DOI: 10.1073/pnas.93.24.13665. Energy considerations show that low-barrier hydrogen bonds do not offer a catalytic advantage over ordinary hydrogen bonds

Energy considerations show that low-barrier hydrogen bonds do not offer a catalytic advantage over ordinary hydrogen bonds

10.1073/pnas.93.24.13665

Crossref journal-article

Proceedings of the National Academy of Sciences

Proceedings of the National Academy of Sciences (341)

Abstract

Low-barrier hydrogen bonds have recently been proposed as a major factor in enzyme catalysis. Here we evaluate the feasibility of transition state (TS) stabilization by low-barrier hydrogen bonds in enzymes. Our analysis focuses on the facts that ( i ) a low-barrier hydrogen bond is less stable than a regular hydrogen bond in water, ( ii ) TSs are more stable in the enzyme active sites than in water, and ( iii ) a nonpolar active site would destabilize the TS relative to its energy in water. Combining these points and other experimental and theoretical facts in a physically consistent framework shows that a low-barrier hydrogen bond cannot stabilize the TS more than an ordinary hydrogen bond. The reason for the large catalytic effect of active site hydrogen bonds is that their formation entails a lower reorganization energy than their solution counterparts, due to the preorganized enzyme environment.

Bibliography

Warshel, A., & Papazyan, A. (1996). Energy considerations show that low-barrier hydrogen bonds do not offer a catalytic advantage over ordinary hydrogenâbonds. Proceedings of the National Academy of Sciences, 93(24), 13665â13670.

Authors 2

Arieh Warshel (first)
Arno Papazyan (additional)

References 36 Referenced 179

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Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 10:34 a.m.)
Deposited	3 years, 4 months ago (April 13, 2022, 3:06 p.m.)
Indexed	1 month, 2 weeks ago (July 11, 2025, 6:39 a.m.)
Issued	28 years, 9 months ago (Nov. 26, 1996)
Published	28 years, 9 months ago (Nov. 26, 1996)
Published Online	28 years, 9 months ago (Nov. 26, 1996)
Published Print	28 years, 9 months ago (Nov. 26, 1996)

Funders 0

None

BibTeX

@article{Warshel_1996, title={Energy considerations show that low-barrier hydrogen bonds do not offer a catalytic advantage over ordinary hydrogen bonds}, volume={93}, ISSN={1091-6490}, url={http://dx.doi.org/10.1073/pnas.93.24.13665}, DOI={10.1073/pnas.93.24.13665}, number={24}, journal={Proceedings of the National Academy of Sciences}, publisher={Proceedings of the National Academy of Sciences}, author={Warshel, Arieh and Papazyan, Arno}, year={1996}, month=nov, pages={13665–13670} }

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