Naoya Kanbayashi, Sora Odagaki, Nano Kobayakawa, Hiroyuki S. Kato, Kiyotaka Onitsuka
{"title":"将半胱氨酸衍生物直接引入螺旋状聚(喹啉-2,3-二基亚甲基)的链端:金基底上的致密单层膜","authors":"Naoya Kanbayashi, Sora Odagaki, Nano Kobayakawa, Hiroyuki S. Kato, Kiyotaka Onitsuka","doi":"10.1021/acs.macromol.4c00561","DOIUrl":null,"url":null,"abstract":"Highly reactive functional groups at polymer chain ends, integral for creating structurally diverse functional polymers and composites, present challenges in their introduction both pre- and postpolymerization. This study reported a method for directly introducing a sulfhydryl group, known for its specific reactivity, to the chain ends of polymers. Utilizing poly(quinoline-2,3-diylmethylene)s (PQMs) that form π-stacked helical structures via living polymerization initiated by a palladium complex, a novel approach was employed, where a cysteine derivative was added after converting the terminal palladium complex into an acyl palladium complex using carbon monoxide. The sulfhydryl group of cysteine formed a thioester bond, subsequently undergoing an S→N acyl shift to bond the cysteine derivative at the chain end of PQM through an amide bond while preserving the reactivity of the sulfhydryl group. This functionalization facilitated the easy introduction of various substituents at the end of the PQMs, enhancing their functional versatility. We finally focused on monolayer formation by specifically binding SH groups to Au. A cysteine derivative was introduced at the chain end of a π-stacked helical PQM that formed a monolayer film on a Au substrate. Remarkably, atomic force microscopy and scanning tunneling microscopy confirmed the formation of a uniform film containing densely packed π-stacked helical polymers on the Au substrate.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":null,"pages":null},"PeriodicalIF":5.1000,"publicationDate":"2024-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Direct Introduction of Cysteine Derivatives into the Chain End of Helical Poly(quinoline-2,3-diylmethylene)s: Densely Packed Monolayers on Au Substrates\",\"authors\":\"Naoya Kanbayashi, Sora Odagaki, Nano Kobayakawa, Hiroyuki S. Kato, Kiyotaka Onitsuka\",\"doi\":\"10.1021/acs.macromol.4c00561\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Highly reactive functional groups at polymer chain ends, integral for creating structurally diverse functional polymers and composites, present challenges in their introduction both pre- and postpolymerization. This study reported a method for directly introducing a sulfhydryl group, known for its specific reactivity, to the chain ends of polymers. Utilizing poly(quinoline-2,3-diylmethylene)s (PQMs) that form π-stacked helical structures via living polymerization initiated by a palladium complex, a novel approach was employed, where a cysteine derivative was added after converting the terminal palladium complex into an acyl palladium complex using carbon monoxide. The sulfhydryl group of cysteine formed a thioester bond, subsequently undergoing an S→N acyl shift to bond the cysteine derivative at the chain end of PQM through an amide bond while preserving the reactivity of the sulfhydryl group. This functionalization facilitated the easy introduction of various substituents at the end of the PQMs, enhancing their functional versatility. We finally focused on monolayer formation by specifically binding SH groups to Au. A cysteine derivative was introduced at the chain end of a π-stacked helical PQM that formed a monolayer film on a Au substrate. Remarkably, atomic force microscopy and scanning tunneling microscopy confirmed the formation of a uniform film containing densely packed π-stacked helical polymers on the Au substrate.\",\"PeriodicalId\":51,\"journal\":{\"name\":\"Macromolecules\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.1000,\"publicationDate\":\"2024-06-08\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Macromolecules\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.macromol.4c00561\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.macromol.4c00561","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Direct Introduction of Cysteine Derivatives into the Chain End of Helical Poly(quinoline-2,3-diylmethylene)s: Densely Packed Monolayers on Au Substrates
Highly reactive functional groups at polymer chain ends, integral for creating structurally diverse functional polymers and composites, present challenges in their introduction both pre- and postpolymerization. This study reported a method for directly introducing a sulfhydryl group, known for its specific reactivity, to the chain ends of polymers. Utilizing poly(quinoline-2,3-diylmethylene)s (PQMs) that form π-stacked helical structures via living polymerization initiated by a palladium complex, a novel approach was employed, where a cysteine derivative was added after converting the terminal palladium complex into an acyl palladium complex using carbon monoxide. The sulfhydryl group of cysteine formed a thioester bond, subsequently undergoing an S→N acyl shift to bond the cysteine derivative at the chain end of PQM through an amide bond while preserving the reactivity of the sulfhydryl group. This functionalization facilitated the easy introduction of various substituents at the end of the PQMs, enhancing their functional versatility. We finally focused on monolayer formation by specifically binding SH groups to Au. A cysteine derivative was introduced at the chain end of a π-stacked helical PQM that formed a monolayer film on a Au substrate. Remarkably, atomic force microscopy and scanning tunneling microscopy confirmed the formation of a uniform film containing densely packed π-stacked helical polymers on the Au substrate.
期刊介绍:
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.