Skip to main content

Hierarchically Fabrication of Amylosic Supramolecular Nanocomposites by Means of Inclusion Complexation in Phosphorylase-Catalyzed Enzymatic Polymerization Field

  • Chapter
  • First Online:

Part of the book series: Advanced Structured Materials ((STRUCTMAT,volume 75))

Abstract

This chapter reviews hierarchically fabrication of eco-friendly supramolecular nanocomposites by means of inclusion complexation by amylose in phosphorylase-catalyzed enzymatic polymerization field. Amylose is a well-known polysaccharide and forms inclusion nanocomplex with various hydrophobic small molecules. A pure amylose is produced by the enzymatic polymerization using α-d-glucose 1-phosphate as a monomer and maltooligosaccharide as a primer catalyzed by phosphorylase. The author has found that a propagating chain of amylose in the enzymatic polymerization twines around hydrophobic polymers present in the reaction system to form inclusion nanocomplexes. The author named this polymerization system as ‘vine-twining polymerization’ because it is similar as the way that vine of plant grows twining around a rod. Amylosic supramolecular nanocomposite materials such as hydrogel and film were hierarchically fabricated by means of the vine-twining polymerization approach in the presence of copolymers covalently grafting with hydrophobic guest polymers. The enzymatically produced amyloses induced complexation with guest polymers in intermolecular graft copolymers, which acted as cross-linking points to form a supramolecular nanocomposite hydrogel. By using a film-formable main-chain in the graft copolymer, a supramolecular nanocomposite film was also obtained through hydrogelation. A supramolecular polymeric nanocomposite was successfully fabricated by the vine-twining polymerization using a primer-guest conjugate. The product in the vine-twining polymerization system formed a polymeric continuum of an inclusion nanocomplex, where the enzymatically produced amylose chain elongated from the conjugate included the guest segment in the other conjugate.

This is a preview of subscription content, log in via an institution.

Buying options

Chapter
USD   29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD   129.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD   169.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD   169.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Learn about institutional subscriptions

References

  • Frampton MJ, Claridge TDW, Latini G, Brovelli S, Cacialli F, Anderson L (2008) Amylose-wrapped luminescent conjugated polymers. Chem Commun 2797–2799

    Google Scholar 

  • 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 21:167–172

    Article  CAS  Google Scholar 

  • 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 45:6491–6495

    Article  CAS  Google Scholar 

  • Kadokawa J (2011) Precision polysaccharide synthesis catalyzed by enzymes. Chem Rev 111:4308–4345

    Article  CAS  Google Scholar 

  • Kadokawa J (2012) Preparation and applications of amylose supramolecules by means of phosphorylase-catalyzed enzymatic polymerization. Polymers 4:116–133

    Article  CAS  Google Scholar 

  • Kadokawa J (2013) Architecture of amylose supramolecules in form of inclusion complexes by phosphorylase-catalyzed enzymatic polymerization. Biomolecules 3:369–385

    Article  Google Scholar 

  • Kadokawa J (2014) Chemoenzymatic synthesis of functional amylosic materials. Pure Appl Chem 86:701–709

    Article  CAS  Google Scholar 

  • Kadokawa J, Kaneko Y (2013) Engineering of polysaccharide materials by Phosphorylase-catalyzed enzymatic chain-elongation. Pan Stanford Publishing Pte Ltd, Singapore

    Google Scholar 

  • Kadokawa J, Kobayashi S (2010) Polymer synthesis by enzymatic catalysis. Curr Opin Chem Biol 14:145–153

    Article  CAS  Google Scholar 

  • 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 34:6536–6538

    Article  CAS  Google Scholar 

  • 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 449–450

    Google Scholar 

  • 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 8:3321–3326

    Article  CAS  Google Scholar 

  • 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 204:1451–1457

    Article  CAS  Google Scholar 

  • Kadokawa J, Nomura S, Hatanaka D, Yamamoto K (2013) Preparation of polysaccharide supramolecular films by vine-twining polymerization approach. Carbohydr Polym 98:611–617

    Article  CAS  Google Scholar 

  • Kaneko Y, Beppu K, Kadokawa J (2007) Amylose selectively includes one from a mixture of two resemblant polyethers in vine-twining polymerization. Biomacromolecules 8:2983–2985

    Article  CAS  Google Scholar 

  • Kaneko Y, Beppu K, Kadokawa J (2008a) Preparation of amylose/polycarbonate inclusion complexes by means of vine-twining polymerization. Macromol Chem Phys 209:1037–1042

    Article  CAS  Google Scholar 

  • Kaneko Y, Beppu K, Kadokawa J (2009a) Amylose selectively includes a specific range of molecular weights in poly(tetrahydrofuran)s in vine-twining polymerization. Polym J 41:792–796

    Article  CAS  Google Scholar 

  • Kaneko Y, Beppu K, Kyutoku T, Kadokawa J (2009b) Selectivity and priority on inclusion of amylose toward guest polyethers and polyesters in vine-twining polymerization. Polym J 41:279–286

    Article  CAS  Google Scholar 

  • 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 5:1627–1633

    Article  CAS  Google Scholar 

  • Kaneko Y, Kadokawa J (2005) Vine-twining polymerization: a new preparation method for well-defined supramolecules composed of amylose and synthetic polymers. Chem Rec 5:36–46

    Article  CAS  Google Scholar 

  • Kaneko Y, Kyutoku T, Shimomura N, Kadokawa J (2011a) Formation of amylose-poly(tetrahydrofuran) inclusion complexes in ionic liquid media. Chem Lett 40:31–33

    Article  CAS  Google Scholar 

  • Kaneko Y, Saito Y, Nakaya A, Kadokawa J, Tagaya H (2008b) Preparation of inclusion complexes composed of amylose and strongly hydrophobic polyesters in parallel enzymatic polymerization system. Macromolecules 41:5665–5670

    Article  CAS  Google Scholar 

  • 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 11:1407–1415

    Article  CAS  Google Scholar 

  • Kida T, Minabe T, Nakano S, Akashi M (2008) Fabrication of novel multilayered thin films based on inclusion complex formation between amylose derivatives and guest polymers. Langmuir 24:9227–9229

    Article  CAS  Google Scholar 

  • Kida T, Minabe T, Okabe S, Akashi M (2007) Partially-methylated amyloses as effective hosts for inclusion complex formation with polymeric guests. Chem Commun 1559–1561

    Google Scholar 

  • Kitaoka M, Hayashi K (2002) Carbohydrate-processing phosphorolytic enzymes. Trends Glycosci Glycotechnol 14:35–50

    Article  CAS  Google Scholar 

  • Kobayashi S, Makino A (2009) Enzymatic polymer synthesis: an opportunity for green polymer chemistry. Chem Rev 109:5288–5353

    Article  CAS  Google Scholar 

  • Lenz RW (1993) Biodegradable polymers. Adv Polym Sci 107:1–40

    CAS  Google Scholar 

  • Nakai H, Kitaoka M, Svensson B, Ohtsubo K (2013) Recent development of phosphorylases possessing large potential for oligosaccharide synthesis. Curr Opin Chem Biol 17:301–309

    Article  CAS  Google Scholar 

  • Nomura S, Kyotoku 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 43:971–977

    Article  CAS  Google Scholar 

  • Ohdan K, Fujii K, Yanase M, Takaha T, Kuriki T (2006) Enzymatic synthesis of amylose. Biocatal Biotransform 24:77–81

    Article  CAS  Google Scholar 

  • Rouilly A, Rigal L (2002) Agro-materials: a bibliographic review. J Macromol Sci Polym Rev C42:441–479

    Article  CAS  Google Scholar 

  • Singha AS, Thakur VK (2009a) Fabrication and characterization of H. sabdariffa fiber-reinforced green polymer composites. Polym-Plast Technol Eng 48:482–487

    Article  CAS  Google Scholar 

  • Singha AS, Thakur VK (2009b) Physical, chemical and mechanical properties of Hibiscus sabdariffa fiber/polymer composite. Int J Polym Mater 58:217–228

    Article  CAS  Google Scholar 

  • Singha AS, Thakur VK (2009c) Fabrication and characterization of S. cilliare fibre reinforced polymer composites. Bull Mater Sci 32:49–58

    Article  CAS  Google Scholar 

  • Singha AS, Thakur VK (2009d) Grewia optiva fiber reinforced novel, low cost polymer composites. J Chem 6:71–76

    CAS  Google Scholar 

  • Singha AS, Thakur VK (2009e) Synthesis, characterization and analysis of Hibiscus Sabdariffa fibre reinforced polymer matrix based composites. Polym Polym Compos 17:189–194

    CAS  Google Scholar 

  • Sarko A, Zugenmaier P (1980) Crystal structures of amylose and its derivatives. In: French AD, Gardner KCH (eds) Fiber diffraction methods, vol 141. American Chemical Society, Washington DC, pp 459–482

    Google Scholar 

  • 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 87–162

    Google Scholar 

  • Seibel J, Jördening H-J, Buchholz K (2006) Glycosylation with activated sugars using glycosyltransferases and transglycosidases. Biocatal Biotransform 24:311–342

    Article  CAS  Google Scholar 

  • Shogren RL (1993) Complexes of starch with telechelic poly(ε-caprolactone) phosphate. Carbohydr Polym 22:93–98

    Article  CAS  Google Scholar 

  • 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 42:1701–1709

    Article  CAS  Google Scholar 

  • Takata H, Takaha T, Okada S, Takagi M, Imanaka T (1998) Purification and characterization of α-glucan phosphorylase from Bacillus stearothermophilus. J Ferment Bioeng 85:156–161

    Article  CAS  Google Scholar 

  • Tanaka T, Sasayama S, Nomura S, Yamamoto K, Kimura Y, Kadokawa J (2013) An amylose-poly(l-lactide) inclusion supramolecular polymer: enzymatic synthesis by means of vine-twining polymerization using a primer–guest conjugate. Macromol Chem Phys 214:2829–2834

    Article  CAS  Google Scholar 

  • Thakur VK, Thakur MK, Gupta RK (2014a) Review: raw natural fiber-based polymer composites. Int J Polym Anal Charact 19(3):256–271

    Article  CAS  Google Scholar 

  • Thakur VK, Thakur MK, Raghavan P, Kessler MR (2014b) Progress in green polymer composites from lignin for multifunctional applications: a review. ACS Sustain Chem Eng 2(5):1072–1092

    Article  CAS  Google Scholar 

  • Thakur VK, Vennerberg D, Kessler MR (2014c) Green aqueous surface modification of polypropylene for novel polymer nanocomposites. ACS Appl Mater Interf 6:9349–9356

    Article  CAS  Google Scholar 

  • Thakur VK, Vennerberg D, Madbouly SA, Kessler MR (2014d) Bio-inspired green surface functionalization of PMMA for multifunctional capacitors. RSC Adv 4:6677–6684

    Article  CAS  Google Scholar 

  • Thakur VK, Thunga M, Madbouly SA, Kessler MR (2014e) PMMA-g-SOY as a sustainable novel dielectric material. RSC Adv 4:18240–18249

    Article  CAS  Google Scholar 

  • Yanase M, Takaha T, Kuriki T (2006) α-Glucan phosphorylase and its use in carbohydrate engineering. J Sci Food Agric 86:1631–1635

    Article  CAS  Google Scholar 

  • Ziegast G, Pfannemüller B (1987) Phosphorolytic syntheses with di-, oligo- and multi-functional primers. Carbohydr Res 160:185–204

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to J Kadokawa .

Editor information

Editors and Affiliations

Rights and permissions

Reprints and permissions

Copyright information

© 2015 Springer India

About this chapter

Cite this chapter

Kadokawa, J. (2015). Hierarchically Fabrication of Amylosic Supramolecular Nanocomposites by Means of Inclusion Complexation in Phosphorylase-Catalyzed Enzymatic Polymerization Field. In: Thakur, V., Thakur, M. (eds) Eco-friendly Polymer Nanocomposites. Advanced Structured Materials, vol 75. Springer, New Delhi. https://doi.org/10.1007/978-81-322-2470-9_17

Download citation

Publish with us

Policies and ethics