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Light-driven Enzymatic Decarboxylation
Published on: May 22, 2016
一个高效的质子合电子转移过程,在氧化ferulic 酸的胡卜过氧化酶:即将到来完整的循环
1Department of Organic Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Hebrew University of Jerusalem, Givat Ram Campus, 91904 Jerusalem, Israel.
Journal of the American Chemical Society
|October 19, 2006
概括
量子力学/分子力学计算揭示了的过氧化酶.
科学领域:
- 生物化学和计算化学.
- 酶动力学和反应机制
背景情况:
- 卜过氧化酶 (HRP) 是各种生物过程中的关键酶.
- 了解HRP的活性物种化合物I和化合物II的氧化机制对于酶功能至关重要.
- 费鲁酸作为HRP的原生基质.
研究的目的:
- 用计算方法阐明ferulic acid由HRP的化合物I和化合物II的氧化机制.
- 研究特定的氨基酸残留物和水分子在酶的催化循环中的作用.
- 解释化合物I和化合物II对酸的类似反应性.
主要方法:
- 使用量子力学/分子力学 (QM/MM) 的计算.
- 该研究模拟了HRP活性物种对铁酸的氧化过程.
- 酶返回其静止状态也被模拟.
主要成果:
- 氧化是由一个质子合电子转移 (PCET) 步骤启动的.
- 一个水分子 (W402) 作为基质和His42残留物之间的质子继电器.
- 化合物I和II的相似反应性归因于化合物II的一个反应性Por () * () + () Fe (III) OH同位素.
结论:
- 他的42和W402对于HRP的基质氧化功能至关重要.
- PCET机制提供了对HRP的催化循环的详细了解.
- 这些发现表明,有可能利用磁场等外部场来操纵HRP活动.
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