We develop a novel strategy to more effectively and controllably process continuous enzymatic or homogeneous catalysis reactions based on nonaqueous Pickering emulsions. A key element of this strategy is “bottom-up” construction of a macroscale continuous flow reaction system through packing catalyst-containing micron-sized ionic liquid (IL) droplet in oil in a column reactor. Due to the continuous influx of reactants into the droplet microreactors and the continuous release of products from the droplet microreactors, catalysis reactions in such a system can take place without limitations arising from establishment of the reaction equilibrium and catalyst separation, inherent in conventional batch reactions. As proof of the concept, enzymatic enantioselective trans-esterification and CuI-catalyzed cycloaddition reactions using this IL droplet-based flow system both exhibit 8 to 25-fold enhancement in catalysis efficiency compared to their batch counterparts, and a durability of at least 4000 h for the enantioselective trans-esterification of 1-phenylethyl alcohol, otherwise unattainable in their batch counterparts. We further establish a theoretical model for such a catalysis system working under nonequilibrium conditions, which not only supports the experimental results but also helps to predict reaction progress at a microscale level. Being operationally simple, efficient, and adaptive, this strategy provides an unprecedented platform for practical applications of enzymes and homogeneous catalysts even at a controllable level.

中文翻译：

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离子液滴微反应器，催化反应不平衡

我们开发了一种新颖的策略，可以更有效地控制基于非水Pickering乳液的连续酶或均相催化反应。该策略的关键要素是通过在塔式反应器中的油中填充含催化剂的微米级离子液体（IL）小滴，从而“自下而上”构建大规模连续流反应系统。由于反应物连续流入液滴微反应器中并且产物从液滴微反应器中连续释放，因此可以在这种系统中进行催化反应而不受常规间歇反应中固有的反应平衡和催化剂分离的建立的限制。作为概念的证明，使用这种基于IL液滴的流动系统进行酶促对映选择性酯交换和CuI催化的环加成反应，与批次反应相比，催化效率均提高了8到25倍，对映选择性酯交换的持久性至少为4000 h 1-苯基乙醇，否则在批量生产中无法达到。我们进一步建立了这种在非平衡条件下工作的催化体系的理论模型，该模型不仅支持实验结果，而且有助于在微观水平上预测反应进程。该策略操作简单，高效且具有适应性，即使在可控制的水平上，也为酶和均相催化剂的实际应用提供了前所未有的平台。