Synthetic catalysts offer an opportunity for more chemical versatility operating over a wider range of conditions but currently do not reach the remarkable performance of natural enzymes. Here we consider some new design strategies based on the contributions of nonlocal electric fields and thermodynamic fluctuations to both improve the catalytic step and turnover for rate acceleration in arbitrary synthetic catalysts through bioinspired studies of natural enzymes. With a focus on the enzyme as a whole catalytic construct, we illustrate how electric field optimization can be used to mitigate or lower reorganization costs for both synthetic enzymes and supramolecular capsules, as well as the remarkable ability of enzymes to utilize thermal fluctuations for activity that has given insight into theoretical approaches to analyzing heterogeneous catalysts.

Catalytic principles from natural enzymes for design of synthetic catalysts

ACS Fall 2021

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