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Synthesis of regioselective chitosan copolymers with β-cyclodextrin and poly(N-isopropyl acrylamide)

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Abstract

This work aimed to design a synthetic route under mild conditions allowing the main chitosan chain to be grafted with β-cyclodextrin (β-CD) and poly(N-isopropyl acrylamide) (PNIPAm), at C2 and C6 positions, respectively. For this reason, the regioselectivity of proposed reactions is an important factor to be considered. β-CD is an oligosaccharide with a cyclic structure capable of forming inclusion complexes with hydrophobic molecules. Grafting β-CD onto the chitosan backbone by reductive N-alkylation at C2 position was carried out. With this purpose, the previous preparation of β-CD monoaldehyde was required. PNIPAm is a thermosensitive polymer with a transition temperature near 33 °C. To regioselectively anchor poly(N-isopropyl acrylamide) chains onto chitosan at C6 position, it was required to attach at the C6 position of chitosan an alkyl group for the subsequent grafting of PNIPAm-N3 by means of copper-catalyzed azide-alkyne cycloaddition click reaction. To guarantee the regioselectivity of the functionalization of chitosan with a C6 terminal alkyne, its oxyalkylation with glycidyl propargyl ether in a solvent composed of LiOH/KOH/urea was used. The structure of all derivatives was confirmed by FT-IR and 1H-NMR spectroscopy.

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Acknowledgments

ICS acknowledges CONACyT for his scholarship for Ph.D. studies (664924). The authors are grateful to Dr. Refugio Pérez-González from the Spectroscopy Laboratory of the Department of Polymers and Materials of the University of Sonora for providing the 1H-NMR spectra.

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Authors and Affiliations

  1. Centro de Investigación en Alimentación y Desarrollo, Biopolymer Research Group, 83304, Hermosillo, Sonora, Mexico

    Iván Canale-Salazar, Jaime Lizardi-Mendoza, Yolanda López-Franco & Waldo Argüelles-Monal

  2. Faculty of Chemistry, Universidad de La Habana, 10400, Havana, Cuba

    Carlos Peniche-Covas

  3. Universidad Veracruzana, Unidad de Servicios de Apoyo en Resolución Analítica, 91190, Xalapa, Veracruz, Mexico

    Javier Hernández

  4. School of Food Science and Nutrition, University of Leeds, Leeds, LS2 9JT, UK

    Francisco M. Goycoolea

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  1. Iván Canale-Salazar
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  2. Jaime Lizardi-Mendoza
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  3. Yolanda López-Franco
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Correspondence to Waldo Argüelles-Monal.

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Canale-Salazar, I., Lizardi-Mendoza, J., López-Franco, Y. et al. Synthesis of regioselective chitosan copolymers with β-cyclodextrin and poly(N-isopropyl acrylamide). J Polym Res 27, 112 (2020). https://doi.org/10.1007/s10965-020-02076-7

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