Two Synthetic Replicators Compete To Process a Dynamic Reagent Pool
Two Synthetic Replicators Compete To Process a Dynamic Reagent Pool
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DOI：
10.1021/jacs.8b12077
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发表时间：
2019-02-20
影响因子：
15
通讯作者：
Philp, Douglas
中科院分区：
文献类型：
--
作者：
Kosikova, Tamara;Philp, Douglas
互补的结构单元，包括一组的四个芳香醛和一组的四个亲核试剂-三个苯胺和一个羟胺-通过缩合反应结合，以提供一个动态共价库（DCL）组成的8个起始材料和16个缩合产物。醛之一，因此，所有的DCL成员衍生自该化合物带有一个氨基吡啶识别位点。暴露的DCL的两个马来酰亚胺，M-P和M-M，每个配备有一个羧酸识别位点，结果在形成一系列的产品，通过不可逆的1，3-偶极环加成反应与DCL中存在的四个硝酮。然而，只有两个环加合物在产品池中，纳入两个识别位点，T-P和T-m，是自我复制，可以利用DCL作为原料，为自己的形成，促进自己的合成通过自催化和交叉催化途径。通过一系列定量F-19{H-1} NMR光谱实验证明了这些复制子响应于以预先形成的复制子形式输入的指令而从动态试剂池中存在的组分引导其自身形成的能力。模拟建立了复制子的动力学和热力学参数、初始试剂浓度和DCL的存在或不存在及其对T-P和T-m之间竞争的影响之间的关键关系。因此，我们建立的规则，管理的竞争复制的条件下，他们的形成是紧密耦合到DCL的处理的行为。
Complementary building blocks, comprising a set of four aromatic aldehydes and a set of four nucleophiles-three anilines and one hydroxylamine-combine through condensation reactions to afford a dynamic covalent library (DCL) consisting of the eight starting materials and 16 condensation products. One of the aldehydes and, consequently, all of the DCL members derived from this compound bear an amidopyridine recognition site. Exposure of this DCL to two maleimides, M-P and M-m, each equipped with a carboxylic acid recognition site, results in the formation of a series of products through irreversible 1,3-dipolar cycloaddition reactions with the four nitrones present in the DCL. However, only the two cyclo-adducts in the product pool that incorporate both recognition sites, T-P and T-m, are self-replicators that can harness the DCL as feedstock for their own formation, facilitating their own synthesis via autocatalytic and cross-catalytic pathways. The ability of these replicators to direct their own formation from the components present in the dynamic reagent pool in response to the input of instructions in the form of preformed replicators is demonstrated through a series of quantitative F-19{H-1} NMR spectroscopy experiments. Simulations establish the critical relationships between the kinetic and thermodynamic parameters of the replicators, the initial reagent concentrations, and the presence or absence of the DCL and their influence on the competition between T-P and T-m. Thus, we establish the rules that govern the behavior of the competing replicators under conditions where their formation is coupled tightly to the processing of a DCL.