| dc.description.abstract | An in-depth mass spectrometric, computational, and kinetics study
of glyoxylate (deprotonated glyoxylic acid) and pyruvate (deprotonated
pyruvic acid) has been performed, along with a brief experimental
and computational investigation on deprotonated trifluoropyruvic acid (trifluoropyruvate). Their corresponding acids are all α-oxo carboxylic acids of the form XCOCOOH, with X being H, CH3 , and CF3 for glyoxylate, pyruvate, and trifluoropyruvate respectively.
In addition, glycolate (deprotonated glycolic acid) has been
subjected to mass spectrometric studies with the computational
investigation done by Simakov and co-workers (2013).
Based on the results, a comprehensive description of the unimolec-
ular dissociation behaviour of the deprotonated acids, with special attention to the decarboxylation behaviour, is presented.
The decarboxylation behaviour of the anions is compared, and the
reactivity with respect to decarboxylation is shown to depend strongly
on the nature of X-group. Also, the exchange reaction with CO2 of
the glyoxylate, pyruvate, and glycolate anions was investigated with
FT-ICR mass spectrometry and computational methods.
Lastly, possible synthesis routes to glyoxylate and pyruvate in the
interstellar medium, with relevance to interstellar and prebiotic
chemistry, is proposed based on the suggested unimolecular dissociation mechanisms. | eng |