(S) - 谷氨酸和 (2S,3S) - 3 - 甲基酸盐的相互转化:一种独特的B(12) - 取决于碳骨重新排列的碳骨
S D Wetmore1, D M Smith, B T Golding
1Contribution from the Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.
Journal of the American Chemical Society
|August 17, 2001
概括
这项研究使用先进的计算方法来探索维生素B12依赖的谷氨酸突变酶是如何促进 (S) 谷氨酸转化为3-甲基亚斯巴酸的. 研究结果表明,激素生成和质子转移是这种酶反应的关键步骤.
科学领域:
- 生物化学 生物化学
- 计算化学的计算化学
- 酶学 是一种酶学.
背景情况:
- 酶谷氨酸突变酶依赖于维生素B,它催化了 (S) - 谷氨酸和 (2S,3S) - 3 - 甲基酸的相互转化.
- 了解这种反应的机制对于阐明基于基因的酶变化至关重要.
研究的目的:
- 通过高水平的ab initio分子轨道计算,研究B(12) 依赖的谷氨酸酸突变酶的反应机制.
- 探索辅酶-B的作用在基质激活,产品形成和基因生成中.
- 为关于碎片-重组路径的实验发现提供计算支持.
主要方法:
- 使用了高水平的初始分子轨道计算.
- 计算了电子磁共振 (EPR) 参数,以支持激素的参与.
- 使用包括氨基和碳酸替代物的计算模型来计算重排障碍.
主要成果:
- 计算的电子磁共振参数与基质衍生激素的实验证据一致.
- 计算的重新排列屏障高度支持反应的碎片-重组路径.
- 计算结果表明,酶通过影响迁移群的质子状态的质子转移过程来促进重排.
结论:
- 同酶-B(12) 可能在基质激活和产物形成中发挥作用,通过激素生成.
- (S) 谷氨酸和3-甲基酸的相互转化通过碎片-重组路径进行.
- 酶催化可能涉及质子转移机制来控制关键分子组的质子化状态.
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