title: Permanganate oxidation of α-amino acids: kinetic correlations for the nonautocatalytic and autocatalytic reaction pathways.
abstract: The reactions of permanganate ion with seven α-amino acids in aqueous KH(2)PO(4)/K(2)HPO(4) buffers have been followed spectrophotometrically at two different wavelengths: 526 nm (decay of MnO(4)(-)) and 418 nm (formation of colloidal MnO(2)). All of the reactions studied were autocatalyzed by colloidal MnO(2), with the contribution of the autocatalytic reaction pathway decreasing in the order glycine > l-threonine > l-alanine > l-glutamic acid > l-leucine > l-isoleucine > l-valine. The rate constants corresponding to the nonautocatalytic and autocatalytic pathways were obtained by means of either a differential rate law or an integrated one, the latter requiring the use of an iterative method for its implementation. The activation parameters for the two pathways were determined and analyzed to obtain statistically significant correlations for the series of reactions studied. The activation enthalpy of the nonautocatalytic pathway showed a strong, positive dependence on the standard Gibbs energy for the dissociation of the protonated amino group of the α-amino acid. Linear enthalpy-entropy correlations were found for both pathways, leading to isokinetic temperatures of 370 ± 21 K (nonautocatalytic) and 364 ± 28 K (autocatalytic). Mechanisms in agreement with the experimental data are proposed for the two reaction pathways.
authors.affiliation: Departamento de Quimica Fisica, Facultad de Quimica, Universidad de Barcelona, Marti i Franques, Spain. jfperezdebenito@ub.edu
authors.forename: Joaquin F
authors.initials: JF
authors.lastname: Perez-Benito
mesh_terms: D000596:Amino Acids / Q000737:chemistry*; D002021:Buffers; D002384:Catalysis; D007700:Kinetics; D017895:Manganese Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010087:Oxides / Q000737:chemistry*; D011196:Potassium Permanganate / Q000737:chemistry; D013053:Spectrophotometry; D013816:Thermodynamics
chemical_list: D000596:Amino Acids; D002021:Buffers; D017895:Manganese Compounds; D010087:Oxides; D011196:Potassium Permanganate; C048856:permanganic acid; C016552:manganese dioxide