In the far from equilibrium state of living matter, energy is consumed to fuel the metabolic networks of enzymatic reactions. The emergence of protometabolic pathways in primeval earth is intricately related to the evolutionary journey of modern enzymes. Fundamental understanding of such energy driven generation of early catalytic systems would help us recognize the conditions required for the minimal metabolism that predated the chemical emergence of life. Herein, we report substrate driven generation of a non-equilibrium catalytic machinery from a single amino acid functionalized fatty acid in presence of a cofactor hemin. The non-equilibrium assembled state showed acceleration of catalytic potential resulting in degradation of the substrate and subsequently led to disassembly. Controls that promoted equilibration could not access the three-dimensional microphases and showed substantially lower catalytic activity. Significantly, the assembled state showed latent catalytic function by hydrolysing a precursor to yield the same substrate. Consequently, the assembly was benefitted with augmented lifetime of the catalytic state exploiting a promiscuous cascade and thus foreshadowing protometabolism. The results contribute towards our understanding of energy driven generation of primitive catalytic machineries that assisted the minimal metabolism of early life.

中文翻译：

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非平衡条件下混杂过氧化物酶的出现

在远非平衡的生物状态下，能量被消耗以促进酶促反应的代谢网络。原始地球中新陈代谢途径的出现与现代酶的进化过程息息相关。对此类能量驱动的早期催化系统生成的基本理解将有助于我们认识到生命化学出现之前进行的最小限度新陈代谢所需的条件。在本文中，我们报道了在辅因子血红素存在下，由单一氨基酸官能化脂肪酸驱动的非平衡催化机制的底物驱动生成。非平衡组装状态显示出催化电位的加速，导致底物降解并随后导致分解。促进平衡的控件无法访问三维微相，并显示大大降低的催化活性。明显地，通过水解前体以产生相同的底物，组装状态显示出潜在的催化功能。因此，利用混杂的级联并由此预示了新陈代谢，延长了催化态的寿命，使该组装受益。这些结果有助于我们理解原始催化机械的能量驱动产生，这些机械有助于早期生命的最小程度的新陈代谢。该组件受益于利用混杂级联反应延长催化状态的寿命，从而预示了新陈代谢。这些结果有助于我们理解原始催化机械的能量驱动产生，这些机械有助于早期生命的最小程度的新陈代谢。该组件受益于利用混杂级联反应延长催化状态的寿命，从而预示了新陈代谢。这些结果有助于我们理解原始催化机械的能量驱动产生，这些机械有助于早期生命的最小程度的新陈代谢。