Polymer Gels pp 247-274 | Cite as

Gel Formation by Non-covalent Cross-Linking from Amylose Through Enzymatic Polymerization

  • Tomonari Tanaka
  • Jun-ichi KadokawaEmail author
Part of the Gels Horizons: From Science to Smart Materials book series (GHFSSM)


Polymer gels are constructed by polymeric network structures with cross-linking points, which stably include a large amount of dispersion media, leading to functional soft materials. The specific formation of cross-linking points contributes to exhibiting unique properties of the resulting gels. In this chapter, we focus on the gel formation through non-covalent cross-linking from amylose, a natural polysaccharide. Amylose has a helical conformation, which is able to form two types of complexes, that is, double helix by two amylose chains and inclusion complex with other molecules having suitable structures and sizes. Because a well-defined amylose can be synthesized by enzymatic polymerization by phosphorylase catalysis, the studies on the dynamic gel formation through non-covalent, double helical, and inclusion complexing, cross-linking from amylose has been achieved by means of the enzymatic polymerization field. The resulting gels showed unique properties and functions.


Amylose Enzymatic polymerization Non-covalent cross-linking Supramolecular gel 


  1. Arimura T, Omagari Y, Yamamoto K, Kadokawa J (2011) Chemoenzymatic synthesis and hydrogelation of amylose-grafted xanthan gums. Int J Biol Macromol 49:498–503CrossRefPubMedGoogle Scholar
  2. Brown RC, Brown TR (2014) Biorenewable resources: engineering new products from agriculture, 2nd edn. Wiley Blackwell, ChichesterCrossRefGoogle Scholar
  3. Calder PC (1991) Glycogen structure and biogenesis. Int J Biochem 23:1335–1352CrossRefPubMedGoogle Scholar
  4. Corobea MC, Muhulet O, Miculescu F, Antoniac IV, Vuluga Z, Florea D et al (2016) Novel nanocomposite membranes from cellulose acetate and clay-silica nanowires. Polym Adv Technol 27(12):1586–1595CrossRefGoogle Scholar
  5. Eisenhaber F, Schulz W (1992) Monte-carlo simulation of the hydration shell of double-helical amylose—a left-handed antiparallel double helix fits best into liquid water-structure. Biopolymers 32:1643–1664CrossRefGoogle Scholar
  6. Fujii K, Takata H, Yanase M, Terada Y, Ohdan K, Takaha T, Okada S, Kuriki T (2003) Bioengineering and application of novel glucose polymers. Biocatal Biotransform 21:167–172CrossRefGoogle Scholar
  7. Hatanaka D, Takemoto Y, Yamamoto K, J-i Kadokawa (2014) Hierarchically self-assembled nanofiber films from amylose-grafted carboxymethyl cellulose. Fibers 2:34–44CrossRefGoogle Scholar
  8. Hinrichs W, Buttner G, Steifa M, Betzel C, Zabel V, Pfannemuller B, Saenger W (1987) An amylose antiparallel double helix at atomic resolution. Science 238:205–208CrossRefPubMedGoogle Scholar
  9. Ikeda M, Furusho Y, Okoshi K, Tanahara S, Maeda K, Nishino S, Mori T, Yashima E (2006) A luminescent poly(phenylenevinylene)-amylose composite with supramolecular liquid crystallinity. Angew Chem Int Ed 45:6491–6495CrossRefGoogle Scholar
  10. Izawa H, Kadokawa J (2009) Preparation of functional amylosic materials by phosphorylase-catalyzed polymerization. In: Kadoakwa J (ed) Interfacial researches in fundamental and material sciences of oligo- and polysaccharides. Transworld Research Network, Trivandrum, pp 69–86Google Scholar
  11. Izawa H, Nawaji M, Kaneko Y, Kadokawa J (2009) Preparation of glycogen-based polysaccharide materials by phosphorylase-catalyzed chain elongation of glycogen. Macromol Biosci 9:1098–1104CrossRefPubMedGoogle Scholar
  12. Kadoakwa J (2012) Synthesis of amylose-grafted polysaccharide materials by phosphorylase-catalyzed enzymatic polymerization. In: Smith PB, Gross RA (eds) Biobased monomers, polymers, and materials, vol 1043. ACS Symposium Series 1105. American Chemical Society, Washington, DC, pp 237–255CrossRefGoogle Scholar
  13. Kadoakwa J (2013) Synthesis of new polysaccharide materials by phosphorylase-catalyzed enzymatic α-glycosylations using polymeric glycosyl acceptors. In: Cheng HN, Gross RA, Smith PB (eds) Green polymer chemistry: biocatalysis and materials II, vol 1144. ACS Symposium Series 1144. American Chemical Society, Washington, DC, pp 141–161CrossRefGoogle Scholar
  14. Kadokawa J (2011a) Facile synthesis of unnatural oligosaccharides by phosphorylase-catalyzed enzymatic glycosylations using new glycosyl donors. In: Gordon NS (ed) Oligosaccharides: sources, properties and applications. Nova Science Publishers Inc, Hauppauge, pp 269–281Google Scholar
  15. Kadokawa J (2011b) Precision polysaccharide synthesis catalyzed by enzymes. Chem Rev 111:4308–4345CrossRefPubMedGoogle Scholar
  16. Kadokawa J (2012) Preparation and applications of amylose supramolecules by means of phosphorylase-catalyzed enzymatic polymerization. Polymers 4:116–133CrossRefGoogle Scholar
  17. Kadokawa J (2013a) Architecture of amylose supramolecules in form of inclusion complexes by phosphorylase-catalyzed enzymatic polymerization. Biomolecules 3:369–385CrossRefPubMedPubMedCentralGoogle Scholar
  18. Kadokawa J (2013b) Synthesis of non-natural oligosaccharides by α-glucan phosphorylase-catalyzed enzymatic glycosylations using analogue substrates of α-D-glucose 1-phosphate. Trends Glycosci Glycotechnol 25:57–69CrossRefGoogle Scholar
  19. Kadokawa J (2014) Chemoenzymatic synthesis of functional amylosic materials. Pure Appl Chem 86:701–709CrossRefGoogle Scholar
  20. Kadokawa J (2015a) Chemoenzymatic synthesis of amylose-grafted cellulose derivatives. In: Mondal MIH (ed) Cellulose and cellulose derivatives. Nova Science Publishers Inc, Hauppauge, pp 299–311Google Scholar
  21. Kadokawa J (2015b) Enzymatic synthesis of non-natural oligo- and polysaccharides by phosphorylase-catalyzed glycosylations using analogue substrates. In: Cheng HN, Gross RA, Smith PB (eds) Green polymer chemistry: biobased materials and biocatalysis, vol 1192. ACS Symposium Series 1192. American Chemical Society, Washington, DC, pp 87–99CrossRefGoogle Scholar
  22. Kadokawa J (2015c) Hierarchically fabrication of amylosic supramolecular nanocomposites by means of inclusion complexation in phosphorylase-catalyzed enzymatic polymerization field. In: Thakur KV, Thakur KM (eds) Eco-friendly polymer nanocomposites: processing and properties. Springer, New Delhi, pp 513–525Google Scholar
  23. Kadokawa J, Kaneko Y (2013) Engineering of polysaccharide materials—by phosphorylase-catalyzed enzymatic chain-elongation. Pan Stanford Publishing Pte Ltd., SingaporeGoogle Scholar
  24. Kadokawa J, Kobayashi S (2010) Polymer synthesis by enzymatic catalysis. Curr Opin Chem Biol 14:145–153CrossRefPubMedGoogle Scholar
  25. Kadokawa J, Kaneko Y, Nakaya A, Tagaya H (2001a) Formation of an amylose-polyester inclusion complex by means of phosphorylase-catalyzed enzymatic polymerization of α-D-glucose 1-phosphate monomer in the presence of poly(ε-caprolactone). Macromolecules 34:6536–6538CrossRefGoogle Scholar
  26. Kadokawa J, Kaneko Y, Tagaya H, Chiba K (2001b) Synthesis of an amylose-polymer inclusion complex by enzymatic polymerization of glucose 1-phosphate catalyzed by phosphorylase enzyme in the presence of polythf: a new method for synthesis of polymer-polymer inclusion complexes. Chem Commun, 449–450Google Scholar
  27. Kadokawa J, Kaneko Y, Nagase S, Takahashi T, Tagaya H (2002) Vine-twining polymerization: Amylose twines around polyethers to form amylose—polyether inclusion complexes. Chem Eur J 8:3321–3326CrossRefPubMedGoogle Scholar
  28. Kadokawa J, Nakaya A, Kaneko Y, Tagaya H (2003) Preparation of inclusion complexes between amylose and ester-containing polymers by means of vine-twining polymerization. Macromol Chem Phys 204:1451–1457CrossRefGoogle Scholar
  29. Kadokawa J, Nomura S, Hatanaka D, Yamamoto K (2013) Preparation of polysaccharide supramolecular films by vine-twining polymerization approach. Carbohydr Polym 98:611–617CrossRefPubMedGoogle Scholar
  30. Kadokawa J, Tanaka K, Hatanaka D, Yamamoto K (2015) Preparation of multiformable supramolecular gels through helical complexation by amylose in vine-twining polymerization. Polym Chem 6:6402–6408CrossRefGoogle Scholar
  31. Kaneko Y, Kadokawa J (2005) Vine-twining polymerization: a new preparation method for well-defined supramolecules composed of amylose and synthetic polymers. Chem Rec 5:36–46CrossRefPubMedGoogle Scholar
  32. Kaneko Y, Kadokawa J (2006) Synthesis of nanostructured bio-related materials by hybridization of synthetic polymers with polysaccharides or saccharide residues. J Biomater Sci Polym Ed 17:1269–1284CrossRefPubMedGoogle Scholar
  33. Kaneko Y, Kadokawa J (2009a) Chemoenzymatic synthesis of amylose-grafted polymers. In: Ito R, Matsuo Y (eds) Handbook of carbohydrate polymers: development, properties and applications. Nova Science Publishers Inc, Hauppauge, pp 671–691Google Scholar
  34. Kaneko Y, Kadokawa J (2009b) Preparation of polymers with well-defined nanostructure in the polymerization field. In: Lee JN (ed) Modern trends in macromolecular chemistry. Nova Science Publishers Inc, Hauppauge, pp 199–217Google Scholar
  35. Kaneko Y, Matsuda S, Kadokawa J (2007) Chemoenzymatic syntheses of amylose-grafted chitin and chitosan. Biomacromol 8:3959–3964CrossRefGoogle Scholar
  36. Kaneko Y, Fujisaki K, Kyutoku T, Furukawa H, Kadokawa J (2010) Preparation of enzymatically recyclable hydrogels through the formation of inclusion complexes of amylose in a vine-twining polymerization. Chem Asian J 5:1627–1633CrossRefPubMedGoogle Scholar
  37. Kaneko Y, Kyutoku T, Shimomura N, Kadokawa J (2011a) Formation of amylose-poly(tetrahydrofuran) inclusion complexes in ionic liquid media. Chem Lett 40:31–33CrossRefGoogle Scholar
  38. Kaneko Y, Ueno K, Yui T, Nakahara K, Kadokawa J (2011b) Amylose’s recognition of chirality in polylactides on formation of inclusion complexes in vine-twining polymerization. Macromol Biosci 11:1407–1415CrossRefPubMedGoogle Scholar
  39. Kida T, Minabe T, Okabe S, Akashi M (2007) Partially-methylated amyloses as effective hosts for inclusion complex formation with polymeric guests. Chem Commun, 1559–1561Google Scholar
  40. Kitamura S (1996) Starch polymers, natural and synthetic. In: Salamone C (ed) The polymeric materials encyclopedia, synthesis, properties and applications, vol 10. CRC Press, New York, pp 7915–7922Google Scholar
  41. Kitamura S, Yunokawa H, Mitsuie S, Kuge T (1982) Study on polysaccharide by the fluorescence method 2. Micro-brownian motion and conformational change of amylose in aqueous-solution. Polym J 14:93–99CrossRefGoogle Scholar
  42. Kitaoka M, Hayashi K (2002) Carbohydrate-processing phosphorolytic enzymes. Trends Glycosci Glycotechnol 14:35–50CrossRefGoogle Scholar
  43. Klemm D, Heublein B, Fink HP, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Ed 44:3358–3393CrossRefGoogle Scholar
  44. Kobayashi K, Kamiya S, Enomoto N (1996) Amylose-carrying styrene macromonomer and its homo- and copolymers: synthesis via enzyme-catalyzed polymerization and complex formation with iodine. Macromolecules 29:8670–8676CrossRefGoogle Scholar
  45. Kumar K, Woortman AJJ, Loos K (2013) Synthesis of amylose-polystyrene inclusion complexes by a facile preparation route. Biomacromol 14:1955–1960CrossRefGoogle Scholar
  46. Lejeune A, Deprez T (2009) Cellulose: structure and properties, derivatives and industrial uses. Nova Science Publishers, HauppaugeGoogle Scholar
  47. Lenz RW (1993) Biodegradable polymers. Adv Polym Sci 107:1–40CrossRefGoogle Scholar
  48. Manners DJ (1991) Recent developments in our understanding of glycogen structure. Carbohydr Polym 16:37–82CrossRefGoogle Scholar
  49. Matsuda S, Kaneko Y, Kadokawa J (2007) Chemoenzymatic synthesis of amylose-grafted chitosan. Macromol Rapid Commun 28:863–867CrossRefGoogle Scholar
  50. Melton LD, Mindt L, Rees DA (1976) Covalent structure of the extracellular polysaccharide from Xanthomonas campestris: evidence from partial hydrolysis studies. Carbohydr Res 46:245–257CrossRefPubMedGoogle Scholar
  51. Miculescu M, Thakur VK, Miculescu F, Voicu SI (2016) Graphene-based polymer nanocomposite membranes: a review. Polym Adv Technol 27(7):844–859CrossRefGoogle Scholar
  52. Mohanty AK, Misra M, Drzal LT (2002) Sustainable bio-composites from renewable resources: opportunities and challenges in the green materials world. J Polym Environ 10:19–26CrossRefGoogle Scholar
  53. Nakai H, Kitaoka M, Svensson B, Ohtsubo K (2013) Recent development of phosphorylases possessing large potential for oligosaccharide synthesis. Curr Opin Chem Biol 17:301–309CrossRefPubMedGoogle Scholar
  54. Nawaji M, Izawa H, Kaneko Y, Kadokawa J (2008) Enzymatic α-glucosaminylation of maltooligosaccharides catalyzed by phosphorylase. Carbohydr Res 343:2692–2696CrossRefPubMedGoogle Scholar
  55. Nishinari K, Takahashi R (2003) Interaction in polysaccharide solutions and gels. Curr Opin Colloid Interface Sci 8:396–400CrossRefGoogle Scholar
  56. Nishinari K, Zhang H, Ikeda S (2000) Hydrocolloid gels of polysaccharides and proteins. Curr Opin Colloid Interface Sci 5:195–201CrossRefGoogle Scholar
  57. Nomura S, Kyutoku T, Shimomura N, Kaneko Y, Kadokawa J (2011) Preparation of inclusion complexes composed of amylose and biodegradable poly(glycolic acid-co-ε-caprolactone) by vine-twining polymerization and their lipase-catalyzed hydrolysis behavior. Polym J 43:971–977CrossRefGoogle Scholar
  58. Ohdan K, Fujii K, Yanase M, Takaha T, Kuriki T (2006) Enzymatic synthesis of amylose. Biocatal Biotransform 24:77–81CrossRefGoogle Scholar
  59. Omagari Y, Matsuda S, Kaneko Y, Kadokawa J (2009) Chemoenzymatic synthesis of amylose-grafted cellulose. Macromol Biosci 9:450–455CrossRefPubMedGoogle Scholar
  60. Pappu A, Patil V, Jain S, Mahindrakar A, Haque R, Thakur VK (2015) Advances in industrial prospective of cellulosic macromolecules enriched banana biofibre resources: a review. Int J Biol Macromol 79:449–458CrossRefPubMedGoogle Scholar
  61. Pappu A, Saxena M, Thakur VK, Sharma A, Haque R (2016) Facile extraction, processing and characterization of biorenewable sisal fibers for multifunctional applications. J Macromol Sci Part A 53(7):424–432CrossRefGoogle Scholar
  62. Piculell L (1998) Gelling polysaccharides. Curr Opin Colloid Interface Sci 3:643–650CrossRefGoogle Scholar
  63. Pillai CKS, Paul W, Sharma CP (2009) Chitin and chitosan polymers: chemistry, solubility and fiber formation. Prog Polym Sci 34:641–678CrossRefGoogle Scholar
  64. Putseys JA, Lamberts L, Delcour JA (2010) Amylose-inclusion complexes: formation, identity and physico-chemical properties. J Cereal Sci 51:238–247CrossRefGoogle Scholar
  65. Rachmawati R, Woortman AJJ, Loos K (2013a) Facile preparation method for inclusion complexes between amylose and polytetrahydrofurans. Biomacromol 14:575–583CrossRefGoogle Scholar
  66. Rachmawati R, Woortman AJJ, Loos K (2013b) Tunable properties of inclusion complexes between amylose and polytetrahydrofuran. Macromol Biosci 13:767–776CrossRefPubMedGoogle Scholar
  67. Rachmawati R, Woortman AJJ, Loos K (2014) Solvent-responsive behavior of inclusion complexes between amylose and polytetrahydrofuran. Macromol Biosci 14:56–68CrossRefPubMedGoogle Scholar
  68. Rouilly A, Rigal L (2002) Agro-materials: a bibliographic review. J Macromol Sci Polym Rev C42:441–479CrossRefGoogle Scholar
  69. Sarko A, Zugenmaier P (1980) Crystal structures of amylose and its derivatives. In: French AD, Gardner KH (eds) Fiber diffraction methods, vol 141. ACS Symposium Series 141. American Chemical Society, Washington, DC, pp 459–482CrossRefGoogle Scholar
  70. Schuerch C (1986) Polysaccharides. In: Mark HF, Bilkales N, Overberger CG (eds) Encyclopedia of polymer science and engineering, vol 13. 2nd edn. Wiley, New York, pp 87–162Google Scholar
  71. Seibel J, Beine R, Moraru R, Behringer C, Buchholz K (2006a) A new pathway for the synthesis of oligosaccharides by the use of non-leloir glycosyltransferases. Biocatal Biotransform 24:157–165CrossRefGoogle Scholar
  72. Seibel J, Jordening HJ, Buchholz K (2006b) Glycosylation with activated sugars using glycosyltransferases and transglycosidases. Biocatal Biotransform 24:311–342CrossRefGoogle Scholar
  73. Shoda S, Uyama H, Kadokawa J, Kimura S, Kobayashi S (2016) Enzymes as green catalysts for precision macromolecular synthesis. Chem Rev 116:2307–2413CrossRefPubMedGoogle Scholar
  74. Shogren RL (1993) Complexes of starch with telechelic poly(ε-caprolactone) phosphate. Carbohydr Polym 22:93–98CrossRefGoogle Scholar
  75. Shogren RL, Greene RV, Wu YV (1991) Complexes of starch polysaccharides and poly(ethylene-co-acrylic acid)—structure and stability in solution. J Appl Polym Sci 42:1701–1709CrossRefGoogle Scholar
  76. Star A, Steuerman DW, Heath JR, Stoddart JF (2002) Starched carbon nanotubes. Angew Chem Int Ed 41:2508–2512CrossRefGoogle Scholar
  77. Stephen AM, Phillips GO, Williams PA (2006) Food polysaccharides and their applications. Food science and technology, 2nd edn. CRC/Taylor & Francis, Boca RatonGoogle Scholar
  78. Takata Y, Yamamoto K, Kadokawa J (2015) Preparation of pH-responsive amphoteric glycogen hydrogels by α-glucan phosphorylase-catalyzed successive enzymatic reactions. Macromol Chem Phys 216:1415–1420CrossRefGoogle Scholar
  79. Tanaka T, Fukuhara H, Shoda S, Kimura Y (2013a) Facile synthesis of oligosaccharide-poly(l-lactide) conjugates forming nanoparticles with saccharide core and shell. Chem Lett 42:197–199CrossRefGoogle Scholar
  80. Tanaka T, Sasayama S, Nomura S, Yamamoto K, Kimura Y, Kadokawa J (2013b) An amylose-poly(L-lactide) inclusion supramolecular polymer: enzymatic synthesis by means of vine-twining polymerization using a primer-guest conjugate. Macromol Chem Phys 214:2829–2834CrossRefGoogle Scholar
  81. Tanaka T, Gotanda R, Tsutsui A, Sasayama S, Yamamoto K, Kimura Y, Kadokawa J (2015a) Synthesis and gel formation of hyperbranched supramolecular polymer by vine-twining polymerization using branched primer-guest conjugate. Polymer 73:9–16CrossRefGoogle Scholar
  82. Tanaka T, Tsutsui A, Gotanda R, Sasayama S, Yamamoto K, Kadokawa J (2015b) Synthesis of amylose-polyether inclusion supramolecular polymers by vine-twining polymerization using maltoheptaose-functionalized poly(tetrahydrofuran) as a primer-guest conjugate. J Appl Glycosci 62:135–141CrossRefGoogle Scholar
  83. Trache D, Hazwan Hussin M, Mohamad Haafiz MK, Kumar Thakur V (2017) Recent progress in cellulose nanocrystals: sources and production. Nanoscale 9(5):1763–1786CrossRefPubMedGoogle Scholar
  84. Umegatani Y, Izawa H, Nawaji M, Yamamoto K, Kubo A, Yanase M, Takaha T, Kadokawa J (2012) Enzymatic α-glucuronylation of maltooligosaccharides using α-glucuronic acid 1-phosphate as glycosyl donor catalyzed by a thermostable phosphorylase from Aquifex aeolicus VF5. Carbohydr Res 350:81–85CrossRefPubMedGoogle Scholar
  85. Voicu SI, Condruz RM, Mitran V, Cimpean A, Miculescu F, Andronescu C, Thakur VK et al (2016) Sericin covalent immobilization onto cellulose acetate membrane for biomedical applications. ACS Sustain Chem Eng 4(3):1765–1774CrossRefGoogle Scholar
  86. Yanase M, Takaha T, Kuriki T (2006) α-Glucan phosphorylase and its use in carbohydrate engineering. J Sci Food Agric 86:1631–1635CrossRefGoogle Scholar
  87. Ziegast G, Pfannemüller B (1987) Linear and star-shaped hybrid polymers. 4. phosphorolytic syntheses with Di-functional, Oligo-Functional and Multifunctional Primers. Carbohyd Res 160:185–204CrossRefGoogle Scholar

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© Springer Nature Singapore Pte Ltd. 2018

Authors and Affiliations

  1. 1.Department of Biobased Materials Science, Graduate School of Science and TechnologyKyoto Institute of TechnologyKyotoJapan
  2. 2.Department of Chemistry, Biotechnology, and Chemical Engineering, Graduate School of Science and EngineeringKagoshima UniversityKagoshimaJapan

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