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On the possibility of detecting low barrier hydrogen bonds with UV spectroscopy and kinetic measurements

UNCW Author/Contributor (non-UNCW co-authors, if there are any, appear on document)
Jeff Miller (Creator)
The University of North Carolina Wilmington (UNCW )
Web Site:
Michael Messina

Abstract: Recent Experimental evidence has pointed that in many enzyme-catalyzed biochemical pathways a short, strong hydrogen bond between an enzyme and substrate leads to an important contribution to enzyme catalysis. These bonds are termed low barrier hydrogen bonds. In this paper we show that the presence of low barrier hydrogen bonds can be determined in systems by UV spectroscopy and kinetic measurements. In using the time-dependent view of UV spectroscopy, we apply several different UV spectra: photoabsorption, photodissociation, and emission, on systems containing a low barrier hydrogen bond. We find several distinguishing features in the UV spectra for systems that possess a low barrier hydrogen bond. In using kinetic measurements, we find non-trivial differences among rate constant ratios of protonated to deuterated hydrogen bonds between strong and weak hydrogen bonds of proton transfer between donor and acceptor sites. This kinetic isotope effect is determined by performing full dynamic calculations of these rate constants by computing reactive flux through a dividing surface. This reactive flux is computed by evolving classical trajectories on an effective quantum mechanical potential energy surface.

Additional Information

A Thesis Submitted to the University of North Carolina at Wilmington in Partial Fulfillment Of the Requirements for the Degree of Master of Science
Language: English
Date: 2009
Hydrogen bonding, Spectroscopy
Hydrogen bonding