Outer-Sphere Effects on the Copper Sites of Pseudomonas Aeruginosa Azurins

Author: Lancaster, Kyle Matthew

Year: 2011

Degree: Dissertation (Ph.D.)

Advisor: Gray, Harry B.

Committee Members: Richards, John H.; Mayo, Stephen L.; Winkler, Jay Richmond; Agapie, Theodor; Gray, Harry B.

Option: Chemistry

DOI: 10.7907/9HZZ-XE74

Abstract

This thesis describes structural, spectroscopic, and reactivity studies of mutants of the cupredoxin azurin from Pseudomonas aeruginosa. Emphasis is given to the effects of outer-sphere coordination on spectroscopic observables and reduction potentials. Among the key findings are that the characteristics of the classical "type 1" copper site can be largely reproduced in the absence of canonically necessary cysteine thiolate ligation. Mutants exhibiting this behavior have been classified as "type zero" copper proteins.

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