Chemical modification of chitosan: synthesis and biological activity of new heterocyclic chitosan derivatives

BACKGROUND: Numerous works have been published on the chemical modification of chitosan; this polymer is still being modified, leading to various derivatives with improved properties. In the present study, heterocyclic aldehydes including furan-2-carbaldehyde, 5-methylfuran-2-carbaldehyde, 3-pyridine carboxyaldehyde, benzo[d][1,3]dioxole-5-carbaldehyde and 4-oxo-4H-chromene-3-carbaldehyde were reacted with chitosan by a reductive alkylation reaction to produce for the first time five new N-heterocyclic chitosan derivatives to improve the biological activity of chitosan against the most important economic plant pests including fungi and insects, in particular the cotton leafworm Spodoptera littoralis. RESULTS: The chemical structures of the synthesized compounds were confirmed by H-1 NMR spectroscopy and the degree of substitution ranged from 0.30 to 0.43. The fungicidal assessment was investigated in vitro using a mycelia radial growth inhibition technique against soil-borne pathogenic fungi Fusarium oxysporum and Pythium debaryanum and the rice leaf blast Pyricularia grisea. The results showed that N-[(5-methylfuran-2-yl)methyl] chitosan was the most active against P. grisea with an EC50 value of 0.919mg mL(-1) while N-(benzo[d][1,3]dioxol5-ylmethyl) chitosan and N-(methyl-4H-chromen-4-one) chitosan exhibited the most potent fungicidal activity against P. debaryanum and F. oxysporum. An insecticidal bioassay against the larvae of S. littoralis showed that N-(methyl-4H-chromen-4-one) chitosan exhibited a significant growth inhibition and antifeedant activity among the synthesized compounds. CONCLUSION: The chemical modification of chitosan molecule with a heterocyclic moiety led to an enhancement in the biological activity against the plant pathogenic fungi F. oxysporum, P. debaryanum and P. grisea and the cotton leafworm insect S. littoralis. (C) 2007 Society of Chemical Industry.