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Updated: Mar 29, 2026

Synthesis of an Intein-mediated Artificial Protein Hydrogel
Published on: January 27, 2014
Protein-like proton exchange in a synthetic host cavity
William M Hart-Cooper1, Carmelo Sgarlata1, Charles L Perrin2
1Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720; Department of Chemistry, University of California, Berkeley, CA 94720;
Abstract:
The mechanism of proton exchange in a metal-ligand enzyme active site mimic (compound 1) is described through amide hydrogen-deuterium exchange kinetics. The type and ratio of cationic guest to host in solution affect the rate of isotope exchange, suggesting that the rate of exchange is driven by a host whose cavity is occupied by water. Rate constants for acid-, base-, and water-mediated proton exchange vary by orders of magnitude depending on the guest, and differ by up to 200 million-fold relative to an alanine polypeptide. These results suggest that the unusual microenvironment of the cavity of 1 can dramatically alter the reactivity of associated water by magnitudes comparable to that of enzymes.
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