MacromoleculesPub Date : 2024-09-24DOI: 10.1021/acs.chemrev.4c0029910.1021/acs.chemrev.4c00299
Wenjie Zhou, Yuanwei Li, Benjamin E. Partridge and Chad A. Mirkin*,
{"title":"Engineering Anisotropy into Organized Nanoscale Matter","authors":"Wenjie Zhou, Yuanwei Li, Benjamin E. Partridge and Chad A. Mirkin*, ","doi":"10.1021/acs.chemrev.4c0029910.1021/acs.chemrev.4c00299","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00299https://doi.org/10.1021/acs.chemrev.4c00299","url":null,"abstract":"<p >Programming the organization of discrete building blocks into periodic and quasi-periodic arrays is challenging. Methods for organizing materials are particularly important at the nanoscale, where the time required for organization processes is practically manageable in experiments, and the resulting structures are of interest for applications spanning catalysis, optics, and plasmonics. While the assembly of isotropic nanoscale objects has been extensively studied and described by empirical design rules, recent synthetic advances have allowed anisotropy to be programmed into macroscopic assemblies made from nanoscale building blocks, opening new opportunities to engineer periodic materials and even quasicrystals with unnatural properties. In this review, we define guidelines for leveraging anisotropy of individual building blocks to direct the organization of nanoscale matter. First, the nature and spatial distribution of local interactions are considered and three design rules that guide particle organization are derived. Subsequently, recent examples from the literature are examined in the context of these design rules. Within the discussion of each rule, we delineate the examples according to the dimensionality (0D–3D) of the building blocks. Finally, we use geometric considerations to propose a general inverse design-based construction strategy that will enable the engineering of colloidal crystals with unprecedented structural control.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"124 19","pages":"11063–11107 11063–11107"},"PeriodicalIF":51.4,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142408431","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}
MacromoleculesPub Date : 2024-09-23DOI: 10.1021/acs.chemrev.4c0037510.1021/acs.chemrev.4c00375
Vera Wanka, Maximilian Fottner, Marko Cigler and Kathrin Lang*,
{"title":"Genetic Code Expansion Approaches to Decipher the Ubiquitin Code","authors":"Vera Wanka, Maximilian Fottner, Marko Cigler and Kathrin Lang*, ","doi":"10.1021/acs.chemrev.4c0037510.1021/acs.chemrev.4c00375","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00375https://doi.org/10.1021/acs.chemrev.4c00375","url":null,"abstract":"<p >The covalent attachment of Ub (ubiquitin) to target proteins (ubiquitylation) represents one of the most versatile PTMs (post-translational modifications) in eukaryotic cells. Substrate modifications range from a single Ub moiety being attached to a target protein to complex Ub chains that can also contain Ubls (Ub-like proteins). Ubiquitylation plays pivotal roles in most aspects of eukaryotic biology, and cells dedicate an orchestrated arsenal of enzymes to install, translate, and reverse these modifications. The entirety of this complex system is coined the Ub code. Deciphering the Ub code is challenging due to the difficulty in reconstituting enzymatic machineries and generating defined Ub/Ubl–protein conjugates. This Review provides a comprehensive overview of recent advances in using GCE (genetic code expansion) techniques to study the Ub code. We highlight strategies to site-specifically ubiquitylate target proteins and discuss their advantages and disadvantages, as well as their various applications. Additionally, we review the potential of small chemical PTMs targeting Ub/Ubls and present GCE-based approaches to study this additional layer of complexity. Furthermore, we explore methods that rely on GCE to develop tools to probe interactors of the Ub system and offer insights into how future GCE-based tools could help unravel the complexity of the Ub code.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"124 20","pages":"11544–11584 11544–11584"},"PeriodicalIF":51.4,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemrev.4c00375","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142517688","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}
MacromoleculesPub Date : 2024-09-17DOI: 10.1021/acs.chemrev.4c0008710.1021/acs.chemrev.4c00087
Shasha Zheng, Zhenlei Zhang, Songbo He, Huaizhou Yang, Hanan Atia, Ali M. Abdel-Mageed, Sebastian Wohlrab, Eszter Baráth, Sergey Tin, Hero J. Heeres*, Peter J. Deuss* and Johannes G. de Vries*,
{"title":"Benzenoid Aromatics from Renewable Resources","authors":"Shasha Zheng, Zhenlei Zhang, Songbo He, Huaizhou Yang, Hanan Atia, Ali M. Abdel-Mageed, Sebastian Wohlrab, Eszter Baráth, Sergey Tin, Hero J. Heeres*, Peter J. Deuss* and Johannes G. de Vries*, ","doi":"10.1021/acs.chemrev.4c0008710.1021/acs.chemrev.4c00087","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00087https://doi.org/10.1021/acs.chemrev.4c00087","url":null,"abstract":"<p >In this Review, all known chemical methods for the conversion of renewable resources into benzenoid aromatics are summarized. The raw materials that were taken into consideration are CO<sub>2</sub>; lignocellulose and its constituents cellulose, hemicellulose, and lignin; carbohydrates, mostly glucose, fructose, and xylose; chitin; fats and oils; terpenes; and materials that are easily obtained via fermentation, such as biogas, bioethanol, acetone, and many more. There are roughly two directions. One much used method is catalytic fast pyrolysis carried out at high temperatures (between 300 and 700 °C depending on the raw material), which leads to the formation of biochar; gases, such as CO, CO<sub>2</sub>, H<sub>2</sub>, and CH<sub>4</sub>; and an oil which is a mixture of hydrocarbons, mostly aromatics. The carbon selectivities of this method can be reasonably high when defined small molecules such as methanol or hexane are used but are rather low when highly oxygenated compounds such as lignocellulose are used. The other direction is largely based on the multistep conversion of platform chemicals obtained from lignocellulose, cellulose, or sugars and a limited number of fats and terpenes. Much research has focused on furan compounds such as furfural, 5-hydroxymethylfurfural, and 5-chloromethylfurfural. The conversion of lignocellulose to xylene via 5-chloromethylfurfural and dimethylfuran has led to the construction of two large-scale plants, one of which has been operational since 2023.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"124 19","pages":"10701–10876 10701–10876"},"PeriodicalIF":51.4,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemrev.4c00087","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142407477","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}
MacromoleculesPub Date : 2024-09-17DOI: 10.1021/acs.chemrev.4c00087
Shasha Zheng, Zhenlei Zhang, Songbo He, Huaizhou Yang, Hanan Atia, Ali M. Abdel-Mageed, Sebastian Wohlrab, Eszter Baráth, Sergey Tin, Hero J. Heeres, Peter J. Deuss, Johannes G. de Vries
{"title":"Benzenoid Aromatics from Renewable Resources","authors":"Shasha Zheng, Zhenlei Zhang, Songbo He, Huaizhou Yang, Hanan Atia, Ali M. Abdel-Mageed, Sebastian Wohlrab, Eszter Baráth, Sergey Tin, Hero J. Heeres, Peter J. Deuss, Johannes G. de Vries","doi":"10.1021/acs.chemrev.4c00087","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00087","url":null,"abstract":"In this Review, all known chemical methods for the conversion of renewable resources into benzenoid aromatics are summarized. The raw materials that were taken into consideration are CO<sub>2</sub>; lignocellulose and its constituents cellulose, hemicellulose, and lignin; carbohydrates, mostly glucose, fructose, and xylose; chitin; fats and oils; terpenes; and materials that are easily obtained via fermentation, such as biogas, bioethanol, acetone, and many more. There are roughly two directions. One much used method is catalytic fast pyrolysis carried out at high temperatures (between 300 and 700 °C depending on the raw material), which leads to the formation of biochar; gases, such as CO, CO<sub>2</sub>, H<sub>2</sub>, and CH<sub>4</sub>; and an oil which is a mixture of hydrocarbons, mostly aromatics. The carbon selectivities of this method can be reasonably high when defined small molecules such as methanol or hexane are used but are rather low when highly oxygenated compounds such as lignocellulose are used. The other direction is largely based on the multistep conversion of platform chemicals obtained from lignocellulose, cellulose, or sugars and a limited number of fats and terpenes. Much research has focused on furan compounds such as furfural, 5-hydroxymethylfurfural, and 5-chloromethylfurfural. The conversion of lignocellulose to xylene via 5-chloromethylfurfural and dimethylfuran has led to the construction of two large-scale plants, one of which has been operational since 2023.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"136 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142235457","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}
MacromoleculesPub Date : 2024-09-16DOI: 10.1021/acs.chemrev.3c00498
Chenggong Xu, Yi Chen, Siyang Zhao, Deke Li, Xing Tang, Haili Zhang, Jinxia Huang, Zhiguang Guo, Weimin Liu
{"title":"Mechanical Regulation of Polymer Gels","authors":"Chenggong Xu, Yi Chen, Siyang Zhao, Deke Li, Xing Tang, Haili Zhang, Jinxia Huang, Zhiguang Guo, Weimin Liu","doi":"10.1021/acs.chemrev.3c00498","DOIUrl":"https://doi.org/10.1021/acs.chemrev.3c00498","url":null,"abstract":"The mechanical properties of polymer gels devote to emerging devices and machines in fields such as biomedical engineering, flexible bioelectronics, biomimetic actuators, and energy harvesters. Coupling network architectures and interactions has been explored to regulate supportive mechanical characteristics of polymer gels; however, systematic reviews correlating mechanics to interaction forces at the molecular and structural levels remain absent in the field. This review highlights the molecular engineering and structural engineering of polymer gel mechanics and a comprehensive mechanistic understanding of mechanical regulation. Molecular engineering alters molecular architecture and manipulates functional groups/moieties at the molecular level, introducing various interactions and permanent or reversible dynamic bonds as the dissipative energy. Molecular engineering usually uses monomers, cross-linkers, chains, and other additives. Structural engineering utilizes casting methods, solvent phase regulation, mechanochemistry, macromolecule chemical reactions, and biomanufacturing technology to construct and tailor the topological network structures, or heterogeneous modulus compositions. We envision that the perfect combination of molecular and structural engineering may provide a fresh view to extend exciting new perspectives of this burgeoning field. This review also summarizes recent representative applications of polymer gels with excellent mechanical properties. Conclusions and perspectives are also provided from five aspects of concise summary, mechanical mechanism, biofabrication methods, upgraded applications, and synergistic methodology.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"28 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142235458","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}
MacromoleculesPub Date : 2024-09-16DOI: 10.1021/acs.chemrev.3c0049810.1021/acs.chemrev.3c00498
Chenggong Xu, Yi Chen, Siyang Zhao, Deke Li, Xing Tang, Haili Zhang, Jinxia Huang*, Zhiguang Guo* and Weimin Liu*,
{"title":"Mechanical Regulation of Polymer Gels","authors":"Chenggong Xu, Yi Chen, Siyang Zhao, Deke Li, Xing Tang, Haili Zhang, Jinxia Huang*, Zhiguang Guo* and Weimin Liu*, ","doi":"10.1021/acs.chemrev.3c0049810.1021/acs.chemrev.3c00498","DOIUrl":"https://doi.org/10.1021/acs.chemrev.3c00498https://doi.org/10.1021/acs.chemrev.3c00498","url":null,"abstract":"<p >The mechanical properties of polymer gels devote to emerging devices and machines in fields such as biomedical engineering, flexible bioelectronics, biomimetic actuators, and energy harvesters. Coupling network architectures and interactions has been explored to regulate supportive mechanical characteristics of polymer gels; however, systematic reviews correlating mechanics to interaction forces at the molecular and structural levels remain absent in the field. This review highlights the molecular engineering and structural engineering of polymer gel mechanics and a comprehensive mechanistic understanding of mechanical regulation. Molecular engineering alters molecular architecture and manipulates functional groups/moieties at the molecular level, introducing various interactions and permanent or reversible dynamic bonds as the dissipative energy. Molecular engineering usually uses monomers, cross-linkers, chains, and other additives. Structural engineering utilizes casting methods, solvent phase regulation, mechanochemistry, macromolecule chemical reactions, and biomanufacturing technology to construct and tailor the topological network structures, or heterogeneous modulus compositions. We envision that the perfect combination of molecular and structural engineering may provide a fresh view to extend exciting new perspectives of this burgeoning field. This review also summarizes recent representative applications of polymer gels with excellent mechanical properties. Conclusions and perspectives are also provided from five aspects of concise summary, mechanical mechanism, biofabrication methods, upgraded applications, and synergistic methodology.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"124 18","pages":"10435–10508 10435–10508"},"PeriodicalIF":51.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142318076","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}
MacromoleculesPub Date : 2024-09-13DOI: 10.1021/acs.chemrev.4c0030310.1021/acs.chemrev.4c00303
Akira Yoshimura*, and , Viktor V. Zhdankin*,
{"title":"Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents","authors":"Akira Yoshimura*, and , Viktor V. Zhdankin*, ","doi":"10.1021/acs.chemrev.4c0030310.1021/acs.chemrev.4c00303","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00303https://doi.org/10.1021/acs.chemrev.4c00303","url":null,"abstract":"<p >Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. Hypervalent iodine reagents are commonly used in synthetically important halogenations, oxidations, aminations, heterocyclizations, and various oxidative functionalizations of organic substrates. Iodonium salts are important arylating reagents, while iodonium ylides and imides are excellent carbene and nitrene precursors. Various derivatives of benziodoxoles, such as azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, and alkenylbenziodoxoles have found wide application as group transfer reagents in the presence of transition metal catalysts, under metal-free conditions, or using photocatalysts under photoirradiation conditions. Development of hypervalent iodine catalytic systems and discovery of highly enantioselective reactions using chiral hypervalent iodine compounds represent a particularly important recent achievement in the field of hypervalent iodine chemistry. Chemical transformations promoted by hypervalent iodine in many cases are unique and cannot be performed by using any other common, non-iodine-based reagent. This review covers literature published mainly in the last 7–8 years, between 2016 and 2024.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"124 19","pages":"11108–11186 11108–11186"},"PeriodicalIF":51.4,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.chemrev.4c00303","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142403141","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}
MacromoleculesPub Date : 2024-09-13DOI: 10.1021/acs.chemrev.4c00303
Akira Yoshimura, Viktor V. Zhdankin
{"title":"Recent Progress in Synthetic Applications of Hypervalent Iodine(III) Reagents","authors":"Akira Yoshimura, Viktor V. Zhdankin","doi":"10.1021/acs.chemrev.4c00303","DOIUrl":"https://doi.org/10.1021/acs.chemrev.4c00303","url":null,"abstract":"Hypervalent iodine(III) compounds have found wide application in modern organic chemistry as environmentally friendly reagents and catalysts. Hypervalent iodine reagents are commonly used in synthetically important halogenations, oxidations, aminations, heterocyclizations, and various oxidative functionalizations of organic substrates. Iodonium salts are important arylating reagents, while iodonium ylides and imides are excellent carbene and nitrene precursors. Various derivatives of benziodoxoles, such as azidobenziodoxoles, trifluoromethylbenziodoxoles, alkynylbenziodoxoles, and alkenylbenziodoxoles have found wide application as group transfer reagents in the presence of transition metal catalysts, under metal-free conditions, or using photocatalysts under photoirradiation conditions. Development of hypervalent iodine catalytic systems and discovery of highly enantioselective reactions using chiral hypervalent iodine compounds represent a particularly important recent achievement in the field of hypervalent iodine chemistry. Chemical transformations promoted by hypervalent iodine in many cases are unique and cannot be performed by using any other common, non-iodine-based reagent. This review covers literature published mainly in the last 7–8 years, between 2016 and 2024.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"37 1","pages":""},"PeriodicalIF":62.1,"publicationDate":"2024-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142198100","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}
MacromoleculesPub Date : 2024-09-11Epub Date: 2024-08-08DOI: 10.1021/acs.chemrev.4c00188
Xinghua Wang, Jing He, Ya-Nan Wang, Zhenyan Zhao, Kui Jiang, Wei Yang, Tao Zhang, Shiqi Jia, Kangbao Zhong, Linbin Niu, Yu Lan
{"title":"Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C-H Functionalization.","authors":"Xinghua Wang, Jing He, Ya-Nan Wang, Zhenyan Zhao, Kui Jiang, Wei Yang, Tao Zhang, Shiqi Jia, Kangbao Zhong, Linbin Niu, Yu Lan","doi":"10.1021/acs.chemrev.4c00188","DOIUrl":"10.1021/acs.chemrev.4c00188","url":null,"abstract":"<p><p>Radical C-H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) are Earth-abundant and can be employed to regulate radical C-H functionalization. The use of such metals is desirable because of the diverse interaction modes between first-row transition metal complexes and radical species including radical addition to the metal center, radical addition to the ligand of metal complexes, radical substitution of the metal complexes, single-electron transfer between radicals and metal complexes, hydrogen atom transfer between radicals and metal complexes, and noncovalent interaction between the radicals and metal complexes. Such interactions could improve the reactivity, diversity, and selectivity of radical transformations to allow for more challenging radical C-H functionalization reactions. This review examines the achievements in this promising area over the past decade, with a focus on the state-of-the-art while also discussing existing limitations and the enormous potential of high-value radical C-H functionalization regulated by these metals. The aim is to provide the reader with a detailed account of the strategies and mechanisms associated with such functionalization.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":" ","pages":"10192-10280"},"PeriodicalIF":51.4,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141900076","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}
MacromoleculesPub Date : 2024-09-11Epub Date: 2024-08-01DOI: 10.1021/acs.chemrev.3c00915
Tze-Fei Wong
{"title":"Triphasic Development of the Genetic Code.","authors":"Tze-Fei Wong","doi":"10.1021/acs.chemrev.3c00915","DOIUrl":"10.1021/acs.chemrev.3c00915","url":null,"abstract":"<p><p>The genetic code contains an alphabet of genetically encoded amino acids. The ten Phase 1 amino acids, including Gly, Ala, Ser, Asp, Glu, Val, Leu, Ile, Pro and Thr, were available from the prebiotic environment, whereas the ten Phase 2 amino acids, including Phe, Tyr, Arg, His, Trp, Asn, Gln, Lys, Cys, and Met, became available only later from amino acid biosyntheses. In the archaeon <i>Methanopyrus kandleri</i>, the oldest organism known, the standard alphabet of 20 amino acids was \"frozen\" and no additional amino acid was encoded in the subsequent 3 Gyrs. Four decades ago, it was discovered that the code was frozen because all the organisms were so well adapted to the standard amino acids that oligogenic barriers, consisting of genes that are thoroughly dependent on the standard code, would cause loss of viability upon the deletion of any one amino acid from the code. Once the reason for the freezing of the code was ascertained, procedures were devised by scientists worldwide to enable the encoding of novel noncanonical amino acids (ncAAs). These encoded Phase 3 ncAAs now surpass the 20 canonical Phase 2 amino acids in the code.</p>","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":" ","pages":"9866-9872"},"PeriodicalIF":51.4,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11393795/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141858205","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}