Reactions of CH3SH and CH3SSCH3 with Gas-Phase Hydrated Radical Anions (H2O)n鈥⑩€?/sup>, CO2鈥⑩€?/sup>(H2
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- 作者：Robert F. H枚ckendorf ; Qiang Hao ; Zheng Sun ; Brigitte S. Fox-Beyer ; Yali Cao ; O. Petru Balaj ; Vladimir E. Bondybey ; Chi-Kit Siu ; Martin K. Beyer
- 刊名：The Journal of Physical Chemistry A
- 出版年：2012
- 出版时间：April 19, 2012
- 年：2012
- 卷：116
- 期：15
- 页码：3824-3835
- 全文大小：686K
- 年卷期：v.116,no.15(April 19, 2012)
- ISSN：1520-5215
文摘
The chemistry of (H2O)n鈥⑩€?/sup>, CO2鈥⑩€?/sup>(H2O)n, and O2鈥⑩€?/sup>(H2O)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 CH3SSCH3 and activation of the thiol group of CH3SH. No reactions were observed with CH3SCH3. 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鈥?/sup> and CO2鈥⑩€?/sup> to O2鈥⑩€?/sup> deactivates highly reactive species and may actually reduce oxidative stress. For reactions of (H2O)n鈥⑩€?/sup> with CH3SH as well as CO2鈥⑩€?/sup>(H2O)n with CH3SSCH3, 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.
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