Enhanced Chemical Synthesis at Soft Interfaces: A Universal Reaction-Adsorption Mechanism in Microcompartments
Enhanced Chemical Synthesis at Soft Interfaces: A Universal Reaction-Adsorption Mechanism in Microcompartments
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DOI：
10.1103/physrevlett.112.028301
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发表时间：
2014-01-13
影响因子：
8.6
通讯作者：
Griffiths, Andrew D.
中科院分区：
文献类型：
--
作者：
Fallah-Araghi, Ali;Meguellati, Kamel;Griffiths, Andrew D.
在微米直径的乳液液滴中进行双分子合成反应（亚胺合成）。表观平衡常数（K-eq）和表观前向速率常数（k（1））均与液滴半径成反比。结果解释了一个非催化反应吸附模型，其中反应物吸附到液滴界面的结合能相对较低的几个k（B）T，反应和扩散回散装。因此，反应热力学通过在介观尺度上的区室化而被修改，而不受分子尺度的限制，从而导致改善不利反应的通用机制。
A bimolecular synthetic reaction (imine synthesis) was performed compartmentalized in micrometer-diameter emulsion droplets. The apparent equilibrium constant (K-eq) and apparent forward rate constant (k(1)) were both inversely proportional to the droplet radius. The results are explained by a noncatalytic reaction-adsorption model in which reactants adsorb to the droplet interface with relatively low binding energies of a few k(B)T, react and diffuse back to the bulk. Reaction thermodynamics is therefore modified by compartmentalization at the mesoscale-without confinement on the molecular scale-leading to a universal mechanism for improving unfavorable reactions.