Chemical Society Reviews最新文献

{"title":"Body fluid diagnostics using activatable optical probes","authors":"Jie Zhan, Yanbin Cai, Penghui Cheng, Lei Zheng and Kanyi Pu","doi":"10.1039/D4CS01315H","DOIUrl":"10.1039/D4CS01315H","url":null,"abstract":"<p > <em>In vitro</em> diagnostics often detects biomarkers in body fluids (such as blood, urine, sputum, and cerebrospinal fluids) to identify life-threatening diseases at an early stage, monitor overall health, or provide information to help cure, treat, or prevent diseases. Most clinically used optical <em>in vitro</em> diagnostic tests utilize dye-labeled biomolecules for biomarker recognition and signal readout, which typically involve complex steps and long processing times. Activatable optical probes (AOPs), which spontaneously activate their optical signals only in the presence of disease biomarkers, offer higher signal-to-background ratios and improved detection specificity. They also have the potential to simplify detection procedures by eliminating multiple washing steps. In this review, we summarize recent advances in the use of AOPs for pre-clinical and clinical body fluid diagnostics across various diseases, including cancer, nephro-urological disorders, infectious diseases, and digestive diseases. We begin by discussing the molecular design strategies of AOPs to achieve different optical signal readouts and biomarker specificity. We then highlight their diagnostic applications in various disease models and body fluids. Finally, we address the challenges and future perspectives of AOPs in enhancing body fluid diagnostics and advancing precision medicine.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 8","pages":" 3906-3929"},"PeriodicalIF":40.4,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cs/d4cs01315h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618521","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Coacervates as enzymatic microreactors","authors":"Rif Harris, Nofar Berman and Ayala Lampel","doi":"10.1039/D4CS01203H","DOIUrl":"10.1039/D4CS01203H","url":null,"abstract":"<p >Compartmentalization, a key aspect of biochemical regulation, naturally occurs in cellular organelles, including biomolecular condensates formed through liquid–liquid phase separation (LLPS). Inspired by biological compartments, synthetic coacervates have emerged as versatile microreactors, which can provide customed environments for enzymatic reactions. In this review, we explore recent advances in coacervate-based microreactors, while emphasizing the mechanisms by which coacervates accelerate enzymatic reactions, namely by enhancing substrate and enzyme concentrations, stabilizing intermediates, and providing molecular crowding. We discuss diverse coacervate systems, including those based on synthetic polymers, peptides, and nucleic acids, and describe the selection of enzymatic model systems, as well as strategies for enzyme recruitment and their impact on reaction kinetics. Furthermore, we discuss the challenges in monitoring reactions within coacervates and review the currently available techniques including fluorescence techniques, chromatography, and NMR spectroscopy. Altogether, this review offers a comprehensive perspective on recent progress and challenges in the design of coacervate microreactors, and addresses their potential in biocatalysis, synthetic biology, and nanotechnology.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 9","pages":" 4183-4199"},"PeriodicalIF":40.4,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cs/d4cs01203h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618519","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Breaking symmetry for better catalysis: insights into single-atom catalyst design","authors":"Pingping Cao, Xueqin Mu, Fanjiao Chen, Shengchen Wang, Yuru Liao, Hui Liu, Yapeng Du, Yuxuan Li, Yudi Peng, Mingzhu Gao, Suli Liu, Dingsheng Wang and Zhihui Dai","doi":"10.1039/D4CS01031K","DOIUrl":"10.1039/D4CS01031K","url":null,"abstract":"<p >Breaking structural symmetry has emerged as a powerful strategy for fine-tuning the electronic structure of catalytic sites, thereby significantly enhancing the electrocatalytic performance of single-atom catalysts (SACs). The inherent symmetric electron density in conventional SACs, such as M–N<small>₄</small> configurations, often leads to suboptimal adsorption and activation of reaction intermediates, limiting their catalytic efficiency. By disrupting this symmetry of SACs, the electronic distribution around the active center can be modulated, thereby improving both the selectivity and adsorption strength for key intermediates. These changes directly impact the reaction pathways, lowering energy barriers, and enhancing catalytic activity. However, achieving precise modulation through SAC symmetry breaking for better catalysis remains challenging. This review focuses on the atomic-level symmetry-breaking strategies of catalysts, including charge breaking, coordination breaking, and geometric breaking, as well as their electrocatalytic applications in electronic structure tuning and active site modulation. Through modifications to the M–N<small>₄</small> framework, three primary configurations are achieved: unsaturated coordination M–N<small>_{<em>x</em>(<em>x</em>=1,2,3)}</small>, non-metallic doping MX–N<small>_{<em>x</em>(<em>x</em>=1,2,3)}</small>, and bimetallic doping M<small>₁</small>M<small>₂</small>–N<small>₄</small>. Advanced characterization techniques combined with density functional theory (DFT) elucidate the impact of these strategies on oxidation, reduction, and bifunctional catalytic reactions. This review highlights the significance of symmetry-breaking structures in catalysis and underscores the need for further research to achieve precise control at the atomic-level.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 8","pages":" 3848-3905"},"PeriodicalIF":40.4,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608133","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}

{"title":"Bis(trimethylsilyl)phosphide chemistry: a half-century of advances across the periodic table","authors":"Jack Baldwin and David P. Mills","doi":"10.1039/D4CS01141D","DOIUrl":"10.1039/D4CS01141D","url":null,"abstract":"<p >Whilst bis(trimethylsilyl)amide has been used extensively as a ligand across the periodic table, the chemistry of its heavier group 15 congeners is relatively underdeveloped. However, bis(trimethylsilyl)phosphide coordination chemistry has provided unique structural motifs and has also shown potential applications in catalysis, materials science, and bioinorganic chemistry. This review, which marks 55 years since the first report of a bis(trimethylsilyl)phosphide complex, provides a comprehensive overview of the synthesis, characterisation and reactivity of structurally authenticated s-, p-, d- and f-block metal complexes of this ligand, focusing on salient single crystal XRD and NMR spectroscopic data. We discuss the factors influencing the diverse coordination modes and reactivity profiles of bis(trimethylsilyl)phosphide complexes, together with an overview of their potential as precursors for novel solid-state materials, aiming to inspire future research endeavours using this ligand. We also review the small number of bis(triisopropylsilyl)phosphide complexes, in order to provide motivation for the future study of other bis(silyl)phosphide ligands.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 8","pages":" 3819-3847"},"PeriodicalIF":40.4,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cs/d4cs01141d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143598956","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Metal–organic frameworks (MOFs) toward SO2 detection","authors":"Juan L. Obeso, Catalina V. Flores, Ricardo A. Peralta, Margarita Viniegra, N. Martín-Guaregua, Michael T. Huxley, Diego Solis-Ibarra, Ilich A. Ibarra and Christoph Janiak","doi":"10.1039/D4CS00997E","DOIUrl":"10.1039/D4CS00997E","url":null,"abstract":"<p >Developing technology that can precisely monitor specific air pollutants in diverse settings is essential to control emissions and ensure safe exposure limits are not exceeded. Metal–organic frameworks (MOFs) are crystalline organic–inorganic hybrid materials, which are promising candidates for SO<small>₂</small> detection. Their chemically mutable periodic structure confers outstanding surface area, thermal stability, and a well-defined pore distribution. Moreover, MOFs have exhibited extraordinary performance for SO<small>₂</small> capture. Therefore, research has focused on their possible applications for SO<small>₂</small> sequestration due to the selective and robust chemical and physical interactions of SO<small>₂</small> molecules within MOFs. The variable SO<small>₂</small> affinity presented by MOFs enables the adsorption mechanism and preferential adsorption sites to be resolved. However, for MOF-based SO<small>₂</small> detection, selective SO<small>₂</small> capture at shallow partial pressure (0.01–0.1 bar) is required. Thus, capturing SO<small>₂</small> at low concentration is crucial for SO<small>₂</small> detection, where textural properties of MOFs, mainly the pore-limiting diameter, are essential to achieve selective detection. In this review, we discuss the fundamental aspects of SO<small>₂</small> detection in MOFs, providing a step-by-step methodology for SO<small>₂</small> detection in MOFs. We hope this review can provide valuable background around SO<small>₂</small> detection in MOFs and inspire further research within this new and exciting field.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 9","pages":" 4135-4163"},"PeriodicalIF":40.4,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cs/d4cs00997e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143582941","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Metal pyrazolate frameworks: crystal engineering access to stable functional materials","authors":"Xiang-Jing Kong, Guang-Rui Si, Tao He and Jian-Rong Li","doi":"10.1039/D4CS00989D","DOIUrl":"10.1039/D4CS00989D","url":null,"abstract":"<p >As the focus evolves from structure discovery/characterization (what it is) to property/performance exploration (what it is for), the pursuit of stable functional metal–organic frameworks (MOFs) has been ongoing in terms of both fundamental research and industrial implementation. Under the guidance of crystal engineering principles, a plethora of research has developed pyrazolate MOFs (metal pyrazaolate frameworks, MPFs) featuring strong coordination M–N bonding. This attribution helps them retain their structures and functions under the alkaline conditions required for practical use. Based on poly-topic pyrazolate ligands, various classic MOFs, such as Co(bdp), Fe<small>₂</small>(BDP)<small>₃</small>, Ni<small>₈</small>L<small>₆</small>, PCN-601, and BUT-55, to name a few, have revealed fascinating architectures, intriguing properties, and record-breaking performances in applications during the past decade. This review will present the full scope of MPFs to date: (1) the superiority and significance of constructing MPFs through the crystal engineering approach, (2) synthetic strategies adopted in building and/or modifying MPFs, (3) structural features and stability of the MPF community, and (4) potential applications in energy and environmental related fields. The future opportunities of MPFs are also discussed for designing the next-generation of smart materials. Overall, this review attempts to provide insights and guidelines for the customization of pyrazolate-based MOFs for specific purposes, which would also promote the development of stable functional porous materials for addressing societal challenges.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 8","pages":" 3647-3680"},"PeriodicalIF":40.4,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570154","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}

{"title":"Formulation principles and synergistic effects of high-voltage electrolytes","authors":"Zewei Wei, Du Yuan, Xuedi Yuan, Yalin Zhang, Jianmin Ma, Suojiang Zhang and Haitao Zhang","doi":"10.1039/D4CS00826J","DOIUrl":"10.1039/D4CS00826J","url":null,"abstract":"<p >The energy density of lithium-ion batteries (LIBs) is primarily determined by the working potential of devices and the specific capacity of cathode compounds. Carbonate-based electrolytes have received considerable attention due to their significance for advancing current cell-assembly process. However, the commercially available liquid LiPF<small>₆</small> based electrolytes cannot withstand the harsh high-voltage environment and the effects of cathode, due to issues such as the undesired oxidative decomposition of ethylene carbonate (EC), the catalytic influence of dissolved transition metal ions (TMs), and the poor performance of interphases with unstable morphologies and components. Furthermore, the complex working mechanisms of high-voltage electrolytes (HVEs) are not fully understood. This review presents a comprehensive summary of the HVEs, including their physical properties, solvation structures, and interface chemistry. Specifically, chemical environment of high-voltage cathode compounds and failure mechanisms of commercial electrolytes are investigated, followed by a discussion of expected functions of HVEs. Then, screening criteria for single-component electrolytes, considering their oxidation resistance and decomposition mechanism, and screening mechanism of interphase species are explored based on their energy level positions. Next, a cross-scale evolution framework is proposed, from the solvation structure to interphase characteristics, aimed at uncovering the formulation principles and synergistic effects of HVEs. Operational mechanisms are systematically scrutinized, starting from the conventional tuning of solvation structure to the incorporation of multiple components and further to the role of entropy-driven effects, all of which will favor the understanding of formulation principles and synergistic effects. Finally, integration of advanced computational methods and mature experimental techniques is expected to foster the development of novel perspectives and promising electrolyte candidates.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 8","pages":" 3775-3818"},"PeriodicalIF":40.4,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561345","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}

{"title":"Synthesis innovations for crystallizing covalent organic framework thin films on biological and non-biological substrates","authors":"Ashok Kumar Mahato, Satyadip Paul and Rahul Banerjee","doi":"10.1039/D4CS01222D","DOIUrl":"10.1039/D4CS01222D","url":null,"abstract":"<p >Thin film technology has emerged as a pivotal field with numerous industrial applications. Depending on their properties—such as magnetic characteristics, conductivity, architectural structure, stability, and functional backbones—thin films are widely utilized in optoelectronics, thin-film coatings, solar cells, energy storage devices, semiconductors, and separation applications. However, for all these applications, thin films must be securely attached to specific substrates, and substrate compatibility with both the thin film and the film-growth process is crucial for optimal performance. In this review, we emphasize the significance of growing thin films, particularly covalent organic framework (COF) thin films, on suitable substrates tailored for various applications. For separation technologies, polymer thin films are commonly fabricated on porous polymeric or metal-based membranes. In contrast, thin films of metals and metal oxides are typically deposited on conducting substrates, serving as current collectors for energy storage devices. Semiconductor thin films, on the other hand, are often grown on silicon or glass substrates for transistor applications. Emerging COF thin films, with their tunable properties, well-defined pore channels, and versatile functional backbones, have demonstrated exceptional potential in separation, energy storage, and electronic and optoelectronic applications. However, the interplay between COF thin films and the substrates, as well as the compatibility of growth conditions, remains underexplored. Studies investigating COF thin film growth on substrates such as metals, metal oxides, glass, silicon, polymers, ITO, and FTO have provided insights into substrate properties that promote superior film growth. The quality of the film formed on these substrates significantly influences performance in applications. Additionally, we discuss the stabilization of biological substrates, like peptide-based biomimetic catalysts and enzymes, which often suffer from instability in non-aqueous environments, limiting their industrial use. Growing COF membranes on these biological substrates can enhance their stability under harsh conditions. We also highlight techniques for growing COF membranes on biological substrates, ensuring the preservation of their structural integrity and functional properties.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 7","pages":" 3578-3598"},"PeriodicalIF":40.4,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cs/d4cs01222d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555376","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Opto-digital molecular analytics","authors":"Chelsea Violita Stanley, Yi Xiao, Tong Ling, Dong-Sheng Li and Peng Chen","doi":"10.1039/D5CS00023H","DOIUrl":"10.1039/D5CS00023H","url":null,"abstract":"<p >In contrast to conventional ensemble-average-based methods, opto-digital molecular analytic approaches digitize detection by physically partitioning individual detection events into discrete compartments or directly locating and analyzing the signals from single molecules. The sensitivity can be enhanced by signal amplification reactions, signal enhancement interactions, labelling by strong signal emitters, advanced optics, image processing, and machine learning, while specificity can be improved by designing target-selective probes and profiling molecular dynamics. With the capabilities to attain a limit of detection several orders lower than the conventional methods, reveal intrinsic molecular information, and achieve multiplexed analysis using a small-volume sample, the emerging opto-digital molecular analytics may be revolutionarily instrumental to clinical diagnosis, molecular chemistry and science, drug discovery, and environment monitoring. In this article, we provide a comprehensive review of the recent advances, offer insights into the underlying mechanisms, give comparative discussions on different strategies, and discuss the current challenges and future possibilities.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 7","pages":" 3557-3577"},"PeriodicalIF":40.4,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cs/d5cs00023h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538584","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"C3-symmetric aromatic triimides as useful building blocks for supramolecular chemistry and advanced materials","authors":"De-Hui Tuo, Xu-Dong Wang and De-Xian Wang","doi":"10.1039/D4CS00892H","DOIUrl":"10.1039/D4CS00892H","url":null,"abstract":"<p > <em>C</em> <small>₃</small>-symmetric aromatic triimides (ATIs) represent an interesting class of electron-deficient molecular backbones, characterized by π-conjugated aromatic cores symmetrically substituted with three imide groups. Their unique structural and electronic features, combined with exceptional stability and straightforward <em>N</em>-functionalization at three imide sites, make ATIs promising as versatile building blocks for applications in supramolecular chemistry and materials science. Despite their promising attributes, research on ATIs remains underexplored compared to the extensively studied aromatic imides and diimides, largely due to the synthetic challenges involved in constructing three imide groups on the aromatic frameworks. In recent years, advances in synthetic protocols have significantly propelled ATI-related chemistry, expanding their applications in the realm of functional materials. This review compiles advancements in the synthesis, structural and physicochemical properties, and applications of ATIs in supramolecular chemistry and advanced materials. We anticipate that this review will not only draw greater attention to ATIs but also serve as a valuable guide for future research into these molecular building blocks.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 7","pages":" 3535-3556"},"PeriodicalIF":40.4,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538711","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}