Chemical Society Reviews最新文献

{"title":"Designed functions of oxide/hydroxide nanosheets via elemental replacement/doping","authors":"Kanji Saito, Masashi Morita, Tomohiko Okada, Rattanawadee (Ploy) Wijitwongwan and Makoto Ogawa","doi":"10.1039/D4CS00339J","DOIUrl":"10.1039/D4CS00339J","url":null,"abstract":"<p >Partial replacement of one structural element in a solid with another of a similar size was conducted to impart functionality to the solids and modify their properties. This phenomenon is found in nature in coloured gemstones and clay minerals and is used in materials chemistry and physics, endowing materials with useful properties that can be controlled by incorporated heteroelements and their amounts. Depending on the area of research (or expected functions), the replacement is referred to as “isomorphous substitution”, “doping”, <em>etc.</em> Herein, elemental replacement in two-dimensional (2D) oxides and hydroxides (nanosheets or layered materials) is summarised with emphasis on the uniqueness of their preparation, characterisation and application compared with those of the corresponding bulk materials. Among the 2D materials (graphene, metallenes, transition metal chalcogenides, metal phosphate/phosphonates, MXenes, <em>etc.</em>), 2D oxides and hydroxides are characterised by their presence in nature, facile synthesis and storage under ambient conditions, and possible structural variation from atomic-level nanosheets to thicker nanosheets composed of multilayered structures. The heteroelements to be doped were selected depending on the target application objectively; however, there are structural and synthetic limitations in the doping of heteroelements. In the case of layered double hydroxides (single layer) and layered alkali silicates (from single layer to multiple layers), including layered clay minerals (2 : 1 layer), the replacement (commonly called isomorphous substitution) is discussed to understand/design characteristics such as catalytic, adsorptive (including ion exchange), and swelling properties. Due to the variation in their main components, the design of layered transition metal oxide/hydroxide materials <em>via</em> isomorphous substitution is more versatile; in this case, tuning their band structure, doping both holes and electrons, and creating impurity levels are examined by the elemental replacement of the main components. As typical examples, material design for the photocatalytic function of an ion-exchangeable layered titanate (lepidocrocite-type titanate) and a perovskite niobate (KCa<small>₂</small>Nb<small>₃</small>O<small>₁₀</small>) is discussed, where elemental replacement is effective in designing their multiple functions.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 21","pages":" 10523-10574"},"PeriodicalIF":40.4,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cs/d4cs00339j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142379529","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":"Reactive oxygen species-mediated organic long-persistent luminophores light up biomedicine: from two-component separated nano-systems to integrated uni-luminophores","authors":"Zhe Li, Hongwen Liu and Xiao-Bing Zhang","doi":"10.1039/D4CS00443D","DOIUrl":"10.1039/D4CS00443D","url":null,"abstract":"<p >Organic luminophores have been widely utilized in cells and <em>in vivo</em> fluorescence imaging but face extreme challenges, including a low signal-to-noise ratio (SNR) and even false signals, due to non-negligible background signals derived from real-time excitation lasers. To overcome these challenges, in the last decade, functionalized organic long-persistent luminophores have gained much attention. Such luminophores could not only overcome the biological toxicity of inorganic long-persistent luminescent materials (metabolic toxicity and leakage risk of inorganic heavy metals), but also continue to emit long-persistent luminescence after removing the excitation source, thus effectively improving imaging quality. More importantly, organic long-persistent luminophores have good structure tailorability for the construction of activable probes, which is favorable for biosensing. Recently, the development of reactive oxygen species (ROS)-mediated long-persistent (ROSLP) luminophores (especially organic small-molecule ROSLP luminophores) is still in the rising stage. Notably, ROSLP luminophores for <em>in vivo</em> imaging have experienced from two-component separated nano-systems to integrated uni-luminophores, which obtained gradually better designability and biocompatibility. In this review, we summarize the progress and challenges of organic long-persistent luminophores, focusing on their development history, long-persistent luminescence working mechanisms, and biomedical applications. We hope that these insights will help scientists further develop functionalized organic long-persistent luminophores for the biomedical field.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 22","pages":" 11207-11227"},"PeriodicalIF":40.4,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370274","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":"From sugars to aliphatic amines: as sweet as it sounds? Production and applications of bio-based aliphatic amines†","authors":"Benjamin Vermeeren, Sofie Van Praet, Wouter Arts, Thomas Narmon, Yingtuan Zhang, Cheng Zhou, Hans P. Steenackers and Bert F. Sels","doi":"10.1039/D4CS00244J","DOIUrl":"10.1039/D4CS00244J","url":null,"abstract":"<p >Aliphatic amines encompass a diverse group of amines that include alkylamines, alkyl polyamines, alkanolamines and aliphatic heterocyclic amines. Their structural diversity and distinctive characteristics position them as indispensable components across multiple industrial domains, ranging from chemistry and technology to agriculture and medicine. Currently, the industrial production of aliphatic amines is facing pressing sustainability, health and safety issues which all arise due to the strong dependency on fossil feedstock. Interestingly, these issues can be fundamentally resolved by shifting toward biomass as the feedstock. In this regard, cellulose and hemicellulose, the carbohydrate fraction of lignocellulose, emerge as promising feedstock for the production of aliphatic amines as they are available in abundance, safe to use and their aliphatic backbone is susceptible to chemical transformations. Consequently, the academic interest in bio-based aliphatic amines <em>via</em> the catalytic reductive amination of (hemi)cellulose-derived substrates has systematically increased over the past years. From an industrial perspective, however, the production of bio-based aliphatic amines will only be the middle part of a larger, ideally circular, value chain. This value chain additionally includes, as the first part, the refinery of the biomass feedstock to suitable substrates and, as the final part, the implementation of these aliphatic amines in various applications. Each part of the bio-based aliphatic amine value chain will be covered in this Review. Applying a holistic perspective enables one to acknowledge the requirements and limitations of each part and to efficiently spot and potentially bridge knowledge gaps between the different parts.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 24","pages":" 11804-11849"},"PeriodicalIF":40.4,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cs/d4cs00244j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370272","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–phenolic network composites: from fundamentals to applications","authors":"Zhixing Lin, Hai Liu, Joseph J. Richardson, Wanjun Xu, Jingqu Chen, Jiajing Zhou and Frank Caruso","doi":"10.1039/D3CS00273J","DOIUrl":"10.1039/D3CS00273J","url":null,"abstract":"<p >Composites with tailored compositions and functions have attracted widespread scientific and industrial interest. Metal–phenolic networks (MPNs), which are composed of phenolic ligands and metal ions, are amorphous adhesive coordination polymers that have been combined with various functional components to create composites with potential in chemistry, biology, and materials science. This review aims to provide a comprehensive summary of both fundamental knowledge and advancements in the field of MPN composites. The advantages of amorphous MPNs, over crystalline metal–organic frameworks, for fabricating composites are highlighted, including their mild synthesis, diverse interactions, and numerous intrinsic functionalities. The formation mechanisms and state-of-the-art synthesis strategies of MPN composites are summarized to guide their rational design. Subsequently, a detailed overview of the chemical interactions and structure–property relationships of composites based on different functional components (<em>e.g.</em>, small molecules, polymers, biomacromolecules) is provided. Finally, perspectives are offered on the current challenges and future directions of MPN composites. This tutorial review is expected to serve as a fundamental guide for researchers in the field of metal–organic materials and to provide insights and avenues to enhance the performance of existing functional materials in applications across diverse fields.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 22","pages":" 10800-10826"},"PeriodicalIF":40.4,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cs/d3cs00273j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370273","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":"From cyclotrons to chromatography and beyond: a guide to the production and purification of theranostic radiometals","authors":"Brooke L. McNeil and Caterina F. Ramogida","doi":"10.1039/D4CS00802B","DOIUrl":"10.1039/D4CS00802B","url":null,"abstract":"<p >Recent clinical success with metal-based radiopharmaceuticals has sparked an interest in the potential of these drugs for personalized medicine. Although often overlooked, the success and global impact of nuclear medicine is contingent upon the purity and availability of medical isotopes, commonly referred to as radiometals. For nuclear medicine to reach its true potential and change patient lives, novel production and purification techniques that increase inventory of radiometals are desperately needed. This tutorial review serves as a resource for those both new and experienced in nuclear medicine by providing a detailed explanation of the foundations for the production and purification of radiometals, stemming from nuclear physics, analytical chemistry, and so many other fields, all in one document. The fundamental science behind targetry, particle accelerators, nuclear reactors, nuclear reactions, and radiochemical separation are presented in the context of the field. Finally, a summary of the latest breakthroughs and a critical discussion of the threats and future potential of the most utilized radiometals is also included. With greater understanding of the fundamentals, fellow scientists will be able to better interpret the literature, identify knowledge gaps or problems and ultimately invent new production and purification pathways to increase the global availability of medical isotopes.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 21","pages":" 10409-10449"},"PeriodicalIF":40.4,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142363522","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":"Metal–support interactions in metal oxide-supported atomic, cluster, and nanoparticle catalysis†","authors":"Denis Leybo, Ubong J. Etim, Matteo Monai, Simon R. Bare, Ziyi Zhong and Charlotte Vogt","doi":"10.1039/D4CS00527A","DOIUrl":"10.1039/D4CS00527A","url":null,"abstract":"<p >Supported metal catalysts are essential to a plethora of processes in the chemical industry. The overall performance of these catalysts depends strongly on the interaction of adsorbates at the atomic level, which can be manipulated and controlled by the different constituents of the active material (<em>i.e.</em>, support and active metal). The description of catalyst activity and the relationship between active constituent and the support, or metal–support interactions (MSI), in heterogeneous (thermo)catalysts is a complex phenomenon with multivariate (dependent and independent) contributions that are difficult to disentangle, both experimentally and theoretically. So-called “strong metal–support interactions” have been reported for several decades and summarized in excellent review articles. However, in recent years, there has been a proliferation of new findings related to atomically dispersed metal sites, metal oxide defects, and, for example, the generation and evolution of MSI under reaction conditions, which has led to the designation of (sub)classifications of MSI deserving to be critically and systematically evaluated. These include dynamic restructuring under alternating redox and reaction conditions, adsorbate-induced MSI, and evidence of strong interactions in oxide-supported metal oxide catalysts. Here, we review recent literature on MSI in oxide-supported metal particles to provide an up-to-date understanding of the underlying physicochemical principles that dominate the observed effects in supported metal atomic, cluster, and nanoparticle catalysts. Critical evaluation of different subclassifications of MSI is provided, along with discussions on the formation mechanisms, theoretical and characterization advances, and tuning strategies to manipulate catalytic reaction performance. We also provide a perspective on the future of the field, and we discuss the analysis of different MSI effects on catalysis quantitatively.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 21","pages":" 10450-10490"},"PeriodicalIF":40.4,"publicationDate":"2024-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11445804/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142360780","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":"Supramolecular and molecular capsules, cages and containers","authors":"Cameron J. T. Cox, Jessica Hale, Paulina Molinska and James E. M. Lewis","doi":"10.1039/D4CS00761A","DOIUrl":"10.1039/D4CS00761A","url":null,"abstract":"<p >Stemming from early seminal notions of molecular recognition and encapsulation, three-dimensional, cavity-containing capsular compounds and assemblies have attracted intense interest due to the ability to modulate chemical and physical properties of species encapsulated within these confined spaces compared to bulk environments. With such a diverse range of covalent motifs and non-covalent (supramolecular) interactions available to assemble building blocks, an incredibly wide-range of capsular-type architectures have been developed. Furthermore, synthetic tunability of the internal environments gives chemists the opportunity to engineer systems for uses in sensing, sequestration, catalysis and transport of molecules, just to name a few. In this tutorial review, an overview is provided into the design principles, synthesis, characterisation, structural facets and properties of coordination cages, porous organic cages, supramolecular capsules, foldamers and mechanically interlocked molecules. Using seminal and recent examples, the advantages and limitations of each system are explored, highlighting their application in various tasks and functions.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 21","pages":" 10380-10408"},"PeriodicalIF":40.4,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cs/d4cs00761a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142330420","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":"Enantioselective synthesis of molecules with multiple stereogenic elements","authors":"Arthur Gaucherand, Expédite Yen-Pon, Antoine Domain, Alix Bourhis, Jean Rodriguez and Damien Bonne","doi":"10.1039/D3CS00238A","DOIUrl":"10.1039/D3CS00238A","url":null,"abstract":"<p >This review explores the fascinating world of molecules featuring multiple stereogenic elements, unraveling the different strategies designed over the years for their enantioselective synthesis. Specifically, (dynamic) kinetic resolutions, desymmetrisations and simultaneous installation of stereogenic elements exploiting either metal- or organo-catalysis are the principal approaches to efficiently create and control the three-dimensional shapes of these attractive molecules. Although most molecules presented in this review possess a stereogenic carbon atom in combination with a stereogenic axis, other combinations with helices or planes of chirality have started to emerge, as well as molecules displaying more than two different stereogenic elements.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 22","pages":" 11165-11206"},"PeriodicalIF":40.4,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cs/d3cs00238a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142329599","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":"Carbon encapsulated nanoparticles: materials science and energy applications","authors":"Kun Guo, Lipiao Bao, Zhixin Yu and Xing Lu","doi":"10.1039/D3CS01122D","DOIUrl":"10.1039/D3CS01122D","url":null,"abstract":"<p >The technological implementation of electrochemical energy conversion and storage necessitates the acquisition of high-performance electrocatalysts and electrodes. Carbon encapsulated nanoparticles have emerged as an exciting option owing to their unique advantages that strike a high-level activity–stability balance. Ever-growing attention to this unique type of material is partly attributed to the straightforward rationale of carbonizing ubiquitous organic species under energetic conditions. In addition, on-demand precursors pave the way for not only introducing dopants and surface functional groups into the carbon shell but also generating diverse metal-based nanoparticle cores. By controlling the synthetic parameters, both the carbon shell and the metallic core are facilely engineered in terms of structure, composition, and dimensions. Apart from multiple easy-to-understand superiorities, such as improved agglomeration, corrosion, oxidation, and pulverization resistance and charge conduction, afforded by the carbon encapsulation, potential core–shell synergistic interactions lead to the fine-tuning of the electronic structures of both components. These features collectively contribute to the emerging energy applications of these nanostructures as novel electrocatalysts and electrodes. Thus, a systematic and comprehensive review is urgently needed to summarize recent advancements and stimulate further efforts in this rapidly evolving research field.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 22","pages":" 11100-11164"},"PeriodicalIF":40.4,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306608","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":"Recent synthetic strategies for the functionalization of fused bicyclic heteroaromatics using organo-Li, -Mg and -Zn reagents†","authors":"Vasudevan Dhayalan, Vishal S. Dodke, Marappan Pradeep Kumar, Hatice Seher Korkmaz, Anja Hoffmann-Röder, Pitchamuthu Amaladass, Rambabu Dandela, Ragupathy Dhanusuraman and Paul Knochel","doi":"10.1039/D4CS00369A","DOIUrl":"10.1039/D4CS00369A","url":null,"abstract":"<p >This review highlights the use of functionalized organo-Li, -Mg and -Zn reagents for the construction and selective functionalization of 5- and 6-membered fused bicyclic heteroaromatics. Special attention is given to the discussion of advanced syntheses for the preparation of highly functionalized heteroaromatic scaffolds, including quinolines, naphthyridines, indoles, benzofurans, benzothiophenes, benzoxazoles, benzothiazoles, benzopyrimidines, anthranils, thienothiophenes, purine coumarins, chromones, quinolones and phthalazines and their fused heterocyclic derivatives. The organometallic reagents used for the desired functionalizations of these scaffolds are generally prepared <em>in situ</em> using the following methods: (i) through directed selective metalation reactions (DoM), (ii) by means of halogen/metal exchange reactions, (iii) through oxidative metal insertions (Li, Mg, Zn), and (iv) by transmetalation reactions (organo-Li and Mg transmetalations with ZnCl<small>₂</small> or ZnO(Piv)<small>₂</small>). The resulting reactive organometallic reagents allow a wide range of C–C, C–N and C–X cross-coupling reactions with different electrophiles, employing in particular Kumada or Negishi protocols among other transition metal (Pd, Ni, Co, Cu, Cr, Fe, <em>etc.</em>)-catalyzed processes. In addition, key developments concerning selective metalation techniques will be presented, which rely on the use of RLi, LDA and TMP metal bases. These methods are now widely employed in organic synthetic chemistry and have proven to be particularly valuable for drug development programs in the pharmaceutical industry. New and improved protocols have resulted in many Li, Mg and Zn organyls now being compatible with functionalized aryl, heteroaryl, alkenyl, alkynyl and alkyl compounds even in the presence of labile functional groups, making these reagents well-suited for C(sp<small>²</small>)–C(sp<small>²</small>), C(sp<small>²</small>)–C(sp) and C(sp<small>²</small>)–C(sp<small>³</small>) cross-coupling reactions with fused heteroaryl halides. In addition, the use of some transition metal-catalyzed processes occasionally allows a reversed role of the reactants in cross-coupling reactions, providing alternative synthetic routes for the preparation of fused heteroaromatic-based bioactive drugs and natural products. In line with this, this article points to novel methods for the functionalization of bicyclic heteroaromatic scaffolds by organometallic reagents that have been published in the period 2010–2023.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 22","pages":" 11045-11099"},"PeriodicalIF":40.4,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/cs/d4cs00369a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142276811","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}