title: Kinetics and activation parameters of the reaction of organoarsenic(V) compounds with glutathione.
abstract: In this work the kinetics of the reaction of glutathione (GSH) with the organoarsenic(V) compounds phenylarsonic acid (PAA), 4-hydroxy-3-nitrophenylarsonic acid (HNPAA), p-aminophenylarsonic acid (p-APAA) and o-aminophenylarsonic acid (o-APAA) as well as monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA) is investigated. The reaction progress is monitored in real time by (1)H NMR, allowing the determination of rate coefficients and half-lives as well as activation parameters. The reaction consists of two steps: redox reaction and conjugation. In all investigated systems the conjugation is fast compared to the redox reaction and, therefore, rate determining. All investigated phenylarsonic acids follow the same rate law, showing overall reaction orders of 3 and half-lives between 47.7 ± 0.2 and 71.0 ± 3.6 min. The methylated compounds react slower, showing half-lives of 76.6 ± 0.4 and 444 ± 10 min for DMAA and MMAA, respectively. Enthalpies of activation range from 20 to 36 (± 2) kJ mol(-1) and the entropies of activation are within -154 and -97(± 7)J mol(-1)K(-1). The results reveal a correlation of the toxicity of the arsenic compound and the reaction rate with GSH. This may pave the way for the estimation of the toxicity of such compounds by simple kinetic studies.
authors.affiliation: Institute of Analytical Chemistry, TU Bergakademie Freiberg, 09596 Freiberg, Germany. Electronic address: j.kretzschmar@hzdr.de.
authors.forename: Jerome
authors.initials: J
authors.lastname: Kretzschmar
authors.affiliation: Institute of Analytical Chemistry, TU Bergakademie Freiberg, 09596 Freiberg, Germany. Electronic address: Erica.Brendler@chemie.tu-freiberg.de.
authors.forename: Erica
authors.initials: E
authors.lastname: Brendler
authors.affiliation: Institute of Inorganic Chemistry, TU Bergakademie Freiberg, 09596 Freiberg, Germany. Electronic address: joerg.wagler@chemie.tu-freiberg.de.
authors.forename: Jörg
authors.initials: J
authors.lastname: Wagler
authors.affiliation: Institute of Analytical Chemistry, TU Bergakademie Freiberg, 09596 Freiberg, Germany. Electronic address: chris_acs1@gmx.de.
authors.forename: Anne-Christine
authors.initials: AC
authors.lastname: Schmidt
mesh_terms: D001152:Arsenicals / Q000737:chemistry*; D004785:Environmental Pollutants / Q000737:chemistry*; D005978:Glutathione / Q000737:chemistry*; D007700:Kinetics; D015394:Molecular Structure; D010084:Oxidation-Reduction
chemical_list: D001152:Arsenicals; D004785:Environmental Pollutants; D005978:Glutathione
keywords: Arsenic detoxification; GSH; Kinetics; NMR; Phenylarsonic acid; Roxarsone