中的二氧化-基对
Zhuang Wu1, Changyun Chen1, Jie Liu1
1College of Chemistry, Chemical Engineering and Materials Science , Soochow University , Suzhou 215123 , China.
Journal of the American Chemical Society
|February 14, 2019
概括
研究人员从S-Nitrosothiols (RSNO) 分解中发现了难以捉摸的结基对. 红光照射将RSNO从这些基因对中重塑,揭示了氧化释放机制的洞察力.
科学领域:
- 化学物理
- 摄影化学
- 生物物理化学
背景情况:
- S-Nitrosothiols (RSNO) 是重要的生物分子,可以作为氧化 (NO) 的来源.
- 在RSNO中,S-N键的容易同解裂使得NO释放容易.
- 了解RSNO分解中的中间物种对于阐明NO信号通路至关重要.
研究的目的:
- 在低温下研究S-Nitrosothiols (RSNO) 的光分解.
- 识别和描述RSNO光解过程中形成的难以捉摸的子基对.
- 探索这些基因对的可逆形成和解离.
主要方法:
- 使用Ne,Ar和N2矩阵在冷温度下进行矩阵隔离光谱 (IR和UV/vis).
- 用紫外线和可见光对原型RSNO (R=Me和Et) 的光解.
- 计算化学计算 (CASPT2) 来确定解离能.
主要成果:
- 通过O·S和H·N相互作用稳定了含有氧化物 (NO•) 和基 (RS•) 的结基对的识别.
- 在红光照射下观察中的激素对的消失.
- 在红光照射时,从子中的基因对进行原始RSNO的改造.
- 在 4.7 kcal mol-1 时计算出甲基对 (MeS····ON) 的解离能量.
结论:
- 该研究成功地在RSNO光解中确定了短暂的结基对.
- 红光照射提供了从基数对中改造RSNO的途径,这表明光化学过程是可逆的.
- 这些发现为S-Nitrosothiols释放氧化的机制提供了关键的见解.
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