Vanessa Regina Azevedo Ferreira

Abstract Imprinting chondroitin sulfate (CS)/silica composites with Pb(II) and Cu(II) cations was explored with CS of bovine and different fish species origin. The process was based on the assumption that particular arrangements of the linear CS chains in aqueous solution, induced so as to accommodate cross complexation with the cations, would be embodied into a tridimensional matrix created through an organoalkoxysilane sol-gel scheme. The presence of Cu(II) in the synthesis of the composites did not result in the production of significantly stronger Cu(II)-oriented binding arrangements, and therefore, the imprinting was not successful. Inversely, for Pb(II), the materials obtained exhibited a memory effect for the Pb(II) ions, expressed in the observation of stronger (13%-44%) binding as compared to the nonimprinted counterparts, and increased selectivity (1.5-2 folds) against Cd(II). The imprinting features observed were dependent on the CS source. However, it was not possible to identify, among a set of their properties (carboxylate and sulfate abundance, percent of disulfated units, 4S/6S ratio, and molecular weight), any that correlated directly with the observed imprinting features. The augmented selectivity provided by the cation-imprinting process may be advantageous in areas such as analytical separation, remediation, purification, sensing, and others, particularly in those cases where a certain cation is of special interest within a mixture of them.

Abstract L-tyrosine controlled release systems, based on imprinted polymers radically polymerized in modified organic solvents (dimethyl sulfoxide and methanol) were developed. A set of copolymers synthesized with different functional monomers and the crosslinker ethylene glycol dimethylacrylate were evaluated regarding both the imprinting and controlled release features. Those prepared in modified-DMSO were mesoporous (surface area ranging 370-690 m(2)/g) but not the ones prepared in modified methanol with the exception of the imprinted polymer prepared with the monomer vinylbenzoic acid (209 m(2)/g). The swelling degree ranged 32 to 64% and appeared to be mostly dependent on the functional group employed in the synthesis of the polymers. When tested in dynamic mode a clear imprinting effect has been observed in some of the imprinted polymers. However, selectivity for L-Tyr against similar compounds could not be found in these conditions. Selectivity could be observed when carrying out the isothermal analysis, with selectivity factors up to 2.7. A few polymers exhibited also other remarkable features such as high L-Tyr load capacity (up to 253 mg L-Tyr/g) and large binding strength (up to 55 L(m)mg((1-m)))/g). Therefore, imprinted polymers capable of a selective sorption of L-Tyr upon equilibration, containing stronger binding sites for L-Tyr, appeared promising vehicles for its controlled release. In fact, the release assays with L-Tyr impregnation by adsorption, showed profiles corresponding to controlled release systems, with high yield (40-50%) and continuous release (up to at least 7 h). In addition, release mechanisms recommended for controlled release systems were deduced from kinetic data fitting to the Korsmeyer and Order 0 models.