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重新检查HO的情况
Dinh Hieu Truong1,2, Thi Huong Lan Nguyen3, Duy Quang Dao1,2
1Institute of Research and Development, Duy Tan University, Da Nang 550000, Vietnam.
Royal Society open science
|June 9, 2023
概括
由基 (HO●) 氧化L-proline (Pro) 的氧化主要发生在β-和gamma-carbon. 铁和铜等过渡金属离子可以增强Pro氧化,特别是在低氧化状态下.
科学领域:
- 计算化学计算化学
- 生物化学 生物化学
- 环境化学环境化学
背景情况:
- L- (Pro) 是一种易受氧化作用的氨基酸.
- 基基 (HO●) 是一个关键的活性氧物种,参与氧化过程.
- 过渡金属离子 (Fe,Cu) 可以影响激进反应和生物氧化.
研究的目的:
- 为了研究L-proline由基基的氧化机制.
- 探索过渡金属离子 (Fe,Cu) 对L-proline氧化的影响.
- 为了确定L-proline与金属离子的反应性和复杂化行为.
主要方法:
- 密度函数理论 (DFT) 在M05-2X/6-311++G(3df,3pd)//M05-2X/6-311++G(d,p) 层面的计算.
- 分析原子转移 (HAT) 路径和反应速率常数.
- 用Fe和Cu离子对L-氨酸复合的建模.
主要成果:
- Pro的HO●启动氧化主要发生在β和碳中 (44.6%和39.5%的分支比).
- 通过HO●氧化Pro的总速率常数为6.04 × 10^8 M^-1 s^-1.
- 通过碳酸盐组,Pro与Fe和Cu离子形成稳定的复合体.
- 低氧化状态的金属复合物 (Fe(II) -Pro,Cu(I) -Pro) 显著增加了Pro的氧化风险.
结论:
- 这项研究阐明了由基基氧化L-proline氧化的主要部位和动力学.
- 与过渡金属的复合,特别是在低氧化状态下,增加了L-proline对氧化的易感性.
- 这些发现与理解氧化应激机制和金属催化降解过程有关.
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