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Structural changes in α-chitin through nanofibrillation by high-pressure homogenization in water

Polymer Journal volume 52, pages 813–818 (2020)Cite this article

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Abstract

Chitin nanofiber was prepared from purified crab shell chitin by repeated high-pressure homogenization in water. The chitin nanofiber/water dispersion thus prepared was viscous and translucent, and maintained a stable dispersion at room temperature for several months. AFM images showed that the chitin nanofibers had heterogeneous network structures with widths ranging from several nanometers to several tens of nanometers. Some kinks and twisted structures were also observed in the AFM images. X-ray diffraction patterns showed that both the crystallinity index and crystal width of the original alpha-chitin decreased with nanofibrillation. Solid-state 13C-NMR spectra showed that the chemical shifts of all carbons were unchanged before and after nanofibrillation, and that all C6–OH groups had the gauche-gauche conformation irrespective of the crystalline fibril surfaces and insides. The degree of N-acetylation increased from 0.83 to 0.98, which was probably due to C2–NH2 groups present in the original chitin being partially removed during high-pressure homogenization in water. The original chitin and chitin nanofiber were dissolved in 8% LiCl/DMAc, and the solutions after dilution to 1% LiCl/DMAc were subjected to size-exclusion chromatography combined with multi-angle laser-light scattering to determine their molar masses and molar mass distributions. The weight-average molar mass (Mw) value of the original chitin was 271,200 (degree of polymerization [DP] ~1340). The Mw value of the chitin nanofiber was 165,500 (DP 820), showing that the DP of the original chitin decreased by 40% through the nanofibrillation in water to form the chitin nanofiber.

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References

  1. Fan Y, Saito T, Isogai A. Preparation of chitin nanofibers from squid pen β-chitin by simple mechanical treatment under acid conditions. Biomacromolecules. 2008;9:1919–23. https://doi.org/10.1021/bm800178b

    Article  CAS  PubMed  Google Scholar 

  2. Fan Y, Saito T, Isogai A. Chitin nanocrystals prepared by TEMPO-mediated oxidation of chitin. Biomacromolecules. 2008;9:192–8. https://doi.org/10.1021/bm700966g

    Article  CAS  PubMed  Google Scholar 

  3. Ifuku S, Nogi M, Abe K, Yoshioka M, Morimoto M, Saimoto H, et al. Preparation of chitin nanofibers with a uniform width as chitin from crab shells. Biomacromolecules. 2009;10:1584–88. https://doi.org/10.1021/bm900163d

    Article  CAS  PubMed  Google Scholar 

  4. Fan Y, Saito T, Isogai A. Individual chitin nano-whiskers prepared from partially deacetylated α-chitin by fibril surface cationization. Carbohydr Polym. 2010;79:1046–51. https://doi.org/10.1016/j.carbpol.2009.10.044

    Article  CAS  Google Scholar 

  5. Ifuku S, Yamada K, Morimoto M, Saimoto H. Nanofibrillation of dry chitin powder by Star Burst system. J Nanomater. 2012;64524:1–7. https://doi.org/10.1155/2012/645624

    Article  CAS  Google Scholar 

  6. Ifuku S, Saimoto H. Chitin nanofibers: preparations, modifications, and applications. Nanoscale. 2012;4:3308–18.

    Article  CAS  Google Scholar 

  7. Fan Y, Fukuzumi H, Saito T, Isogai A. Comparative characterization of aqueous dispersions and cast films of different chitin nanowiskers/nanofibers. Int J Biol Macromol. 2012;50:69–76. https://doi.org/10.1016/j.ijbiomac.2011.09.026

    Article  CAS  PubMed  Google Scholar 

  8. Qi ZD, Fan Y, Saito T, Fukuzumi H, Tsutsumi Y, Isogai A. Improvement of nanofibrillation efficiency of α-chitin in water by selecting acid used for surface cationisation. RSC Adv. 2013;3:2613–9. https://doi.org/10.1039/c2ra22271j

    Article  CAS  Google Scholar 

  9. Hasegawa M, Isogai A, Onabe F. Molecular mass distribution of chitin and chitosan. Carbohydr Res. 1994;262:161–6. https://doi.org/10.1016/0008-6215(94)84013-X

    Article  CAS  Google Scholar 

  10. Funahashi R, Ono Y, Qi ZD, Saito T, Isogai A. Molar masses and molar mass distributions of chitin and acid-hydrolyzed chitin. Biomacromolecules. 2017;18:4357–63. https://doi.org/10.1021/acs.biomac.7b01413

    Article  CAS  PubMed  Google Scholar 

  11. Ono Y, Tanaka R, Funahashi R, Takeuchi M, Saito T, Isogai A. SEC–MALLS analysis of ethylenediamine-pretreated native celluloses in LiCl/N,N-dimethylacetamide: softwood kraft pulp and highly crystalline bacterial, tunicate, and algal celluloses. Cellulose 2016;23:1639–47. https://doi.org/10.1007/s10570-016-0948-4

    Article  CAS  Google Scholar 

  12. Funahashi R, Okita Y, Hondo H, Zhao M, Saito T, Isogai A. Different conformations of surface cellulose molecules in native cellulose microfibrils revealed by layer-by-layer peeling. Biomacromolecules. 2017;18:3687–94. https://doi.org/10.1021/acs.biomac.7b01173

    Article  CAS  PubMed  Google Scholar 

  13. Heux L, Brugnerotto J, Desbrieres J, Versali MF, Rinaudo M. Solid state NMR for determination of degree of acetylation of chitin and chitosan. Biomacromolecules. 2000;1:746–51. https://doi.org/10.1021/bm000070y

    Article  CAS  PubMed  Google Scholar 

  14. Zhou Y, Fujisawa S, Saito T, Isogai A. Characterization of concentration-dependent gelation behavior of aqueous 2,2,6,6-tetramethylpiperidine-1-oxyl−cellulose nanocrystal dispersions using dynamic light scattering. Biomacromolecules. 2019;20:750–7. https://doi.org/10.1021/acs.biomac.8b01689

    Article  CAS  PubMed  Google Scholar 

  15. Cárdenas G, Cabrera G, Taboada E, Miranda P. Chitin characterization by SEM, FTIR, XRD, and 13C cross polarization/mass angle spinning NMR. J Appl Polym Sci. 2004;93:1876–85. https://doi.org/10.1002/app.20647

    Article  CAS  Google Scholar 

  16. Isogai A, Usuda M, Kato T, Uryu T, Atalla RH. Solid-state CP/MAS carbon-13 NMR study of cellulose polymorphs. Macromolecules. 1989;22:3168–72. https://doi.org/10.1021/ma00197a045

    Article  CAS  Google Scholar 

  17. Larsson PT, Westlund PO. Line shapes in CP/MAS 13C NMR spectra of cellulose I. Spectrochim Acta A. 2005;62:539–46. https://doi.org/10.1016/j.saa.2005.01.021

    Article  CAS  Google Scholar 

  18. Horii F, Hirai A, Kitamaru R. Solid-state 13C-NMR study of conformations of oligosaccharides and cellulose. Polym Bull. 1998;10:357–61. https://doi.org/10.1007/BF00281948

    Article  Google Scholar 

  19. Tanner SF, Chanzy H, Vincendon M, Roux JC, Gaill F. High-resolution solid-state carbon-13 nuclear magnetic resonance study of chitin. Macromolecules. 1990;23:3576–83. https://doi.org/10.1021/ma00217a008

    Article  CAS  Google Scholar 

  20. Shigemasa Y, Matsumura H, Sashiwa H, Saimoto H. Evaluation of different absorbance ratios from infrared spectroscopy for analyzing the degree of deacetylation in chitin. Int J Biol Macromol. 1996;18:237–42. https://doi.org/10.1016/0141-8130(95)01079-3

    Article  CAS  PubMed  Google Scholar 

  21. Goodrich JD, Winter WT. α-Chitin nanocrystals prepared from shrimp shells and their specific surface area measurement. Biomacromolecules. 2007;8:252–7. https://doi.org/10.1021/bm0603589

    Article  CAS  PubMed  Google Scholar 

  22. Fan Y, Saito T, Isogai A. Preparation of chitin nanofibers from squid pen α-chitin by simple mechanical treatment under acid conditions. Biomacromolecules. 2008;9:1919–23. https://doi.org/10.1021/bm800178b

    Article  CAS  PubMed  Google Scholar 

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Acknowledgements

This research was supported by Core Research for Evolutional Science and Technology (CREST, Grant no. JPMJCR13B2) of the Japan Science and Technology Agency (JST). We thank the Edanz Group for editing a draft of this manuscript.

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Authors and Affiliations

  1. Department of Biomaterial Sciences, The University of Tokyo, Bunkyo-ku, Tokyo, 113-8657, Japan

    Yuko Ono, Yuto Kaku, Shuji Fujisawa & Akira Isogai

  2. Cooperate Planning Division, Sugino, Co., Ltd., 2410 Hongo, Uozu, Toyama, 937-8511, Japan

    Kota Ogura

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  1. Yuko Ono
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Correspondence to Akira Isogai.

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Ono, Y., Ogura, K., Kaku, Y. et al. Structural changes in α-chitin through nanofibrillation by high-pressure homogenization in water. Polym J 52, 813–818 (2020). https://doi.org/10.1038/s41428-020-0322-0

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