极化XANES监视器 摄影激发维生素B12的结构演变
Nicholas A Miller1, Aniruddha Deb1,2, Roberto Alonso-Mori3
1Department of Chemistry, University of Michigan , 930 N University Avenue, Ann Arbor, Michigan 48109-1055, United States.
Journal of the American Chemical Society
|January 31, 2017
概括
超快速的X射线吸收光谱显示了维生素B12的光化学成分. 沿着轴键发生快速的结构变化,其次是科林环放松,提供了对可巴胺活性的见解.
科学领域:
- 摄影化学
- 生物物理化学
- 光谱学
背景情况:
- 包括维生素B12 (?? 科巴胺,CNCbl) 在内的可巴胺是重要的生物辅助因子.
- 它们在甲基转移,基因重组和光激活基因调节中起作用.
- 科巴胺具有作为光激活治疗剂的潜力.
研究的目的:
- 使用超快速,偏振选择性X射线吸收近边缘结构 (XANES) 来描述溶液中的维生素B12 (?? 科巴胺) 的光化学反应.
- 揭示CNCbl在激发电子状态中的序列结构演变.
- 使用 femtosecond极化XANES将计算的潜在能量表面与光学瞬态吸收光谱联系起来.
主要方法:
- 极速,偏振选择性时间解析的X射线吸收近边缘结构 (XANES).
- 紫外线可见光谱
- 使用Femtosecond XANES进行结构动态分析.
主要成果:
- CNCbl的光激发导致主要在轴向上的结构变化.
- 轴 Co-CN 和 Co-NIm 键的延长发生在 110 fs 的时间尺度上.
- 在260 fs的时间尺度下,科林环放松.
结论:
- 五秒极化XANES为理解可巴胺光化学提供了关键的结构动态信息.
- 极化选择性可以识别同位素样本中的电子贡献和结构变化.
- 观察到的动态揭示了潜在能量表面的特征,这些特征决定了胺的反应性和失活性.
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