Pub Date : 2024-11-05DOI: 10.1021/acs.chemrev.4c00369
Guanglong Ding, Hang Li, JiYu Zhao, Kui Zhou, Yongbiao Zhai, Ziyu Lv, Meng Zhang, Yan Yan, Su-Ting Han, Ye Zhou
The quest to imbue machines with intelligence akin to that of humans, through the development of adaptable neuromorphic devices and the creation of artificial neural systems, has long stood as a pivotal goal in both scientific inquiry and industrial advancement. Recent advancements in flexible neuromorphic electronics primarily rely on nanomaterials and polymers owing to their inherent uniformity, superior mechanical and electrical capabilities, and versatile functionalities. However, this field is still in its nascent stage, necessitating continuous efforts in materials innovation and device/system design. Therefore, it is imperative to conduct an extensive and comprehensive analysis to summarize current progress. This review highlights the advancements and applications of flexible neuromorphics, involving inorganic nanomaterials (zero-/one-/two-dimensional, and heterostructure), carbon-based nanomaterials such as carbon nanotubes (CNTs) and graphene, and polymers. Additionally, a comprehensive comparison and summary of the structural compositions, design strategies, key performance, and significant applications of these devices are provided. Furthermore, the challenges and future directions pertaining to materials/devices/systems associated with flexible neuromorphics are also addressed. The aim of this review is to shed light on the rapidly growing field of flexible neuromorphics, attract experts from diverse disciplines (e.g., electronics, materials science, neurobiology), and foster further innovation for its accelerated development.
{"title":"Nanomaterials for Flexible Neuromorphics","authors":"Guanglong Ding, Hang Li, JiYu Zhao, Kui Zhou, Yongbiao Zhai, Ziyu Lv, Meng Zhang, Yan Yan, Su-Ting Han, Ye Zhou","doi":"10.1021/acs.chemrev.4c00369","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00369","url":null,"abstract":"The quest to imbue machines with intelligence akin to that of humans, through the development of adaptable neuromorphic devices and the creation of artificial neural systems, has long stood as a pivotal goal in both scientific inquiry and industrial advancement. Recent advancements in flexible neuromorphic electronics primarily rely on nanomaterials and polymers owing to their inherent uniformity, superior mechanical and electrical capabilities, and versatile functionalities. However, this field is still in its nascent stage, necessitating continuous efforts in materials innovation and device/system design. Therefore, it is imperative to conduct an extensive and comprehensive analysis to summarize current progress. This review highlights the advancements and applications of flexible neuromorphics, involving inorganic nanomaterials (zero-/one-/two-dimensional, and heterostructure), carbon-based nanomaterials such as carbon nanotubes (CNTs) and graphene, and polymers. Additionally, a comprehensive comparison and summary of the structural compositions, design strategies, key performance, and significant applications of these devices are provided. Furthermore, the challenges and future directions pertaining to materials/devices/systems associated with flexible neuromorphics are also addressed. The aim of this review is to shed light on the rapidly growing field of flexible neuromorphics, attract experts from diverse disciplines (e.g., electronics, materials science, neurobiology), and foster further innovation for its accelerated development.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"29 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580678","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 : 2024-11-05DOI: 10.1021/acs.chemrev.4c00472
Sigitas Mikutis, Gonçalo J. L. Bernardes
The vast majority of the human genome codes for RNA, but RNA-targeting therapeutics account for a small fraction of approved drugs. As such, there is great incentive to improve old and develop new approaches to RNA targeting. For many RNA targeting modalities, just binding is not sufficient to exert a therapeutic effect; thus, targeted RNA degradation and induced decay emerged as powerful approaches with a pronounced biological effect. This review covers the origins and advanced use cases of targeted RNA degrader technologies grouped by the nature of the targeting modality as well as by the mode of degradation. It covers both well-established methods and clinically successful platforms such as RNA interference, as well as emerging approaches such as recruitment of RNA quality control machinery, CRISPR, and direct targeted RNA degradation. We also share our thoughts on the biggest hurdles in this field, as well as possible ways to overcome them.
{"title":"Technologies for Targeted RNA Degradation and Induced RNA Decay","authors":"Sigitas Mikutis, Gonçalo J. L. Bernardes","doi":"10.1021/acs.chemrev.4c00472","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00472","url":null,"abstract":"The vast majority of the human genome codes for RNA, but RNA-targeting therapeutics account for a small fraction of approved drugs. As such, there is great incentive to improve old and develop new approaches to RNA targeting. For many RNA targeting modalities, just binding is not sufficient to exert a therapeutic effect; thus, targeted RNA degradation and induced decay emerged as powerful approaches with a pronounced biological effect. This review covers the origins and advanced use cases of targeted RNA degrader technologies grouped by the nature of the targeting modality as well as by the mode of degradation. It covers both well-established methods and clinically successful platforms such as RNA interference, as well as emerging approaches such as recruitment of RNA quality control machinery, CRISPR, and direct targeted RNA degradation. We also share our thoughts on the biggest hurdles in this field, as well as possible ways to overcome them.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"5 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580682","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 : 2024-10-31DOI: 10.1021/acs.chemrev.4c00261
Matthijs P. J. M. van der Ham, Jordi Creus, Johannes H. Bitter, Marc T. M. Koper, Paolo P. Pescarmona
In this contribution, we review the electrochemical upgrading of saccharides (e.g., glucose) and sugar alcohols (e.g., glycerol) on metal and metal-oxide electrodes by drawing conclusions on common trends and differences between these two important classes of biobased compounds. For this purpose, we critically review the literature on the electrocatalytic oxidation of saccharides and sugar alcohols, seeking trends in the effect of reaction conditions and electrocatalyst design on the selectivity for the oxidation of specific functional groups toward value-added compounds. Importantly, we highlight and discuss the competition between electrochemical and non-electrochemical pathways. This is a crucial and yet often neglected aspect that should be taken into account and optimized for achieving the efficient electrocatalytic conversion of monosaccharides and related sugar alcohols into valuable products, which is a target of growing interest in the context of the electrification of the chemical industry combined with the utilization of renewable feedstock.
{"title":"Electrochemical and Non-Electrochemical Pathways in the Electrocatalytic Oxidation of Monosaccharides and Related Sugar Alcohols into Valuable Products","authors":"Matthijs P. J. M. van der Ham, Jordi Creus, Johannes H. Bitter, Marc T. M. Koper, Paolo P. Pescarmona","doi":"10.1021/acs.chemrev.4c00261","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00261","url":null,"abstract":"In this contribution, we review the electrochemical upgrading of saccharides (e.g., glucose) and sugar alcohols (e.g., glycerol) on metal and metal-oxide electrodes by drawing conclusions on common trends and differences between these two important classes of biobased compounds. For this purpose, we critically review the literature on the electrocatalytic oxidation of saccharides and sugar alcohols, seeking trends in the effect of reaction conditions and electrocatalyst design on the selectivity for the oxidation of specific functional groups toward value-added compounds. Importantly, we highlight and discuss the competition between electrochemical and non-electrochemical pathways. This is a crucial and yet often neglected aspect that should be taken into account and optimized for achieving the efficient electrocatalytic conversion of monosaccharides and related sugar alcohols into valuable products, which is a target of growing interest in the context of the electrification of the chemical industry combined with the utilization of renewable feedstock.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"112 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556166","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 : 2024-10-31DOI: 10.1021/acs.chemrev.4c00438
Michele Stofella, Antonio Grimaldi, Jochem H. Smit, Jürgen Claesen, Emanuele Paci, Frank Sobott
Hydrogen–deuterium exchange (HDX) has become a pivotal method for investigating the structural and dynamic properties of proteins. The versatility and sensitivity of mass spectrometry (MS) made the technique the ideal companion for HDX, and today HDX-MS is addressing a growing number of applications in both academic research and industrial settings. The prolific generation of experimental data has spurred the concurrent development of numerous computational tools, designed to automate parts of the workflow while employing different strategies to achieve common objectives. Various computational methods are available to perform automated peptide searches and identification; different statistical tests have been implemented to quantify differences in the exchange pattern between two or more experimental conditions; alternative strategies have been developed to deconvolve and analyze peptides showing multimodal behavior; and different algorithms have been proposed to computationally increase the resolution of HDX-MS data, with the ultimate aim to provide information at the level of the single residue. This review delves into a comprehensive examination of the merits and drawbacks associated with the diverse strategies implemented by software tools for the analysis of HDX-MS data.
{"title":"Computational Tools for Hydrogen–Deuterium Exchange Mass Spectrometry Data Analysis","authors":"Michele Stofella, Antonio Grimaldi, Jochem H. Smit, Jürgen Claesen, Emanuele Paci, Frank Sobott","doi":"10.1021/acs.chemrev.4c00438","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00438","url":null,"abstract":"Hydrogen–deuterium exchange (HDX) has become a pivotal method for investigating the structural and dynamic properties of proteins. The versatility and sensitivity of mass spectrometry (MS) made the technique the ideal companion for HDX, and today HDX-MS is addressing a growing number of applications in both academic research and industrial settings. The prolific generation of experimental data has spurred the concurrent development of numerous computational tools, designed to automate parts of the workflow while employing different strategies to achieve common objectives. Various computational methods are available to perform automated peptide searches and identification; different statistical tests have been implemented to quantify differences in the exchange pattern between two or more experimental conditions; alternative strategies have been developed to deconvolve and analyze peptides showing multimodal behavior; and different algorithms have been proposed to computationally increase the resolution of HDX-MS data, with the ultimate aim to provide information at the level of the single residue. This review delves into a comprehensive examination of the merits and drawbacks associated with the diverse strategies implemented by software tools for the analysis of HDX-MS data.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"30 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556459","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 : 2024-10-31DOI: 10.1021/acs.chemrev.4c00282
Mingrui Wang, Guanghui Zhang, Hao Wang, Zhiqun Wang, Yu Zhou, Xiaowa Nie, Ben Hang Yin, Chunshan Song, Xinwen Guo
Catalytic COx (CO and CO2) hydrogenation to valued chemicals is one of the promising approaches to address challenges in energy, environment, and climate change. H2O is an inevitable side product in these reactions, where its existence and effect are often ignored. In fact, H2O significantly influences the catalytic active centers, reaction mechanism, and catalytic performance, preventing us from a definitive and deep understanding on the structure-performance relationship of the authentic catalysts. It is necessary, although challenging, to clarify its effect and provide practical strategies to tune the concentration and distribution of H2O to optimize its influence. In this review, we focus on how H2O in COx hydrogenation induces the structural evolution of catalysts and assists in the catalytic processes, as well as efforts to understand the underlying mechanism. We summarize and discuss some representative tuning strategies for realizing the rapid removal or local enrichment of H2O around the catalysts, along with brief techno-economic analysis and life cycle assessment. These fundamental understandings and strategies are further extended to the reactions of CO and CO2 reduction under an external field (light, electricity, and plasma). We also present suggestions and prospects for deciphering and controlling the effect of H2O in practical applications.
催化 COx（CO 和 CO2）加氢制备有价值的化学品是应对能源、环境和气候变化挑战的有效方法之一。H2O 是这些反应中不可避免的副产物，其存在和影响往往被忽视。事实上，H2O 会对催化活性中心、反应机理和催化性能产生重大影响，使我们无法对真实催化剂的结构-性能关系有明确而深入的了解。有必要澄清其影响，并提供实用的策略来调整 H2O 的浓度和分布，以优化其影响，尽管这很有挑战性。在本综述中，我们将重点讨论 COx 加氢过程中的 H2O 如何诱导催化剂的结构演变并协助催化过程，以及为了解其潜在机理所做的努力。我们总结并讨论了一些具有代表性的调整策略，以实现催化剂周围 H2O 的快速去除或局部富集，并进行了简要的技术经济分析和生命周期评估。这些基本认识和策略将进一步扩展到外部场（光、电和等离子体）条件下的 CO 和 CO2 还原反应。我们还提出了在实际应用中破解和控制 H2O 影响的建议和前景。
{"title":"Understanding and Tuning the Effects of H2O on Catalytic CO and CO2 Hydrogenation","authors":"Mingrui Wang, Guanghui Zhang, Hao Wang, Zhiqun Wang, Yu Zhou, Xiaowa Nie, Ben Hang Yin, Chunshan Song, Xinwen Guo","doi":"10.1021/acs.chemrev.4c00282","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00282","url":null,"abstract":"Catalytic CO<sub><i>x</i></sub> (CO and CO<sub>2</sub>) hydrogenation to valued chemicals is one of the promising approaches to address challenges in energy, environment, and climate change. H<sub>2</sub>O is an inevitable side product in these reactions, where its existence and effect are often ignored. In fact, H<sub>2</sub>O significantly influences the catalytic active centers, reaction mechanism, and catalytic performance, preventing us from a definitive and deep understanding on the structure-performance relationship of the authentic catalysts. It is necessary, although challenging, to clarify its effect and provide practical strategies to tune the concentration and distribution of H<sub>2</sub>O to optimize its influence. In this review, we focus on how H<sub>2</sub>O in CO<sub><i>x</i></sub> hydrogenation induces the structural evolution of catalysts and assists in the catalytic processes, as well as efforts to understand the underlying mechanism. We summarize and discuss some representative tuning strategies for realizing the rapid removal or local enrichment of H<sub>2</sub>O around the catalysts, along with brief techno-economic analysis and life cycle assessment. These fundamental understandings and strategies are further extended to the reactions of CO and CO<sub>2</sub> reduction under an external field (light, electricity, and plasma). We also present suggestions and prospects for deciphering and controlling the effect of H<sub>2</sub>O in practical applications.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"126 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556112","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}
The copolymerization of CO2 and epoxides presents a transformative approach to converting greenhouse gases into aliphatic polycarbonates (CO2-PCs), thereby reducing the polymer industry’s dependence on fossil resources. Over the past 50 years, a wide array of metallic catalysts, both heterogeneous and homogeneous, have been developed to achieve precise control over polymer selectivity, sequence, regio-, and stereoselectivity. This review details the evolution of metal-based catalysts, with a particular focus on the emergence of organoborane catalysts, and explores how these catalysts effectively address kinetic and thermodynamic challenges in CO2/epoxides copoly2merization. Advances in the synthesis of CO2-PCs with varied sequence and chain architectures through diverse polymerization protocols are examined, alongside the applications of functional CO2-PCs produced by incorporating different epoxides. The review also underscores the contributions of computational techniques to our understanding of copolymerization mechanisms and highlights recent advances in the closed-loop chemical recycling of CO2-sourced polycarbonates. Finally, the industrialization efforts of CO2-PCs are discussed, offering readers a comprehensive understanding of the evolution and future potential of epoxide copolymerization with CO2.
{"title":"Evolution of Copolymers of Epoxides and CO2: Catalysts, Monomers, Architectures, and Applications","authors":"Guan-Wen Yang, Rui Xie, Yao-Yao Zhang, Cheng-Kai Xu, Guang-Peng Wu","doi":"10.1021/acs.chemrev.4c00517","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00517","url":null,"abstract":"The copolymerization of CO<sub>2</sub> and epoxides presents a transformative approach to converting greenhouse gases into aliphatic polycarbonates (CO<sub>2</sub>-PCs), thereby reducing the polymer industry’s dependence on fossil resources. Over the past 50 years, a wide array of metallic catalysts, both heterogeneous and homogeneous, have been developed to achieve precise control over polymer selectivity, sequence, regio-, and stereoselectivity. This review details the evolution of metal-based catalysts, with a particular focus on the emergence of organoborane catalysts, and explores how these catalysts effectively address kinetic and thermodynamic challenges in CO<sub>2</sub>/epoxides copoly<sub>2</sub>merization. Advances in the synthesis of CO<sub>2</sub>-PCs with varied sequence and chain architectures through diverse polymerization protocols are examined, alongside the applications of functional CO<sub>2</sub>-PCs produced by incorporating different epoxides. The review also underscores the contributions of computational techniques to our understanding of copolymerization mechanisms and highlights recent advances in the closed-loop chemical recycling of CO<sub>2</sub>-sourced polycarbonates. Finally, the industrialization efforts of CO<sub>2</sub>-PCs are discussed, offering readers a comprehensive understanding of the evolution and future potential of epoxide copolymerization with CO<sub>2</sub>.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"6 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142489456","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 : 2024-10-25DOI: 10.1021/acs.chemrev.4c00185
Tadeusz Bak, SA Sherif, David StClair Black, Janusz Nowotny
This work, which overviews defect chemistry of TiO2 (rutile), is focused on atomic-size structural defects that are thermodynamically reversible. Here it is shown that thermodynamics can be used in defect engineering of TiO2-based energy materials, such as photoelectrodes and photocatalysts. We show that surface segregation of defects leads to the building-up of new surface structures that are responsible for reactivity. Since rational design of surface properties requires in situ surface characterization in operational conditions, expansion of bulk defect chemistry to surface defect chemistry requires a defect-related surface-sensitive tool for in situ monitoring of defect-related properties at elevated temperatures corresponding to defect equilibria and in a controlled gas-phase environment. Here we show that the high-temperature electron probe is a defect-related surface-sensitive tool that is uniquely positioned to aid surface defect engineering and determine unequivocal surface properties. The related applied aspects are considered for photoelectrochemical water splitting and the performance of solid oxide fuel cells. Here we report that trail-blazing studies on in situ surface monitoring of TiO2 during gas/solid equilibration, along with in situ characterization of surface semiconducting properties, leads to the discovery of a segregation-induced low-dimensional surface structure that is responsible for stable performance of oxide semiconductors, such as TiO2, in operational conditions.
{"title":"Defect Chemistry of Titanium Dioxide (Rutile). Progress Toward Sustainable Energy","authors":"Tadeusz Bak, SA Sherif, David StClair Black, Janusz Nowotny","doi":"10.1021/acs.chemrev.4c00185","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00185","url":null,"abstract":"This work, which overviews defect chemistry of TiO<sub>2</sub> (rutile), is focused on atomic-size structural defects that are thermodynamically reversible. Here it is shown that thermodynamics can be used in defect engineering of TiO<sub>2</sub>-based energy materials, such as photoelectrodes and photocatalysts. We show that surface segregation of defects leads to the building-up of new surface structures that are responsible for reactivity. Since rational design of surface properties requires <i>in situ</i> surface characterization in operational conditions, expansion of bulk defect chemistry to surface defect chemistry requires a defect-related surface-sensitive tool for <i>in situ</i> monitoring of defect-related properties at elevated temperatures corresponding to defect equilibria and in a controlled gas-phase environment. Here we show that the high-temperature electron probe is a defect-related surface-sensitive tool that is uniquely positioned to aid surface defect engineering and determine unequivocal surface properties. The related applied aspects are considered for photoelectrochemical water splitting and the performance of solid oxide fuel cells. Here we report that trail-blazing studies on <i>in situ</i> surface monitoring of TiO<sub>2</sub> during gas/solid equilibration, along with <i>in situ</i> characterization of surface semiconducting properties, leads to the discovery of a segregation-induced low-dimensional surface structure that is responsible for stable performance of oxide semiconductors, such as TiO<sub>2</sub>, in operational conditions.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"236 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142489983","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 : 2024-10-25DOI: 10.1021/acs.chemrev.4c00422
Kilian Colas, Daniel Bindl, Hiroaki Suga
Technological advances and breakthrough developments in the pharmaceutical field are knocking at the door of the “undruggable” fortress with increasing insistence. Notably, the 21st century has seen the emergence of macrocyclic compounds, among which cyclic peptides are of particular interest. This new class of potential drug candidates occupies the vast chemical space between classic small-molecule drugs and larger protein-based therapeutics, such as antibodies. As research advances toward clinical targets that have long been considered inaccessible, macrocyclic peptides are well-suited to tackle these challenges in a post-rule of 5 pharmaceutical landscape. Facilitating their discovery is an arsenal of high-throughput screening methods that exploit massive randomized libraries of genetically encoded compounds. These techniques benefit from the incorporation of non-natural moieties, such as non- proteinogenic amino acids or stabilizing hydrocarbon staples. Exploiting these features for the strategic architectural design of macrocyclic peptides has the potential to tackle challenging targets such as protein–protein interactions, which have long resisted research efforts. This Review summarizes the basic principles and recent developments of the main high-throughput techniques for the discovery of macrocyclic peptides and focuses on their specific deployment for targeting undruggable space. A particular focus is placed on the development of new design guidelines and principles for the cyclization and structural stabilization of cyclic peptides and the resulting success stories achieved against well-known inaccessible drug targets.
{"title":"Selection of Nucleotide-Encoded Mass Libraries of Macrocyclic Peptides for Inaccessible Drug Targets","authors":"Kilian Colas, Daniel Bindl, Hiroaki Suga","doi":"10.1021/acs.chemrev.4c00422","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00422","url":null,"abstract":"Technological advances and breakthrough developments in the pharmaceutical field are knocking at the door of the “undruggable” fortress with increasing insistence. Notably, the 21st century has seen the emergence of macrocyclic compounds, among which cyclic peptides are of particular interest. This new class of potential drug candidates occupies the vast chemical space between classic small-molecule drugs and larger protein-based therapeutics, such as antibodies. As research advances toward clinical targets that have long been considered inaccessible, macrocyclic peptides are well-suited to tackle these challenges in a post-rule of 5 pharmaceutical landscape. Facilitating their discovery is an arsenal of high-throughput screening methods that exploit massive randomized libraries of genetically encoded compounds. These techniques benefit from the incorporation of non-natural moieties, such as non- proteinogenic amino acids or stabilizing hydrocarbon staples. Exploiting these features for the strategic architectural design of macrocyclic peptides has the potential to tackle challenging targets such as protein–protein interactions, which have long resisted research efforts. This Review summarizes the basic principles and recent developments of the main high-throughput techniques for the discovery of macrocyclic peptides and focuses on their specific deployment for targeting undruggable space. A particular focus is placed on the development of new design guidelines and principles for the cyclization and structural stabilization of cyclic peptides and the resulting success stories achieved against well-known inaccessible drug targets.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"98 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142489458","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 : 2024-10-23DOI: 10.1021/acs.chemrev.4c00464
Matthew C. Lamb, Keri A. Steiniger, Leslie K. Trigoura, Jason Wu, Gourab Kundu, He Huang, Tristan H. Lambert
Electrocatalysis and photocatalysis have been the focus of extensive research efforts in organic synthesis in recent decades, and these powerful strategies have provided a wealth of new methods to construct complex molecules. Despite these intense efforts, only recently has there been a significant focus on the combined use of these two modalities. Nevertheless, the past five years have witnessed rapidly growing interest in the area of electrophotocatalysis. This hybrid strategy capitalizes on the enormous benefits of using photons as reagents while also employing an electric potential as a convenient and tunable source or sink of electrons. Research on this topic has led to a number of methods for C–H functionalization, reductive cross-coupling, and olefin addition among others. This field has also seen the use of a broad range of catalyst types, including both metal and organocatalysts. Of particular note has been work with open-shell photocatalysts, which tend to have comparatively large redox potentials. Electrochemistry provides a convenient means to generate such species, making electrophotocatalysis particularly amenable to this intriguing class of redox catalyst. This review surveys methods in the area of electrophotocatalysis as applied to organic synthesis, organized broadly into oxidative, reductive, and redox neutral transformations.
{"title":"Electrophotocatalysis for Organic Synthesis","authors":"Matthew C. Lamb, Keri A. Steiniger, Leslie K. Trigoura, Jason Wu, Gourab Kundu, He Huang, Tristan H. Lambert","doi":"10.1021/acs.chemrev.4c00464","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00464","url":null,"abstract":"Electrocatalysis and photocatalysis have been the focus of extensive research efforts in organic synthesis in recent decades, and these powerful strategies have provided a wealth of new methods to construct complex molecules. Despite these intense efforts, only recently has there been a significant focus on the combined use of these two modalities. Nevertheless, the past five years have witnessed rapidly growing interest in the area of electrophotocatalysis. This hybrid strategy capitalizes on the enormous benefits of using photons as reagents while also employing an electric potential as a convenient and tunable source or sink of electrons. Research on this topic has led to a number of methods for C–H functionalization, reductive cross-coupling, and olefin addition among others. This field has also seen the use of a broad range of catalyst types, including both metal and organocatalysts. Of particular note has been work with open-shell photocatalysts, which tend to have comparatively large redox potentials. Electrochemistry provides a convenient means to generate such species, making electrophotocatalysis particularly amenable to this intriguing class of redox catalyst. This review surveys methods in the area of electrophotocatalysis as applied to organic synthesis, organized broadly into oxidative, reductive, and redox neutral transformations.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"10 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142490339","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 : 2024-10-23DOI: 10.1021/acs.chemrev.3c00643
Jonathan D. Schultz, Jonathon L. Yuly, Eric A. Arsenault, Kelsey Parker, Sutirtha N. Chowdhury, Reshmi Dani, Sohang Kundu, Hanggai Nuomin, Zhendian Zhang, Jesús Valdiviezo, Peng Zhang, Kaydren Orcutt, Seogjoo J. Jang, Graham R. Fleming, Nancy Makri, Jennifer P. Ogilvie, Michael J. Therien, Michael R. Wasielewski, David N. Beratan
Coherence refers to correlations in waves. Because matter has a wave-particle nature, it is unsurprising that coherence has deep connections with the most contemporary issues in chemistry research (e.g., energy harvesting, femtosecond spectroscopy, molecular qubits and more). But what does the word “coherence” really mean in the context of molecules and other quantum systems? We provide a review of key concepts, definitions, and methodologies, surrounding coherence phenomena in chemistry, and we describe how the terms “coherence” and “quantum coherence” refer to many different phenomena in chemistry. Moreover, we show how these notions are related to the concept of an interference pattern. Coherence phenomena are indeed complex, and ambiguous definitions may spawn confusion. By describing the many definitions and contexts for coherence in the molecular sciences, we aim to enhance understanding and communication in this broad and active area of chemistry.
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