Kinetics and mechanistic approach to the oxidative behavior of biological anticancer platinum(IV) complex toward L-asparagine in acid medium and the effect of copper(II) catalyst

Abstract

The catalytic effect of copper(II) ions toward the oxidation of L-asparagine (Asn) by an anticancer platinum(IV) complex in the form of hexachloroplatinate(IV) (HCP) has been investigated in aqueous acid medium at the constant ionic strength and temperature. The progress of both uncatalyzed and copper(II)-catalyzed oxidation reactions has been monitored spectrophotometrically. The stoichiometry in both cases is [Asn]/[HCP] = 1:1. The kinetics of both redox reactions is first order with respect to [oxidant] and less than the unit order in [acid]. The order with respect to [Asn]T decreases from unity in the uncatalyzed path to less than unity in the catalyzed one. The catalyzed path is first order in [CuII]T. Increasing ionic strength and dielectric constant decreases the oxidation rates. The final oxidation products of L-asparagine are identified as the corresponding aldehyde (α-formyl acetamide), ammonium ion, and carbon dioxide. Tentative mechanisms of both reactions have been suggested. The appropriate rate laws are deduced. The activation parameters of the uncatalyzed reaction have been evaluated and discussed.