Pub Date : 2024-04-17DOI: 10.1021/acs.chemrev.3c00742
Qiuyang Li*, Kaifeng Wu*, Haiming Zhu*, Ye Yang*, Sheng He and Tianquan Lian*,
The properties of colloidal quantum-confined semiconductor nanocrystals (NCs), including zero-dimensional (0D) quantum dots, 1D nanorods, 2D nanoplatelets, and their heterostructures, can be tuned through their size, dimensionality, and material composition. In their photovoltaic and photocatalytic applications, a key step is to generate spatially separated and long-lived electrons and holes by interfacial charge transfer. These charge transfer properties have been extensively studied recently, which is the subject of this Review. The Review starts with a summary of the electronic structure and optical properties of 0D–2D nanocrystals, followed by the advances in wave function engineering, a novel way to control the spatial distribution of electrons and holes, through their size, dimension, and composition. It discusses the dependence of NC charge transfer on various parameters and the development of the Auger-assisted charge transfer model. Recent advances in understanding multiple exciton generation, decay, and dissociation are also discussed, with an emphasis on multiple carrier transfer. Finally, the applications of nanocrystal-based systems for photocatalysis are reviewed, focusing on the photodriven charge separation and recombination processes that dictate the function and performance of these materials. The Review ends with a summary and outlook of key remaining challenges and promising future directions in the field.
{"title":"Charge Transfer from Quantum-Confined 0D, 1D, and 2D Nanocrystals","authors":"Qiuyang Li*, Kaifeng Wu*, Haiming Zhu*, Ye Yang*, Sheng He and Tianquan Lian*, ","doi":"10.1021/acs.chemrev.3c00742","DOIUrl":"10.1021/acs.chemrev.3c00742","url":null,"abstract":"<p >The properties of colloidal quantum-confined semiconductor nanocrystals (NCs), including zero-dimensional (0D) quantum dots, 1D nanorods, 2D nanoplatelets, and their heterostructures, can be tuned through their size, dimensionality, and material composition. In their photovoltaic and photocatalytic applications, a key step is to generate spatially separated and long-lived electrons and holes by interfacial charge transfer. These charge transfer properties have been extensively studied recently, which is the subject of this Review. The Review starts with a summary of the electronic structure and optical properties of 0D–2D nanocrystals, followed by the advances in wave function engineering, a novel way to control the spatial distribution of electrons and holes, through their size, dimension, and composition. It discusses the dependence of NC charge transfer on various parameters and the development of the Auger-assisted charge transfer model. Recent advances in understanding multiple exciton generation, decay, and dissociation are also discussed, with an emphasis on multiple carrier transfer. Finally, the applications of nanocrystal-based systems for photocatalysis are reviewed, focusing on the photodriven charge separation and recombination processes that dictate the function and performance of these materials. The Review ends with a summary and outlook of key remaining challenges and promising future directions in the field.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":62.1,"publicationDate":"2024-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemrev.3c00742","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140603794","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}
Pub Date : 2024-04-17DOI: 10.1021/acs.chemrev.4c00094
Adam Cook, and , Stephen G. Newman*,
Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods for their functionalization require them to first be converted into a more activated derivative, while recent years have seen a vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can be used toward this goal. These transformations are broadly classified into three categories. Deoxygenative functionalizations, representing derivatization of the C–O bond, enable the alcohol to act as a leaving group toward the formation of new C–C bonds. Etherifications, characterized by derivatization of the O–H bond, represent classical reactivity that has been modernized to include mild reaction conditions, diverse reaction partners, and high selectivities. Lastly, chain functionalization reactions are described, wherein the alcohol group acts as a mediator in formal C–H functionalization reactions of the alkyl backbone. Each of these three classes of transformation will be discussed in context of intermolecular arylation, alkylation, and related reactions, illustrating how catalysis can enable alcohols to be directly harnessed for organic synthesis.
{"title":"Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions","authors":"Adam Cook, and , Stephen G. Newman*, ","doi":"10.1021/acs.chemrev.4c00094","DOIUrl":"10.1021/acs.chemrev.4c00094","url":null,"abstract":"<p >Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods for their functionalization require them to first be converted into a more activated derivative, while recent years have seen a vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can be used toward this goal. These transformations are broadly classified into three categories. Deoxygenative functionalizations, representing derivatization of the C–O bond, enable the alcohol to act as a leaving group toward the formation of new C–C bonds. Etherifications, characterized by derivatization of the O–H bond, represent classical reactivity that has been modernized to include mild reaction conditions, diverse reaction partners, and high selectivities. Lastly, chain functionalization reactions are described, wherein the alcohol group acts as a mediator in formal C–H functionalization reactions of the alkyl backbone. Each of these three classes of transformation will be discussed in context of intermolecular arylation, alkylation, and related reactions, illustrating how catalysis can enable alcohols to be directly harnessed for organic synthesis.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":62.1,"publicationDate":"2024-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140603956","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 : 2024-04-16DOI: 10.1021/acs.chemrev.3c00705
Maximilian A. Beach, Umeka Nayanathara, Yanting Gao, Changhe Zhang, Yijun Xiong, Yufu Wang and Georgina K. Such,
The recent emergence of nanomedicine has revolutionized the therapeutic landscape and necessitated the creation of more sophisticated drug delivery systems. Polymeric nanoparticles sit at the forefront of numerous promising drug delivery designs, due to their unmatched control over physiochemical properties such as size, shape, architecture, charge, and surface functionality. Furthermore, polymeric nanoparticles have the ability to navigate various biological barriers to precisely target specific sites within the body, encapsulate a diverse range of therapeutic cargo and efficiently release this cargo in response to internal and external stimuli. However, despite these remarkable advantages, the presence of polymeric nanoparticles in wider clinical application is minimal. This review will provide a comprehensive understanding of polymeric nanoparticles as drug delivery vehicles. The biological barriers affecting drug delivery will be outlined first, followed by a comprehensive description of the various nanoparticle designs and preparation methods, beginning with the polymers on which they are based. The review will meticulously explore the current performance of polymeric nanoparticles against a myriad of diseases including cancer, viral and bacterial infections, before finally evaluating the advantages and crucial challenges that will determine their wider clinical potential in the decades to come.
{"title":"Polymeric Nanoparticles for Drug Delivery","authors":"Maximilian A. Beach, Umeka Nayanathara, Yanting Gao, Changhe Zhang, Yijun Xiong, Yufu Wang and Georgina K. Such, ","doi":"10.1021/acs.chemrev.3c00705","DOIUrl":"10.1021/acs.chemrev.3c00705","url":null,"abstract":"<p >The recent emergence of nanomedicine has revolutionized the therapeutic landscape and necessitated the creation of more sophisticated drug delivery systems. Polymeric nanoparticles sit at the forefront of numerous promising drug delivery designs, due to their unmatched control over physiochemical properties such as size, shape, architecture, charge, and surface functionality. Furthermore, polymeric nanoparticles have the ability to navigate various biological barriers to precisely target specific sites within the body, encapsulate a diverse range of therapeutic cargo and efficiently release this cargo in response to internal and external stimuli. However, despite these remarkable advantages, the presence of polymeric nanoparticles in wider clinical application is minimal. This review will provide a comprehensive understanding of polymeric nanoparticles as drug delivery vehicles. The biological barriers affecting drug delivery will be outlined first, followed by a comprehensive description of the various nanoparticle designs and preparation methods, beginning with the polymers on which they are based. The review will meticulously explore the current performance of polymeric nanoparticles against a myriad of diseases including cancer, viral and bacterial infections, before finally evaluating the advantages and crucial challenges that will determine their wider clinical potential in the decades to come.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":62.1,"publicationDate":"2024-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140603960","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 : 2024-04-15DOI: 10.1021/acs.chemrev.3c00760
Xiangjun Hou, Yao Jiang, Keyan Wei, Cairong Jiang*, Tien-Chien Jen, Yali Yao*, Xinying Liu, Jianjun Ma and John T. S. Irvine*,
Highly efficient coelectrolysis of CO2/H2O into syngas (a mixture of CO/H2), and subsequent syngas conversion to fuels and value-added chemicals, is one of the most promising alternatives to reach the corner of zero carbon strategy and renewable electricity storage. This research reviews the current state-of-the-art advancements in the coelectrolysis of CO2/H2O in solid oxide electrolyzer cells (SOECs) to produce the important syngas intermediate. The overviews of the latest research on the operating principles and thermodynamic and kinetic models are included for both oxygen-ion- and proton-conducting SOECs. The advanced materials that have recently been developed for both types of SOECs are summarized. It later elucidates the necessity and possibility of regulating the syngas ratios (H2:CO) via changing the operating conditions, including temperature, inlet gas composition, flow rate, applied voltage or current, and pressure. In addition, the sustainability and widespread application of SOEC technology for the conversion of syngas is highlighted. Finally, the challenges and the future research directions in this field are addressed. This review will appeal to scientists working on renewable-energy-conversion technologies, CO2 utilization, and SOEC applications. The implementation of the technologies introduced in this review offers solutions to climate change and renewable-power-storage problems.
{"title":"Syngas Production from CO2 and H2O via Solid-Oxide Electrolyzer Cells: Fundamentals, Materials, Degradation, Operating Conditions, and Applications","authors":"Xiangjun Hou, Yao Jiang, Keyan Wei, Cairong Jiang*, Tien-Chien Jen, Yali Yao*, Xinying Liu, Jianjun Ma and John T. S. Irvine*, ","doi":"10.1021/acs.chemrev.3c00760","DOIUrl":"10.1021/acs.chemrev.3c00760","url":null,"abstract":"<p >Highly efficient coelectrolysis of CO<sub>2</sub>/H<sub>2</sub>O into syngas (a mixture of CO/H<sub>2</sub>), and subsequent syngas conversion to fuels and value-added chemicals, is one of the most promising alternatives to reach the corner of zero carbon strategy and renewable electricity storage. This research reviews the current state-of-the-art advancements in the coelectrolysis of CO<sub>2</sub>/H<sub>2</sub>O in solid oxide electrolyzer cells (SOECs) to produce the important syngas intermediate. The overviews of the latest research on the operating principles and thermodynamic and kinetic models are included for both oxygen-ion- and proton-conducting SOECs. The advanced materials that have recently been developed for both types of SOECs are summarized. It later elucidates the necessity and possibility of regulating the syngas ratios (H<sub>2</sub>:CO) via changing the operating conditions, including temperature, inlet gas composition, flow rate, applied voltage or current, and pressure. In addition, the sustainability and widespread application of SOEC technology for the conversion of syngas is highlighted. Finally, the challenges and the future research directions in this field are addressed. This review will appeal to scientists working on renewable-energy-conversion technologies, CO<sub>2</sub> utilization, and SOEC applications. The implementation of the technologies introduced in this review offers solutions to climate change and renewable-power-storage problems.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":62.1,"publicationDate":"2024-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140553267","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 : 2024-04-15DOI: 10.1021/acs.chemrev.3c00420
Ksenia S. Egorova*, Alexey V. Kibardin, Alexandra V. Posvyatenko and Valentine P. Ananikov*,
The review presents a detailed discussion of the evolving field studying interactions between ionic liquids (ILs) and biological systems. Originating from molten salt electrolytes to present multiapplication substances, ILs have found usage across various fields due to their exceptional physicochemical properties, including excellent tunability. However, their interactions with biological systems and potential influence on living organisms remain largely unexplored. This review examines the cytotoxic effects of ILs on cell cultures, biomolecules, and vertebrate and invertebrate organisms. Our understanding of IL toxicity, while growing in recent years, is yet nascent. The established findings include correlations between harmful effects of ILs and their ability to disturb cellular membranes, their potential to trigger oxidative stress in cells, and their ability to cause cell death via apoptosis. Future research directions proposed in the review include studying the distribution of various ILs within cellular compartments and organelles, investigating metabolic transformations of ILs in cells and organisms, detailed analysis of IL effects on proteins involved in oxidative stress and apoptosis, correlation studies between IL doses, exposure times and resulting adverse effects, and examination of effects of subtoxic concentrations of ILs on various biological objects. This review aims to serve as a critical analysis of the current body of knowledge on IL-related toxicity mechanisms. Furthermore, it can guide researchers toward the design of less toxic ILs and the informed use of ILs in drug development and medicine.
这篇综述详细讨论了研究离子液体(IL)与生物系统之间相互作用的不断发展的领域。从熔盐电解质到现在的多用途物质,离子液体因其卓越的物理化学特性(包括出色的可调性)已在各个领域得到广泛应用。然而,它们与生物系统的相互作用以及对生物体的潜在影响在很大程度上仍未得到探索。本综述探讨了 ILs 对细胞培养物、生物大分子以及脊椎动物和无脊椎动物的细胞毒性作用。近年来,我们对 IL 毒性的了解不断加深,但仍处于起步阶段。已有的研究结果包括:ILs 的有害影响与其扰乱细胞膜的能力、引发细胞氧化应激的潜力以及通过细胞凋亡导致细胞死亡的能力之间的相关性。综述提出的未来研究方向包括:研究各种ILs在细胞区室和细胞器中的分布;研究ILs在细胞和生物体内的代谢转化;详细分析IL对参与氧化应激和细胞凋亡的蛋白质的影响;IL剂量、暴露时间和由此产生的不良影响之间的相关性研究;以及研究亚毒性浓度的ILs对各种生物对象的影响。这篇综述旨在对当前有关 IL 相关毒性机制的知识体系进行批判性分析。此外,它还能指导研究人员设计毒性较低的 IL,并在药物开发和医疗中明智地使用 IL。
{"title":"Mechanisms of Biological Effects of Ionic Liquids: From Single Cells to Multicellular Organisms","authors":"Ksenia S. Egorova*, Alexey V. Kibardin, Alexandra V. Posvyatenko and Valentine P. Ananikov*, ","doi":"10.1021/acs.chemrev.3c00420","DOIUrl":"10.1021/acs.chemrev.3c00420","url":null,"abstract":"<p >The review presents a detailed discussion of the evolving field studying interactions between ionic liquids (ILs) and biological systems. Originating from molten salt electrolytes to present multiapplication substances, ILs have found usage across various fields due to their exceptional physicochemical properties, including excellent tunability. However, their interactions with biological systems and potential influence on living organisms remain largely unexplored. This review examines the cytotoxic effects of ILs on cell cultures, biomolecules, and vertebrate and invertebrate organisms. Our understanding of IL toxicity, while growing in recent years, is yet nascent. The established findings include correlations between harmful effects of ILs and their ability to disturb cellular membranes, their potential to trigger oxidative stress in cells, and their ability to cause cell death via apoptosis. Future research directions proposed in the review include studying the distribution of various ILs within cellular compartments and organelles, investigating metabolic transformations of ILs in cells and organisms, detailed analysis of IL effects on proteins involved in oxidative stress and apoptosis, correlation studies between IL doses, exposure times and resulting adverse effects, and examination of effects of subtoxic concentrations of ILs on various biological objects. This review aims to serve as a critical analysis of the current body of knowledge on IL-related toxicity mechanisms. Furthermore, it can guide researchers toward the design of less toxic ILs and the informed use of ILs in drug development and medicine.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":62.1,"publicationDate":"2024-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140553476","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 : 2024-04-12DOI: 10.1021/acs.chemrev.3c00701
Arnab Chakraborty, and , Siddhesh S. Kamat*,
Lysophosphatidylserine (lyso-PS) has emerged as yet another important signaling lysophospholipid in mammals, and deregulation in its metabolism has been directly linked to an array of human autoimmune and neurological disorders. It has an indispensable role in several biological processes in humans, and therefore, cellular concentrations of lyso-PS are tightly regulated to ensure optimal signaling and functioning in physiological settings. Given its biological importance, the past two decades have seen an explosion in the available literature toward our understanding of diverse aspects of lyso-PS metabolism and signaling and its association with human diseases. In this Review, we aim to comprehensively summarize different aspects of lyso-PS, such as its structure, biodistribution, chemical synthesis, and SAR studies with some synthetic analogs. From a biochemical perspective, we provide an exhaustive coverage of the diverse biological activities modulated by lyso-PSs, such as its metabolism and the receptors that respond to them in humans. We also briefly discuss the human diseases associated with aberrant lyso-PS metabolism and signaling and posit some future directions that may advance our understanding of lyso-PS-mediated mammalian physiology.
溶血磷脂酰丝氨酸(lyso-PS)已成为哺乳动物体内另一种重要的信号溶血磷脂,其代谢失调与一系列人类自身免疫性疾病和神经系统疾病直接相关。溶血磷脂在人类的多个生物过程中发挥着不可或缺的作用,因此,细胞中的溶血磷脂浓度受到严格调控,以确保在生理环境中实现最佳的信号传递和功能。鉴于溶菌-PS 在生物学上的重要性,过去二十年来,有关溶菌-PS 代谢和信号转导及其与人类疾病的关系的现有文献激增。在这篇综述中,我们旨在全面总结溶菌-PS 的各个方面,如其结构、生物分布、化学合成以及一些合成类似物的 SAR 研究。从生物化学的角度,我们详尽地介绍了受溶菌-PS 调节的各种生物活性,如其在人体中的新陈代谢和对其产生反应的受体。我们还简要讨论了与溶菌-PS 代谢和信号传导异常有关的人类疾病,并提出了一些未来的研究方向,这些方向可能会促进我们对溶菌-PS 介导的哺乳动物生理学的了解。
{"title":"Lysophosphatidylserine: A Signaling Lipid with Implications in Human Diseases","authors":"Arnab Chakraborty, and , Siddhesh S. Kamat*, ","doi":"10.1021/acs.chemrev.3c00701","DOIUrl":"10.1021/acs.chemrev.3c00701","url":null,"abstract":"<p >Lysophosphatidylserine (lyso-PS) has emerged as yet another important signaling lysophospholipid in mammals, and deregulation in its metabolism has been directly linked to an array of human autoimmune and neurological disorders. It has an indispensable role in several biological processes in humans, and therefore, cellular concentrations of lyso-PS are tightly regulated to ensure optimal signaling and functioning in physiological settings. Given its biological importance, the past two decades have seen an explosion in the available literature toward our understanding of diverse aspects of lyso-PS metabolism and signaling and its association with human diseases. In this Review, we aim to comprehensively summarize different aspects of lyso-PS, such as its structure, biodistribution, chemical synthesis, and SAR studies with some synthetic analogs. From a biochemical perspective, we provide an exhaustive coverage of the diverse biological activities modulated by lyso-PSs, such as its metabolism and the receptors that respond to them in humans. We also briefly discuss the human diseases associated with aberrant lyso-PS metabolism and signaling and posit some future directions that may advance our understanding of lyso-PS-mediated mammalian physiology.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":62.1,"publicationDate":"2024-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140547855","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 : 2024-04-12DOI: 10.1021/acs.chemrev.3c00811
Javier O. Cifuente*, Christophe Colleoni, Rainer Kalscheuer and Marcelo E. Guerin*,
Bacteria have acquired sophisticated mechanisms for assembling and disassembling polysaccharides of different chemistry. α-d-Glucose homopolysaccharides, so-called α-glucans, are the most widespread polymers in nature being key components of microorganisms. Glycogen functions as an intracellular energy storage while some bacteria also produce extracellular assorted α-glucans. The classical bacterial glycogen metabolic pathway comprises the action of ADP-glucose pyrophosphorylase and glycogen synthase, whereas extracellular α-glucans are mostly related to peripheral enzymes dependent on sucrose. An alternative pathway of glycogen biosynthesis, operating via a maltose 1-phosphate polymerizing enzyme, displays an essential wiring with the trehalose metabolism to interconvert disaccharides into polysaccharides. Furthermore, some bacteria show a connection of intracellular glycogen metabolism with the genesis of extracellular capsular α-glucans, revealing a relationship between the storage and structural function of these compounds. Altogether, the current picture shows that bacteria have evolved an intricate α-glucan metabolism that ultimately relies on the evolution of a specific enzymatic machinery. The structural landscape of these enzymes exposes a limited number of core catalytic folds handling many different chemical reactions. In this Review, we present a rationale to explain how the chemical diversity of α-glucans emerged from these systems, highlighting the underlying structural evolution of the enzymes driving α-glucan bacterial metabolism.
{"title":"Architecture, Function, Regulation, and Evolution of α-Glucans Metabolic Enzymes in Prokaryotes","authors":"Javier O. Cifuente*, Christophe Colleoni, Rainer Kalscheuer and Marcelo E. Guerin*, ","doi":"10.1021/acs.chemrev.3c00811","DOIUrl":"10.1021/acs.chemrev.3c00811","url":null,"abstract":"<p >Bacteria have acquired sophisticated mechanisms for assembling and disassembling polysaccharides of different chemistry. α-<span>d</span>-Glucose homopolysaccharides, so-called α-glucans, are the most widespread polymers in nature being key components of microorganisms. Glycogen functions as an intracellular energy storage while some bacteria also produce extracellular assorted α-glucans. The classical bacterial glycogen metabolic pathway comprises the action of ADP-glucose pyrophosphorylase and glycogen synthase, whereas extracellular α-glucans are mostly related to peripheral enzymes dependent on sucrose. An alternative pathway of glycogen biosynthesis, operating via a maltose 1-phosphate polymerizing enzyme, displays an essential wiring with the trehalose metabolism to interconvert disaccharides into polysaccharides. Furthermore, some bacteria show a connection of intracellular glycogen metabolism with the genesis of extracellular capsular α-glucans, revealing a relationship between the storage and structural function of these compounds. Altogether, the current picture shows that bacteria have evolved an intricate α-glucan metabolism that ultimately relies on the evolution of a specific enzymatic machinery. The structural landscape of these enzymes exposes a limited number of core catalytic folds handling many different chemical reactions. In this Review, we present a rationale to explain how the chemical diversity of α-glucans emerged from these systems, highlighting the underlying structural evolution of the enzymes driving α-glucan bacterial metabolism.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":62.1,"publicationDate":"2024-04-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemrev.3c00811","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140547847","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}
Pub Date : 2024-04-10DOI: 10.1021/acs.chemrev.3c00919
Weiqi Yao, Kameron Liao, Tianxing Lai, Hyunki Sul and Arumugam Manthiram*,
Rechargeable metal-sulfur batteries are considered promising candidates for energy storage due to their high energy density along with high natural abundance and low cost of raw materials. However, they could not yet be practically implemented due to several key challenges: (i) poor conductivity of sulfur and the discharge product metal sulfide, causing sluggish redox kinetics, (ii) polysulfide shuttling, and (iii) parasitic side reactions between the electrolyte and the metal anode. To overcome these obstacles, numerous strategies have been explored, including modifications to the cathode, anode, electrolyte, and binder. In this review, the fundamental principles and challenges of metal-sulfur batteries are first discussed. Second, the latest research on metal-sulfur batteries is presented and discussed, covering their material design, synthesis methods, and electrochemical performances. Third, emerging advanced characterization techniques that reveal the working mechanisms of metal-sulfur batteries are highlighted. Finally, the possible future research directions for the practical applications of metal-sulfur batteries are discussed. This comprehensive review aims to provide experimental strategies and theoretical guidance for designing and understanding the intricacies of metal-sulfur batteries; thus, it can illuminate promising pathways for progressing high-energy-density metal-sulfur battery systems.
{"title":"Rechargeable Metal-Sulfur Batteries: Key Materials to Mechanisms","authors":"Weiqi Yao, Kameron Liao, Tianxing Lai, Hyunki Sul and Arumugam Manthiram*, ","doi":"10.1021/acs.chemrev.3c00919","DOIUrl":"10.1021/acs.chemrev.3c00919","url":null,"abstract":"<p >Rechargeable metal-sulfur batteries are considered promising candidates for energy storage due to their high energy density along with high natural abundance and low cost of raw materials. However, they could not yet be practically implemented due to several key challenges: (i) poor conductivity of sulfur and the discharge product metal sulfide, causing sluggish redox kinetics, (ii) polysulfide shuttling, and (iii) parasitic side reactions between the electrolyte and the metal anode. To overcome these obstacles, numerous strategies have been explored, including modifications to the cathode, anode, electrolyte, and binder. In this review, the fundamental principles and challenges of metal-sulfur batteries are first discussed. Second, the latest research on metal-sulfur batteries is presented and discussed, covering their material design, synthesis methods, and electrochemical performances. Third, emerging advanced characterization techniques that reveal the working mechanisms of metal-sulfur batteries are highlighted. Finally, the possible future research directions for the practical applications of metal-sulfur batteries are discussed. This comprehensive review aims to provide experimental strategies and theoretical guidance for designing and understanding the intricacies of metal-sulfur batteries; thus, it can illuminate promising pathways for progressing high-energy-density metal-sulfur battery systems.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":62.1,"publicationDate":"2024-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140541953","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 : 2024-04-10DOI: 10.1021/acs.chemrev.4c00231
Stephen G. Newman,
{"title":"Optimizing Chemical Reactions","authors":"Stephen G. Newman, ","doi":"10.1021/acs.chemrev.4c00231","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00231","url":null,"abstract":"","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":62.1,"publicationDate":"2024-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140539100","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 : 2024-04-05DOI: 10.1021/acs.chemrev.3c00575
Elsa Zacco, Laura Broglia, Misuzu Kurihara, Michele Monti, Stefano Gustincich, Annalisa Pastore, Kathrin Plath, Shinichi Nagakawa, Andrea Cerase, Natalia Sanchez de Groot and Gian Gaetano Tartaglia*,
This comprehensive Review delves into the chemical principles governing RNA-mediated crowding events, commonly referred to as granules or biological condensates. We explore the pivotal role played by RNA sequence, structure, and chemical modifications in these processes, uncovering their correlation with crowding phenomena under physiological conditions. Additionally, we investigate instances where crowding deviates from its intended function, leading to pathological consequences. By deepening our understanding of the delicate balance that governs molecular crowding driven by RNA and its implications for cellular homeostasis, we aim to shed light on this intriguing area of research. Our exploration extends to the methodologies employed to decipher the composition and structural intricacies of RNA granules, offering a comprehensive overview of the techniques used to characterize them, including relevant computational approaches. Through two detailed examples highlighting the significance of noncoding RNAs, NEAT1 and XIST, in the formation of phase-separated assemblies and their influence on the cellular landscape, we emphasize their crucial role in cellular organization and function. By elucidating the chemical underpinnings of RNA-mediated molecular crowding, investigating the role of modifications, structures, and composition of RNA granules, and exploring both physiological and aberrant phase separation phenomena, this Review provides a multifaceted understanding of the intriguing world of RNA-mediated biological condensates.
{"title":"RNA: The Unsuspected Conductor in the Orchestra of Macromolecular Crowding","authors":"Elsa Zacco, Laura Broglia, Misuzu Kurihara, Michele Monti, Stefano Gustincich, Annalisa Pastore, Kathrin Plath, Shinichi Nagakawa, Andrea Cerase, Natalia Sanchez de Groot and Gian Gaetano Tartaglia*, ","doi":"10.1021/acs.chemrev.3c00575","DOIUrl":"10.1021/acs.chemrev.3c00575","url":null,"abstract":"<p >This comprehensive Review delves into the chemical principles governing RNA-mediated crowding events, commonly referred to as granules or biological condensates. We explore the pivotal role played by RNA sequence, structure, and chemical modifications in these processes, uncovering their correlation with crowding phenomena under physiological conditions. Additionally, we investigate instances where crowding deviates from its intended function, leading to pathological consequences. By deepening our understanding of the delicate balance that governs molecular crowding driven by RNA and its implications for cellular homeostasis, we aim to shed light on this intriguing area of research. Our exploration extends to the methodologies employed to decipher the composition and structural intricacies of RNA granules, offering a comprehensive overview of the techniques used to characterize them, including relevant computational approaches. Through two detailed examples highlighting the significance of noncoding RNAs, <i>NEAT1</i> and <i>XIST</i>, in the formation of phase-separated assemblies and their influence on the cellular landscape, we emphasize their crucial role in cellular organization and function. By elucidating the chemical underpinnings of RNA-mediated molecular crowding, investigating the role of modifications, structures, and composition of RNA granules, and exploring both physiological and aberrant phase separation phenomena, this Review provides a multifaceted understanding of the intriguing world of RNA-mediated biological condensates.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":null,"pages":null},"PeriodicalIF":62.1,"publicationDate":"2024-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemrev.3c00575","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140534082","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}