, Volume 25, Issue 12, pp 6873–6885 | Cite as

Parameters of hydrothermal gelation of chitin nanofibers determined using a severity factor

  • Shin Suenaga
  • Mitsumasa OsadaEmail author
Original Paper


The hydrothermal gelation of α- and β-chitin nanofibers (α- and β-ChNFs) prepared at neutral and acidic pH was conducted by heating them to 120, 160, 180, and 200 °C in a sealed reactor. The optical transmittance and mechanical strength of β-ChNFs gelated at the acidic pH were determined for the first time using a severity factor defined as a function of the integrated heating time and temperature. The width of β-ChNFs increased after the hydrothermal treatment, indicating that these fibers strongly adhered to each other to form a network structure during gelation. Furthermore, the hydrothermal gelation of α- and β-ChNFs with different degrees of disintegration prepared at the neutral and acidic pH was conducted. It was found that the hydrothermal treatment of α-chitin must be performed at the acidic pH to obtain a self-sustaining hydrogel of well-disintegrated NFs. The disintegration of β-chitin into NFs occurred more easily at the acidic pH than under the neutral conditions; however, in the latter case, the same disintegration degree of β-ChNFs could be achieved by increasing the number of disintegration steps. At the same disintegration degree, the strength of the self-sustaining hydrogel obtained at the neutral conditions was greater than that of the gel prepared at the acidic pH, indicating that the electrostatic repulsion caused by acid addition negatively affected the formation of the hydrogel network structure. To maximize the efficiency of the hydrothermal gelation process, ChNFs should be as thin as possible and electrostatic repulsion forces must be controlled.

Graphical abstract


α-Chitin nanofiber β-Chitin nanofiber Hydrothermal gelation Severity factor 



This work was supported by JSPS KAKENHI [Grant No.: 17H04893]. We thank Dr. Nobuhide Takahashi, Dr. Hiroshi Fukunaga, Dr. Iori Shimada, Dr. Kazuhide Totani, Dr. Yoshihiro Nomura, and Mr. Kazuhiko Yamashita for their substantial intellectual contributions to the conception of the project.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10570_2018_2053_MOESM1_ESM.docx (5.8 mb)
Supplementary material 1 (DOCX 5938 kb)


  1. Abe K, Ifuku S, Kawata M, Yano H (2014) Preparation of tough hydrogels based on β-chitin nanofibers via NaOH treatment. Cellulose 21:535–540CrossRefGoogle Scholar
  2. Aida TM, Oshima K, Abe C, Maruta R, Iguchi M, Watanabe M, Smith RL (2014) Dissolution of mechanically milled chitin in high temperature water. Carbohydr Polym 106:172–178CrossRefGoogle Scholar
  3. Brugnerotto J, Lizardi J, Goycoolea FM, Argüelles-Monal W, Desbrières J, Rinaudo M (2001) An infrared investigation in relation with chitin and chitosan characterization. Polymer 42:3569–3580CrossRefGoogle Scholar
  4. Chang C, Chen S, Zhang L (2011) Novel hydrogels prepared via direct dissolution of chitin at low temperature: structure and biocompatibility. J Mater Chem 21:3865–3871CrossRefGoogle Scholar
  5. Dutta AK, Izawa H, Morimoto M, Saimoto H, Ifuku S (2013) Simple preparation of chitin nanofibers from dry squid pen β-chitin powder by the star burst system. J Chitin Chitosan Sci 1:186–191CrossRefGoogle Scholar
  6. Fan Y, Saito T, Isogai A (2008) Preparation of chitin nanofibers from squid pen β-chitin by simple mechanical treatment under acid conditions. Biomacromolecules 9:1919–1923CrossRefGoogle Scholar
  7. Gautier S, Xhauflaire-Uhoda E, Gonry P, Piérard GE (2008) Chitin-glucan, a natural cell scaffold for skin moisturization and rejuvenation. Int J Cosmet Sci 30:459–469CrossRefGoogle Scholar
  8. Han LK, Kimura Y, Okuda H (1999) Reduction in fat storage during chitin–chitosan treatment in mice fed a high-fat diet. Int J Obes 23:174–179CrossRefGoogle Scholar
  9. Izumi R, Komada S, Ochi K, Karasawa L, Osaki T, Murahata Y, Tsuka T, Imagawa T, Itoh N, Okamoto Y, Izawa H, Morimoto M, Saimoto H, Azuma K, Ifuku S (2015) Favorable effects of superficially deacetylated chitin nanofibrils on the wound healing process. Carbohydr Polym 123:461–467CrossRefGoogle Scholar
  10. Jayakumar R, Divya Rani VV, Shalumon KT, Kumar PS, Nair SV, Furuike T, Tamura H (2009) Bioactive and osteoblast cell attachment studies of novel α- and β-chitin membranes for tissue-engineering applications. Int J Biol Macromol 45:260–264CrossRefGoogle Scholar
  11. Klinchongkon K, Khuwijitjaru P, Wiboonsirikul J, Adachi S (2015) Extraction of oligosaccharides from passion fruit peel by subcritical water treatment. J Food Process Eng 40:e12269CrossRefGoogle Scholar
  12. Lewis L, Derakhshandeh M, Hatzikiriakos SG, Hamad WY, MacLachlan MJ (2016) Hydrothermal gelation of aqueous cellulose nanocrystal suspensions. Biomacromolecules 17:2747–2754CrossRefGoogle Scholar
  13. Madhumathi K, Binulal NS, Nagahama H, Tamura H, Shalumon KT, Selvamurugan N, Nair SV, Jayakumar R (2009) Preparation and characterization of novel β-chitin-hydroxyapatite composite membranes for tissue engineering applications. Int J Biol Macromol 44:1–5CrossRefGoogle Scholar
  14. Mushi NE, Kochumalayil J, Cervin NT, Zhou Q, Berglund LA (2016) Nanostructurally controlled hydrogel based on small-diameter native chitin nanofibers: preparation, structure, and properties. Chemsuschem 9:989–995CrossRefGoogle Scholar
  15. Nata IF, Wang SSS, Wu TM, Lee CK (2012) β-Chitin nanofibrils for self-sustaining hydrogels preparation via hydrothermal treatment. Carbohydr Polym 90:1509–1514CrossRefGoogle Scholar
  16. Ogawa Y, Kimura S, Wada M (2011) Electron diffraction and high-resolution imaging on highly-crystalline β-chitin microfibril. J Struct Biol 176:83–90CrossRefGoogle Scholar
  17. Osada M, Miura C, Nakagawa YS, Kaihara M, Nikaido M, Totani K (2012) Effect of sub- and supercritical water pretreatment on enzymatic degradation of chitin. Carbohydr Polym 88:308–312CrossRefGoogle Scholar
  18. Osada M, Kikuta K, Yoshida K, Totani K, Ogata M, Usui T (2013) Non-catalytic synthesis of chromogen I and III from N-acetyl-D-glucosamine in high-temperature water. Green Chem 15:2960–2966CrossRefGoogle Scholar
  19. Osada M, Miura C, Nakagawa YS, Kaihara M, Nikaido M, Totani K (2015) Effect of sub- and supercritical water treatments on the physicochemical properties of crab shell chitin and its enzymatic degradation. Carbohydr Polym 134:718–725CrossRefGoogle Scholar
  20. Overend RP, Chornet E (1987) Fractionation of lignocellulosics by steam-aqueous pretreatments. Philos Trans R Soc A 321:523–536CrossRefGoogle Scholar
  21. Rodríguez-Meizoso I, Jaime L, Santoyo S, Señoráns FJ, Cifuentes A, Ibáñez E (2010) Subcritical water extraction and characterization of bioactive compounds from Haematococcus pluvialis microalga. J Pharm Biomed Anal 51:456–463CrossRefGoogle Scholar
  22. Sevilla M, Fuertes AB (2009) Chemical and structural properties of carbonaceous products obtained by hydrothermal carbonization of saccharides. Chem Eur J 15:4195–4203CrossRefGoogle Scholar
  23. Shen X, Shamshina JL, Berton P, Bandomir J, Wang H, Gurau G, Rogers RD (2016) Comparison of hydrogels prepared with ionic-liquid-isolated vs commercial chitin and cellulose. ACS Sustain Chem Eng 4:471–480CrossRefGoogle Scholar
  24. Sowmya S, Kumar PTS, Chennazhi KP, Nair SV, Tamura H, Jayakumar R (2011) Biocompatible β-chitin hydrogel/nanobioactive glass ceramic nanocomposite scaffolds for periodontal bone regeneration. Trends Biomater Artif Organs 25:1–11Google Scholar
  25. Suenaga S, Osada M (2018a) Self-sustaining cellulose nanofiber hydrogel produced by hydrothermal gelation without additives. ACS Biomater Sci Eng 4:1536–1545Google Scholar
  26. Suenaga S, Osada M (2018b) Systematic dynamic viscoelasticity measurements for chitin nanofibers prepared with various concentrations, disintegration times, acidities, and crystalline structres. Int J Biol Macromol 115:431–437CrossRefGoogle Scholar
  27. Suenaga S, Nikaido N, Totani K, Kawasaki K, Ito Y, Yamashita K, Osada M (2016) Effect of purification method of β-chitin from squid pen on the properties of β-chitin nanofibers. Int J Biol Macromol 91:987–993CrossRefGoogle Scholar
  28. Suenaga S, Totani K, Nomura Y, Yamashita K, Shimada I, Fukunaga H, Takahashi N, Osada M (2017) Effect of acidity on the physicochemical properties of α- and β-chitin nanofibers. Int J Biol Macromol 102:358–366CrossRefGoogle Scholar
  29. Tamura H, Nagahama H, Tokura S (2006) Preparation of chitin hydrogel under mild conditions. Cellulose 13:357–364CrossRefGoogle Scholar
  30. Wagner W, Pruß A (2002) The IAPWS formulation 1995 for the thermodynamic properties of ordinary water substance for general and scientific use. J Phys Chem Ref Data 31:387–535CrossRefGoogle Scholar
  31. Xu D, Huang J, Zhao D, Ding B, Zhang L, Cai J (2016) High-flexibility, high-toughness double-cross-linked chitin hydrogels by sequential chemical and physical cross-linkings. Adv Mater 28:5844–5849CrossRefGoogle Scholar
  32. Yan N, Chen X (2015) Don’t waste seafood waste. Turning cast-off shells into nitrogen-rich chemicals would benefit economies and the environment. Nature 524:155–158CrossRefGoogle Scholar
  33. Zhang Y, Xue C, Xue Y, Gao R, Zhang X (2005) Determination of the degree of deacetylation of chitin and chitosan by X-ray powder diffraction. Carbohydr Res 340:1914–1917CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  1. 1.Department of Chemistry and Materials, Faculty of Textile Science and TechnologyShinshu UniversityUedaJapan

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