{"title":"过氧基和c中心自由基与巯基的反应机理","authors":"Michael G. Simic, Edward P.L. Hunter","doi":"10.1016/S0748-5514(86)80074-5","DOIUrl":null,"url":null,"abstract":"<div><p>Rate constants for reactions of a peroxyl (CCl<sub>3</sub>OO·) and C-centered radicals, that is, phenyl (·C<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>COO<sup>−</sup>) and vinyl (uracil-5-yl), with an aromatic thiol (p-CH<sub>3</sub>OC<sub>6</sub>H<sub>4</sub>SH) were measured over a pH range (3–12) to include ArSH and ArS<sup>−</sup> forms. The pH dependence of these rate constants indicates that peroxyl radicals react by a redox mechanism while the C-centered radicals react by an H-atom transfer process. The different mechanisms encountered in the repair of various radicals suggest design features to be incorporated into antiagents, such as radioprotectors and anticarcinogens.</p></div>","PeriodicalId":77737,"journal":{"name":"Journal of free radicals in biology & medicine","volume":"2 3","pages":"Pages 227-230"},"PeriodicalIF":0.0000,"publicationDate":"1986-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/S0748-5514(86)80074-5","citationCount":"22","resultStr":"{\"title\":\"Reaction mechanisms of peroxyl and c-centered radicals with sulfhydryls\",\"authors\":\"Michael G. Simic, Edward P.L. Hunter\",\"doi\":\"10.1016/S0748-5514(86)80074-5\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Rate constants for reactions of a peroxyl (CCl<sub>3</sub>OO·) and C-centered radicals, that is, phenyl (·C<sub>6</sub>H<sub>4</sub>CH<sub>2</sub>COO<sup>−</sup>) and vinyl (uracil-5-yl), with an aromatic thiol (p-CH<sub>3</sub>OC<sub>6</sub>H<sub>4</sub>SH) were measured over a pH range (3–12) to include ArSH and ArS<sup>−</sup> forms. The pH dependence of these rate constants indicates that peroxyl radicals react by a redox mechanism while the C-centered radicals react by an H-atom transfer process. The different mechanisms encountered in the repair of various radicals suggest design features to be incorporated into antiagents, such as radioprotectors and anticarcinogens.</p></div>\",\"PeriodicalId\":77737,\"journal\":{\"name\":\"Journal of free radicals in biology & medicine\",\"volume\":\"2 3\",\"pages\":\"Pages 227-230\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"1986-01-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1016/S0748-5514(86)80074-5\",\"citationCount\":\"22\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of free radicals in biology & medicine\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0748551486800745\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of free radicals in biology & medicine","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0748551486800745","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Reaction mechanisms of peroxyl and c-centered radicals with sulfhydryls
Rate constants for reactions of a peroxyl (CCl3OO·) and C-centered radicals, that is, phenyl (·C6H4CH2COO−) and vinyl (uracil-5-yl), with an aromatic thiol (p-CH3OC6H4SH) were measured over a pH range (3–12) to include ArSH and ArS− forms. The pH dependence of these rate constants indicates that peroxyl radicals react by a redox mechanism while the C-centered radicals react by an H-atom transfer process. The different mechanisms encountered in the repair of various radicals suggest design features to be incorporated into antiagents, such as radioprotectors and anticarcinogens.
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