CAAC and related carbenes) govern stability and speciation. Comparative analysis of NHC–M and M–F metrics, typical geometries, and <sup>19</sup>F NMR ranges reveals periodic trends and recurring structural motifs, providing a unified reference framework for designing new NHC-stabilized fluoride compounds and leveraging their distinctive reactivity.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"555 ","pages":"Article 217604"},"PeriodicalIF":23.5,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076454","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-31DOI: 10.1016/j.ccr.2026.217628
Yuhan Wang , Xiaoyu Li , Zhangdong Wang , Peng Wang , Zhen Chen , Jing Yang
Reactive oxygen species (ROS), reactive nitrogen species (RNS), and reactive sulfur species (RSS), when overproduced during sustained inflammatory responses, cause oxidative stress and contribute to various acute and chronic diseases. Monitoring these molecules is crucial for understanding pathological mechanisms and evaluating therapeutic effects. This review provides a systematic comparison of fluorescent, bioluminescent, and chemiluminescent probes for in vivo imaging of ROS, RNS and RSS in inflammatory diseases. Over the past decade, each modality has developed distinct advantages: fluorescence offers high-resolution real-time visualization, bioluminescence enables deep-tissue imaging with ultra-low background, and chemiluminescence allows direct, excitation-free detection of redox activity. To clarify this landscape, we employ a “building-block” logic to dissect the design principles and evolutionary trajectories of these probes. Focusing on inflammation and related disease models, we highlight the transformative potential of bioluminescent and chemiluminescent probes for real-time monitoring of oxidative stress. This work provides a structured guide for selecting and innovating optical probes in redox biology.
{"title":"Optical probes for redox imaging: A comparative review of fluorescent, bioluminescent, and chemiluminescent strategies for in vivo sensing of ROS, RNS, and RSS","authors":"Yuhan Wang , Xiaoyu Li , Zhangdong Wang , Peng Wang , Zhen Chen , Jing Yang","doi":"10.1016/j.ccr.2026.217628","DOIUrl":"10.1016/j.ccr.2026.217628","url":null,"abstract":"<div><div>Reactive oxygen species (ROS), reactive nitrogen species (RNS), and reactive sulfur species (RSS), when overproduced during sustained inflammatory responses, cause oxidative stress and contribute to various acute and chronic diseases. Monitoring these molecules is crucial for understanding pathological mechanisms and evaluating therapeutic effects. This review provides a systematic comparison of fluorescent, bioluminescent, and chemiluminescent probes for <em>in vivo</em> imaging of ROS, RNS and RSS in inflammatory diseases. Over the past decade, each modality has developed distinct advantages: fluorescence offers high-resolution real-time visualization, bioluminescence enables deep-tissue imaging with ultra-low background, and chemiluminescence allows direct, excitation-free detection of redox activity. To clarify this landscape, we employ a “building-block” logic to dissect the design principles and evolutionary trajectories of these probes. Focusing on inflammation and related disease models, we highlight the transformative potential of bioluminescent and chemiluminescent probes for real-time monitoring of oxidative stress. This work provides a structured guide for selecting and innovating optical probes in redox biology.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"555 ","pages":"Article 217628"},"PeriodicalIF":23.5,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076406","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-31DOI: 10.1016/j.ccr.2026.217645
Fangbin Xiao , Tao Yang , Miral Javed , Chaoyong Yang , Xingyu Lin
Bacterial infections are one of the main threats to human health, and the rapid, highly sensitive monitoring of bacteria is crucial for ensuring public health safety. However, most reviews have focused on discussing the progress of bacterial identification and sensing technologies, overlooking the significance of monitoring bacterial activity. In recent years, advanced nanotechnologies based on optical, electrochemical, and spatiotemporal resolved imaging have rapidly developed and been applied to the monitoring of bacterial activity at the single-cell resolution, providing powerful tools for high-resolution bacterial analysis. Here, the progress and application of advanced nanotechnologies for monitoring bacterial activity at the single-cell resolution are comprehensively reviewed. We comprehensively discuss the behaviors of single bacterial activity (including nanovibration, motion, bioelectricity, growth, and metabolism), coordination engineering strategies for improving the sensing performance of nanomaterials, and the latest developments in advanced nanotechnologies for monitoring various physiological activities of bacteria, introducing their principles, performance, and applicability. Finally, the challenges and prospects for the application of advanced nanotechnologies in single-cell bacterial activity monitoring are proposed to guide the design and development of novel single-cell bacterial monitoring platforms.
{"title":"Nanotechnology for single-cell bacterial activity monitoring","authors":"Fangbin Xiao , Tao Yang , Miral Javed , Chaoyong Yang , Xingyu Lin","doi":"10.1016/j.ccr.2026.217645","DOIUrl":"10.1016/j.ccr.2026.217645","url":null,"abstract":"<div><div>Bacterial infections are one of the main threats to human health, and the rapid, highly sensitive monitoring of bacteria is crucial for ensuring public health safety. However, most reviews have focused on discussing the progress of bacterial identification and sensing technologies, overlooking the significance of monitoring bacterial activity. In recent years, advanced nanotechnologies based on optical, electrochemical, and spatiotemporal resolved imaging have rapidly developed and been applied to the monitoring of bacterial activity at the single-cell resolution, providing powerful tools for high-resolution bacterial analysis. Here, the progress and application of advanced nanotechnologies for monitoring bacterial activity at the single-cell resolution are comprehensively reviewed. We comprehensively discuss the behaviors of single bacterial activity (including nanovibration, motion, bioelectricity, growth, and metabolism), coordination engineering strategies for improving the sensing performance of nanomaterials, and the latest developments in advanced nanotechnologies for monitoring various physiological activities of bacteria, introducing their principles, performance, and applicability. Finally, the challenges and prospects for the application of advanced nanotechnologies in single-cell bacterial activity monitoring are proposed to guide the design and development of novel single-cell bacterial monitoring platforms.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"555 ","pages":"Article 217645"},"PeriodicalIF":23.5,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076411","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Covalent organic frameworks (COFs), particularly nanoscale COFs (NCOFs), have emerged as architecturally precise, metal-free nanocarriers with the potential to mitigate persistent limitations of conventional delivery platforms, including premature leakage, dilution-driven destabilization, and limited microenvironmental responsiveness, in appropriately designed systems. High loading, prolonged retention, and stimulus-triggered release have been reported, enabled by crystalline, permanent porosity combined with chemically programmable backbones and pore surfaces. In this review, a chemically grounded design framework is presented in which drug-delivery performance is linked to three interdependent variables: linkage chemistry, by which the balance between stability and triggerability is defined, namely, acid-labile, redox-responsive, ROS-responsive, or long-lived backbones; framework architecture and pore geometry, by which surface area, diffusion pathways, confinement, and partitioning are regulated; and surface and interface engineering, including postsynthetic modification (PSM), polymer coronas, and ligand decoration, by which colloidal stability, pharmacokinetics, protein corona formation, and cellular trafficking are governed. Although discussed as three variables for clarity, they are frequently coupled in practice; for instance, surface functionalization or polymer coronas can alter adequate pore accessibility and apparent crystallinity, and defects or terminations can dominate local binding environments and transport pathways.
Mechanistic design routes are summarized for representative linkages and architectures, including 2D and 3D frameworks, core and shell particles, nanosheets, nanofibers, and hollow constructs, and the resulting impacts on loading capacity, retention strength, and on-demand release under pH, redox, and ROS, light, or enzymatic cues are synthesized across reported studies. Practical considerations affecting the transferability of conclusions, including mass-balanced loading and release, trigger validation, stability budgets, and benchmarkable characterization packages, are highlighted alongside scalability and biointerface constraints. Actionable guidelines are provided for the rational selection of linkage, architecture, and surface and interfacial chemistry to engineer NCOF nanocarriers toward robust circulation and spatially and temporally programmed drug release.
{"title":"Nanoscale covalent organic frameworks for drug delivery: Linking structure and surface to stimuli-responsive release","authors":"Ghasem Rezanejade Bardajee , Hossein Mahmoodian , Amirhosein Amini , Mahdieh Sharifi , Mohsen Adeli , Rajender Boddula","doi":"10.1016/j.ccr.2026.217617","DOIUrl":"10.1016/j.ccr.2026.217617","url":null,"abstract":"<div><div>Covalent organic frameworks (COFs), particularly nanoscale COFs (NCOFs), have emerged as architecturally precise, metal-free nanocarriers with the potential to mitigate persistent limitations of conventional delivery platforms, including premature leakage, dilution-driven destabilization, and limited microenvironmental responsiveness, in appropriately designed systems. High loading, prolonged retention, and stimulus-triggered release have been reported, enabled by crystalline, permanent porosity combined with chemically programmable backbones and pore surfaces. In this review, a chemically grounded design framework is presented in which drug-delivery performance is linked to three interdependent variables: linkage chemistry, by which the balance between stability and triggerability is defined, namely, acid-labile, redox-responsive, ROS-responsive, or long-lived backbones; framework architecture and pore geometry, by which surface area, diffusion pathways, confinement, and partitioning are regulated; and surface and interface engineering, including postsynthetic modification (PSM), polymer coronas, and ligand decoration, by which colloidal stability, pharmacokinetics, protein corona formation, and cellular trafficking are governed. Although discussed as three variables for clarity, they are frequently coupled in practice; for instance, surface functionalization or polymer coronas can alter adequate pore accessibility and apparent crystallinity, and defects or terminations can dominate local binding environments and transport pathways.</div><div>Mechanistic design routes are summarized for representative linkages and architectures, including 2D and 3D frameworks, core and shell particles, nanosheets, nanofibers, and hollow constructs, and the resulting impacts on loading capacity, retention strength, and on-demand release under pH, redox, and ROS, light, or enzymatic cues are synthesized across reported studies. Practical considerations affecting the transferability of conclusions, including mass-balanced loading and release, trigger validation, stability budgets, and benchmarkable characterization packages, are highlighted alongside scalability and biointerface constraints. Actionable guidelines are provided for the rational selection of linkage, architecture, and surface and interfacial chemistry to engineer NCOF nanocarriers toward robust circulation and spatially and temporally programmed drug release.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"555 ","pages":"Article 217617"},"PeriodicalIF":23.5,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076365","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-30DOI: 10.1016/j.ccr.2026.217594
Zhaoran Wang , Qiong Chen , Xuejie Chen, Lin Lv, Wukun Liu
Tumor occurrence and progression are intimately linked to immunity, so one strategy for the therapy of malignancies is the regulation of tumor immune environment. Despite the fact that metal ions are rarely noticed and are found in extremely small amounts in cells, they are crucial for many biological functions. It is noteworthy that intracellular metal ions significantly affect the immune system and the development of tumors. This review synthesizes current understanding of how intracellular metal ions influence multiple facets of immune function, including macrophage polarization, T cell activation, and cell death pathways such as ferroptosis and pyroptosis. Our primary focus is on the metal ions, including Ca2+, Mn2+, K+, Fe2+/Fe3+, Zn2+, Cu+ and Mg2+. It is worth mentioning that a few of these metal ions play a double-edged role in modulating tumor immunity, and they are deeply intertwined in several pivotal immunological pathways. Moreover, we reviewed a series of complexes that affect intracellular metal ions to influence tumor immunity. By elucidating the mechanism of intracellular metal ions regulating the immune response, this review focuses on the recent advances in metal ion-targeted therapeutic approaches, providing innovative strategies for improving tumor immunotherapy and addressing the limitations of existing cancer treatments.
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