Synthesis and unambiguous NMR characterization of linear and branched N-alkyl chitosan derivatives

Abstract

Chitosan, sourced from abundant chitin-rich waste streams, emerges as a promising candidate in the realm of future functional materials and chemicals. While showing numerous advantageous properties, chitosan sometimes falls short of competing with today's non-renewable alternatives. Chemical derivatization, particularly through N-alkylation, proves promising in enhancing hydrophobic functionalities. This study synthesizes fifteen chitosan derivatives (degree of substitution = 2-10 %) using an improved reductive amination method. Next, selective depolymerization through acid hydrolysis reduced the chain rigidity imposed by the polymer backbone. This facilitated unambiguous structural characterization of the synthesized compounds using a combination of common NMR techniques. Two potential side reactions are identified for the first time, emphasizing the need for detailed structural information to unlock the true potential of these derivatives in future applications. HYPOTHESIS: The increase in chain mobility induced by the selective depolymerization of aliphatic N-alkyl chitosan derivatives allows for an unambiguous NMR characterization.

Keywords: Analysis; Chitosan; Chitosan derivatives; N-alkylation; NMR.