Title:Synthesis of Dibenzo-24-crown-8 Conjugated Chitosan with Different Amide Bond Coupling Methods
VOLUME: 15 ISSUE: 3
Author(s):Da-Ming Wang*, Tomonari Tanaka, Takashi Aoki, Yuji Aso, Hideaki Minami and Hitomi Ohara*
Affiliation:Department of Biobased Materials Science, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Department of Biobased Materials Science, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Department of Biobased Materials Science, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Department of Biobased Materials Science, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Kyoto Municipal Institute of Industrial Technology and Culture, 91 Chudoji Awata-cho, Shimogyo-ku, Kyoto 600-8815, Department of Biobased Materials Science, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585
Keywords:Amide bond coupling, carbodiimide, chitosan, degree of substitution, dibenzo-24-crown-8, N-hydroxysuccinimide.
Abstract:Background: Chitosan is well-known as a metal chelating agent for removing metal ions in
near-neutral conditions. Chemical modification of chitosan has attracted attention to improve its metalion
adsorbent properties. Recently, dibenzo-24-crown-8 derivatives were synthesized and reported to
chelate with metal ions such as cesium. However, to date, to the best of our knowledge, there is no report
on the use of dibenzo-24-crown-8 to modify chitosan. In this paper, the modification of amino
groups on chitosan by amide formation with dibenzo-24-crown-8 moieties in aqueous solution was investigated
by three different methods: two dehydrative condensing reactions with dibenzo-24-crown-8
having a COOH group and the use of an activated ester derivative of dibenzo-24-crown-8.
Methods: Three methods, i.e., the reactions of dibenzo-24-crown-8 having a COOH group with either
EDC-1-hydroxybenzotriazole (HOBt) or EDC-N-hydroxysuccinimide (NHS) and the reaction using the
succinimide-activated ester of dibenzo-24-crown-8, were compared on chitosan. The prepared chitosan-
dibenzo-24-crown-8 conjugates were characterized by 1H NMR and IR spectroscopy. The degree
of substitution (DS) by the dibenzo-24-crown-8 moieties at the amino groups on chitosan was calculated
by 1H NMR analysis.
Results: In both the EDC-HOBt and EDC-NHS methods, the maximum DS was only 4.1%. Conversely,
a higher DS (15.2%) was afforded when the succinimide ester of dibenzo-24-crown-8 was reacted
with chitosan under pH 6.0. The 1H NMR spectrum of the product showed signals from both chitosan
and the crown ether. C=O bands attributable to the amide linkage between chitosan and the
crown ether appeared at 1656 and 1552 cm−1 in the IR spectra.
Conclusion: The use of the activated ester of dibenzo-24-crown-8 resulted in a higher DS at amino
groups on chitosan when compared with the EDC-HOBt or EDC-NHS systems. This result implies that
the use of activated ester derivatives is efficient for the modification of chitosan in aqueous solution.
