Numerous reactions within metabolic pathways have been reported to occur nonenzymatically, supporting the hypothesis that life arose upon a primitive nonenzymatic precursor to metabolism. However, most of those studies reproduce individual transformations or segments of pathways without providing a common set of conditions for classes of reactions that span multiple pathways. In this study, we search across pathways for common nonenzymatic conditions for a recurring chemical transformation in metabolism: alkene hydration. The mild conditions that we identify (Fe oxides such as green rust) apply to all hydration reactions of the rTCA cycle and gluconeogenesis, including the hydration of phosphoenolpyruvate (PEP) to 2‐phosphoglycerate (2PGA), which had not previously been reported under nonenzymatic conditions. Mechanistic insights were obtained by studying analogous substrates and through anoxic and radical trapping experiments. Searching for nonenzymatic conditions across pathways provides a complementary strategy to triangulate conditions conducive to the nonenzymatic emergence of a protometabolism.

中文翻译：

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磷酸烯醇式丙酮酸的非酶水合：通过跨途径搜索原生代谢水合的一般条件


据报道，代谢途径中的许多反应都是以非酶方式发生的，这支持了生命产生于新陈代谢的原始非酶前体的假设。然而，这些研究中的大多数都再现了单个转化或通路片段，而没有为跨越多个通路的反应类别提供一组通用的条件。在这项研究中，我们搜索了新陈代谢中反复发生化学转化的常见非酶条件：烯烃水合。我们确定的温和条件（铁氧化物，如绿锈病）适用于 rTCA 循环和糖异生的所有水合反应，包括磷酸烯醇式丙酮酸 （PEP） 水合为 2-磷酸甘油酸酯 （2PGA），这在以前在非酶条件下没有报道过。通过研究类似底物以及通过缺氧和自由基捕获实验获得机理见解。跨途径寻找非酶条件提供了一种补充策略，以三角测量有利于原生代谢的非酶出现的条件。