Conventional
synthesis of N-methylated chitosan involves the use
of organic solvents in alkaline conditions, using methyl iodide as
the methylating agent. However, the method does not result in selective
N-methylation and is known to cause heavy polymer scission. In this
investigation, we have reported alternative “green”
approaches for methylated chitosan synthesis. Two types of deep eutectic
solvents (DESs), viz., DES(Urea) and DES(Gly), either alone or in
combination with other solvents, were screened as media for facilitating
the methylation of chitosan. Our results indicated that DESs mediated
selective N-methylation in the absence of NaOH, with no polymer scission,
when compared with the reported methods. 1H NMR spectra
confirmed selective N-methylation in the case of products obtained
using DES(Urea), while that obtained using DES(Gly) demonstrated some
O-methylation. Another green method investigated the unexplored property
of biocatalyst lipase for methylating chitosan in the presence of
“green” methylating agents in DESs systems. Furthermore,
lipase from Burkhorlderia species exhibited ability
to methylate the chitosan polymer, while the enzyme from Candida
Antartica failed to methylate the polymer. Our investigation
also confirmed the possibility of using dimethyl carbonate as a benign
methylating agent.
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