{"title":"DIBMA模型化合物的分子内氢键","authors":"Cornelis A. van Walree","doi":"10.1002/mats.202200042","DOIUrl":null,"url":null,"abstract":"<p>The structure of model compounds for the amphiphilic copolymer poly(diisobutylene-<i>alt</i>-maleic acid), DIBMA, is investigated with (gas phase) B3LYP/6-31G** and PM7 calculations. It is found that in the monoprotonated state of the repeating unit strong (about 70 kJ mol<sup>−1</sup>) ionic hydrogen bonds are formed within the hydrogen succinate rings, which impart partial structural rigidity on the backbone of the copolymer. Based on literature p<i>K</i><sub>a</sub> values of the first and second deprotonation step of the succinic acid units, it is argued that the ionic hydrogen bonds are likely to be present in aqueous solution as well. The main chain conformation depends strongly on the stereochemical configuration of the carbon atoms in the hydrogen succinate rings. The possible consequences of the hydrogen bonding for the mechanism of membrane solubilization by maleic acid-based amphiphilic copolymers are discussed.</p>","PeriodicalId":18157,"journal":{"name":"Macromolecular Theory and Simulations","volume":"32 1","pages":""},"PeriodicalIF":1.8000,"publicationDate":"2022-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mats.202200042","citationCount":"0","resultStr":"{\"title\":\"Intramolecular Hydrogen Bonding in DIBMA Model Compounds\",\"authors\":\"Cornelis A. van Walree\",\"doi\":\"10.1002/mats.202200042\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The structure of model compounds for the amphiphilic copolymer poly(diisobutylene-<i>alt</i>-maleic acid), DIBMA, is investigated with (gas phase) B3LYP/6-31G** and PM7 calculations. It is found that in the monoprotonated state of the repeating unit strong (about 70 kJ mol<sup>−1</sup>) ionic hydrogen bonds are formed within the hydrogen succinate rings, which impart partial structural rigidity on the backbone of the copolymer. Based on literature p<i>K</i><sub>a</sub> values of the first and second deprotonation step of the succinic acid units, it is argued that the ionic hydrogen bonds are likely to be present in aqueous solution as well. The main chain conformation depends strongly on the stereochemical configuration of the carbon atoms in the hydrogen succinate rings. The possible consequences of the hydrogen bonding for the mechanism of membrane solubilization by maleic acid-based amphiphilic copolymers are discussed.</p>\",\"PeriodicalId\":18157,\"journal\":{\"name\":\"Macromolecular Theory and Simulations\",\"volume\":\"32 1\",\"pages\":\"\"},\"PeriodicalIF\":1.8000,\"publicationDate\":\"2022-08-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/mats.202200042\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Macromolecular Theory and Simulations\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/mats.202200042\",\"RegionNum\":4,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecular Theory and Simulations","FirstCategoryId":"5","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/mats.202200042","RegionNum":4,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Intramolecular Hydrogen Bonding in DIBMA Model Compounds
The structure of model compounds for the amphiphilic copolymer poly(diisobutylene-alt-maleic acid), DIBMA, is investigated with (gas phase) B3LYP/6-31G** and PM7 calculations. It is found that in the monoprotonated state of the repeating unit strong (about 70 kJ mol−1) ionic hydrogen bonds are formed within the hydrogen succinate rings, which impart partial structural rigidity on the backbone of the copolymer. Based on literature pKa values of the first and second deprotonation step of the succinic acid units, it is argued that the ionic hydrogen bonds are likely to be present in aqueous solution as well. The main chain conformation depends strongly on the stereochemical configuration of the carbon atoms in the hydrogen succinate rings. The possible consequences of the hydrogen bonding for the mechanism of membrane solubilization by maleic acid-based amphiphilic copolymers are discussed.
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Macromolecular Theory and Simulations is the only high-quality polymer science journal dedicated exclusively to theory and simulations, covering all aspects from macromolecular theory to advanced computer simulation techniques.
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