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A kinetic description of how interfaces accelerate reactions in micro-compartments.


ABSTRACT: 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.

SUBMITTER: Wilson KR 

PROVIDER: S-EPMC8163377 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature

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A kinetic description of how interfaces accelerate reactions in micro-compartments.

Wilson Kevin R KR   Prophet Alexander M AM   Rovelli Grazia G   Willis Megan D MD   Rapf Rebecca J RJ   Jacobs Michael I MI  

Chemical science 20200727 32


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  ...[more]

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