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Mechanistic studies of a model reaction for enzymatic hydroxylation

Citation

Mog, David Michael (1970) Mechanistic studies of a model reaction for enzymatic hydroxylation. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/RTHJ-0E62. https://resolver.caltech.edu/CaltechTHESIS:08182015-100458662

Abstract

A study has been made of the reaction mechanism of a model system for enzymatic hydroxylation. The results of a kinetic study of the hydroxylation of 2-hydroxyazobenzene derivatives by cupric ion and hydrogen peroxide are presented. An investigation of kinetic orders indicates that hydroxylation proceeds by way of a coordinated intermediate complex consisting of cupric ion and the mono anions of 2-hydroxyazobenzene and hydrogen peroxide. Studies with deuterated substrate showed the absence of a primary kinetic isotope effect and no evidence of an NIH shift. The effect of substituents on the formation of intermediate complexes and the overall rate of hydroxylation was studied quantitatively in aqueous solution. The combined results indicate that the hydroxylation step is only slightly influenced by ring substitution. The substituent effect is interpreted in terms of reaction by a radical path or a concerted mechanism in which the formation of ionic intermediates is avoided. The reaction mechanism is discussed as a model for enzymatic hydroxylation.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Richards, John H.
Thesis Committee:
  • Unknown, Unknown
Defense Date:9 March 1970
Funders:
Funding AgencyGrant Number
Woodrow Wilson FoundationUNSPECIFIED
NIHUNSPECIFIED
Paint Research FoundationUNSPECIFIED
CaltechUNSPECIFIED
Record Number:CaltechTHESIS:08182015-100458662
Persistent URL:https://resolver.caltech.edu/CaltechTHESIS:08182015-100458662
DOI:10.7907/RTHJ-0E62
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:9105
Collection:CaltechTHESIS
Deposited By: Leslie Granillo
Deposited On:18 Aug 2015 19:43
Last Modified:21 Dec 2019 04:51

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