Solvent-less carboxymethylation-induced electrostatic crosslinking of chitosan

Abstract

The successful N-carboxymethylation and concomitant crosslinking of solid chitosan upon heating its mixture with solid monochloroacetic acid, without the use of solvents or catalysts, is reported. The N-carboxymethylation was confirmed through the analysis of the partially depolymerized product using NMR spectroscopy, as well as a control reaction with lysine. This transformation was facilitated by the nucleophilic nature of the free amine group in the repeating unit of chitosan, which possesses lone pair of electrons capable of attacking the carbon center bearing the leaving group and displacing the leaving group in a concerted manner. The crosslinking, on the other hand, was established by the observed insolubility in aqueous acidic solutions, even when subjected to prolonged heating at 60 °C. This crosslinking occurs due to the electrostatic interactions between the carboxylate groups and the adjacent ammonium groups, as supported by evidence from FTIR spectroscopy and a control reaction involving ethyl chloroacetate. The resulting crosslinked carboxymethyl chitosan demonstrated its usefulness in the adsorption of methyl orange and fluorescein, as well as functioning as an organic catalyst for aza-Michael addition, Hantzsch reaction, and substituted perimidine synthesis.