RESUMO
We have described a new route for the preparation of partially methylated polygalacturonic acid containing hydrolyzed (acidic) and unhydrolyzed (methyl esterified) carboxylate groups in a ratio of 1:1 (PGA, compound 1), and one of its basic FeIII-salts (compound 2) with a ~1:2 FeIII:GA stoichiometry (GA means galacturonic acid and methylated galacturonic acid units). The partially hydrolyzed pectin was transformed into compound 1 with the use of double ion exchange with a strongly acidic macroreticular sulfonated styrene-divinylbenzene copolymer as a hydrogen ion source. The reaction of compound 1 with FeCl3 resulted in compound 2. Compound 2 has a polymeric nature and contains binuclear FeIII(µ-O)(µ-OH)FeIII core units with two kinds of distorted octahedral iron geometries. The salt-forming acidic and methylated GA units of compound 1 are coordinated to FeIII centers in asymmetric bidentate-chelating and -bridging (via C=O group and glycosidic oxygen) modes, respectively. Two kinds of outer-sphere chloride anions were also detected by XPS in various chemical environments fixed by different sets of hydrogen bonds. We also observed a partial reduction of FeIII into FeII due to the ring-opening of the chain-end GA units of compound 1. This reaction provides a new route to determine the number of chain-ends in compound 2, and with the use of the number of GA units calculated from charge neutrality, the average length of these chains and the average molecular weight were also determined. The average molecular weight of the partially methylated polygalacturonic acid used in the industrial-scale production of commercial anti-anemic iron-polygalacturonate agents was ~50,000 g/mol. Compound 2 was also characterized by IR, Mössbauer, and X-ray photoelectron spectroscopy, and magnetic susceptibility measurements. These results on the structure and average molecular weight of basic iron(III) polygalacturonate provide a tool to design Fe-PGA complexes with tuned iron-releasing properties.
RESUMO
Electrodeposited Ni65Co35/Cu multilayers were prepared with Cu spacer layer thicknesses between 0.5 nm and 7 nm. Their structure and magnetic and magnetoresistance properties were investigated. An important feature was that the Cu layers were deposited at the electrochemically optimized Cu deposition potential, ensuring a reliable control of the spacer layer thickness to reveal the true evolution of the giant magnetoresistance (GMR). X-ray diffraction indicated satellite reflections, demonstrating the highly coherent growth of these multilayer stacks. All of the multilayers exhibited a GMR effect, the magnitude of which did not show an oscillatory behavior with spacer layer thickness, just a steep rise of GMR around 1.5 nm and then, after 3 nm, it remained nearly constant, with a value around 4%. The high relative remanence of the magnetization hinted at the lack of an antiferromagnetic coupling between the magnetic layers, explaining the absence of oscillatory GMR. The occurrence of GMR can be attributed to the fact that, for spacer layer thicknesses above about 1.5 nm, the adjacent magnetic layers become uncoupled and their magnetization orientation is random, giving rise to a GMR effect. The coercive field and magnetoresistance peak field data also corroborate this picture: with increasing spacer layer thickness, both parameters progressively approached values characteristic of individual magnetic layers. At the end, a critical analysis of previously reported GMR data on electrodeposited Ni-Co/Cu multilayers is provided in view of the present results. A discussion of the layer formation processes in electrodeposited multilayers is also included, together with a comparison with physically deposited multilayers.