Date of Award

Summer 1987

Degree Type

Thesis - Restricted

Degree Name

Master of Science (MS)

Department

Chemistry

First Advisor

Kincaid, James R.

Second Advisor

Strommen, Dennis P.

Third Advisor

Nakamoto, Kazuo

Abstract

Resonance Raman spectroscopic studies of modified hemoglobins and their met-cyanide hybrids, stabilized in either the R or the T quaternary structure, have been conducted. The effect of heme modification on the tertiary and quaternary structures of hemoglobin is discussed by utilizing RR spectra and previously published NMR data. In deutero-proto valency hybrids, the VFe - His mode is apparently downshifted by less than 4 cm- 1 from that of proto-proto valency hybrids, and the large shift (15 cm - 1 ) of the VFe-His mode in the proto-proto methybrids is no longer present in the proto-deutero methybrids. It is also found that, in a reconstituted hybrid, oxidation marker lines increase with the decrease of VFe - His, indicating that there is a correlation between these two modes as previously noted by other workers. Moreover, no significant difference was found between the oxy-like proto- and deutero-hemoglobins. It thus follows t hat the modification of one subunit contributes little effect on the distal side geometry of another subunit in oxygenated hemoglobin. In addition, the VFe-co, 6Fe - c - o and vc - o modes in proto- and deuterohemoglobin and their subunits are measured and discussed. Selective enhancements of proto- and deutero- carbon rnonoxy hybrids are found.

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