Speciation in the vanadate-alanylhistidine-peroxide system

The speciation in the quaternary aqueous H+-H2VO4--H2O2-L-alpha-alanyl-L-hi stidine (Ah) system has been determined from quantitative V-51 NMR measurem ents and potentiometric data (glass electrode). The study was performed in 0.150 M Na(CI) medium at 25 degrees C. Data were evaluated with the compute r program LAKE, which is able to treat combined potentiometric and NMR data . In the ternary H+-H2VO4--Ah system, two complexes, (H+)(p)(H2VO4-)(q)(Ah) (r), having (p, q, r) values (0, 1, 1) and (1, 1, 1) (pK(a) = 6.88) explain all data. In the quaternary H+-H2VO4--H2O2-Ah system, seven complexes were determined in addition to all binary and ternary complexes, four with a V/ X/Ah ratio 1:1:1 and three with a ratio 1:2:1 (X = peroxo ligand). VX(2)Ah( 2)(-) and VX(2)Ah(-) (pK(a) = 8.26) are the main quaternary complexes and p redominate in the pH range 5 to 9. Chemical shifts, compositions and format ion constants for all the quaternary complexes are given, and equilibrium c onditions are illustrated in distribution diagrams. (C) 2000 Elsevier Scien ce Inc. All rights reserved.