Journalartikel

Jahr der Veröffentlichung: 2015

Seiten: 693-703

Zeitschrift: Journal of Physical Chemistry B (Soft Condensed Matter and Biophysical Chemistry)

Bandnummer: 119

Heftnummer: 3

DOI Link: https://doi.org/10.1021/jp503633m

Verlag: American Chemical Society

Abstract: 

Quantum mechanical tunneling governs the C–O bond rotamerization of
simple alkyl and aryl carboxylic acid conformers at cryogenic
temperatures. In this study, we report tunneling investigations on a
series of electronically different α-ketocarboxylic acids including
glyoxylic, pyruvic, cyclopropylglyoxylic, and phenylglyoxylic acid in
solid Ar and Ne as host materials at temperatures ranging from 3 to 20
K. The higher-lying rotamers generated through photoirradiation with
wavelengths of λ = 313 nm or λ > 850 nm convert to their low-energy
conformers through hydrogen-tunneling, as evident from the time
evolution of their infrared spectra, and the complete suppression of
this process by deuteration. The conversion rates sensitively depend on
the choice of matrix material and the tunneling half-lives range from a
few hours to several days and are higher in Ne than in Ar for glyoxylic,
pyruvic, and cyclopropylglyoxylic acid. The advent of tunneling in
α-ketocarboxylic acids dominates their conformational preferences and
conceivably also the reactivity of biologically and pharmacologically
relevant acid congeners.

Harvard-Zitierstil: Gerbig, D. and Schreiner, P. (2015) Hydrogen-Tunneling in Biologically Relevant Small Molecules: The Rotamerizations of α-Ketocarboxylic Acids, Journal of Physical Chemistry B (Soft Condensed Matter and Biophysical Chemistry), 119(3), pp. 693-703. https://doi.org/10.1021/jp503633m

APA-Zitierstil: Gerbig, D., & Schreiner, P. (2015). Hydrogen-Tunneling in Biologically Relevant Small Molecules: The Rotamerizations of α-Ketocarboxylic Acids. Journal of Physical Chemistry B (Soft Condensed Matter and Biophysical Chemistry). 119(3), 693-703. https://doi.org/10.1021/jp503633m