Supplementary material from "Oxidation of l-leucine amino acid initiated by hydroxyl radical : are transition metal ions an enhancement factor?"

Hydroxyl radical (HO·) formation initiated by the Fenton-type reactions of Fe and Cu complexes of l-leucine (Leu) amino acid as well as its oxidation reaction by HO· was computationally investigated by using the density functional theory method at the M05-2X/6-311++G(3df,2pd)//M05-2X/6-311++G(d,p) level of theory in the aqueous phase. The results showed that dipole-salt is the main form of Leu in the physiological condition. Leu exhibits high chelating potential towards both Fe(III)/Fe(II) and Cu(II)/Cu(I) ions with the most favourable coordinating positions at two oxygen atoms of the –COO functional groups. Furthermore, the Leu-ions complexes show a high risk of HO·formationvia Fenton-like reactions, especially when ascorbate anion exists in the environment as a reducing agent. Finally, the oxidation reaction of l-leucine by HO· demonstrated a relatively high overall apparent reaction rate, k_overall, being 1.18 × 10⁹ M⁻¹ s⁻¹, in which formal hydrogen transfer reactions of the dipole-salt form occur as the primary mechanism. Consequently, the Leu oxidation by HO· radical can be promoted by the Fenton reaction enhancement of its transition metal complexes.