, Volume 25, Issue 4, pp 2217–2234 | Cite as

Dependence of dissolution, dispersion, and aggregation characteristics of cationic polysaccharides made from euglenoid β-1,3-glucan on degree of substitution

  • Motonari Shibakami
  • Tadashi Nemoto
  • Mitsugu Sohma
Original Paper


Dissolution, dispersion, and aggregation characteristics of 2-hydroxy-3-trimethylammoniopropyl polysaccharides made from β-1,3-glucan extracted from Euglena (referred to as paramylon) differing in the degree of substitution (DS) of a 2-hydroxy-3-trimethylammoniopropyl group were examined. Freeze-dried solids made from cationic paramylon derivatives with a DS ranging from 0.07 to 0.16 spontaneously formed crystalline nanofibers upon being mechanically stirred in water. Derivatives with a DS greater than 0.31 lacked similar fiber formability. Nevertheless, they formed a distinctly outlined, transparent thin film featuring a nanometer-level flat surface using an aqueous solution casting method in which water is gradually removed from the aqueous homogeneous solution and a methanolic solution casting method featuring rapid removal of methanol from a heterogeneous solution. Those that had a DS less than 0.06 lacked solution solubility and dispersibility; they formed a thin film from a heterogeneous solution. These results demonstrate that cationic paramylon derivatives can be used as a constituent of well-organized polymeric materials.


β-1,3-Glucan Paramylon Euglena Cationization Nanofiber Film 



The authors are grateful to KOBELCO Eco-Solutions Co. Ltd. for providing the paramylon. They are also grateful to Dr. Kijima (AIST) for technical assistance in obtaining the WAXD data.

Supplementary material

10570_2018_1740_MOESM1_ESM.pptx (590 kb)
Supplementary material 1 (PPTX 590 kb)


  1. Barsanti L, Vismara R, Passarelli V, Gualtieri P (2001) Paramylon (beta-1,3-glucan) content in wild type and WZSL mutant of Euglena gracilis. Effects of growth conditions. J Appl Phycol 13:59–65CrossRefGoogle Scholar
  2. Bluhm TL, Sarko A (1977) Triple helical structure of Lentinan, a linear beta-(1-]3)-d-glucan. Can J Chem 55:293–299. CrossRefGoogle Scholar
  3. Booy FP, Chanzy H, Boudet A (1981) An electron-diffraction study of paramylon storage granules from Euglena gracilis. J Microsc 121:133–140CrossRefGoogle Scholar
  4. Chuah CT, Sarko A, Deslandes Y, Marchessault RH (1983) Packing analysis of carbohydrates and polysaccharides. 14. Triple-helical crystalline-structure of curdlan and paramylon hydrates. Macromolecules 16:1375–1382. CrossRefGoogle Scholar
  5. Clarke AE, Stone BA (1960) Structure of the paramylon from Euglena gracilis. Biochim Biophys Acta 44:161–163CrossRefGoogle Scholar
  6. Deslandes Y, Marchessault RH, Sarko A (1980) Packing analysis of carbohydrates and polysaccharides. 13. Triple-helical structure of (1-]3)-beta-d-glucan. Macromolecules 13:1466–1471. CrossRefGoogle Scholar
  7. Edgar KJ, Buchanan CM, Debenham JS, Rundquist PA, Seiler BD, Shelton MC, Tindall D (2001) Advances in cellulose ester performance and application. Prog Polym Sci 26:1605–1688. CrossRefGoogle Scholar
  8. Ifuku S, Saimoto H (2012) Chitin nanofibers: preparations, modifications, and applications. Nanoscale 4:3308–3318. CrossRefGoogle Scholar
  9. Ifuku S, Ikuta A, Egusa M, Kaminaka H, Izawa H, Morimoto M, Saimoto H (2013) Preparation of high-strength transparent chitosan film reinforced with surface-deacetylated chitin nanofibers. Carbohyd Polym 98:1198–1202. CrossRefGoogle Scholar
  10. Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–85. CrossRefGoogle Scholar
  11. Iwatake A, Nogi M, Yano H (2008) Cellulose nanofiber-reinforced polylactic acid. Compos Sci Technol 68:2103–2106. CrossRefGoogle Scholar
  12. Kobayashi K, Kimura S, Togawa E, Wada M, Kuga S (2010) Crystal transition of paramylon with dehydration and hydration. Carbohyd Polym 80:491–497CrossRefGoogle Scholar
  13. Marchessault RH, Deslandes Y (1979) Fine-structure of (1-]3)-beta-d-glucans—curdlan and paramylon. Carbohyd Res 75:231–242CrossRefGoogle Scholar
  14. Marubayashi H, Yukinaka K, Enomoto-Rogers Y, Takemura A, Iwata T (2014) Curdlan ester derivatives: synthesis, structure, and properties. Carbohyd Polym 103:427–433. CrossRefGoogle Scholar
  15. Nichifor M, Stanciu MC, Simionescu BC (2010) New cationic hydrophilic and amphiphilic polysaccharides synthesized by one pot procedure. Carbohyd Polym 82:965–975. CrossRefGoogle Scholar
  16. Puanglek S, Kimura S, Iwata T (2017) Thermal and mechanical properties of tailor-made unbranched alpha-1,3-glucan esters with various carboxylic acid chain length. Carbohyd Polym 169:245–254. CrossRefGoogle Scholar
  17. Sakagami H et al (1989) Chemical modification potentiates paramylon induction of antimicrobial activity. In Vivo 3:243–248Google Scholar
  18. Santek B, Friehs K, Lotz M, Flaschel E (2012) Production of paramylon, a ss-1,3-glucan, by heterotrophic growth of Euglena gracilis on potato liquor in fed-batch and repeated-batch mode of cultivation. Eng Life Sci 12:89–94. CrossRefGoogle Scholar
  19. Shibakami M (2017) Thickening and water-absorbing agent made from euglenoid polysaccharide. Carbohyd Polym 173:451–464. CrossRefGoogle Scholar
  20. Shibakami M, Sohma M (2017) Synthesis and thermal properties of paramylon mixed esters and optical, mechanical, and crystal properties of their hot-pressed films. Carbohyd Polym 155:416–424. CrossRefGoogle Scholar
  21. Shibakami M, Sohma M, Hayashi M (2012) Fabrication of doughnut-shaped particles from spheroidal paramylon granules of Euglena gracilis using acetylation reaction. Carbohyd Polym 87:452–456. CrossRefGoogle Scholar
  22. Shibakami M, Tsubouchi G, Nakamura M, Hayashi M (2013a) Polysaccharide nanofiber made from euglenoid alga. Carbohyd Polym 93:499–505. CrossRefGoogle Scholar
  23. Shibakami M, Tsubouchi G, Nakamura M, Hayashi M (2013b) Preparation of carboxylic acid-bearing polysaccharide nanofiber made from euglenoid beta-1,3-glucans. Carbohyd Polym 98:95–101. CrossRefGoogle Scholar
  24. Shibakami M, Tsubouchi G, Hayashi M (2014) Thermoplasticization of euglenoid beta-1,3-glucans by mixed esterification. Carbohyd Polym 105:90–96. CrossRefGoogle Scholar
  25. Shibakami M, Tsubouchi G, Sohma M, Hayashi M (2015) One-pot synthesis of thermoplastic mixed paramylon esters using trifluoroacetic anhydride. Carbohydr Polym 119:1–7. CrossRefGoogle Scholar
  26. Shibakami M, Tsubouchi G, Sohma M, Hayashi M (2016) Synthesis of nanofiber-formable carboxymethylated Euglena-derived β-1,3-glucan. Carbohyd Polym 152:468–478. CrossRefGoogle Scholar
  27. Suflet DM, Popescu I, Pelin IM, Nicolescu A, Hitruc G (2015) Cationic curdlan: synthesis, characterization and application of quaternary ammonium salts of curdlan. Carbohyd Polym 123:396–405. CrossRefGoogle Scholar
  28. Teramoto Y, Yoshioka M, Shiraishi N, Nishio Y (2002) Plasticization of cellulose diacetate by graft copolymerization of epsilon-caprolactone and lactic acid. J Appl Polym Sci 84:2621–2628. CrossRefGoogle Scholar
  29. Tezuka Y (1993) 13C NMR determination of the distribution of two ester substituents in cellulose acetate butyrate. Carbohyd Res 241:285–290. CrossRefGoogle Scholar
  30. Tezuka Y, Tsuchiya Y (1995) Determination of substituent distribution in cellulose acetate by means of a 13C NMR study on its propanoated derivative. Carbohyd Res 273:83–91. CrossRefGoogle Scholar
  31. Tezuka Y, Imai K, Oshima M, K-i I (1991) 13C-N.m.r. structural study on an enteric pharmaceutical coating cellulose derivative having ether and ester substituents. Carbohyd Res 222:255–259. CrossRefGoogle Scholar

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© Springer Science+Business Media B.V., part of Springer Nature 2018

Authors and Affiliations

  1. 1.Biomedical Research InstituteNational Institute of Advanced Industrial Science and Technology (AIST)TsukubaJapan
  2. 2.Advanced Coating Technology Research CenterNational Institute of Advanced Industrial Science and Technology (AIST)TsukubaJapan

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