Synlett 2020; 31(07): 648-656
DOI: 10.1055/s-0039-1690804
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© Georg Thieme Verlag Stuttgart · New York

Synthesis of Amylosic Supramolecular Materials by Glucan Phosphorylase-Catalyzed Enzymatic Polymerization According to the Vine-Twining Approach

Jun-ichi Kadokawa
Department of Chemistry, Biotechnology, and Chemical Engineering, Graduate School of Science and Engineering, Kagoshima University, 1-21-40 Korimoto, Kagoshima 890-0065, Japan   Email: kadokawa@eng.kagoshima-u.ac.jp
› Author Affiliations
The author acknowledges support from the Ministry of Education, Sports, Science and Culture, Japan (Nos. 14550830, 17550118, 19550126, 25620177, and 17K06001), Asahi Glass Foundation, Sekisui Foundation, and Ezaki Glico Co, Japan.
Further Information

Publication History

Received: 04 December 2019

Accepted after revision: 07 January 2020

Publication Date:
30 January 2020 (online)


Abstract

This article overviews the synthesis of amylosic supramolecular materials through inclusion complexation in glucan phosphorylase (GP)-catalyzed enzymatic polymerization. Amylose is a polysaccharide that is known to form inclusion complexes with a number of hydrophobic small guest molecules. A pure amylose can be synthesized by the enzymatic polymerization of α-d-glucose 1-phosphate monomer with a maltooligosaccharide primer catalyzed by GP. The author has reported that the propagating amylosic chain in the enzymatic polymerization twines around hydrophobic polymers present in aqueous reaction media to form supramolecular inclusion complexes. As it is similar to the way that vines of a plant grow around a rod, this polymerization is termed ‘vine-twining polymerization’. Amylosic supramolecular network materials have been obtained through the vine-twining polymerization by using copolymers, where hydrophobic guest polymers are covalently grafted on hydrophilic main-chain polymers. The enzymatically produced amylosic chains form complexes with the guest polymers among graft copolymers, which act as cross-linking points to form supramolecular networks, resulting in the formation of soft materials, such as gels and films. Vine-twining polymerization using appropriately designed guest polymers has also been performed, which leads to supramolecular products that exhibit new functionality.

1 Introduction

2 Vine-Twining Polymerization to Form Supramolecular Inclusion Complexes

3 Selective Complexation of Amylose toward Guest Polymers in Vine-Twining Polymerization

4 Hierarchical Architecture of Amylosic Supramolecular Network Materials by Vine-Twining Polymerization Approach

5 Hierarchical Fabrication of Amylosic Supramolecular Materials by Vine-Twining Polymerization Using Designed Guest Polymers

6 Conclusions

 
  • References

  • 1 Schuerch C. Polysaccharides . In Encyclopedia of Polymer Science and Engineering, 2nd ed., Vol. 13. Mark HF, Bilkales N, Overberger CG. John Wiley & Sons; New York: 1986: 87-162
    • 2a Kasapis S, Norton IT, Ubbink JB. Modern Biopolymer Science: Bridging the Divide between Fundamental Treatise and Industrial Application. Academic Press; San Diego: 2009
    • 2b Berg JM, Tymoczko JL, Stryer L. Biochemistry, 7th ed. W. H. Freeman; New York: 2012
    • 3a Lehn JM. Polym. Int. 2002; 51: 825
    • 3b Lehn JM. Prog. Polym. Sci. 2005; 30: 814
    • 3c Steed JW, Gale PA. Supramolecular Chemistry: From Molecules to Nanomaterials, 1st ed. Wiley; Hoboken: 2012
  • 4 Wei P, Yan X, Huang F. Chem. Soc. Rev. 2015; 44: 815
  • 5 Putseys JA, Lamberts L, Delcour JA. J. Cereal Sci. 2010; 51: 238
    • 6a Shogren RL. Carbohydr. Polym. 1993; 22: 93
    • 6b Shogren RL, Greene RV, Wu YV. J. Appl. Polym. Sci. 1991; 42: 1701
    • 7a Star A, Steuerman DW, Heath JR, Stoddart JF. Angew. Chem. Int. Ed. 2002; 41: 2508
    • 7b Ikeda M, Furusho Y, Okoshi K, Tanahara S, Maeda K, Nishino S, Mori T, Yashima E. Angew. Chem. Int. Ed. 2006; 45: 6491
    • 7c Kumar K, Woortman AJ. J, Loos K. Biomacromolecules 2013; 14: 1955
    • 8a Rachmawati R, Woortman AJ. J, Loos K. Biomacromolecules 2013; 14: 575
    • 8b Rachmawati R, Woortman AJ. J, Loos K. Macromol. Biosci. 2013; 13: 767
    • 8c Rachmawati R, Woortman AJ. J, Loos K. Macromol. Biosci. 2014; 14: 56
    • 9a Kobayashi S, Uyama H, Kimura S. Chem. Rev. 2001; 101: 3793
    • 9b Shoda S, Izumi R, Fujita M. Bull. Chem. Soc. Jpn. 2003; 76: 1
    • 9c Kobayashi S, Makino A. Chem. Rev. 2009; 109 (11) 5288
    • 9d Kadokawa J. Chem. Rev. 2011; 111: 4308
    • 9e Shoda S, Uyama H, Kadokawa J, Kimura S, Kobayashi S. Chem. Rev. 2016; 116: 2307
    • 10a Ziegast G, Pfannemüller B. Carbohydr. Res. 1987; 160: 185
    • 10b Fujii K, Takata H, Yanase M, Terada Y, Ohdan K, Takaha T, Okada S, Kuriki T. Biocatal. Biotransform. 2003; 21: 167
    • 10c Seibel J, Jordening HJ, Buchholz K. Biocatal. Biotransform. 2006; 24: 311
    • 10d Yanase M, Takaha T, Kuriki T. J. Sci. Food Agric. 2006; 86: 1631
    • 11a Kitaoka M, Hayashi K. Trends Glycosci. Glycotechnol. 2002; 14: 35
    • 11b Nakai H, Kitaoka M, Svensson B, Ohtsubo K. Curr. Opin. Chem. Biol. 2013; 17: 301
    • 11c Puchart V. Biotechnol. Adv. 2015; 33: 261
    • 11d O’Neill EC, Field RA. Carbohydr. Res. 2015; 403: 23
    • 11e Kadokawa J. Curr. Org. Chem. 2017; 21: 1192
    • 11f Kadokawa J. Catalysts 2018; 8: 473
  • 12 Kitamura S. Starch polymers, natural and synthetic. In The Polymeric Materials Encyclopedia, Synthesis, Properties and Applications, Vol. 10. Salamone C. CRC Press; New York: 1996: 7915-7922
    • 13a Kaneko Y, Kadokawa J. Chem. Rec. 2005; 5, 36
    • 13b Kaneko Y, Kadokawa J. J. Biomater. Sci., Polym. Ed. 2006; 17: 1269
    • 13c Kaneko Y, Kadokawa J. Preparation of Polymers with Well-Defined Nanostructure in the Polymerization Field. In Modern Trends in Macromolecular Chemistry. Lee JN. Nova Science Publishers, Inc; Hauppauge: 2009: 199-217
    • 13d Kadokawa J. Polymers 2012; 4: 116
    • 13e Kadokawa J. Biomolecules 2013; 3: 369
  • 15 Kadokawa J, Kaneko Y, Tagaya H, Chiba K. Chem. Commun. 2001; 449
  • 16 Kadokawa J, Kaneko Y, Nagase S, Takahashi T, Tagaya H. Chem. Eur. J. 2002; 8: 3321
    • 17a Kadokawa J, Kaneko Y, Nakaya A, Tagaya H. Macromolecules 2001; 34: 6536
    • 17b Nomura S, Kyutoku T, Shimomura N, Kaneko Y, Kadokawa J. Polym. J. 2011; 43: 971
  • 18 Kadokawa J, Nakaya A, Kaneko Y, Tagaya H. Macromol. Chem. Phys. 2003; 204: 1451
  • 19 Kaneko Y, Beppu K, Kadokawa J. Macromol. Chem. Phys. 2008; 209: 1037
  • 20 Kaneko Y, Saito Y, Nakaya A, Kadokawa J, Tagaya H. Macromolecules 2008; 41: 5665
    • 21a Kobayashi S, Uyama H, Suda S, Namekawa S. Chem. Lett. 1997; 105
    • 21b Suda S, Uyama H, Kobayashi S. Proc. Jpn. Acad., Ser. B 1999; 75: 201
  • 22 Kaneko Y, Beppu K, Kadokawa J. Biomacromolecules 2007; 8: 2983
  • 23 Kaneko Y, Beppu K, Kyutoku T, Kadokawa J. Polym. J. 2009; 41: 279
  • 24 Kaneko Y, Beppu K, Kadokawa J. Polym. J. 2009; 41: 792
  • 25 Kaneko Y, Ueno K, Yui T, Nakahara K, Kadokawa J. Macromol. Biosci. 2011; 11: 1407
  • 26 Gotanda R, Yamamoto K, Kadokawa J.-i. Macromol. Chem. Phys. 2016; 217: 1074
  • 27 Tanaka T, Tsutsui A, Tanaka K, Yamamoto K, Kadokawa J. Biomolecules 2017; 7: 28
  • 28 Kaneko Y, Fujisaki K, Kyutoku T, Furukawa H, Kadokawa J. Chem. Asian J. 2010; 5: 1627
  • 29 Kadokawa J, Nomura S, Kyutoku T. Polym. Bull. 2017; 74: 4499
  • 30 Kadokawa J, Nomura S, Hatanaka D, Yamamoto K. Carbohydr. Polym. 2013; 98: 611
  • 31 Kadokawa J, Tanaka K, Hatanaka D, Yamamoto K. Polym. Chem. 2015; 6: 6402
  • 32 Kadokawa J, Tanaka K, Yamamoto K. J. Electrochem. Soc. 2019; 166: B3171
  • 33 Kadokawa J, Shoji T, Yamamoto K. Polymer 2018; 140: 73
  • 34 Orio S, Shoji T, Yamamoto K, Kadokawa J. Polymers 2018; 10: 1277
  • 35 Kadokawa J, Shoji T, Yamamoto K. Catalysts 2019; 9: 211
    • 36a Tanaka T, Sasayama S, Nomura S, Yamamoto K, Kimura Y, Kadokawa J. Macromol. Chem. Phys. 2013; 214: 2829
    • 36b Tanaka T, Tsutsui A, Gotanda R, Sasayama S, Yamamoto K, Kadokawa J. J. Appl. Glycosci. 2015; 62: 135
  • 37 Tanaka T, Gotanda R, Tsutsui A, Sasayama S, Yamamoto K, Kimura Y, Kadokawa J. Polymer 2015; 73: 9
  • 38 Tanaka T, Sasayama S, Yamamoto K, Kimura Y, Kadokawa J. Macromol. Chem. Phys. 2015; 216: 794
  • 39 Kadokawa J, Yano K, Orio S, Yamamoto K. ACS Omega 2019; 4: 6331