A kinetic description of how interfaces accelerate reactions in micro-compartments.
A kinetic description of how interfaces accelerate reactions in micro-compartments.
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DOI：
10.1039/d0sc03189e
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发表时间：
2020-07-27
期刊：
影响因子：
8.4
通讯作者：
Jacobs MI
中科院分区：
文献类型：
--
作者：
Wilson KR;Prophet AM;Rovelli G;Willis MD;Rapf RJ;Jacobs MI
推导出动力学表达式来解释界面如何改变整体化学平衡并加速微室中的反应。该描述在随机模型的开发的帮助下，定量预测了先前在微米级乳液中加速亚胺合成的实验观察结果。该表达式解释了反应物浓度和隔室尺寸如何共同导致微约束下反应速率加快。这些速率不仅仅取决于浓度，还取决于界面处隔室中总分子的分数。尽管典型的微室中有约 107 至 1013 个溶质分子，但当室大小和试剂浓度产生几乎相等数量的本体分子和界面分子时，就会出现一种“随机性”。尽管这与纳米限制产生的随机性不同，但这些结果表明界面如何控制更大的大气、地质和生物区室中的化学转变。表面在加速微室反应速率方面发挥着关键作用。
A kinetic expression is derived to explain how interfaces alter bulk chemical equilibria and accelerate reactions in micro-compartments. This description, aided by the development of a stochastic model, quantitatively predicts previous experimental observations of accelerated imine synthesis in micron-sized emulsions. The expression accounts for how reactant concentration and compartment size together lead to accelerated reaction rates under micro-confinement. These rates do not depend solely on concentration, but rather the fraction of total molecules in the compartment that are at the interface. Although there are ∼107 to 1013 solute molecules in a typical micro-compartment, a kind of “stochasticity” appears when compartment size and reagent concentration yield nearly equal numbers of bulk and interfacial molecules. Although this is distinct from the stochasticity produced by nano-confinement, these results show how interfaces can govern chemical transformations in larger atmospheric, geologic and biological compartments. Surfaces play a critical role in accelerating reaction rates in micro-compartments.