DOI: 10.1073/pnas.050316997. Low dielectric response in enzyme active site

Low dielectric response in enzyme active site

10.1073/pnas.050316997

Crossref journal-article

Proceedings of the National Academy of Sciences

Proceedings of the National Academy of Sciences (341)

Abstract

The kinetics of charge transfer depend crucially on the dielectric reorganization of the medium. In enzymatic reactions that involve charge transfer, atomic dielectric response of the active site and of its surroundings determines the efficiency of the protein as a catalyst. We report direct spectroscopic measurements of the reorganization energy associated with the dielectric response in the active site of α-chymotrypsin. A chromophoric inhibitor of the enzyme is used as a spectroscopic probe. We find that water strongly affects the dielectric reorganization in the active site of the enzyme in solution. The reorganization energy of the protein matrix in the vicinity of the active site is similar to that of low-polarity solvents. Surprisingly, water exhibits an anomalously high dielectric response that cannot be described in terms of the dielectric continuum theory. As a result, sequestering the active site from the aqueous environment inside low-dielectric enzyme body dramatically reduces the dielectric reorganization. This reduction is particularly important for controlling the rate of enzymatic reactions.

Authors 2

Edward L. Mertz (first)
Lev I. Krishtalik (additional)

References 64 Referenced 120

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Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 10:38 a.m.)
Deposited	3 years, 4 months ago (April 12, 2022, 1:44 p.m.)
Indexed	3 weeks, 5 days ago (Aug. 7, 2025, 5:03 p.m.)
Issued	25 years, 6 months ago (Feb. 11, 2000)
Published	25 years, 6 months ago (Feb. 11, 2000)
Published Online	25 years, 6 months ago (Feb. 11, 2000)
Published Print	25 years, 6 months ago (Feb. 29, 2000)

Funders 0

None

BibTeX

@article{Mertz_2000, title={Low dielectric response in enzyme active site}, volume={97}, ISSN={1091-6490}, url={http://dx.doi.org/10.1073/pnas.050316997}, DOI={10.1073/pnas.050316997}, number={5}, journal={Proceedings of the National Academy of Sciences}, publisher={Proceedings of the National Academy of Sciences}, author={Mertz, Edward L. and Krishtalik, Lev I.}, year={2000}, month=feb, pages={2081–2086} }

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  ]
}