在非酶转胺中金属-皮里多克萨尔的合作性
Quentin Dherbassy1, Robert J Mayer1, Kamila B Muchowska1
1Université de Strasbourg, CNRS, ISIS & icFRC, 8 Allée Gaspard Monge, 67000 Strasbourg, France.
Journal of the American Chemical Society
|June 6, 2023
概括
像铁和这样的金属离子在转胺反应中显著增强了辅酶氧 (PL) 的催化活性. 这表明,在酶的进化之前,共酶可能已经起到了催化作用,为早期生命化学提供了洞察力.
科学领域:
- 生命研究的起源
- 生物化学
- 催化剂
背景情况:
- 共酶在超过30%的酶反应中至关重要,并且可能比酶更早.
- 作为有机催化剂的共酶的催化潜力,特别是在前生物化学中,仍然不太清楚.
- 金属离子是已知的代谢反应的催化剂,即使没有酶.
研究的目的:
- 在与生命起源相关的条件下研究金属离子对辅酶催化物的影响.
- 探索丰富的金属离子 (Fe,Al) 与酸盐 (PL) 在转胺反应中的协同作用.
主要方法:
- 在Fe3+和Al3+离子的存在下,研究了由氧化 (PL) 和氧化 (PLP) 催化的转胺反应.
- 在模仿早期地球 (20-75°C,pH5-7.5) 的条件下进行实验.
- 使用实验和理论机制研究来阐明反应途径.
主要成果:
- 与单独的PL或金属离子相比,Fe3+-PL和Al3+-PL复合体显著增强了转胺催化.
- 在较温和的条件下,Al3+-PL的催化速度是单独的PL的1000倍以上.
- 金属对PL的协调改变了反应机制,并减缓了胺中间溶解.
结论:
- 皮里多克萨尔衍生物与金属离子结合,可能在酶进化之前具有显著的催化活性.
- 这一发现为前生物环境中的早期生化反应提供了可信的机制.
- 同酶可能在生命的出现中起到了至关重要的催化作用.
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