MALDI mass spectrometric determination of dendritic iron chelation stoichiometries and conditional affinity constants

The iron chelation stoichiometries of a dendritic iron(III) chelator with N-1, N-3, N-5-trimethylbenzene-1,3,5-tricarboxamide at its core, and containing 3 identical hexadentate tris-hydroxypyridinone branches D was studied by MALDI mass spectrometry. At pH 7.2, the speciation of the system included FeD, Fe2D and Fe3D species with the respective conditional stability constants of 26.74, 26.03 and 25.36. The differences in the stepwise affinity constants arise from the statistical distribution of iron(III), and there was no evidence for cooperativity between the iron-binding sites. Copyright (C) 2008 John Wiley & Sons, Ltd.