Functionalization of an Alginate-Based Material by Oxidation and Reductive Amination

Abstract

This research focused on the synthesis of a functional alginate-based material via chemical modification processes with two steps: oxidation and reductive amination. In previous alginate functionalization with a target molecule such as cysteine, the starting material was purified and characterized by UV-Vis, ¹H-NMR and HSQC. Additionally, the application of FT-IR techniques during each step of alginate functionalization was very useful, since new bands and spiked signals around the pyranose ring (1200-1000 cm^-1) and anomeric region (1000-750 cm^-1) region were identified by a second derivative. Additionally, the presence of C₁-H₁ of β-D-mannuronic acid residue as well as C₁-H₁ of α-L-guluronic acid residue was observed in the FT-IR spectra, including a band at 858 cm^-1 with characteristics of the N-H moiety from cysteine. The possibility of attaching cysteine molecules to an alginate backbone by oxidation and post-reductive amination processes was confirmed through ¹³C-NMR in solid state; a new peak at 99.2 ppm was observed, owing to a hemiacetal group formed in oxidation alginate. Further, the peak at 31.2 ppm demonstrates the presence of carbon -CH₂-SH in functionalized alginate-clear evidence that cysteine was successfully attached to the alginate backbone, with 185 μmol of thiol groups per gram polymer estimated in alginate-based material by UV-Visible. Finally, it was observed that guluronic acid residue of alginate are preferentially more affected than mannuronic acid residue in the functionalization.