pH responsive graft copolymers of chitosan.

Grafting suitable polymers onto chitosan can produce cationic or polyampholyte polymers or hydrogels that are potential smart biomedical materials. Chitosan-graft-[poly(diethylamino)ethyl methacrylate] has been prepared in three different physical forms as linear free chains in solution, chemical gels crosslinked with glutaraldehyde, and poly(diethylamino)ethyl methacrylate] grafted onto chitosan tripolyphosphate gel beads. In addition to chemical structure, the graft copolymers were characterized with respect to their dissolution and swelling behavior in aqueous solution. It has been established that solubility of the products is controlled by the grafting yield. While pH sensitive polymers, which collapse at a given pH value are obtained at lower grafting yields, hydrogels form at higher grafting yields with pH responsive swelling behavior. Glutaraldehyde crosslinked chitosan-graft-[poly(diethylamino)ethyl methacrylate] gels and chitosan tripolyphosphate gel beads grafted with poly[(diethylamino)ethyl methacrylate] exhibit pH sensitive swelling with highest equilibrium swelling capacity at pH=1.2.

Effect of CaCO3/HCl pretreatment on the surface modification of chitin gel beads via graft copolymerization of 2-hydroxy ethyl methacrylate and 4-vinylpyridine.

Although chitin, poly(N-acetylglucosamine), possesses considerable potential as a biomaterial, it has not been as thoroughly studied as its derivative chitosan. In this study, the potential of chitin gel beads has been evaluated for surface modification via vinyl polymer grafting. Grafting behavior of two well-established vinyl monomers, namely 2-hydroxyethylmethacrylate (HEMA) and 4-vinylpyridine (4-VP) were investigated using cerium (IV) ammonium nitrate as the redox initiator with the aim of obtaining chemically functionalized more hydrophilic chitin surfaces. The intractable nature of chitin, which is one of its primary drawbacks as a grafting substrate was overcome by applying a CaCO3 treatment during bead preparation. The maximum grafting percentage of poly(HEMA) onto chitin bead without CaCO3 treatment was found to be 65%, while the value for CaCO3 treated chitin beads was 515%. The maximum grafting yield of poly(4-VP) on to CaCO3 treated chitin powder was 380% at optimum conditions. The grafting system was extensively characterized before and after grafting by FT-IR, SEM, C-13 NMR and XRD analyses. Significant improvement on the swelling capacities of chitin based gel beads in aqueous acidic, basic and neutral media was obtained. An account of the pros and cons of the system has been presented.