화학공학소재연구정보센터
Reactive & Functional Polymers, Vol.36, No.3, 257-264, 1998
Coordinating ability of the acetate ion towards cis-(1,3-diamine-2-hydroxypropane)palladium(II) chelate units in aqueous solutions. Preliminary study about the possibility of the acetato ligand to be involved in complex formation equilibria with palladium(II)-based anticancer drugs
Cis-dichloro(l,3-diamino-2-propanol)palladium(II) cis-[Pd(dapol)Cl-2], reacts with stoichiometric amounts of AgClO4 to give chloride free solutions of cis-[Pd(dapol)(H2O)(2)](ClO4)(2) (compound I). Twelve mixed compound I/acetic acid (AcOH) solutions having three different I/AcOH molar ratios and/or total molar complex concentration have been titrated with NaOH 0.1 mol dm(-3) at 37 degrees C and I = 0.15 mol dm-3 (NaClO4). Formation constants (log beta(pqr)) of mixed hydroxo-acetato complexes were fitted for the equilibrium: pPdL(H2O)(2) + qAcO - rH reversible arrow (PdL)(p)(AcO)(q) (H2O)(2-r)(OH)(r) using the log beta of acetate ion protonation (also determined) and the corresponding log beta(pqr) data for aqua- and/or hydroxo-complexes previously reported (as fixed values). New calculations were performed by the HYPERQUAD program. Simulated and experimental titrations agree well. Several distribution diagrams are used to show that acetate ions prevent the alkaline hydrolysis of compound I to a lesser extent than they do chloride ions. Both chloride and acetate ions could compete but also contribute to preventing such hydrolysis in weakly acid or nearly neutral solutions. These findings also apply inside cells at physiological conditions (pH = 7.2-7.4 and [Cl-] similar to 4 mM) for a total molar complex concentration of similar to 1 mM in which compound I could react with DNA and related biopolymers.