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The local atomic structure around iron atoms of two synthetic analogues of malarial pigment product is characterized by iron K-edge X-ray absorption fine structure spectroscopy (XAFS). Malarial pigment, also termed hemozoin, is a condensed phase of ferriprotoporphyrin-IX dimers, and is structurally identical to the synthetic material hematin anhydride, which is also termed IS-hematin. Synthetic hemozoin analogues might serve as surrogates or models of malaria pigment for a range of fundamental laboratory methods, for example the design of new antimalarials. Two new iron(III)(protoporphyrin-IX) analogues, based on meso- and deuteroporphyrin are considered. Both new condensed phases are slightly soluble in many organic solvents. In the present work, the detailed examination of X-ray absorption spectra of monomer- and dimer-ferriprotoporphyrin-IX-based compounds is discussed. Parameters obtained by quantitative spectra analysis allow us to classify the new synthetic equivalents of the parasite product as dimer materials. X-ray absorption technique was able to distinguish dimer from monomer structures based on the structural disorder parameters of oxygen ligand bonding. (C) 2010 Elsevier B.V. All rights reserved.
Francesco Stellacci, Matteo Gasbarri