Reactions of CH3SH and CH3SSCH3 with gas-phase hydrated radical anions (H2O)n(•-), CO2(•-)(H2O)n, and O2(•-)(H2O)n.
Reactions of CH3SH and CH3SSCH3 with gas-phase hydrated radical anions (H2O)n(•-), CO2(•-)(H2O)n, and O2(•-)(H2O)n.
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CH3SH 和 CH3SSCH3 与气相水合自由基阴离子 (H2O)n(•-)、CO2(•-)(H2O)n 和 O2(•-)(H2O)n 的反应。
DOI：
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发表时间：
2012
影响因子：
2.9
通讯作者：
M. Beyer
中科院分区：
文献类型：
--
作者：
Robert F. Höckendorf;Q. Hao;Zheng Sun;Brigitte S. Fox;Yali Cao;O. Balaj;V. Bondybey;C. Siu;M. Beyer
本文用傅里叶变换离子回旋共振质谱法研究了（H（2）O）（n）（·-）、CO（2）（·-）（H（2）O）（n）和O（2）（·-）（H（2）O）（n）与含硫小分子的化学反应。利用水合电子和水合二氧化碳自由基阴离子，观察到与生物辐射损伤相关的两个反应，CH（3）SSCH（3）的二硫键断裂和CH（3）SH的巯基活化。未观察到与CH（3）SCH（3）的反应。水合超氧自由基阴离子，通常被视为氧化应激的主要来源，不与任何化合物反应。纳米量热法和量子化学计算给出了一个一致的反应机理的图片。结果表明，e（-）和CO（2）（·-）转化为O（2）（·-）使高活性物种失活，实际上可能降低氧化应激。对于（H（2）O）（n）（·-）与CH（3）SH以及CO（2）（·-）（H（2）O）（n）与CH（3）SSCH（3）的反应，气相中的反应产物与文献报道的脉冲辐解研究结果不同。这一观察是合理的减少笼效应的气相团簇反应。
The chemistry of (H(2)O)(n)(•-), CO(2)(•-)(H(2)O)(n), and O(2)(•-)(H(2)O)(n) with small sulfur-containing molecules was studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. With hydrated electrons and hydrated carbon dioxide radical anions, two reactions with relevance for biological radiation damage were observed, cleavage of the disulfide bond of CH(3)SSCH(3) and activation of the thiol group of CH(3)SH. No reactions were observed with CH(3)SCH(3). The hydrated superoxide radical anion, usually viewed as major source of oxidative stress, did not react with any of the compounds. Nanocalorimetry and quantum chemical calculations give a consistent picture of the reaction mechanism. The results indicate that the conversion of e(-) and CO(2)(•-) to O(2)(•-) deactivates highly reactive species and may actually reduce oxidative stress. For reactions of (H(2)O)(n)(•-) with CH(3)SH as well as CO(2)(•-)(H(2)O)(n) with CH(3)SSCH(3), the reaction products in the gas phase are different from those reported in the literature from pulse radiolysis studies. This observation is rationalized with the reduced cage effect in reactions of gas-phase clusters.
影响因子：
5.5
作者：
Wheeler, Steven E.;Houk, K. N.
通讯作者：
Houk, K. N.
DOI：
10.1016/s0021-9258(18)48020-9
发表时间：
1987-07
期刊：
The Journal of biological chemistry
影响因子：
--
作者：
K. Davies;M. Delsignore
通讯作者：
K. Davies;M. Delsignore