High Pressure Effects on the Dynamics and Kinetics of Two Model Biochemical Systems
Mabry, Stephanie Ann
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https://hdl.handle.net/2142/84361
Description
Title
High Pressure Effects on the Dynamics and Kinetics of Two Model Biochemical Systems
Author(s)
Mabry, Stephanie Ann
Issue Date
1997
Doctoral Committee Chair(s)
Jonas, Jiri
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Physical
Language
eng
Abstract
Pressure effects on rate constants for hydrogen exchange between N-methylacetamide (NMA) and water were measured at pressures up to 5 kbar at three different pH values and temperatures using proton/nitrogen-14 decoupled NMR inversion transfer, and the apparent activation volumes of exchange determined. Hydrogen exchange between NMA and water serves as a model for amide-water hydrogen exchange in peptides and proteins which is sensitive to the local environment of the protons and is used to probe fluctuations in the local conformations of proteins. Hydrogen exchange rate constants were also measured as a function of concentration and pH at ambient pressure at each temperature, and the rate constants of the acid-, base-, and uncatalyzed hydrogen exchange reactions determined. With these values, activation volumes of the acid-, base-, and uncatalyzed exchange reactions were calculated. This is the first time the uncatalyzed activation volume, which is required in hydrogen exchange studies of peptides and proteins at high pressures, had been determined. The temperature dependence of the activation volumes and the catalyzed rate constants was also examined.
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