Examining the case for the effect of barrier compression on tunneling, vibrationally enhanced catalysis, catalytic entropy and related issues
Kamerlin, Shina Caroline Lynn LU
; Mavri, Janez
and Warshel, A
(2010)
In FEBS Letters
584(13).
p.66-2759
- Abstract
The idea that tunneling is enhanced by the compression of the donor-acceptor distance has attracted significant interest. In particular, recent studies argued that this proposal is consistent with pressure effects on enzymatic reactions, and that the observed pressure effects support the idea of vibrationally enhanced catalysis. However, a careful analysis of the current works reveals serious inconsistencies in the evidence presented to support these hypotheses. Apparently, tunneling decreases upon compression, and external pressure does not lead to the applicable compression of the free energy surface. Additionally, pressure experiments do not provide actual evidence for vibrationally enhanced catalysis. Finally, the temperature... (More)
The idea that tunneling is enhanced by the compression of the donor-acceptor distance has attracted significant interest. In particular, recent studies argued that this proposal is consistent with pressure effects on enzymatic reactions, and that the observed pressure effects support the idea of vibrationally enhanced catalysis. However, a careful analysis of the current works reveals serious inconsistencies in the evidence presented to support these hypotheses. Apparently, tunneling decreases upon compression, and external pressure does not lead to the applicable compression of the free energy surface. Additionally, pressure experiments do not provide actual evidence for vibrationally enhanced catalysis. Finally, the temperature dependence of the entropy change in hydride transfer reactions is shown to reflect simple electrostatic effects.
(Less)
- author
- Kamerlin, Shina Caroline Lynn
LU
; Mavri, Janez
and Warshel, A
- publishing date
- 2010-07-02
- type
- Contribution to journal
- publication status
- published
- keywords
- Animals, Catalysis, Entropy, Humans, Kinetics, Models, Chemical, Thermodynamics
- in
- FEBS Letters
- volume
- 584
- issue
- 13
- pages
- 8 pages
- publisher
- Wiley-Blackwell
- external identifiers
-
- scopus:77953692230
- pmid:20433839
- ISSN
- 1873-3468
- DOI
- 10.1016/j.febslet.2010.04.062
- language
- English
- LU publication?
- no
- additional info
- Copyright 2010 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.
- id
- e975f21c-7556-4434-8067-80e12942434a
- date added to LUP
- 2025-01-11 22:11:46
- date last changed
- 2025-04-20 11:56:34
@article{e975f21c-7556-4434-8067-80e12942434a,
abstract = {{<p>The idea that tunneling is enhanced by the compression of the donor-acceptor distance has attracted significant interest. In particular, recent studies argued that this proposal is consistent with pressure effects on enzymatic reactions, and that the observed pressure effects support the idea of vibrationally enhanced catalysis. However, a careful analysis of the current works reveals serious inconsistencies in the evidence presented to support these hypotheses. Apparently, tunneling decreases upon compression, and external pressure does not lead to the applicable compression of the free energy surface. Additionally, pressure experiments do not provide actual evidence for vibrationally enhanced catalysis. Finally, the temperature dependence of the entropy change in hydride transfer reactions is shown to reflect simple electrostatic effects.</p>}},
author = {{Kamerlin, Shina Caroline Lynn and Mavri, Janez and Warshel, A}},
issn = {{1873-3468}},
keywords = {{Animals; Catalysis; Entropy; Humans; Kinetics; Models, Chemical; Thermodynamics}},
language = {{eng}},
month = {{07}},
number = {{13}},
pages = {{66--2759}},
publisher = {{Wiley-Blackwell}},
series = {{FEBS Letters}},
title = {{Examining the case for the effect of barrier compression on tunneling, vibrationally enhanced catalysis, catalytic entropy and related issues}},
url = {{http://dx.doi.org/10.1016/j.febslet.2010.04.062}},
doi = {{10.1016/j.febslet.2010.04.062}},
volume = {{584}},
year = {{2010}},
}