Thermodynamic and kinetic aspects on water vs. organic solvent as reaction media in the enzyme-catalysed reduction of ketones
Jönsson, Åsa LU ; Wehtje, Ernst LU ; Adlercreutz, Patrick LU
and Mattiasson, Bo
LU
(1999)
In BBA - Protein Structure and Molecular Enzymology
1430(2).
p.313-322
- Abstract
The stereoselective reduction of ketones catalysed by alcohol dehydrogenase from Thermoanaerobium brockii was studied in different reaction media, hexane at controlled water activities, hexane with 2.5% water (biphasic) and pure water. The reactions were studied in the temperature range from -1 to 50°C. Increasing the water activity from 0.53 to 0.97 increased the reaction rate 16-fold. The rate was further enhanced in hexane when exceeding the water solubility and in pure water the rates were even higher. This was general for all ketones studied. At controlled water activity the entropy of activation (ΔS(≠)) was the dominating factor. Large negative ΔS(≠) values caused low reaction rates at low a(w). When increasing the carbon chain... (More)
The stereoselective reduction of ketones catalysed by alcohol dehydrogenase from Thermoanaerobium brockii was studied in different reaction media, hexane at controlled water activities, hexane with 2.5% water (biphasic) and pure water. The reactions were studied in the temperature range from -1 to 50°C. Increasing the water activity from 0.53 to 0.97 increased the reaction rate 16-fold. The rate was further enhanced in hexane when exceeding the water solubility and in pure water the rates were even higher. This was general for all ketones studied. At controlled water activity the entropy of activation (ΔS(≠)) was the dominating factor. Large negative ΔS(≠) values caused low reaction rates at low a(w). When increasing the carbon chain length of the substrate, for reactions in hexane, the decrease of reaction rate was mainly due to a decrease in ΔS(≠). In the comparison between hexane and pure water, ΔG(≠) values were higher in hexane due to higher ΔH(≠) values. The enantioselectivity (E value) increased from 2.6 at water activity 0.53 to 4.6 at water activity 0.97. Changing media from hexane (2.5%, v/v water) to pure water was not affecting the enantioselectivity or the specificity for different ketones. Copyright (C) 1999.
(Less)
- author
- Jönsson, Åsa
LU
; Wehtje, Ernst
LU
; Adlercreutz, Patrick
LU
and Mattiasson, Bo
LU
- organization
- publishing date
- 1999-03-19
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- Alcohol dehydrogenase, Enantioselectivity, Substrate specificity, Thermoanaerobium brockii, Water activity
- in
- BBA - Protein Structure and Molecular Enzymology
- volume
- 1430
- issue
- 2
- pages
- 10 pages
- publisher
- Elsevier
- external identifiers
-
- pmid:10082959
- scopus:0043213963
- ISSN
- 0167-4838
- DOI
- 10.1016/S0167-4838(99)00012-6
- language
- English
- LU publication?
- yes
- id
- 51b28717-2cf5-4f26-8dda-260b702aab89
- date added to LUP
- 2019-06-20 15:17:54
- date last changed
- 2024-03-03 15:51:31
@article{51b28717-2cf5-4f26-8dda-260b702aab89,
abstract = {{<p>The stereoselective reduction of ketones catalysed by alcohol dehydrogenase from Thermoanaerobium brockii was studied in different reaction media, hexane at controlled water activities, hexane with 2.5% water (biphasic) and pure water. The reactions were studied in the temperature range from -1 to 50°C. Increasing the water activity from 0.53 to 0.97 increased the reaction rate 16-fold. The rate was further enhanced in hexane when exceeding the water solubility and in pure water the rates were even higher. This was general for all ketones studied. At controlled water activity the entropy of activation (ΔS(≠)) was the dominating factor. Large negative ΔS(≠) values caused low reaction rates at low a(w). When increasing the carbon chain length of the substrate, for reactions in hexane, the decrease of reaction rate was mainly due to a decrease in ΔS(≠). In the comparison between hexane and pure water, ΔG(≠) values were higher in hexane due to higher ΔH(≠) values. The enantioselectivity (E value) increased from 2.6 at water activity 0.53 to 4.6 at water activity 0.97. Changing media from hexane (2.5%, v/v water) to pure water was not affecting the enantioselectivity or the specificity for different ketones. Copyright (C) 1999.</p>}},
author = {{Jönsson, Åsa and Wehtje, Ernst and Adlercreutz, Patrick and Mattiasson, Bo}},
issn = {{0167-4838}},
keywords = {{Alcohol dehydrogenase; Enantioselectivity; Substrate specificity; Thermoanaerobium brockii; Water activity}},
language = {{eng}},
month = {{03}},
number = {{2}},
pages = {{313--322}},
publisher = {{Elsevier}},
series = {{BBA - Protein Structure and Molecular Enzymology}},
title = {{Thermodynamic and kinetic aspects on water vs. organic solvent as reaction media in the enzyme-catalysed reduction of ketones}},
url = {{http://dx.doi.org/10.1016/S0167-4838(99)00012-6}},
doi = {{10.1016/S0167-4838(99)00012-6}},
volume = {{1430}},
year = {{1999}},
}