乙醇自由基代谢机理的理论研究*1 |
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引用本文: | 周崇松,李溪,李慧,李素平,肖宇,邓斌. 乙醇自由基代谢机理的理论研究*1[J]. 宝鸡文理学院学报(自然科学版), 2015, 0(4): 40-48. DOI: 10.13467/j.cnki.jbuns.2015.04.008 |
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作者姓名: | 周崇松 李溪 李慧 李素平 肖宇 邓斌 |
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作者单位: | 湘南学院 化学生物与环境工程学院,湖南 郴州,423000 |
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基金项目: | 湖南省教育厅科学研究项目,湖南省大学生研究性学习及创新性实验项目 |
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摘 要: | 目的:从原子尺度对乙醇与自由基的反应进行探索,提高对乙醇自由基代谢机理的微观认识。方法在 CCSD(T)/6-311G(2d,2p)//B3LYP/6-31G(d,p)计算水平下,采用量子化学方法详细研究了 C2 H5 OH 与·OH、H2 O2和·O2 H 的反应。结果(1)乙醇与·OH 和·O2 H 自由基的反应都存在3类反应(氢抽提、C—C 键断裂和 SN 2取代)。(2)在乙醇与 H2 O2的反应中,以 H 2 O2形成的水合氧自由基(·OOH2)直接插入乙醇的 C—H 键生成乙二醇为主,此外 H2 O2也可均裂为2个·OH 和异裂为· H+·O2 H 自由基。结论乙醇与自由基(·OH、·O2 H)和 H2 O2反应中,分别以α氢抽提过程和· OOH2插入乙醇的α-C—H 键生成乙二醇为主要反应。
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关 键 词: | 乙醇 反应机理 自由基 计算化学 |
Theoretical research into the mechanism of free radical metabolism for ethanol |
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Abstract: | Objective—To improve the microcosmic cognition of the mechanism of free radical me-tabolism for ethanol by making investigations into the reaction between ethanol and radicals on atomic scale.Methods—With the CCSD(T)/6-311G(2d,2p)//B3LYP/6-31G(d,p)level of theory,the re-actions between ethanol and radicals like H2 O2 ,·OH and ·O2 H have been explored in details.Re-sults—(1)There are three reaction channels between ethanol and ·OH or ·O2 H (hydrogen abstrac-tion,C—C bond cleavage and SN 2 substitution).(2)Between H2 O2 and ethanol,H 2 O2 can form the hydrated oxygen radicals (·OOH2 ),which can directly insert into the C—H bond of ethanol.Moreo-ver,the H2 O2 molecule produces two ·OH radicals by homolysis or ·H + ·O2 H radicals by heterol-ysis.Conclusion—Theα-H abstraction reaction is the main channel between ethanol and ·OH or ·O2 H,while,the production of ethylene glycol through the formation of ·OOH 2 and its insertion intoα-C—H bond of ethanol is the main path for the reaction of ethanol with H2 O2 . |
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Keywords: | ethanol reaction mechanism radicals computational chemistry |
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