Chemical Reviews最新文献

{"title":"Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis","authors":"Lauren E. Ehehalt,&nbsp;Omar M. Beleh,&nbsp;Isabella C. Priest,&nbsp;Julianna M. Mouat,&nbsp;Alyssa K. Olszewski,&nbsp;Benjamin N. Ahern,&nbsp;Alexandro R. Cruz,&nbsp;Benjamin K. Chi,&nbsp;Anthony J. Castro,&nbsp;Kai Kang,&nbsp;Jiang Wang and Daniel J. Weix*,&nbsp;","doi":"10.1021/acs.chemrev.4c0052410.1021/acs.chemrev.4c00524","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00524https://doi.org/10.1021/acs.chemrev.4c00524","url":null,"abstract":"<p >Cross-electrophile coupling (XEC), defined by us as the cross-coupling of two different σ-electrophiles that is driven by catalyst reduction, has seen rapid progression in recent years. As such, this review aims to summarize the field from its beginnings up until mid-2023 and to provide comprehensive coverage on synthetic methods and current state of mechanistic understanding. Chapters are split by type of bond formed, which include C(sp³)–C(sp³), C(sp²)–C(sp²), C(sp²)–C(sp³), and C(sp²)–C(sp) bond formation. Additional chapters include alkene difunctionalization, alkyne difunctionalization, and formation of carbon-heteroatom bonds. Each chapter is generally organized with an initial summary of mechanisms followed by detailed figures and notes on methodological developments and ending with application notes in synthesis. While XEC is becoming an increasingly utilized approach in synthesis, its early stage of development means that optimal catalysts, ligands, additives, and reductants are still in flux. This review has collected data on these and various other aspects of the reactions to capture the state of the field. Finally, the data collected on the papers in this review is offered as Supporting Information for readers.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"124 23","pages":"13397–13569 13397–13569"},"PeriodicalIF":51.4,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemrev.4c00524","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850709","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":"Biomimetic Materials to Fabricate Artificial Cells","authors":"Haisheng Peng*,&nbsp;Man Zhao,&nbsp;Xiaoying Liu,&nbsp;Tianjian Tong,&nbsp;Wenyuan Zhang,&nbsp;Chen Gong,&nbsp;Ratul Chowdhury and Qun Wang*,&nbsp;","doi":"10.1021/acs.chemrev.4c0024110.1021/acs.chemrev.4c00241","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00241https://doi.org/10.1021/acs.chemrev.4c00241","url":null,"abstract":"<p >As the foundation of life, a cell is generally considered an advanced microreactor with a complicated structure and function. Undeniably, this fascinating complexity motivates scientists to try to extricate themselves from natural living matter and work toward rebuilding artificial cells <i>in vitro</i>. Driven by synthetic biology and bionic technology, the research of artificial cells has gradually become a subclass. It is not only held import in many disciplines but also of great interest in its synthesis. Therefore, in this review, we have reviewed the development of cell and bionic strategies and focused on the efforts of bottom-up strategies in artificial cell construction. Different from starting with existing living organisms, we have also discussed the construction of artificial cells based on biomimetic materials, from simple cell scaffolds to multiple compartment systems, from the construction of functional modules to the simulation of crucial metabolism behaviors, or even to the biomimetic of communication networks. All of them could represent an exciting advance in the field. In addition, we will make a rough analysis of the bottlenecks in this field. Meanwhile, the future development of this field has been prospecting. This review may bridge the gap between materials engineering and life sciences, forming a theoretical basis for developing various life-inspired assembly materials.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"124 23","pages":"13178–13215 13178–13215"},"PeriodicalIF":51.4,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850710","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":"Biomimetic Materials to Fabricate Artificial Cells","authors":"Haisheng Peng, Man Zhao, Xiaoying Liu, Tianjian Tong, Wenyuan Zhang, Chen Gong, Ratul Chowdhury, Qun Wang","doi":"10.1021/acs.chemrev.4c00241","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00241","url":null,"abstract":"As the foundation of life, a cell is generally considered an advanced microreactor with a complicated structure and function. Undeniably, this fascinating complexity motivates scientists to try to extricate themselves from natural living matter and work toward rebuilding artificial cells <i>in vitro</i>. Driven by synthetic biology and bionic technology, the research of artificial cells has gradually become a subclass. It is not only held import in many disciplines but also of great interest in its synthesis. Therefore, in this review, we have reviewed the development of cell and bionic strategies and focused on the efforts of bottom-up strategies in artificial cell construction. Different from starting with existing living organisms, we have also discussed the construction of artificial cells based on biomimetic materials, from simple cell scaffolds to multiple compartment systems, from the construction of functional modules to the simulation of crucial metabolism behaviors, or even to the biomimetic of communication networks. All of them could represent an exciting advance in the field. In addition, we will make a rough analysis of the bottlenecks in this field. Meanwhile, the future development of this field has been prospecting. This review may bridge the gap between materials engineering and life sciences, forming a theoretical basis for developing various life-inspired assembly materials.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"13 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142719062","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":"Electric Fields in Polymeric Systems","authors":"Mark A. Rothermund, Stephen J. Koehler, Valerie Vaissier Welborn","doi":"10.1021/acs.chemrev.4c00490","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00490","url":null,"abstract":"Polymer-based electronic devices are limited by slow transport and recombination of newly separated charges. Built-in electric fields, which arise from compositional gradients, are known to improve charge separation, directional charge transport, and to reduce recombination. Yet, the optimization of these fields through the rational design of polymeric materials is not prevalent. Indeed, polymers are disordered and generate nonuniform electric fields that are hard to measure, and therefore, hard to optimize. Here, we review work focusing on the intentional optimization of electric fields in polymeric systems with applications to catalysis, energy conversion, and storage. This includes chemical tuning of constituent monomers, linkers, morphology, etc. that result in stronger molecular dipoles, polarizability or crystallinity. We also review techniques to characterize electric fields in polymers and emerging processing strategies based on electric fields. These studies demonstrate the benefits of optimizing electric fields in polymers. However, rational design is often restricted to the molecular scale, deriving new pendants on, or linkers between, monomers. This does not always translate in strong electric fields at the polymer level, because they strongly depend on the monomer orientation. A better control of the morphology and monomer-to-polymer scaling relationship is therefore crucial to enhance electric fields in polymeric materials.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"23 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142713137","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":"Electric Fields in Polymeric Systems","authors":"Mark A. Rothermund,&nbsp;Stephen J. Koehler and Valerie Vaissier Welborn*,&nbsp;","doi":"10.1021/acs.chemrev.4c0049010.1021/acs.chemrev.4c00490","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00490https://doi.org/10.1021/acs.chemrev.4c00490","url":null,"abstract":"<p >Polymer-based electronic devices are limited by slow transport and recombination of newly separated charges. Built-in electric fields, which arise from compositional gradients, are known to improve charge separation, directional charge transport, and to reduce recombination. Yet, the optimization of these fields through the rational design of polymeric materials is not prevalent. Indeed, polymers are disordered and generate nonuniform electric fields that are hard to measure, and therefore, hard to optimize. Here, we review work focusing on the intentional optimization of electric fields in polymeric systems with applications to catalysis, energy conversion, and storage. This includes chemical tuning of constituent monomers, linkers, morphology, etc. that result in stronger molecular dipoles, polarizability or crystallinity. We also review techniques to characterize electric fields in polymers and emerging processing strategies based on electric fields. These studies demonstrate the benefits of optimizing electric fields in polymers. However, rational design is often restricted to the molecular scale, deriving new pendants on, or linkers between, monomers. This does not always translate in strong electric fields at the polymer level, because they strongly depend on the monomer orientation. A better control of the morphology and monomer-to-polymer scaling relationship is therefore crucial to enhance electric fields in polymeric materials.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"124 23","pages":"13331–13369 13331–13369"},"PeriodicalIF":51.4,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemrev.4c00490","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142851050","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":"Data Generation for Machine Learning Interatomic Potentials and Beyond","authors":"Maksim Kulichenko, Benjamin Nebgen, Nicholas Lubbers, Justin S. Smith, Kipton Barros, Alice E. A. Allen, Adela Habib, Emily Shinkle, Nikita Fedik, Ying Wai Li, Richard A. Messerly, Sergei Tretiak","doi":"10.1021/acs.chemrev.4c00572","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00572","url":null,"abstract":"The field of data-driven chemistry is undergoing an evolution, driven by innovations in machine learning models for predicting molecular properties and behavior. Recent strides in ML-based interatomic potentials have paved the way for accurate modeling of diverse chemical and structural properties at the atomic level. The key determinant defining MLIP reliability remains the quality of the training data. A paramount challenge lies in constructing training sets that capture specific domains in the vast chemical and structural space. This Review navigates the intricate landscape of essential components and integrity of training data that ensure the extensibility and transferability of the resulting models. We delve into the details of active learning, discussing its various facets and implementations. We outline different types of uncertainty quantification applied to atomistic data acquisition and the correlations between estimated uncertainty and true error. The role of atomistic data samplers in generating diverse and informative structures is highlighted. Furthermore, we discuss data acquisition via modified and surrogate potential energy surfaces as an innovative approach to diversify training data. The Review also provides a list of publicly available data sets that cover essential domains of chemical space.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"55 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685133","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":"The Chemistry of Phytoplankton","authors":"Xiaoying Liu, Zhiwei Bian, Shian Hu, Cody F. Dickinson, Menny M. Benjamin, Jia Jia, Yintai Tian, Allen Place, George S. Hanna, Hendrik Luesch, Peter Croot, Maggie M. Reddy, Olivier P. Thomas, Gary Hardiman, Melany P. Puglisi, Ming Yang, Zhi Zhong, John J. Lemasters, Jeffrey E. Korte, Amanda L. Waters, Carl E. Heltzel, R. Thomas Williamson, Wendy K. Strangman, Fred Valeriote, Marcus A. Tius, Giacomo R. DiTullio, Daneel Ferreira, Alexander Alekseyenko, Shengpeng Wang, Mark T. Hamann, Xiaojuan Wang","doi":"10.1021/acs.chemrev.4c00177","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00177","url":null,"abstract":"Phytoplankton have a high potential for CO₂ capture and conversion. Besides being a vital food source at the base of oceanic and freshwater food webs, microalgae provide a critical platform for producing chemicals and consumer products. Enhanced nutrient levels, elevated CO₂, and rising temperatures increase the frequency of algal blooms, which often have negative effects such as fish mortalities, loss of flora and fauna, and the production of algal toxins. Harmful algal blooms (HABs) produce toxins that pose major challenges to water quality, ecosystem function, human health, tourism, and the food web. These toxins have complex chemical structures and possess a wide range of biological properties with potential applications as new therapeutics. This review presents a balanced and comprehensive assessment of the roles of algal blooms in generating fixed carbon for the food chain, sequestering carbon, and their unique secondary metabolites. The structural complexity of these metabolites has had an unprecedented impact on structure elucidation technologies and total synthesis, which are highlighted throughout this review. In addition, the influence of biogeochemical environmental perturbations on algal blooms and their influence on biospheric environments is discussed. Lastly, we summarize work on management strategies and technologies for the control and treatment of HABs.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"198 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142685132","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":"The Chemistry of Phytoplankton","authors":"Xiaoying Liu,&nbsp;Zhiwei Bian,&nbsp;Shian Hu,&nbsp;Cody F. Dickinson,&nbsp;Menny M. Benjamin,&nbsp;Jia Jia,&nbsp;Yintai Tian,&nbsp;Allen Place,&nbsp;George S. Hanna,&nbsp;Hendrik Luesch,&nbsp;Peter Croot,&nbsp;Maggie M. Reddy,&nbsp;Olivier P. Thomas,&nbsp;Gary Hardiman,&nbsp;Melany P. Puglisi,&nbsp;Ming Yang,&nbsp;Zhi Zhong,&nbsp;John J. Lemasters,&nbsp;Jeffrey E. Korte,&nbsp;Amanda L. Waters,&nbsp;Carl E. Heltzel,&nbsp;R. Thomas Williamson,&nbsp;Wendy K. Strangman,&nbsp;Fred Valeriote,&nbsp;Marcus A. Tius,&nbsp;Giacomo R. DiTullio,&nbsp;Daneel Ferreira,&nbsp;Alexander Alekseyenko,&nbsp;Shengpeng Wang*,&nbsp;Mark T. Hamann* and Xiaojuan Wang*,&nbsp;","doi":"10.1021/acs.chemrev.4c0017710.1021/acs.chemrev.4c00177","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00177https://doi.org/10.1021/acs.chemrev.4c00177","url":null,"abstract":"<p >Phytoplankton have a high potential for CO₂ capture and conversion. Besides being a vital food source at the base of oceanic and freshwater food webs, microalgae provide a critical platform for producing chemicals and consumer products. Enhanced nutrient levels, elevated CO₂, and rising temperatures increase the frequency of algal blooms, which often have negative effects such as fish mortalities, loss of flora and fauna, and the production of algal toxins. Harmful algal blooms (HABs) produce toxins that pose major challenges to water quality, ecosystem function, human health, tourism, and the food web. These toxins have complex chemical structures and possess a wide range of biological properties with potential applications as new therapeutics. This review presents a balanced and comprehensive assessment of the roles of algal blooms in generating fixed carbon for the food chain, sequestering carbon, and their unique secondary metabolites. The structural complexity of these metabolites has had an unprecedented impact on structure elucidation technologies and total synthesis, which are highlighted throughout this review. In addition, the influence of biogeochemical environmental perturbations on algal blooms and their influence on biospheric environments is discussed. Lastly, we summarize work on management strategies and technologies for the control and treatment of HABs.</p>","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"124 23","pages":"13099–13177 13099–13177"},"PeriodicalIF":51.4,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemrev.4c00177","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142843255","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":"Toward Efficient Utilization of Photogenerated Charge Carriers in Photoelectrochemical Systems: Engineering Strategies from the Atomic Level to Configuration","authors":"Kai Song, Houjiang Liu, Biao Chen, Chuangchuang Gong, Jiawei Ding, Tengfei Wang, Enzuo Liu, Liying Ma, Naiqin Zhao, Fang He","doi":"10.1021/acs.chemrev.4c00382","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00382","url":null,"abstract":"Photoelectrochemical (PEC) systems are essential for solar energy conversion, addressing critical energy and environmental issues. However, the low efficiency in utilizing photogenerated charge carriers significantly limits overall energy conversion. Consequently, there is a growing focus on developing strategies to enhance photoelectrode performance. This review systematically explores recent advancements in PEC system modifications, spanning from atomic and nanoscopic levels to configuration engineering. We delve into the relationships between PEC structures, intrinsic properties, kinetics of photogenerated charge carriers, and their utilization. Additionally, we propose future directions and perspectives for developing more efficient PEC systems, offering valuable insights into potential innovations in the field.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"110 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678810","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":"The Analysis of Electron Densities: From Basics to Emergent Applications","authors":"Daniel Koch, Michele Pavanello, Xuecheng Shao, Manabu Ihara, Paul W. Ayers, Chérif F. Matta, Samantha Jenkins, Sergei Manzhos","doi":"10.1021/acs.chemrev.4c00297","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00297","url":null,"abstract":"The electron density determines all properties of a system of nuclei and electrons. It is both computable and observable. Its topology allows gaining insight into the mechanisms of bonding and other phenomena in a way that is complementary to and beyond that available from the molecular orbital picture and the formal oxidation state (FOS) formalism. The ability to derive mechanistic insight from electron density is also important with methods where orbitals are not available, such as orbital-free density functional theory (OF-DFT). While density topology-based analyses such as QTAIM (quantum theory of atoms-in-molecules) have been widely used, novel, vector-based techniques recently emerged such as next-generation (NG) QTAIM. Density-dependent quantities are also actively used in machine learning (ML)-based methods, in particular, for ML DFT functional development, including machine-learnt kinetic energy functionals. We review QTAIM and its recent extensions such as NG-QTAIM and localization-delocalization matrices (LDM) and their uses in the analysis of bonding, conformations, mechanisms of redox reactions excitations, as well as ultrafast phenomena. We review recent research showing that direct density analysis can circumvent certain pitfalls of the FOS formalism, in particular in the description of anionic redox, and of the widely used (spherically) projected density of states analysis. We discuss uses of density-based quantities for the construction of DFT functionals and prospects of applications of analyses of density topology to get mechanistic insight with OF-DFT and recently developed time-dependent OF-DFT.","PeriodicalId":32,"journal":{"name":"Chemical Reviews","volume":"10 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637820","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}