Influence of polymer network-metal ion complexation on the swelling behaviour of new gels with incorporated α-amino acidgroups

Abstract

New gels based on N-isopropylacrylamide and amino acid L-ornithine were prepared by free radical polymerization in aqueous solutions. To make the amino acid attachable to the polymer chain the acrylic group was added to the δ-amino group of ornithine, to obtain N-δ-acrylic ornithine. After the polymerization process the α-amino acid groups were unbound. The relative content of amino acid incorporated into the polymeric network of the gels was estimated from ¹HNMR spectra, then compared with the molar fraction used for the polymerization process. The presence of free α-amino acid groups attached to the polymeric network of the gels enabled the complexation of some di- and trivalent metal cations. Copper ions, which can form two complexes of different stoichiometry (1 : 1 and 1 : 2) with amino acids, were used to investigate the influence of the complexation process on the swelling behavior of the gels. The influence of amino acid content, temperature and copper ion concentration on the swelling process was also examined. The gels were found to be most sensitive to concentrations of copper ions in the range 10⁻⁶–10⁻⁵ M. As the amount of amino acid in the polymer network increases the gels gradually lose their temperature-sensitivity and become more sensitive to copper ion concentration. The volume-phase-transition temperature decreases significantly after the addition of copper ions. Analysis of the UV-Vis spectra and the swelling behavior indicates that both 1 : 1 and 1 : 2 complexes are present in the swollen state of the gels, whereas the latter complex is more dominant in the shrunken state.