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The interactions between the cationic polymer chitosan (a copolymer, consisting mainly of 2-amino-2-deoxy-D-glucopyranose and, to a lesser extent, of 2-acetamido-2-deoxy-D-glucopyranose, Chit) and iron(III) were investigated. The solution properties were studied by pH-metry, UV-Vis spectrophotometry and viscometry. Solid state iron(III)-Chit samples were also prepared and characterized by IR-spectroscopy and electronmicroscopy. In aqueous solutions, the precipitation pH of the FeO(OH) is significantly shifted towards the higher pH-s in presence of Chit. However, the additivity of the pH-metric titration curves, the lack of variation both in tin presence and absence of iron(III), indicate that there is no specific coordination chemical interaction between the Chit and ferric ions. It is well established that spherical FeO(OH) particles with afew nm diameter, morphologically similar to the core of the iron(III)-storage protein ferritin, are formed during the hydrolysis of iron(III) even in the absence of complexing agents. Such isolated FeO(OH) spheres were observed in samples obtained from solutions containing iron(III) and Chit. The fact, that visible precipitation of FeO(OH) can only be observed, when the Chit itself precipitates from aqueous solutions (i.e., pH approximately 7), indicates that the role of Chit in these systems is to inhibit the aggregation of the subcolloidal FeO(OH) particles. These observations are in strong contrast with those obtained for interactions between iron(III) and various anionic biopolymers, such as heparin, hyaluronate, dextran sulfate and chondroitin sulphate A and C, and suggest that coordination chemical interactions play very important role in determining the nanostructure of composite materials containing iron(III) and polysaccharides.