The inherent structural complexity of the protein makes it difficult to identify the contribution of each non-covalent interaction after the significant rate of acceleration of the enzyme. Coulombic forces are evidently primary, but despite the development of artificial nanoreactor designs, the extent to which these contributions can be made has not yet appeared. Here, we report two supramolecular capsules with identically structured internal spaces that surround their electrostatic potential fields (EPF): one positive, one negative. This structure means that only changes in the EPF will affect the chemistry of the encapsulated species. We quantify these influences via pKa difference of guests, rates of hydrolysis and cyclization measurements for encapsulated guests, and confirm the primary role of Coulombic forces with a simple mathematical model approximating the capsules as born spheres within a continuum dielectric. These results reveal the reaction rate accelerations possible under Coulombic control and highlight important design criteria for nano-reactors.

Electrostatic control of macrocyclization reactions in water-soluble supramolecular capsules

2019 Fall National Meeting

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