Biomimetic models for redox enzyme systems

Kennedy, Andrew A. (2009) Biomimetic models for redox enzyme systems. PhD thesis, University of Glasgow.

Abstract

Supramolecular chemistry involves the study of noncovalent interactions that take place between molecules. A supramolecule or host-guest complex is formed when a noncovalent binding or complexation event occurs between two such molecules. Hydrogen bonds, electrostatics, pi-stacking, hydrophobic effects, solvatophobic effects and van der Waals forces are all types of noncovalent interactions. Biological systems have provided much of the inspiration for the development of supramolecular chemistry, and many synthetic supramolecular systems have been designed to mimic biological and enzymatic processes. Biomimetic modelling involves the synthesis of compounds containing similar functional groups to that of the specific enzyme’s protein and cofactor. Subsequent analysis using chemical, physical or computational techniques can be used to gain a better understanding of the interactions taking place.

This study involves the investigation of various biomimetic redox enzyme systems. Firstly, model systems containing the 1- and 5-deazaflavin cofactor have been synthesised and studied to probe how their redox behaviour compares to that of riboflavin in a supramolecular environment using physical, electrochemical and computational techniques. Secondly, this study has focussed on the flavin cofactor but has expanded upon what factors influence its redox behaviour, and ability to noncovalently interact with other molecules, by examining how the presence of different dendritic architectures can affect its redox properties and noncovalent behaviour. A series of dendrons have been synthesised and studied that have a water-soluble dendron architecture attached to the flavin moiety, as well as a series of dendrons with branching designed to encapsulate the flavin unit. Finally, a biomimetic model of the pyrroloquinoline quinone cofactor has also been synthesised and studies carried out to investigate its redox behaviour in a supramolecular environment, and ability to noncovalently interact with other molecules.

The results of this study will hopefully contribute significantly to the body of chemical research in the area of supramolecular chemistry and biomimetics. Of particular interest will be the results from the flavin-based dendron research, as the prospect of purpose-built synthetic enzymes, designed and synthesised for whatever role is required, would surely be of great significance.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: supramolecular chemistry,organic chemistry,flavin,deazaflavin,dendron,PQQ,molecular modelling,click chemistry,electrochemistry,cyclic voltammetry
• Subjects: Q Science > QD Chemistry
• Colleges/Schools: College of Science and Engineering > School of Chemistry
• Supervisor's Name: Cooke, Dr. Graeme
• Date of Award: 2009
• Embargo Date: 8 October 2016
• Depositing User: Dr Andrew A. Kennedy
• Unique ID: glathesis:2009-1060
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 17 Sep 2009
• Last Modified: 27 Jun 2016 10:30
• URI: https://theses.gla.ac.uk/id/eprint/1060