Abstract
The contribution of electrostriction of water molecules to the stabilization of the negatively charged tetrahedral transition state of a lipase-catalyzed reaction was examined by means of kinetic studies involving high-pressure and solvent dielectric constant. A good correlation was observed between the increased catalytic efficiency of lipase and the decreased solvent dielectric constant. When the dielectric constant of solvents was lowered by 5.00 units, the losses of activation energy and free energy of activation were 7.92 kJ/mol and 11.24 kJ/mol, respectively. The activation volume for kcat decreased significantly as the dielectric constant of solvent decreased, indicating that the degree of electrostriction of water molecules around the charged tetrahedral transition state has been enhanced. These observations demonstrate that the increase in the catalytic efficiency of the lipase reaction with decreasing dielectric constant resulted from the stabilization of electrostatic energy for the formation of an oxyanion hole, and that this stabilization was caused by the increase of electrostricted water around the charged tetrahedral transition state. Therefore, we conclude that the control of solvent dielectric constant can stabilize the tetrahedral transition state, thus lowering the activation energy.
Original language | English |
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Pages (from-to) | 587-594 |
Number of pages | 8 |
Journal | Journal of microbiology and biotechnology |
Volume | 15 |
Issue number | 3 |
Publication status | Published - 2005 Jun |
Keywords
- Activation volume
- Dielectric constant
- Electrostriction
- High-pressure kinetics
- Lipase
- Tetrahedral transition state
ASJC Scopus subject areas
- Biotechnology
- Applied Microbiology and Biotechnology