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Photorelease of caged alcohols from artificial metalloenzymes

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abstract
Nature frequently employs metalloenzymes to catalyze biological reactions. In the literature there is precedent for artificial metalloenzymes that serve to selectively cleave coordinated peptide and ester linkages. These systems take advantage of metal-ligand coordination and activation of a carbonyl functional group, resulting in hydrolysis. This project aims to hydrolyze a caged alcohol or amide with a photoactivated metal-ligand complex. Hydrolysis of the caged molecule is dependent upon metal-ligand complex formation and stoichiometry, photochemical isomerization of an alkene, Lewis acid activation of a carbonyl species, and nucleophilic attack by metal-bound H2O. The photoisomerization from trans to cis is driven to completion by the coordination of the latter to the metal. The ester hydrolysis is most efficient when the ligand to metal ratio is 1:1. Several ligand systems were synthesized with these factors in mind. The synthesis, characterization, and investigation of these systems as well as possible applications are discussed.
subject
artificial metalloenzymes
caged alcohols
caged compounds
ester hydrolysis
ligand
metal complex
metalloenzymes
metalloproteases
organic chemistry
peptidase
photochemistry
photodeprotection
photohydrolysis
photorelease
contributor
Oshige, Eric Stephen (author)
ericoshige@gmail.com (authorEmail)
Paul B. Jones, Ph.D. (committee chair)
Willie L. Hinze, Ph.D. (committee member)
S. Bruce King, Ph.D. (committee member)
creator
Oshige, Eric Stephen
date
2008-09-28T10:50:17Z (accessioned)
2010-06-18T18:59:39Z (accessioned)
2008-07-20 (available)
2008-09-28T10:50:17Z (available)
2010-06-18T18:59:39Z (available)
2007-02-20 (issued)
degree
null (defenseDate)
Chemistry (discipline)
Wake Forest University (grantor)
MS (level)
identifier
oshigees_05_2007.pdf
http://hdl.handle.net/10339/14874 (uri)
migration
etd-06102007-193011 (oldETDId)
rights
Release the entire work immediately for access worldwide. (accessRights)
I hereby certify that, if appropriate, I have obtained and attached hereto a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee. I hereby grant to Wake Forest University or its agents the non-exclusive license to archive and make accessible, under the conditions specified below, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report. (license)
title
Photorelease of caged alcohols from artificial metalloenzymes

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