title: ROS initiated oxidation of dopamine under oxidative stress conditions in aqueous and lipidic environments.
abstract: Dopamine is known to be an efficient antioxidant and to protect neurocytes from oxidative stress by scavenging free radicals. In this work, we have carried out a systematic quantum chemistry and computational kinetics study on the reactivity of dopamine toward hydroxyl (•OH) and hydroperoxyl (•OOH) free radicals in aqueous and lipidic simulated biological environments, within the density functional theory framework. Rate constants and branching ratios for the different paths contributing to the overall reaction, at 298 K, are reported. For the reactivity of dopamine toward hydroxyl radicals, in water at physiological pH, the main mechanism of the reaction is proposed to be the sequential electron proton transfer (SEPT), whereas in the lipidic environment, hydrogen atom transfer (HAT) and radical adduct formation (RAF) pathways contribute almost equally to the total reaction rate. In both environments, dopamine reacts with hydroxyl radicals at a rate that is diffusion-controlled. Reaction with the hydroperoxyl radical is much slower and occurs only by abstraction of any of the phenolic hydrogens. The overall rate coefficients are predicted to be 2.23 × 10(5) and 8.16 × 10(5) M(-1) s(-1), in aqueous and lipidic environment, respectively, which makes dopamine a very good •OOH, and presumably •OOR, radical scavenger.
authors.affiliation: Departamento de Ciencias Básicas, Universidad Autónoma Metropolitana-Azcapotzalco, México. ciuga@xanum.uam.mx
authors.forename: Cristina
authors.initials: C
authors.lastname: Iuga
authors.forename: J Raul
authors.initials: JR
authors.lastname: Alvarez-Idaboy
authors.forename: Annik
authors.initials: A
authors.lastname: Vivier-Bunge
mesh_terms: D004298:Dopamine / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry*; D007700:Kinetics; D010084:Oxidation-Reduction; D018384:Oxidative Stress; D017382:Reactive Oxygen Species / Q000737:chemistry*; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
chemical_list: D017382:Reactive Oxygen Species; D014867:Water; D017665:Hydroxyl Radical; D004298:Dopamine