Coordination Chemistry Reviews最新文献_第6页

Solid-state NMR characterization of weak interactions in molecular crystals 分子晶体中弱相互作用的固态核磁共振表征

IF 23.5 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Coordination Chemistry Reviews

Pub Date : 2026-01-27 DOI: 10.1016/j.ccr.2026.217610

Chiara Sabena , Chiara Rosso , Téodor Iftemie , Roberto Gobetto , David L. Bryce , Michele R. Chierotti

Weak non-covalent interactions, including hydrogen bonds, π–π stacking, and the diverse family of σ-hole interactions (halogen, chalcogen, pnictogen, tetrel, osme, and matere bonds), govern the structure, stability, and properties of molecular crystals. Solid-state Nuclear Magnetic Resonance (SSNMR) spectroscopy provides an unparalleled means of probing these interactions at the atomic level by directly sensing local electronic environments, independent of long-range order. This review surveys recent advances (approximately since 2020) in SSNMR methodologies for detecting, characterizing, and quantifying weak interactions in molecular solids. Particular emphasis is placed on developments in high-field and ultrafast magic-angle spinning (MAS) instrumentation, as well as novel pulse sequences that enhance access to key nuclei involved in non-covalent bonding. SSNMR observables, such as chemical shifts, dipolar and J couplings, quadrupolar parameters, and relaxation rates, are shown to provide quantitative insight into the interaction strength, geometry, and dynamics of hydrogen-bonded, π-stacked, and σ-hole-bonded systems. The review also discusses the synergistic integration of SSNMR with diffraction (single-crystal and powder X-ray diffraction, electron diffraction) and computational methods (Crystal Structure Prediction, DFT calculations, molecular dynamics simulations, machine learning models), yielding a multidimensional framework for elucidating structure–property relationships in both crystalline and disordered materials. Special attention is devoted to complex environments such as multicomponent crystals, host–guest assemblies, and amorphous dispersions. Looking ahead, continued advances in ultrahigh-field instrumentation, pulse-sequence design, and NMR crystallography promise to transform SSNMR from a diagnostic into a predictive tool for supramolecular chemistry and crystal engineering, bridging microscopic interactions with macroscopic material behaviour.

弱非共价相互作用，包括氢键、π -π堆叠和各种σ-空穴相互作用（卤素键、硫键、烟原键、四元键、osme键和物质键），控制着分子晶体的结构、稳定性和性能。固态核磁共振（SSNMR）光谱提供了一种无与伦比的手段，通过直接感知局部电子环境，在原子水平上探测这些相互作用，独立于远程秩序。本文综述了用于检测、表征和量化分子固体中弱相互作用的SSNMR方法的最新进展（大约自2020年以来）。特别强调的是高场和超快魔角旋转（MAS）仪器的发展，以及新的脉冲序列，增强了对参与非共价键的关键原子核的访问。SSNMR的观测结果，如化学位移、偶极和J偶极耦合、四极参数和弛豫速率，为氢键、π-堆叠和σ-空穴键体系的相互作用强度、几何形状和动力学提供了定量的见解。本文还讨论了SSNMR与衍射（单晶和粉末x射线衍射，电子衍射）和计算方法（晶体结构预测，DFT计算，分子动力学模拟，机器学习模型）的协同集成，为阐明晶体和无序材料的结构-性质关系提供了一个多维框架。特别关注复杂的环境，如多组分晶体，主客体组装和非晶分散体。展望未来，超高场仪器、脉冲序列设计和核磁共振晶体学的持续进步有望将SSNMR从诊断工具转变为超分子化学和晶体工程的预测工具，将微观相互作用与宏观材料行为联系起来。

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引用次数: 0

A review of interfacial engineering and performance modulation of hollow/porous nanostructures synthesized via the Kirkendall effect for synergistic remediation of water co-contaminated by heavy metals and organics 基于Kirkendall效应合成的中空/多孔纳米结构的界面工程及性能调控研究进展

IF 23.5 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Coordination Chemistry Reviews

Pub Date : 2026-01-27 DOI: 10.1016/j.ccr.2026.217633

Xiaofei Li , Rui Xu , Guangfei Qu , Dehui Kong , Chenyang Yin , Yingying Cai , Minhua Cheng , Yaoze Wang , Linjin Li , Ping Ning

The synergistic remediation of heavy metal-organic compound pollution has emerged as a major challenge in environmental restoration. Traditional techniques often suffer from low efficiency and secondary pollution risks due to complex interactions between pollutants. This review systematically summarized recent advances in leveraging the Kirkendall effect for the design of environmental functional materials. It specifically elucidated the physical mechanism by which this effect induces the formation of hollow/porous structures through the regulation of non-equilibrium diffusion kinetics in heterogeneous components, highlighting its unique advantages for synergistic pollutant removal. Researches demonstrated that Kirkendall effect derived functional materials possessed high specific surface areas, tunable pore size distributions, and abundant active sites. These properties enabled the simultaneous efficient adsorption-catalytic reduction of heavy metal ions and the deep degradation of organic pollutants. Further optimization of the material's electronic structure and mass transfer behavior, achievable through surface functionalization (e.g., phosphorylation, amination) and heterojunction interface engineering, significantly enhanced pollutant removal efficiency and structural stability within complex environmental matrices. However, the practical application of this technology still faced critical challenges, including complex synthesis procedures, insufficient long-term stability, and an incomplete understanding of synergistic removal mechanisms. Future efforts should focus on developing green, scalable synthesis strategies, providing an in-depth elucidation of interfacial reaction mechanisms under multifactor coupling, and advancing engineering scale validation. These endeavors are crucial for providing the theoretical foundation and technical support necessary for the innovative development of next generation environmental remediation technologies.

重金属-有机化合物污染的协同修复已成为环境修复的一大挑战。传统技术由于污染物之间复杂的相互作用，往往存在效率低下和二次污染风险。这篇综述系统地总结了利用Kirkendall效应设计环境功能材料的最新进展。具体阐述了该效应通过调控非平衡扩散动力学诱导中空/多孔结构形成的物理机制，突出了其协同去除污染物的独特优势。研究表明，Kirkendall效应衍生的功能材料具有高比表面积、可调节的孔径分布和丰富的活性位点。这些特性使其能够同时高效吸附-催化还原重金属离子和深度降解有机污染物。通过表面功能化（如磷酸化、胺化）和异质结界面工程，进一步优化材料的电子结构和传质行为，显著提高了复杂环境基质中的污染物去除效率和结构稳定性。然而，该技术的实际应用仍然面临着严峻的挑战，包括复杂的合成过程、长期稳定性不足以及对协同去除机制的不完全了解。未来的工作应侧重于开发绿色、可扩展的合成策略，深入阐明多因素耦合下的界面反应机制，并推进工程规模验证。这些努力对于为下一代环境修复技术的创新发展提供必要的理论基础和技术支持至关重要。

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引用次数: 0

From coordination spheres to catalytic sites: Defect engineering in metal oxide photocatalysts 从配位球到催化位点：金属氧化物光催化剂的缺陷工程

IF 23.5 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Coordination Chemistry Reviews

Pub Date : 2026-01-27 DOI: 10.1016/j.ccr.2026.217614

Yan Lu , Seunghyun Weon , Ki-Hyun Kim

Lattice defects in metal oxide semiconductors, once regarded as performance-limiting flaws, are recognized as powerful tools for enhancing photocatalytic activity. These structural imperfections, including oxygen vacancies (Vo), cation deficiencies, interstitials, and dopant-induced distortions, are not mere flaws but products of deliberate defect engineering rooted in coordination chemistry principles. The deliberate distortion of the local coordination environment around metal centers introduces specific defects that, in turn, directly modulate the electronic band structure, redefine surface properties, and alter charge carrier transport. In the photocatalytic oxidation of volatile organic compounds (VOCs), defect engineering enables improved light absorption, more efficient charge separation, and increased generation of reactive oxygen species. This review deciphers how engineered defects in metal oxides boost photocatalytic removal performance of VOCs. The connection between synthesis, characterization, and mechanism is thus established to offer mechanistic insights into how coordination sphere distortion at metal sites governs the photomineralization of VOCs. Selected case studies, including TiO₂, ZnO, WO₃, and CeO₂, are used to highlight key structure–function relationships and real-world performance. The review concludes by addressing critical challenges in quantifying and stabilizing defects, scaling up defect-engineered materials, and designing catalysts with enhanced selectivity, sustainability, and long-term usability.

金属氧化物半导体中的晶格缺陷曾经被认为是限制性能的缺陷，现在被认为是增强光催化活性的有力工具。这些结构缺陷，包括氧空位（Vo）、阳离子缺乏、间隙和掺杂剂引起的扭曲，不仅仅是缺陷，而是基于配位化学原理的故意缺陷工程的产物。金属中心周围局部配位环境的故意扭曲引入了特定的缺陷，这些缺陷反过来直接调节电子能带结构，重新定义表面性质，并改变电荷载流子输运。在挥发性有机化合物（VOCs）的光催化氧化中，缺陷工程可以改善光吸收，更有效地分离电荷，并增加活性氧的产生。这篇综述揭示了金属氧化物中的工程缺陷如何提高VOCs光催化去除性能。因此，建立了合成、表征和机制之间的联系，为金属位点的配位球畸变如何控制VOCs的光矿化提供了机制上的见解。选定的案例研究，包括TiO₂、ZnO、WO₃和CeO₂，用来突出关键的结构功能关系和现实世界的性能。本文总结了在量化和稳定缺陷、扩大缺陷工程材料和设计具有增强选择性、可持续性和长期可用性的催化剂方面的关键挑战。

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引用次数: 0

Pushing the boundaries: The path of mechanosynthesis toward the assembly of supramolecular organic frameworks 突破边界：机械合成通往超分子有机框架组装的道路

IF 23.5 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Coordination Chemistry Reviews

Pub Date : 2026-01-27 DOI: 10.1016/j.ccr.2026.217600

Danilo Marchetti, Riccardo Testa, Alessandro Pedrini, Chiara Massera

Supramolecular organic frameworks (SOFs), synthetic frameworks assembled via non-covalent interactions, are being extensively studied for their applications as porous functional solids endowed with flexibility, reversibility and tunability of stimuli-responsive properties. This review explores the use of mechanosynthesis as a versatile strategy for their rational design and green synthesis, while expanding their structural and functional diversity. After an overview of the path followed by supramolecular mechanochemistry from the assembly of cocrystals to the complexation of host-guest systems in the solid state, we have detailed the mechanosynthesis of hydrogen-bonded organic frameworks (HOFs) and the less-explored halogen-bonded organic frameworks (XOFs), highlighting the advantages of solid-state methods in promoting reactivity, sustainability, and access to otherwise unattainable architectures.

超分子有机骨架（SOFs）是通过非共价相互作用组装而成的合成骨架，作为具有柔性、可逆性和可调性的多孔功能固体，正受到广泛的研究。这篇综述探讨了机械合成作为其合理设计和绿色合成的通用策略，同时扩大了其结构和功能的多样性。在概述了超分子机械化学从共晶组装到固态主客系统络合的路径之后，我们详细介绍了氢键有机框架（HOFs）和较少探索的卤素键有机框架（XOFs）的机械合成，强调了固态方法在促进反应性、可持续性和获得其他无法实现的结构方面的优势。

引用次数: 0

Photothermal effect-reinforced cancer treatment: Materials and strategies 光热效应增强癌症治疗：材料与策略

IF 23.5 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Coordination Chemistry Reviews

Pub Date : 2026-01-24 DOI: 10.1016/j.ccr.2025.217503

Pengcheng Hu , Qi Gong , Zhao-Ya Wu , Yang Liu , Fu-Gen Wu

Photothermal therapy (PTT) has emerged as a pivotal strategy for cancer treatment due to its noninvasiveness, high spatiotemporal selectivity, and repeatable therapeutic potential. However, the clinical application of PTT is constrained by the low tissue penetration depth of light, suboptimal targeting efficiency of photothermal agents, and thermoresistance of tumor cells. To overcome these limitations, researchers have recently focused on the development of synergistic PTT-assisted combination strategies. These approaches leverage photothermal effect-mediated localized heat to enhance drug delivery efficiency, modulate the tumor microenvironment (e.g., alleviating hypoxia and promoting reactive oxygen species (ROS) generation), and activate antitumor immune responses, thereby achieving multimodal synergistic effects. This review systematically summarizes the recent advances in the integration of PTT with chemotherapy, radiotherapy, photodynamic therapy, sonodynamic therapy, chemodynamic therapy, thermodynamic therapy, gas therapy, ion therapy, immunotherapy, and gene therapy. Special emphasis is placed on the innovative enhancement mechanisms, including enhanced drug penetration, ROS amplification, and tumor microenvironment modulation. Furthermore, this review critically examines the current technical bottlenecks (e.g., precise treatment of deep-seated tumors and spatiotemporally controlled drug release) and outlines the future research directions. The insights provided herein establish a theoretical foundation and technical reference for developing novel photothermal effect-based combinatorial anticancer strategies.

光热疗法（PTT）由于其非侵入性、高时空选择性和可重复治疗的潜力，已成为癌症治疗的关键策略。然而，PTT的临床应用受到光穿透组织深度低、光热剂靶向效率不理想以及肿瘤细胞耐热性等因素的限制。为了克服这些限制，研究人员最近专注于开发协同ptt辅助联合策略。这些方法利用光热效应介导的局部热来提高药物递送效率，调节肿瘤微环境（如缓解缺氧和促进活性氧（ROS）的产生），激活抗肿瘤免疫反应，从而实现多模态协同效应。本文系统综述了近年来PTT与化疗、放疗、光动力治疗、声动力治疗、化学动力治疗、热力学治疗、气体治疗、离子治疗、免疫治疗和基因治疗结合的研究进展。特别强调的是创新的增强机制，包括增强药物渗透，ROS扩增和肿瘤微环境调节。此外，本文对当前的技术瓶颈（如深部肿瘤的精确治疗和时空控制药物释放）进行了批判性的审查，并概述了未来的研究方向。本文提供的见解为开发基于光热效应的新型联合抗癌策略奠定了理论基础和技术参考。

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引用次数: 0

A review of recent advances in carbon nitride photocatalysts for CO2 reduction 氮化碳光催化剂在CO2还原中的研究进展

IF 23.5 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Coordination Chemistry Reviews

Pub Date : 2026-01-24 DOI: 10.1016/j.ccr.2026.217613

Junpeng Song , Xiaomei Dai , Minqiang He , Yanhua Song , Jinman Yang

The excessive use of fossil fuels has led to a sharp increase in atmospheric CO₂ concentration, intensifying the greenhouse effect and posing serious challenges to environmental protection and energy sustainability. Solar-driven photocatalytic CO₂ reduction has emerged as a green and feasible approach to convert CO₂ into high-value-added fuels, thereby alleviating both environmental and energy pressures. Among various photocatalysts, carbon nitride (C₃N₄) has attracted extensive attention due to its visible-light responsiveness, excellent stability, and low cost. However, its catalytic efficiency is still limited by rapid charge recombination, low carrier mobility, and a small number of active sites. To address these limitations, various modification strategies have been proposed, including morphology control, element doping, heterojunction construction, vacancy engineering, and cocatalyst loading, aiming to enhance light absorption, charge separation, and catalytic activity. This review provides an in-depth overview of recent developments in C₃N₄ photocatalysts for CO₂ reduction and their prospects, discusses the relationship between structure and performance, and briefly outlines the reaction conditions affecting photocatalytic activity. Finally, the challenges and prospects for the practical application of C₃N₄ are presented, providing valuable guidance for the rational design of efficient and sustainable photocatalytic systems.

化石燃料的过度使用导致大气中二氧化碳浓度急剧上升，温室效应加剧，给环境保护和能源可持续性带来严峻挑战。太阳能驱动的光催化二氧化碳还原已经成为将二氧化碳转化为高附加值燃料的一种绿色可行的方法，从而减轻了环境和能源压力。在各种光催化剂中，氮化碳（C3N4）因其对可见光的响应性、优异的稳定性和低廉的成本而受到广泛关注。但其催化效率仍受电荷重组速度快、载流子迁移率低、活性位点数量少等因素的限制。为了解决这些限制，人们提出了各种改性策略，包括形貌控制、元素掺杂、异质结构建、空位工程和助催化剂负载，旨在提高光吸收、电荷分离和催化活性。本文综述了二氧化碳还原C3N4光催化剂的最新研究进展及其前景，讨论了C3N4光催化剂的结构与性能的关系，并简要概述了影响光催化活性的反应条件。最后，提出了C3N4在实际应用中面临的挑战和前景，为合理设计高效、可持续的光催化系统提供了有价值的指导。

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引用次数: 0

Electron deficient fluorous polycyclic aromatic and heteroaromatic hydrocarbons 缺电子的含氟多环芳烃和杂芳烃

IF 23.5 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Coordination Chemistry Reviews

Pub Date : 2026-01-24 DOI: 10.1016/j.ccr.2026.217592

Sebastian Balser, Olga V. Boltalina

Electron-deficient polycyclic aromatic hydrocarbons (PAHs) and their heteroaromatic analogues have emerged as key building blocks for organic semiconductors, photovoltaics, and optoelectronic devices. Incorporation of perfluoroalkyl (R_F) and perfluoroaryl (Ar_F) substituents into these frameworks significantly enhances electron affinity, lowers LUMO energy levels, and imparts air-, photo- and thermal stability, thereby addressing long-standing limitations of pristine PAHs in n-type materials. This review summarizes recent advances in the synthesis of R_F- and Ar_F-polysubstituted PAHs, highlighting one-step high-temperature gas-phase methods, copper-mediated transformations, and emerging photochemical strategies for selective perfluoroalkylation. Structural insights from single-crystal X-ray diffraction reveal how fluorinated substituents govern molecular conformation, π–π stacking, and solid-state packing, thereby tuning electronic and optical properties. Emphasis is placed on acenes, heteroacenes, phenanthrolines, perylenes, coronenes, and buckybowls, which illustrates the versatility of fluorine-based functionalization in accessing stable, strongly electron-accepting materials with diverse structures and properties.

缺乏电子的多环芳烃（PAHs）及其杂芳烃类似物已成为有机半导体，光伏和光电子器件的关键组成部分。在这些框架中加入全氟烷基（RF）和全氟芳基（ArF）取代基显著增强了电子亲和性，降低了LUMO能级，并赋予了空气、光和热稳定性，从而解决了n型材料中原始多环芳烃的长期限制。本文综述了RF-和arf -多取代多环芳烃合成的最新进展，重点介绍了一步高温气相法、铜介导转化和新兴的选择性全氟烷基化光化学策略。来自单晶x射线衍射的结构见解揭示了氟化取代基如何控制分子构象，π -π堆叠和固态包装，从而调整电子和光学性质。重点放在烯类、杂苯类、菲罗啉类、苝类、冕类和巴基碗类，这说明了氟基功能化在获得具有不同结构和性质的稳定、强电子接受材料方面的多功能性。

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引用次数: 0

Molecular recognition-mediated dynamic networks in hydrogel biomaterials 水凝胶生物材料中分子识别介导的动态网络

IF 23.5 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Coordination Chemistry Reviews

Pub Date : 2026-01-24 DOI: 10.1016/j.ccr.2026.217625

Xiangyu Wu , Zhaoyang Yao , Jia Gao, Guoqing Pan

Hydrogels have found extensive applications in the biomedical field, due to their outstanding biocompatibility and tunable physicochemical properties. However, conventional hydrogels often suffer from limited adaptability and inadequate dynamic responsiveness, which significantly hampers their performance in complex physiological environments. Compared with the non-specificity and high reactivity of reversible covalent interactions, molecular recognition relies on specific and spatially complementary noncovalent bonds, thus providing a reversible but powerful and versatile approach to constructing dynamic hydrogel networks. Dynamic hydrogels mediated by molecular recognition exhibit tunable mechanical strength, efficient self-healing capabilities, and precise stimulus-responsive behaviors, thereby expanding their potential in diverse biomedical applications. This review summarizes recent advances in molecular recognition-mediated dynamic hydrogels, covering systems based on purely chemical recognition as well as those derived from natural biological recognition elements. We further discuss their applications in tissue engineering, drug delivery, and biosensors, with particular emphasis on how molecular recognition regulates hydrogel dynamics and modulates cellular responses and tissue healing. The development of molecular recognition-mediated dynamic hydrogels will establish a systematic theoretical foundation and offer a versatile strategy for the next generation of dynamic biomaterials.

水凝胶由于其优异的生物相容性和可调的物理化学性质，在生物医学领域有着广泛的应用。然而，传统水凝胶的适应性有限，动态响应能力不足，严重影响了其在复杂生理环境中的性能。与可逆性共价相互作用的非特异性和高反应性相比，分子识别依赖于特异性和空间互补的非共价键，从而为构建动态水凝胶网络提供了一种可逆但强大且通用的方法。由分子识别介导的动态水凝胶表现出可调节的机械强度、高效的自我修复能力和精确的刺激反应行为，从而扩大了其在各种生物医学应用中的潜力。本文综述了分子识别介导的动态水凝胶的最新进展，包括基于纯化学识别的系统以及源自天然生物识别元件的系统。我们进一步讨论了它们在组织工程、药物输送和生物传感器中的应用，特别强调了分子识别如何调节水凝胶动力学、调节细胞反应和组织愈合。分子识别介导的动态水凝胶的发展将为下一代动态生物材料的发展奠定系统的理论基础，并提供一个通用的策略。

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引用次数: 0

Catalytic mechanisms and systems of the conversion of furfural to γ-valerolactone via transfer hydrogenation pathway: a review 糠醛经转移加氢途径转化为γ-戊内酯的催化机理及体系研究进展

IF 23.5 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Coordination Chemistry Reviews

Pub Date : 2026-01-23 DOI: 10.1016/j.ccr.2026.217615

Tingwei Zhang , Yanyu Jing , Zhaochuan Yu , Chaofeng Zhang , Yongcan Jin , Wenzhi Li , Huining Xiao

In recent years, the one-pot transfer hydrogenation of furfural to γ-valerolactone (GVL) with biomass-derived alcohols as solvents and hydrogen donors has received extensive attention. Within this cascade pathway, furfuryl alcohol (FA) and alkyl levulinates (ALs) not only serve as key intermediates but can also be selectively produced as target products through rational tuning of catalyst active sites. Biomass-derived FA, ALs, and GVL have emerged as highly valuable platform molecules for the production of sustainable fuels and value-added chemicals. This review offers a comprehensive summary of recent progress in the one-pot transfer hydrogenation of furfural to GVL, with an integrated discussion of the related sub-reactions (furfural-to-FA, FA-to-ALs, furfural-to-ALs, and levulinic acid/ALs-to-GVL). Particular emphasis is placed on reaction mechanisms, the rational design of efficient catalysts for different reactions, and the roles of alcohol type and catalyst acidity/basicity in governing product distribution. Finally, feasible suggestions are proposed for enhancing catalytic performance and advancing practical applications.

近年来，以生物质衍生醇为溶剂和供氢体的糠醛一锅转移加氢制γ-戊内酯（GVL）的研究受到了广泛关注。在这一级联途径中，糠醇（FA）和乙酰丙酸烷基酯（ALs）不仅作为关键中间体，还可以通过合理调整催化剂活性位点选择性地产生目标产物。生物质衍生的FA、ALs和GVL已成为生产可持续燃料和增值化学品的极有价值的平台分子。本文综述了糠醛一锅转移加氢制GVL的最新进展，并对相关亚反应（糠醛制fa、fa制als、糠醛制als和乙酰丙酸/ als制GVL）进行了综合讨论。特别强调的是反应机制，不同反应的有效催化剂的合理设计，以及酒精类型和催化剂的酸度/碱度在控制产品分布中的作用。最后提出了提高催化性能和推进实际应用的可行性建议。

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引用次数: 0

Precise control of external stimulus-responsive MXenes for biomedical applications 生物医学外刺激响应MXenes的精确控制

IF 23.5 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Coordination Chemistry Reviews

Pub Date : 2026-01-23 DOI: 10.1016/j.ccr.2026.217602

Haoming Ding , Xiao Tong , Yong Zhang

MXenes, as a prominent class of two-dimensional (2D) transition metal carbides/nitrides, have attracted extensive attention in innovative biomedical applications due to their distinct layered structure, tunable electronic properties, good biocompatibility, and highly tunable surface/interlayer properties. Their biomedical functionalities largely rely on specific responses to external stimuli, e.g., light, mechanical force, ultrasound waves, magnetism, and heat, which are intrinsically linked to their precise structural design. However, the transition from empirical exploration to rational design of MXene-based nanomedicines is hindered by an insufficient understanding of the relationship between precise structural regulation, stimuli-responsive behavior, and biomedical efficacy. Existing reviews primarily focus on cataloging application scenarios rather than on an in-depth analysis of this core structure-functional relationship. To bridge this critical knowledge gap, this review focuses on the precise control of externally stimuli-responsive MXenes for biomedical applications. It systematically summarizes multi-dimensional structural regulation strategies, including atomic structure modulation, surface chemistry, interlayer engineering, and defect control, and dissects their regulatory effects on stimuli-responsive mechanisms. By integrating representative biomedical applications, a comprehensive structure-response-efficacy framework is established, providing critical theoretical support for the interdisciplinary innovation of materials science and biomedicine. Finally, we propose some challenges and future perspectives relevant to the continuous development of MXenes in biomedicine applications. This review addresses the current research gap and offers practical guidelines for designing smart MXene-based materials, which may promote the transformative potential of structurally engineered MXenes in advancing precision nanomedicine.

MXenes作为一类突出的二维（2D）过渡金属碳化物/氮化物，由于其独特的层状结构、可调谐的电子特性、良好的生物相容性和高度可调谐的表面/层间特性，在创新生物医学应用中受到了广泛关注。它们的生物医学功能很大程度上依赖于对外部刺激的特定反应，例如光、机械力、超声波、磁力和热量，这些都与它们精确的结构设计有着内在的联系。然而，由于对精确的结构调节、刺激反应行为和生物医学疗效之间的关系认识不足，阻碍了基于mxene的纳米药物从经验探索到合理设计的过渡。现有的评论主要集中于对应用程序场景进行编目，而不是对这种核心结构-功能关系进行深入分析。为了弥补这一关键的知识差距，本文将重点介绍生物医学应用中外部刺激反应性MXenes的精确控制。系统总结了原子结构调控、表面化学、层间工程、缺陷控制等多维结构调控策略，并剖析了它们对刺激响应机制的调控作用。通过整合具有代表性的生物医学应用，构建结构-反应-功效的综合框架，为材料科学与生物医学的交叉创新提供重要的理论支持。最后，对MXenes在生物医学领域的持续发展提出了挑战和展望。这篇综述弥补了目前的研究空白，并为设计基于MXenes的智能材料提供了实用指南，这可能会促进结构工程化MXenes在推进精密纳米医学方面的变革潜力。

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引用次数: 0