Affordable Access

Publisher Website

Stereoelectronic explanations for the mechanistic details of transimination and HF elimination reactions

Authors
Journal
Journal of Molecular Graphics and Modelling
1093-3263
Publisher
Elsevier
Volume
51
Identifiers
DOI: 10.1016/j.jmgm.2014.05.006
Keywords
  • Density Functional Calculations
  • Transimination
  • Hf Elimination
  • Transferases
Disciplines
  • Biology

Abstract

Abstract The β-fluoroamines are commonly used as substrate analogs to determine the mechanistic details of enzymatic reactions. Presence of fluorine atom gives rise to the alterations in the electronic profile and the pKa of molecules which results in mechanistic deviations. The fluorine-substituted mechanism-based substrate analogs are widely used in the inactivation of pyridoxal 5′-phosphate (PLP)-dependent enzymes. The presence of fluorine atom also alters the sequence of reactions taking place in PLP-dependent enzymes where the HF elimination reaction appears in between the transimination and inactivation reactions. Despite the amount of the works on β-fluoroamines, the effect of stereoelectronic differences on the transimination and HF elimination reactions taking place in PLP-dependent enzymes has not been investigated yet. A density functional theory study is conducted to elucidate mechanistic details of the reactions occurring in PLP-dependent enzymes. In order to understand the mechanistic insights of different isomers and the effect of the fluorine atom, 4-amino-3-fluorobutanoic acid (3-F-GABA) enantiomers are chosen to be investigated besides 4-aminobutanoic acid (GABA), which is the natural substrate for γ-aminobutyric acid aminotransferase (GABA-AT). The investigated β-fluoroamines are the experimentally proposed potential inhibitors of PLP-dependent enzyme GABA-AT.

There are no comments yet on this publication. Be the first to share your thoughts.

Statistics

Seen <100 times
0 Comments

More articles like this

Stereoelectronic explanations for the mechanistic...

on Journal of Molecular Graphics...

Excited state reactions of acridinedione dyes with...

on Journal of Photochemistry and... Jan 01, 2001

Reactions of CF3CH2I+O(3P): competing mechanisms o...

on The Journal of Chemical Physic... Feb 21, 2007

Transimination reactions in [b-3C-im][NTf2] ionic...

on Organic & Biomolecular Chemist... Jun 07, 2011
More articles like this..