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Title: Protein-like proton exchange in a synthetic host cavity

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.

Authors:
; ; ; ; ;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1235186
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 112 Journal Issue: 50; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Hart-Cooper, William M., Sgarlata, Carmelo, Perrin, Charles L., Toste, F. Dean, Bergman, Robert G., and Raymond, Kenneth N. Protein-like proton exchange in a synthetic host cavity. United States: N. p., 2015. Web. doi:10.1073/pnas.1515639112.
Hart-Cooper, William M., Sgarlata, Carmelo, Perrin, Charles L., Toste, F. Dean, Bergman, Robert G., & Raymond, Kenneth N. Protein-like proton exchange in a synthetic host cavity. United States. doi:10.1073/pnas.1515639112.
Hart-Cooper, William M., Sgarlata, Carmelo, Perrin, Charles L., Toste, F. Dean, Bergman, Robert G., and Raymond, Kenneth N. Mon . "Protein-like proton exchange in a synthetic host cavity". United States. doi:10.1073/pnas.1515639112.
@article{osti_1235186,
title = {Protein-like proton exchange in a synthetic host cavity},
author = {Hart-Cooper, William M. and Sgarlata, Carmelo and Perrin, Charles L. and Toste, F. Dean and Bergman, Robert G. and Raymond, Kenneth N.},
abstractNote = {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.},
doi = {10.1073/pnas.1515639112},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 50,
volume = 112,
place = {United States},
year = {2015},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1515639112

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Cited by: 6 works
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