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Applications of surface-enhanced resonance Raman scattering spectroscopy to the study of biological systems
Abstract
The application of surface-enhanced resonance Raman scattering (SERRS) spectroscopy to the study of biological systems is assessed in this dissertation. A brief review of the current popular theories that have been proposed to account for the SERRS effect is presented. A review of the most widely studied of chromophoric systems by SERRS provides examples of the scope of applications of the technique and of the information that may be obtained. Examples of the application of SERRS to the study of the two biologically relevant systems are presented in detail. The flavoprotein glucose oxidase (GO) and its redox active cofactor flavin adenine dinucleotide (FAD) with the silver electrode surface comprise the first system examined. Evidence is presented that the SERRS active species is the flavin N(3) anion, adsorbed in an end-on orientation. The interaction of glucose oxidase with the silver electrode is also investigated. In these studies, the observed SERRS spectrum is shown to arise from free FAD. When adsorbed under carefully controlled conditions, interference from the free flavin is apparently removed, yet no SERRS spectrum of the GO is observed. This result is interpreted to be a consequence of the low surface density of FAD chromophore at the surface and an unfavorable orientation of the protein. In contrast, the SERRS spectrum of native flavodoxin, another flavoprotein, is reported. A further complication in the SERRS analysis of GO is demonstrated to be the corrosion of the silver electrode when catalytically active GO is present. The second system includes the bilin compound biliverdin dimethyl ester (BVDE), its photoisomers, and the interaction of the biliprotein phycocyanin with the silver electrode surface. Changes in the BVDE SERRS spectrum upon isomerization support the conclusion that phycocyanin is denatured upon adsorption to the silver surface. From the literature review and examples presented, conclusions are made regarding the general application of SERRS to the study of biological systems.
Subject Area
Analytical chemistry
Recommended Citation
Holt, Randall Eugene, "Applications of surface-enhanced resonance Raman scattering spectroscopy to the study of biological systems" (1989). ETD collection for University of Nebraska-Lincoln. AAI8914080.
https://digitalcommons.unl.edu/dissertations/AAI8914080