The mystery of the origins of life is one of the most difficult yet intriguing challenges to which humanity has grappled. How did biopolymers emerge in the absence of enzymes (evolved biocatalysts), and how did long-lasting chemical evolution find a path to the highly selective complex biology that we observe today? In this paper, we discuss a chemical framework that explores the very roots of catalysis, demonstrating how standard catalytic activity based on chemical and physical principles can evolve into complex machineries. We provide several examples of how prebiotic catalysis by small molecules can be exploited to facilitate polymerization, which in biology has transformed the nature of catalysis. Thus, catalysis evolved, and evolution was catalyzed, during the transformation of prebiotic chemistry to biochemistry. Traditionally, a catalyst is defined as a substance that (i) speeds up a chemical reaction by lowering activation energy through different chemical mechanisms and (ii) is not consumed during the course of the reaction. However, considering prebiotic chemistry, which involved a highly diverse chemical space (i.e., high number of potential reactants and products) and constantly changing environment that lacked highly sophisticated catalytic machinery, we stress here that a more primitive, broader definition should be considered. Here, we consider a catalyst as any chemical species that lowers activation energy. We further discuss various demonstrations of how simple prebiotic molecules such as hydroxy acids and mercaptoacids promote the formation of peptide bonds via energetically favored exchange reactions. Even though the small molecules are partially regenerated and partially retained within the resulting oligomers, these prebiotic catalysts fulfill their primary role. Catalysis by metal ions and in complex chemical mixtures is also highlighted. We underline how chemical evolution is primarily dictated by kinetics rather than thermodynamics and demonstrate a novel concept to support this notion. Moreover, we propose a new perspective on the role of water in prebiotic catalysis. The role of water as simply a “medium” obscures its importance as an active participant in the chemistry of life, specifically as a very efficient catalyst and as a participant in many chemical transformations. Here we highlight the unusual contribution of water to increasing complexification over the course of chemical evolution. We discuss possible pathways by which prebiotic catalysis promoted chemical selection and complexification. Taken together, this Account draws a connection line between prebiotic catalysis and contemporary biocatalysis and demonstrates that the fundamental elements of chemical catalysis are embedded within today’s biocatalysts. This Account illustrates how the evolution of catalysis was intertwined with chemical evolution from the very beginning.

中文翻译：

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从进化的催化到催化的进化


生命起源之谜是人类努力应对的最困难但最有趣的挑战之一。在没有酶的情况下，生物聚合物是如何出现的（进化的生物催化剂），以及持久的化学进化是如何找到通往我们今天观察到的高选择性复杂生物学的道路的？在本文中，我们讨论了一种探索催化根源的化学框架，展示了基于化学和物理原理的标准催化活性如何演变成复杂的机器。我们提供了几个例子，说明如何利用小分子的益生元催化来促进聚合，这在生物学上已经改变了催化的性质。因此，在益生元化学向生物化学的转变过程中，催化进化进化，进化被催化。传统上，催化剂被定义为 （i） 通过不同的化学机制降低活化能来加速化学反应，并且 （ii） 在反应过程中不消耗的物质。然而，考虑到益生元化学涉及高度多样化的化学空间（即大量潜在反应物和产物）和不断变化的环境，缺乏高度复杂的催化机制，我们在这里强调应该考虑一个更原始、更广泛的定义。在这里，我们将催化剂视为任何降低活化能的化学物质。我们进一步讨论了各种演示，说明简单的益生元分子（如羟基酸和巯基酸）如何通过能量有利的交换反应促进肽键的形成。 尽管小分子部分再生并部分保留在所得的低聚物中，但这些益生元催化剂仍发挥着其主要作用。还强调了金属离子和复杂化学混合物中的催化作用。我们强调了化学进化主要由动力学而不是热力学决定，并展示了一个支持这一概念的新概念。此外，我们提出了关于水在益生元催化中的作用的新观点。水作为一种“介质”的作用掩盖了它作为生命化学的积极参与者的重要性，特别是作为一种非常有效的催化剂和许多化学转化的参与者。在这里，我们强调了水在化学进化过程中对增加络合作用的不寻常贡献。我们讨论了益生元催化促进化学选择和复杂化的可能途径。综上所述，该账户在益生元催化和现代生物催化之间划出了一条连接线，并表明化学催化的基本要素已嵌入到当今的生物催化剂中。这篇报道说明了催化的进化是如何从一开始就与化学进化交织在一起的。