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Relationship Between Enhancement of Electrostriction and Decrease of Activation Energy in Porcine Pancreatic Lipase Catalysis
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  • Relationship Between Enhancement of Electrostriction and Decrease of Activation Energy in Porcine Pancreatic Lipase Catalysis
  • Relationship Between Enhancement of Electrostriction and Decrease of Activation Energy in Porcine Pancreatic Lipase Catalysis
저자명
PARK. HYUN,LEE. KI-SEOG,PARK. SEON-MI,LEE. KWANG-WON,KIM. AUGUSTINE YONGHWI,CHI. YOUNG-MIN
간행물명
Journal of microbiology and biotechnology
권/호정보
2005년|15권 3호|pp.587-594 (8 pages)
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한국미생물생명공학회
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정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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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 $k_{cat}$ 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.