Dipole formation and solvent electrostriction in subtilisin catalysis

Journal of the American Chemical Society

Volumn 119, Issue 40, 1997, Pages 9331-9335

  Michels, Peter C ^a,b   Dordick, Jonathan S ^c   Clark, Douglas S ^a  

^a University of California   (United States)

^b UNIVERSITY OF IOWA   (United States)

^c EnzyMed Inc   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

HEXANE; SOLVENT; SUBTILISIN;

ARTICLE; CATALYSIS; CHEMICAL MODIFICATION; DIELECTRIC CONSTANT; DIPOLE; ENZYME KINETICS; ENZYME MECHANISM; ESTERIFICATION; REACTION ANALYSIS;

EID: 0030778537     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9713892     Document Type: Article

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28. We did not compare ester hydrolysis in aqueous solution to transesterification in organic solvents for two primary reasons. First, the two types of reactions have different rate-limiting steps. The rate-controlling step for subtilisin-catalyzed ester hydrolysis is deacylation (Bonneau, P. R.; Graycar, T. P.; Estell, D. A.; Jones, B. J. J. Am. Chem. Soc. 1991, 113, 1026), whereas the rate-controlling step for transesterification in organic solvents is acylation (Wangikar, P. P.; Graycar, T. P.; Estell, D. A.; Clark, D. S.; Dordick, J. S. J. Am. Chem. Soc. 1993, 115, 12231. Chatterjee, S.; Russell, A. J. Biotechnol. Bioeng. 1992, 40, 1069.) Moreover, water differs in its mechanism of electrostatic solvation compared with more apolar solvents (Whalley, E. J. Chem. Phys., 1963, 38, 1400.) and commonly engages in nonelectrostrictive interactions. These effects often cause deviations from the Kirkwood model for electrostriction (Isaacs, N. Liquid Phase High Pressure Chemistry; John Wiley & Sons: Chichester, 1981 pp 181-343. Hamann, S. D. Mod. Asp. Electochem. 1972, 9, 47.).
29. We did not compare ester hydrolysis in aqueous solution to transesterification in organic solvents for two primary reasons. First, the two types of reactions have different rate-limiting steps. The rate-controlling step for subtilisin-catalyzed ester hydrolysis is deacylation (Bonneau, P. R.; Graycar, T. P.; Estell, D. A.; Jones, B. J. J. Am. Chem. Soc. 1991, 113, 1026), whereas the rate-controlling step for transesterification in organic solvents is acylation (Wangikar, P. P.; Graycar, T. P.; Estell, D. A.; Clark, D. S.; Dordick, J. S. J. Am. Chem. Soc. 1993, 115, 12231. Chatterjee, S.; Russell, A. J. Biotechnol. Bioeng. 1992, 40, 1069.) Moreover, water differs in its mechanism of electrostatic solvation compared with more apolar solvents (Whalley, E. J. Chem. Phys., 1963, 38, 1400.) and commonly engages in nonelectrostrictive interactions. These effects often cause deviations from the Kirkwood model for electrostriction (Isaacs, N. Liquid Phase High Pressure Chemistry; John Wiley & Sons: Chichester, 1981 pp 181-343. Hamann, S. D. Mod. Asp. Electochem. 1972, 9, 47.).
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