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Metal-organic frameworks as the basis for new-generation functional materials 金属有机骨架作为新一代功能材料的基础
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2022-01-01 DOI: 10.1070/RCR5050
Yulia G. Gorbunova, V. Fedin, V. Blatov
coordination chemistry. This is the design, synthesis and detailed investigation of metal-organic frameworks (MOFs), or coordination polymers. The search of the Web of Science database shows an exponential growth of the number of relevant publications in recent years (more than 73 000). The Hirsch index only for papers that have the expression `metal-organic framework' in the title is 420; there are 1983 reviews among these publications. The close attention of researchers to this class of compounds is due to the very broad range of MOFs functional properties and, hence, prospects for high-tech practical applications as components of new-generation functional materials with enhanced or unique characteristics. For example, porous metal-organic frameworks show record-breaking adsorption characteristics among all materials of this type, which dictates their use for compact storage of industrially important hard-to-compress gases (hydrogen, methane, acetylene), purification and separation of complex mixtures, including industrial discharges and biologically active molecules, heterogeneous catalysis, targeted drug delivery and prolongation of drug action and for the development of highly sensitive new type sensors, conductors and so on. A separate important problem is to predict the properties of new MOFs as functions of their structure, in particular, the nature of organic and inorganic components MOFs. This issue includes three reviews covering the main modern trends in the development of this area. The review by Corresponding Member of the RAS V.P.Fedin and coworkers describes strategies and approaches to the development of new porous MOFs as a base for highly efficient and highly selective sorbents for the separation of valuable industrial raw materials such as light hydrocarbons and mixtures of hydrocarbons with similar boiling points and molecule sizes. The review by Professor V.A.Blatov and coworkers is devoted to full systematization of the topological types of metal-organic frameworks and development of mathematical approaches for the prediction of structure and properties of metal-organic frameworks: the search for chemical composition ± structure ± property relationships and development of databases and artificial intelligence systems. Particular attention is paid to the properties of proton-conducting metal-organic frameworks, which have been actively studied in the last decade due to the need to find components for new alternative energy sources. The possibility of varying the properties and potential applications of metal-organic frameworks depending on the nature of the bridging organic ligand and inorganic component is demonstrated in the review by Corresponding Member of the RAS Yu.G.Gorbunova and co-workers in relation to porphyrin ligands. The unique properties of these macrocyclic organic compounds considerably expand the scope of potential applicability of porphyrin-based MOFs in comparison with the traditional metal-organic framew
配位化学。这是金属有机框架(MOFs)或配位聚合物的设计,合成和详细研究。对Web of Science数据库的搜索显示,近年来相关出版物的数量呈指数级增长(超过73000篇)。赫希指数仅适用于标题中带有“金属-有机框架”字样的论文,其指数为420;这些出版物中有1983篇评论。研究人员对这类化合物的密切关注是由于mof的功能特性非常广泛,因此,作为具有增强或独特特性的新一代功能材料的组成部分,具有高科技实际应用的前景。例如,多孔金属有机框架在所有此类材料中表现出破纪录的吸附特性,这决定了它们在紧凑储存工业上重要的难以压缩气体(氢、甲烷、乙炔)、净化和分离复杂混合物(包括工业排放和生物活性分子)、多相催化、靶向给药和延长药物作用以及为开发高灵敏度的新型传感器、导体等。另一个重要的问题是预测新型MOFs的结构函数性质,特别是有机和无机MOFs组分的性质。本期包括三篇综述,涵盖了这一领域发展的主要现代趋势。RAS通讯成员V.P.Fedin及其同事的综述描述了开发新型多孔mof的策略和方法,作为高效和高选择性吸附剂的基础,用于分离有价值的工业原料,如轻烃和具有相似沸点和分子大小的碳氢化合物混合物。由V.A.Blatov教授及其同事撰写的综述致力于金属有机框架的拓扑类型的全面系统化,以及用于预测金属有机框架结构和性质的数学方法的发展:寻找化学成分±结构±性质关系以及开发数据库和人工智能系统。特别关注质子导电金属有机框架的性质,由于需要为新的替代能源寻找组件,在过去十年中对其进行了积极研究。根据桥接有机配体和无机组分的性质不同,金属有机框架的性质和潜在应用的可能性在RAS通讯成员Yu.G.Gorbunova及其同事关于卟啉配体的综述中得到了证明。与传统的金属有机骨架相比,这些大环有机化合物的独特性质大大扩展了卟啉基mof的潜在应用范围。例如,本文综述了卟啉基MOFs在多相催化和光催化、光催化制氢、电化学反应、CO2利用、癌症光动力治疗等诸多方面的应用。最后,值得注意的是,本期的所有评论都是作为俄罗斯基础研究基金会支持的科学评论“Expansion”的编写和出版竞赛的项目而编写的。作者衷心感谢《俄罗斯化学评论》的编辑人员在准备出版稿件的各个阶段所做的高度专业和彻底的工作、效率和细心。
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引用次数: 4
Phase-change materials and their applications 相变材料及其应用
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2022-01-01 DOI: 10.1070/rcr5033
S. Kozyukhin, P. Lazarenko, Anatoli I. Popov, I. Eremenko
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引用次数: 1
Calcium Carbide Residue - A Key Inorganic Component of the Sustainable Carbon Cycle 电石渣——可持续碳循环的关键无机成分
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2022-01-01 DOI: 10.1070/rcr5048
K. Rodygin, Yulia V. Gyrdymova, V. Ananikov
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引用次数: 1
From the chemistry of radicals to molecular spin devices 从自由基化学到分子自旋装置
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2022-01-01 DOI: 10.1070/RCR5043
V. Ovcharenko, A. Terent’ev, E. V. Tretyakov, I. Krylov
rethinking the possibilities provided by the use of free radicals in chemistry, biology, medicine and materials science. The key to this issue is development of the chemistry of stable organic radicals, which paved the path towards compounds for various functional purposes: radical reagents, initiators for controlled radical polymerization, efficient redox catalysts, spin labels, highly sensitive means for analysis, medical diagnostics and theranostics, building blocks for magnetic and redox-active systems, and key components of organic electronics, spintronics and electric batteries. The sharp increase in the applied potential of organic radicals was boosted by the development of methods for studying both stable and short-lived paramagnetic compounds, in particular high-spin systems. These methods include, first of all, pulsed EPR techniques, SQUID magnetometry, X-ray diffraction, including protocols using synchrotron radiation sources, scanning electron and force microscopy, and magneto-structural analysis by polarized neutron diffraction. A huge step forward was made by calculation methods, which have formed an efficient tool for modelling and prediction of the magnetic properties of magnetically active systems. The studies of Russian scientists are making a considerable contribution to the development of chemistry and physics of organic radicals and their applied potential. Russian researchers are traditionally active participants and organizers of conferences devoted to the chemistry of organic radicals, molecule-based magnets, molecular spin devices, and electron paramagnetic resonance. This issue of Russian Chemical Reviews addresses a large area of research related to nitroxide radicals containing an unsaturated moiety at the nitrogen atom, including their physicochemical properties, their computational prediction and fields of their practical application. Among the applications, noteworthy is the design of molecular magnets, development of redoxand photoswitchable molecular systems, redox-active components for organic and hybrid batteries and the use as catalysts and reagents in selective oxidative processes of organic synthesis. Special attention is deserved by a new trend of research related to the design of qubits and qudits based on stable organic radicals and special hybrid systems to solve the problem of scaling and stability in quantum calculations. In all these applied fields, the possibility of varying the structure of stable spin carriers over fairly broad limits will always give rise to new ideas and intentions. We express hope that this issue of Russian Chemical Reviews will contribute to this goal.
重新思考自由基在化学、生物学、医学和材料科学中的应用所提供的可能性。这个问题的关键是稳定的有机自由基的化学发展,这为各种功能用途的化合物铺平了道路:自由基试剂、可控自由基聚合的引发剂、高效氧化还原催化剂、自旋标签、高灵敏度分析手段、医学诊断和治疗、磁性和氧化还原活性系统的构建块、有机电子、自旋电子学和电池的关键组件。研究稳定和短寿命顺磁性化合物,特别是高自旋体系的方法的发展,促进了有机自由基应用潜力的急剧增加。这些方法首先包括脉冲EPR技术、SQUID磁强计、x射线衍射(包括使用同步加速器辐射源的方案)、扫描电子显微镜和力显微镜以及极化中子衍射的磁结构分析。计算方法取得了巨大的进步,形成了对磁活动体系的磁性进行建模和预测的有效工具。俄罗斯科学家的研究对有机自由基的化学和物理学的发展及其应用潜力作出了重大贡献。传统上,俄罗斯的研究人员积极参与和组织有关有机自由基化学、分子基磁体、分子自旋装置和电子顺磁共振的会议。本期《俄罗斯化学评论》讨论了与氮原子上含有不饱和基团的氮氧化物自由基有关的大量研究,包括它们的物理化学性质、计算预测和实际应用领域。在这些应用中,值得注意的是分子磁体的设计、氧化还原和光切换分子体系的开发、有机和混合电池的氧化还原活性成分以及在有机合成的选择性氧化过程中作为催化剂和试剂的使用。基于稳定有机自由基和特殊混合系统的量子比特和量子位设计的新研究趋势值得特别关注,以解决量子计算中的缩放和稳定性问题。在所有这些应用领域中,在相当广泛的范围内改变稳定自旋载流子结构的可能性总是会产生新的想法和意图。我们表示希望本期《俄罗斯化学评论》将有助于实现这一目标。
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引用次数: 1
[3,3]-sigmatropic rearrangements: variety of methods and recent achievements [3,3]-符号型重排:各种方法和最新成果
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2022-01-01 DOI: 10.1070/rcr5039
V. D. Dyachenko, Bogdan Nikolaevich Baryshev, V. Nenajdenko
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引用次数: 0
Targeted nuclear medicine. Seek and destroy 靶向核医学。寻找并摧毁
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2022-01-01 DOI: 10.1070/RCR5034
V. Tolmachev, V. Chernov, S. Deyev
The targeted delivery of radionuclides to tumours holds great promise for diagnosis and treatment of malignant neoplasms. The development of scaffold proteins has significantly simplified the design of targeting agents with desirable properties. This review comprehensively describes the key aspects of the design of radionuclide compounds, including classification of radionuclides, methodology for their attachment to targeting agents and characteristics of these agents that affect their behaviour in the body. Various targeting molecules are compared in terms of their ability to specifically find malignant foci in the body. The most recent achievements of cancer theranostics that aim at increasing the selectivity of antitumour effect are described, such as the fusion of targeting scaffold proteins with the albumin-binding domain and pretargeting. Special attention is paid to the creation of targeted radionanomaterials. Advantages and disadvantages of different strategies are analyzed and approaches for improving the delivery to tumours and for minimizing the undesirable impact on healthy organs and tissues are proposed. Particular emphasis is placed on the results of studies published in 2020–2021 that have not yet been covered by reviews. The bibliography includes 191 references.
放射性核素靶向递送肿瘤对恶性肿瘤的诊断和治疗具有很大的希望。支架蛋白的发展大大简化了具有理想性能的靶向药物的设计。这篇综述全面介绍了放射性核素化合物设计的关键方面,包括放射性核素的分类、它们与靶向剂的附着方法以及影响它们在体内行为的这些剂的特征。比较了不同的靶向分子在体内特异性发现恶性病灶的能力。本文描述了旨在提高抗肿瘤效果选择性的癌症治疗学的最新成就,例如靶向支架蛋白与白蛋白结合结构域的融合和预靶向。特别注意的是目标放射性物质的创造。分析了不同策略的优点和缺点,并提出了改善肿瘤输送和尽量减少对健康器官和组织的不良影响的方法。特别强调的是2020-2021年发表的尚未被评审涵盖的研究结果。参考书目包括191篇参考文献。
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引用次数: 11
N-Heterocycles via Oxidative Intramolecular Cyclization 通过分子内氧化环化生成n -杂环
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2022-01-01 DOI: 10.1070/rcr5052
B. Shainyan
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引用次数: 0
Preliminary modelling as the first stage of targeted organic synthesis 作为目标有机合成第一阶段的初步建模
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2021-08-01 DOI: 10.1070/RCR5012
I. Titov, V. S. Stroylov, P. Rusina, I. Svitanko
The review aims to present a classification and applicability analysis of methods for preliminary molecular modelling for targeted organic, catalytic and biocatalytic synthesis. The following three main approaches are considered as a primary classification of the methods: modelling of the target – ligand coordination without structural information on both the target and the resulting complex; calculations based on experimentally obtained structural information about the target; and dynamic simulation of the target – ligand complex and the reaction mechanism with calculation of the free energy of the reaction. The review is meant for synthetic chemists to be used as a guide for building an algorithm for preliminary modelling and synthesis of structures with specified properties. The bibliography includes 353 references.
本文综述了针对有机、催化和生物催化合成的初步分子建模方法的分类和适用性分析。以下三种主要方法被认为是方法的主要分类:在没有目标和所得复合物的结构信息的情况下对目标-配体配位进行建模;根据实验得到的目标结构信息进行计算;并对靶配体配合物进行了动态模拟,对反应机理进行了计算,计算了反应的自由能。该综述旨在为合成化学家提供指导,用于构建具有特定性质的结构的初步建模和合成算法。参考书目包括353篇参考文献。
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引用次数: 1
Hydrogen energy: development prospects and materials 氢能:发展前景及材料
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2021-06-01 DOI: 10.1070/RCR5014
S. Filippov, A. Yaroslavtsev
The review addresses the prospects of global hydrogen energy development. Particular attention is given to the design of materials for sustainable hydrogen energy applications, including hydrogen production, purification, storage, and conversion to energy. The review highlights the key role of oxide-supported metal or alloy nanoparticles as catalysts in the hydrogen production via the conversion of natural gas or alcohols. An alternative approach is the pyrolysis of hydrocarbons giving hydrogen and carbon. The direct production of high-purity hydrogen can be performed using electrolysis or membrane catalysis. Apart from conventional hydrogen storage methods such as the compression and liquefaction, the hydrogen alloy absorption and chemical conversion to liquid carriers (ammonia and toluene cycles) are considered. Fuel cells, containing catalysts and proton-conducting membranes as the key components, are used for hydrogen energy generation. Binary platinum alloys or core – shell structures supported on carbon or oxides can be employed to facilitate the oxygen electroreduction and CO electrooxidation in low-temperature fuel cells. High conductivity and selectivity are provided by perfluorinated sulfonic acid membranes. The high cost of the latter materials dictates the development of alternative membrane materials. A crucial issue in high-temperature fuel cells is the necessity of reducing the operating temperature and ohmic losses. This problem can be solved by designing thin-film materials and replacing oxygen-conducting ceramic membranes by proton-conducting membranes. The bibliography includes 290 references.
综述了全球氢能发展的前景。特别关注可持续氢能源应用的材料设计,包括氢的生产,净化,储存和转化为能源。该综述强调了氧化物负载的金属或合金纳米颗粒作为催化剂在天然气或醇转化制氢中的关键作用。另一种方法是碳氢化合物的热解产生氢和碳。直接生产高纯度氢可以通过电解或膜催化进行。除压缩和液化等传统储氢方法外,还考虑了氢合金的吸收和化学转化为液体载体(氨和甲苯循环)。燃料电池以催化剂和质子导电膜为关键部件,用于氢能源的生产。以碳或氧化物为载体的二元铂合金或核壳结构可用于低温燃料电池中的氧电还原和CO电氧化。全氟磺酸膜具有高导电性和选择性。后一种材料的高成本决定了替代膜材料的发展。高温燃料电池的一个关键问题是必须降低工作温度和欧姆损耗。这一问题可以通过设计薄膜材料和用质子导电膜代替氧导电陶瓷膜来解决。参考书目包括290篇参考文献。
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引用次数: 63
Furan monomers and polymers from renewable plant biomass 可再生植物生物质中的呋喃单体和聚合物
IF 7.7 2区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2021-06-01 DOI: 10.1070/RCR5018
V. Kashparova, Daria V. Chernysheva, V. Klushin, Veronika E. Andreeva, O. A. Kravchenko, N. Smirnova
Plant biomass is considered the main source of renewable carbon raw materials, which is a viable alternative to crude oil and natural gas and provides compounds with a low carbon footprint. The most promising direction for the conversion of biomass is the synthesis of 5-hydroxymethylfurfural, which is regarded as a platform chemical, the basis for the synthesis of valuable compounds, including monomers and polymers. The move of the polymer industry to renewable plant materials will contribute to solving global environmental problems and ensure the sustainability and environmental safety of plastics production. This review analyzes recent advances in the preparation of key C6-furan platform chemicals, such as 5-hydroxymethylfurfural, 2,5-furandicarboxylic acid, 2,5-diformylfuran, 2,5-bis(hydroxymethyl)furan, levulinic acid, and their use for the production of monomers and polymers based on renewable plant biomass. Production processes of widely known furan polyesters and polyamides, such as polyethylene-, polypropylene-, polybutylene furanoates, polyhexamethylene furanamide, are considered, as well as developments towards novel promising materials that are furan copolymers and polymer mixtures. For the first time, studies have been systematized aimed at converting liquid and solid wastes of the synthesis of platform chemicals, known as humins, into a range of value-added products, including organic compounds, porous carbon materials, thermosetting binders, and anticorrosive coatings that can replace similar materials based on fossil raw materials. Economic and environmental prospects and problems of production and consumption of furan polymers are considered. The bibliography includes 275 references.
植物生物质被认为是可再生碳原料的主要来源,是原油和天然气的可行替代品,并提供低碳足迹的化合物。生物质转化最有希望的方向是合成5-羟甲基糠醛,它被认为是一种平台化学物质,是合成有价值化合物(包括单体和聚合物)的基础。聚合物工业向可再生植物材料的转变将有助于解决全球环境问题,确保塑料生产的可持续性和环境安全性。本文综述了5-羟甲基糠醛、2,5-呋喃二羧酸、2,5-二甲酰呋喃、2,5-双(羟甲基)呋喃、乙酰丙酸等主要c6 -呋喃平台化合物的制备及其在可再生植物生物质单体和聚合物生产中的应用进展。考虑了众所周知的呋喃聚酯和聚酰胺的生产工艺,如聚乙烯、聚丙烯、聚呋喃丁烯酸酯、聚六亚甲基呋喃酰胺,以及呋喃共聚物和聚合物混合物等有前途的新型材料的发展。这是第一次系统化的研究,旨在将合成平台化学品的液体和固体废物转化为一系列增值产品,包括有机化合物、多孔碳材料、热固性粘合剂和防腐涂料,这些产品可以取代基于化石原料的类似材料。讨论了呋喃聚合物生产和消费的经济和环境前景以及存在的问题。参考书目包括275篇参考文献。
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引用次数: 12
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Russian Chemical Reviews
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