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Selenium-77 nuclear magnetic resonance studies of various biological systems

Thesis/Dissertation ·
OSTI ID:5671447
Selenium-77 nuclear magnetic resonance spectroscopy has been used as a valuable technique for the investigation of various biological systems. Several para-substituted phenyl(selenyl) acetates were studied as inhibitors of the serine protease, {alpha}-chymotrypsin, and the results showed that a downfield shift ({minus}15.6 to {minus}53.3 ppm) in the selenium resonance occurred upon the binding of the inhibitor to the enzyme. The {Delta} values determined for these inhibitors are much greater than those values previously determined for similar inhibitors with proton, carbon-13 and fluorine-19 NMR spectroscopy. In past studies, the largest chemical shifts (3-7 ppm) have come from investigations with the fluorine-19 nucleus. The results from these selenium-77 NMR studies clearly show the sensitivity of this multinuclear technique and firmly establishes selenium-77 NMR spectroscopy as a valuable method for investigating the binding of substrates and inhibitors to enzymes. Phenyl isothiocyanate or Edman's reagent has been the compound of choice for determining the amino acid sequence of peptide fragments. The use of p-tolyl isoselenocyanate as a selenium-containing analog of Edman's reagent was investigated and followed very readily by {sup 77}Se NMR spectroscopy. In each of the three steps involved in the degradation process, the intermediates were characterized by several analytical techniques and multinuclear NMR spectroscopy. These studies demonstrate that p-tolyl isoselenocyanate follows a similar pathway during the degradation process, but the conditions required in each step are milder than those required for the sulfur compound. The results from the {sup 77}Se NMR studies also show that the selenium nucleus can differentiate between varying substituents up to six bonds removed from the selenium moiety.
Research Organization:
South Carolina Univ., Columbia, SC (United States)
OSTI ID:
5671447
Country of Publication:
United States
Language:
English