Nature reviews. Chemistry最新文献_第7页

Origins of non-ideal behaviour in voltammetric analysis of redox-active monolayers 氧化还原活性单层膜伏安分析非理想行为的起源。

IF 38.1 1区化学

Nature reviews. Chemistry Pub Date : 2024-07-22 DOI: 10.1038/s41570-024-00629-8

Brittany L. Huffman, Alexandria R. C. Bredar, Jillian L. Dempsey

{"title":"Origins of non-ideal behaviour in voltammetric analysis of redox-active monolayers","authors":"Brittany L. Huffman, Alexandria R. C. Bredar, Jillian L. Dempsey","doi":"10.1038/s41570-024-00629-8","DOIUrl":"10.1038/s41570-024-00629-8","url":null,"abstract":"Disorder in redox-active monolayers convolutes electrochemical characterization. This disorder can come from pinhole defects, loose packing, heterogeneous distribution of redox-active headgroups, and lateral interactions between immobilized redox-active molecules. Identifying the source of non-ideal behaviour in cyclic voltammograms can be challenging as different types of disorder often cause similar non-ideal cyclic voltammetry behaviour such as peak broadening, large peak-to-peak separation, peak asymmetry and multiple peaks for single redox processes. This Review provides an overview of ideal voltammetric behaviour for redox-active monolayers, common manifestations of disorder on voltammetric responses, common experimental parameters that can be varied to interrogate sources of disorder, and finally, examples of different types of disorder and how they impact electrochemical responses. Disorder in redox-active monolayers arising from pinhole defects, loose packing, heterogeneous distribution of redox-active headgroups, and lateral interactions between immobilized redox-active molecules can cause non-ideal cyclic voltammetry behaviour.","PeriodicalId":18849,"journal":{"name":"Nature reviews. Chemistry","volume":"8 8","pages":"628-643"},"PeriodicalIF":38.1,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141748652","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}

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The astrochemical evolutionary traits of phospholipid membrane homochirality 磷脂膜同色性的天体化学进化特征。

IF 38.1 1区化学

Nature reviews. Chemistry Pub Date : 2024-07-18 DOI: 10.1038/s41570-024-00627-w

Jana Bocková, Nykola C. Jones, Søren V. Hoffmann, Cornelia Meinert

{"title":"The astrochemical evolutionary traits of phospholipid membrane homochirality","authors":"Jana Bocková, Nykola C. Jones, Søren V. Hoffmann, Cornelia Meinert","doi":"10.1038/s41570-024-00627-w","DOIUrl":"10.1038/s41570-024-00627-w","url":null,"abstract":"Compartmentalization is crucial for the evolution of life. Present-day phospholipid membranes exhibit a high level of complexity and species-dependent homochirality, the so-called lipid divide. It is possible that less stable, yet more dynamic systems, promoting out-of-equilibrium environments, facilitated the evolution of life at its early stages. The composition of the preceding primitive membranes and the evolutionary route towards complexity and homochirality remain unexplained. Organics-rich carbonaceous chondrites are evidence of the ample diversity of interstellar chemistry, which may have enriched the prebiotic milieu on early Earth. This Review evaluates the detections of simple amphiphiles — likely ancestors of membrane phospholipids — in extraterrestrial samples and analogues, along with potential pathways to form primitive compartments on primeval Earth. The chiroptical properties of the chiral backbones of phospholipids provide a guide for future investigations into the origins of phospholipid membrane homochirality. We highlight a plausible common pathway towards homochirality of lipids, amino acids, and sugars starting from enantioenriched monomers. Finally, given their high recalcitrance and resistance to degradation, lipids are among the best candidate biomarkers in exobiology. Compartmentalization is crucial for life’s evolution. Yet, the origin of modern phospholipid membranes and their species-dependent homochirality remains unknown. Amphiphile detection in extraterrestrial samples suggests diverse interstellar chemistry, enriching Earth’s prebiotic chemistry with vital membrane precursors. Moreover, chiroptical properties guide research into membrane homochirality origins.","PeriodicalId":18849,"journal":{"name":"Nature reviews. Chemistry","volume":"8 9","pages":"652-664"},"PeriodicalIF":38.1,"publicationDate":"2024-07-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141723986","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}

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Monitoring a planetary resource under threat 监测受到威胁的地球资源

IF 38.1 1区化学

Nature reviews. Chemistry Pub Date : 2024-07-16 DOI: 10.1038/s41570-024-00631-0

Dan E. Angelescu

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Three-dimensional saturated C(sp3)-rich bioisosteres for benzene 富含 C(sp3)的三维饱和苯生物异构体

IF 38.1 1区化学

Nature reviews. Chemistry Pub Date : 2024-07-09 DOI: 10.1038/s41570-024-00623-0

Jet Tsien, Chao Hu, Rohan R. Merchant, Tian Qin

{"title":"Three-dimensional saturated C(sp3)-rich bioisosteres for benzene","authors":"Jet Tsien, Chao Hu, Rohan R. Merchant, Tian Qin","doi":"10.1038/s41570-024-00623-0","DOIUrl":"10.1038/s41570-024-00623-0","url":null,"abstract":"Benzenes, the most ubiquitous structural moiety in marketed small-molecule drugs, are frequently associated with poor ‘drug-like’ properties, including metabolic instability, and poor aqueous solubility. In an effort to overcome these limitations, recent developments in medicinal chemistry have demonstrated the improved physicochemical profiles of C(sp3)-rich bioisosteric scaffolds relative to arenes. In the past two decades, we have witnessed an exponential increase in synthetic methods for accessing saturated bioisosteres of monosubstituted and para-substituted benzenes. However, until recent discoveries, analogous three-dimensional ortho-substituted and meta-substituted biososteres have remained underexplored, owing to their ring strain and increased s-character hybridization. This Review summarizes the emerging synthetic methodologies to access such saturated motifs and their impact on the application of bioisosteres for ortho-substituted, meta-substituted and multi-substituted benzene rings. It concludes with a perspective on the development of next-generation bioisosteres, including those within novel chemical space. In this Review, synthetic approaches to polycyclic scaffolds, which can act as saturated, three-dimensional bioisosteric replacements of ortho-substituted, meta-substituted and multi-substituted benzenes, are discussed. Their application in medicinal chemistry is also summarized.","PeriodicalId":18849,"journal":{"name":"Nature reviews. Chemistry","volume":"8 8","pages":"605-627"},"PeriodicalIF":38.1,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141561488","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}

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Manipulating disorder within cathodes of alkali-ion batteries 操纵碱性离子电池阴极内的无序状态

IF 38.1 1区化学

Nature reviews. Chemistry Pub Date : 2024-07-02 DOI: 10.1038/s41570-024-00622-1

Seongkoo Kang, Suwon Lee, Hakwoo Lee, Yong-Mook Kang

{"title":"Manipulating disorder within cathodes of alkali-ion batteries","authors":"Seongkoo Kang, Suwon Lee, Hakwoo Lee, Yong-Mook Kang","doi":"10.1038/s41570-024-00622-1","DOIUrl":"10.1038/s41570-024-00622-1","url":null,"abstract":"The fact that ordered materials are rarely perfectly crystalline is widely acknowledged among materials scientists, but its impact is often overlooked or underestimated when studying how structure relates to properties. Various investigations demonstrate that intrinsic and extrinsic defects, and disorder generated by physicochemical reactions, are responsible for unexpectedly detrimental or beneficial functionalities. The task remains to modulate the disorder to produce desired properties in materials. As disorder is often correlated with local interactions, it is controllable. In this Review, we explore the structural disorder in cathode materials as a novel approach for improving their electrochemical performance. We revisit cathode materials for alkali-ion batteries and outline the origins and beneficial consequences of disorder. Focusing on layered, cubic rocksalt and other metal oxides, we discuss how disorder improves electrochemical properties of cathode materials and which interactions generate the disorder. We also present the potential pitfalls of disorder that must be considered. We conclude with perspectives for enhancing the electrochemical performance of cathode materials by using disorder. Disorder can be used as a design parameter to improve the electrochemical performance of cathode materials. In this Review, the advantages of disorder engineering are highlighted by revisiting cathode materials and the chemical interactions that lead to different types of disorder.","PeriodicalId":18849,"journal":{"name":"Nature reviews. Chemistry","volume":"8 8","pages":"587-604"},"PeriodicalIF":38.1,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489598","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}

引用次数: 0

On the aromaticity of actinide compounds 关于锕系元素化合物的芳香性

IF 38.1 1区化学

Nature reviews. Chemistry Pub Date : 2024-06-21 DOI: 10.1038/s41570-024-00617-y

Zahra Badri, Cina Foroutan-Nejad

{"title":"On the aromaticity of actinide compounds","authors":"Zahra Badri, Cina Foroutan-Nejad","doi":"10.1038/s41570-024-00617-y","DOIUrl":"10.1038/s41570-024-00617-y","url":null,"abstract":"The chemistry of actinides has flourished since the late 2010s with the synthesis of new actinide complexes and clusters. On the theoretical side, a range of tools is available for the characterization of these heavy element-containing compounds, but discrepancies in the assessment of aromaticity using different tools have led to controversies. In this Perspective, we examine the origin of controversies relating to the aromaticity of metallic compounds, with a focus on actinides. The aromaticity of actinides is important, not because these molecules are numerous or have a special role in catalysis or reactivity, but because this topic pushes theories of aromaticity to their limits. Owing to its reference independence, the magnetic criterion of aromaticity has been the most popular choice for the characterization of the aromaticity of metallic compounds, including actinide compounds. Through examination of several case studies, we show why this criterion might be misleading for metallic species and explain how findings relating to actinide compounds could reshape theories of aromaticity, not just for actinides but perhaps also for well-known hydrocarbons. The assessment of the aromaticity of actinide compounds has proven a controversial task. This Perspective highlights the application of state-of-the-art computational tools in assessing the aromaticity of actinide complexes and clusters and explains why commonly used magnetic probes, not just the nucleus-independent chemical shift but also the magnetically induced ring current, might be insufficient for assessing the aromaticity of these species.","PeriodicalId":18849,"journal":{"name":"Nature reviews. Chemistry","volume":"8 7","pages":"551-560"},"PeriodicalIF":38.1,"publicationDate":"2024-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141436051","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}

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Hot electrodes, cool reduction 热电极，冷还原。

IF 38.1 1区化学

Nature reviews. Chemistry Pub Date : 2024-06-20 DOI: 10.1038/s41570-024-00628-9

Sergio Fernández, Alexandria R. C. Bredar

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Mind your electrolytes 注意电解质

IF 38.1 1区化学

Nature reviews. Chemistry Pub Date : 2024-06-18 DOI: 10.1038/s41570-024-00625-y

Sa Suo, Colton Jacob Sheehan, Langqiu Xiao

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Atroposelective catalysis 反选择催化

IF 38.1 1区化学

Nature reviews. Chemistry Pub Date : 2024-06-18 DOI: 10.1038/s41570-024-00618-x

Tanno A. Schmidt, Valeriia Hutskalova, Christof Sparr

{"title":"Atroposelective catalysis","authors":"Tanno A. Schmidt, Valeriia Hutskalova, Christof Sparr","doi":"10.1038/s41570-024-00618-x","DOIUrl":"10.1038/s41570-024-00618-x","url":null,"abstract":"Atropisomeric compounds—stereoisomers that arise from the restricted rotation about a single bond—have attracted widespread attention in recent years due to their immense potential for applications in a variety of fields, including medicinal chemistry, catalysis and molecular nanoscience. This increased interest led to the invention of new molecular motors, the incorporation of atropisomers into drug discovery programmes and a wide range of novel atroposelective reactions, including those that simultaneously control multiple stereogenic axes. A diverse set of synthetic methodologies, which can be grouped into desymmetrizations, (dynamic) kinetic resolutions, cross-coupling reactions and de novo ring formations, is available for the catalyst-controlled stereoselective synthesis of various atropisomer classes. In this Review, we generalize the concepts for the catalyst-controlled stereoselective synthesis of atropisomers within these categories with an emphasis on recent advancements and underdeveloped atropisomeric scaffolds beyond stereogenic C(sp2)–C(sp2) axes. We also discuss more complex systems with multiple stereogenic axes or higher-order stereogenicity. The catalyst-controlled stereoselective synthesis of atropisomers is feasible by four main concepts: desymmetrization, (dynamic) kinetic resolution, direct formation of the stereogenic axis and de novo ring construction. In this Review, pioneering work in atroposelective catalysis is discussed alongside recent advances.","PeriodicalId":18849,"journal":{"name":"Nature reviews. Chemistry","volume":"8 7","pages":"497-517"},"PeriodicalIF":38.1,"publicationDate":"2024-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141419809","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}

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A speedy but thorough interrogation 迅速而彻底的审讯

IF 38.1 1区化学

Nature reviews. Chemistry Pub Date : 2024-06-17 DOI: 10.1038/s41570-024-00630-1

Chenyu Wang

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