pH affected migrational transport of ferrocene derivative of l-cysteine in aqueous solutions: Voltammetric studies

The mass transport of biologically-active l-cysteine derivatized with the ferrocenyl group (FcCH₂Cys) was investigated voltammetrically at a microelectrode in aqueous solutions under the conditions of varying content of supporting electrolyte and at different pH values. By varying the pH conditions one could obtain samples containing differently ionized forms of the l-cysteine derivative, from a monovalent cation via a neutral form (zwitterion) to a monovalent anion. Due to the acid-base equilibrium the obtained solutions were, in fact, mixtures composed predominantly of either anionic or cationic, or neutral species of FcCH₂Cys, respectively. Under the conditions of low ionic support the mass transport of these forms is differently affected by the migrational contribution. The results obtained experimentally were in good agreement with the theoretical predictions. In the calculations it was assumed that the FcCH₂Cys forms, coexisting in the solution, contribute independently to the steady-state transport-limited current. It was also assumed that the diffusion coefficients of the FcCH₂Cys forms were equal. This was validated by the voltammetric measurements at the supporting electrolyte excess (purely diffusional conditions). The diffusion coefficients of different forms of FcCH₂Cys are very similar and the average diffusion coefficient is (5.35 ± 0.05) × 10⁻¹⁰ m²/s.The studies clearly show that the variation in the conditions of pH or/and concentration of electrolyte can change the transport rate of l-cysteine even by several tens percent.