Reactions of CH _3SH and CH _3SSCH _3 with gas-phase hydrated radical anions (H _2O) _n ?-, CO _2 ?-(H _2O) _n, and O _2 ?-(H _2O) _n

H?ckendorf R.F.; Hao Q.; Sun Z.; Fox-Beyer B.S.; Cao Y.; Balaj O.P.; Bondybey V.E.; Siu C.-K.; Beyer M.K.

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Reactions of CH _3SH and CH _3SSCH _3 with gas-phase hydrated radical anions (H _2O) _n ?-, CO _2 ?-(H _2O) _n, and O _2 ?-(H _2O) _n

机译：CH _3SH和CH _3SSCH _3与气相水合自由基阴离子（H _2O）_nα-，CO _2α-（H _2O）_n和O _2α-（H _2O）_n的反应

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The chemistry of (H _2O) _n ?-, CO _2 ?-(H _2O) _n, and O _2 ?-(H _2O) _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 _3SSCH _3 and activation of the thiol group of CH _3SH. No reactions were observed with CH _3SCH _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 _2O) _n ?- with CH _3SH as well as CO _2 ?-(H _2O) _n with CH _3SSCH _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.

机译：通过傅立叶变换离子回旋共振质量研究了含小分子含硫分子的（H _2O）_nα-，CO _2α-（H _2O）_n和O _2α-（H _2O）_n的化学性质光谱法。在水合电子和水合二氧化碳自由基阴离子的作用下，观察到了两个与生物辐射损伤有关的反应：CH _3SSCH _3的二硫键断裂和CH _3SH的硫醇基活化。 CH _3SCH _3未观察到反应。通常被视为氧化应激的主要来源的水合超氧化物自由基阴离子不会与任何化合物发生反应。纳米量热法和量子化学计算给出了反应机理的一致描述。结果表明，e-和CO _2α-向O _2α-的转化使高反应性物质失活，并可能实际上降低了氧化应激。对于（H _2O）_nα-与CH _3SH以及CO _2α-（H _2O）_n与CH _3SSCH _3的反应，气相中的反应产物与脉冲辐射分解研究中文献报道的反应产物不同。通过减少气相簇反应中的笼效应，可以使该观察合理化。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2012年第15期|共12页
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H?ckendorf R.F.; Hao Q.; Sun Z.; Fox-Beyer B.S.; Cao Y.; Balaj O.P.; Bondybey V.E.; Siu C.-K.; Beyer M.K.;
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机译：CH _3SH和CH _3SSCH _3与气相水合自由基阴离子（H _2O）_nα-，CO _2α-（H _2O）_n和O _2α-（H _2O）_n的反应
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Reactions of CH _3SH and CH _3SSCH _3 with gas-phase hydrated radical anions (H _2O) _n ?-, CO _2 ?-(H _2O) _n, and O _2 ?-(H _2O) _n

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