Institute of Supramolecular Science and Engineering (ISIS UMR 7006), University of Strasbourg, National Center for Scientific Research (CNRS), F-67000, Strasbourg, France.
Nat Ecol Evol. 2017 Nov;1(11):1716-1721. doi: 10.1038/s41559-017-0311-7. Epub 2017 Oct 2.
The reverse tricarboxylic acid (rTCA) cycle (also known as the reverse Krebs cycle) is a central anabolic biochemical pathway whose origins are proposed to trace back to geochemistry, long before the advent of enzymes, RNA or cells, and whose imprint remains intimately embedded in the structure of core metabolism. If it existed, a primordial version of the rTCA cycle would necessarily have been catalysed by naturally occurring minerals at the earliest stage of the transition from geochemistry to biochemistry. Here, we report non-enzymatic promotion of multiple reactions of the rTCA cycle in consecutive sequence, whereby 6 of its 11 reactions were promoted by Zn, Cr and Fe in an acidic aqueous solution. Two distinct three-reaction sequences were achieved under a common set of conditions. Selectivity was observed for reduction reactions producing rTCA cycle intermediates compared with those leading off-cycle. Reductive amination of ketoacids to furnish amino acids was observed under similar conditions. The emerging reaction network supports the feasibility of primitive anabolism in an acidic, metal-rich reducing environment.
逆行三羧酸(rTCA)循环(也称为逆行克雷布斯循环)是一种重要的合成代谢生化途径,其起源可追溯到地球化学,远在酶、RNA 或细胞出现之前,其痕迹仍然深深地嵌入核心代谢的结构中。如果存在,rTCA 循环的原始版本必然是在地球化学向生物化学转变的最早阶段由天然存在的矿物质催化的。在这里,我们报告了在酸性水溶液中,Zn、Cr 和 Fe 连续顺序促进 rTCA 循环的多个反应,其中 6 个反应得到了促进。在一组共同的条件下实现了两个不同的三反应序列。与导致脱环的反应相比,观察到产生 rTCA 循环中间体的还原反应具有选择性。在类似的条件下,观察到酮酸的还原胺化以提供氨基酸。新兴的反应网络支持在酸性、富含金属的还原环境中进行原始合成代谢的可行性。