Conversion of pyridoxal to pyridoxamine with NH3 and H2 on nickel generates a protometabolic nitrogen shuttle under serpentinizing conditions.

Manon Laura Schlikker, Max Brabender, Loraine Schwander, Carolina Garcia Garcia, Maximillian Burmeister, Sabine Metzger, Joseph Moran, William F Martin
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Abstract

Serpentinizing hydrothermal vents are likely sites for the origin of metabolism because they produce H2 as a source of electrons for CO2 reduction while depositing zero-valent iron, cobalt, and nickel as catalysts for organic reactions. Recent work has shown that solid-state nickel can catalyze the H2-dependent reduction of CO2 to various organic acids and their reductive amination with H2 and NH3 to biological amino acids under the conditions of H2-producing hydrothermal vents and that amino acid synthesis from NH3, H2, and 2-oxoacids is facile in the presence of Ni0. Such reactions suggest a metallic origin of metabolism during early biochemical evolution because single metals replace the function of over 130 enzymatic reactions at the core of metabolism in microbes that use the acetyl-CoA pathway of CO2 fixation. Yet solid-state catalysts tether primordial amino synthesis to a mineral surface. Many studies have shown that pyridoxal catalyzes transamination reactions without enzymes. Here we show that pyridoxamine, the NH2-transferring intermediate in pyridoxal-dependent transamination reactions, is generated from pyridoxal by reaction with NH3 (as little as 5 mm) and H2 (5 bar) on Ni0 as catalyst at pH 11 and 80 °C within hours. These conditions correspond to those in hydrothermal vents undergoing active serpentinization. The results indicate that at the origin of metabolism, pyridoxamine provided a soluble, organic amino donor for aqueous amino acid synthesis, mediating an evolutionary transition from NH3-dependent amino acid synthesis on inorganic surfaces to pyridoxamine-dependent organic reactions in the aqueous phase.

在蛇纹石化条件下,在镍上用NH3和H2将吡哆醛转化为吡哆胺产生原代谢氮穿梭。
蛇纹岩热液喷口可能是代谢起源的地点,因为它们产生氢气作为二氧化碳还原的电子来源,同时沉积零价铁、钴和镍作为有机反应的催化剂。最近的研究表明,在产生H2的热液喷口条件下,固态镍可以催化CO2依赖H2还原为各种有机酸,并与H2和NH3还原胺化为生物氨基酸,并且在Ni0存在的情况下,NH3、H2和2-氧酸更容易合成氨基酸。这些反应表明在早期生化进化过程中代谢的金属起源,因为在微生物代谢的核心中,使用乙酰辅酶a途径固定二氧化碳,单一金属取代了130多种酶反应的功能。然而,固态催化剂将原始氨基合成束缚在矿物表面。许多研究表明,吡哆醛催化转氨化反应无需酶。本研究表明,吡哆醛在pH 11和80℃条件下,以Ni0为催化剂,与NH3 (5 mm)和H2 (5 bar)在数小时内反应生成吡哆胺(pyridoxamine),这是吡哆醛依赖转氨化反应中的nh2转移中间体。这些条件对应于热液喷口发生活跃蛇纹石化的条件。结果表明,在代谢的起源,吡哆胺为水相氨基酸合成提供了一个可溶性的有机氨基供体,介导了从无机表面上依赖nh3的氨基酸合成到水相中依赖吡哆胺的有机反应的进化转变。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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