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Fast and eco-friendly synthesis of new hydrolysable and biodegradable copolyurethanes derived from L-leucine cyclodipeptide and different molecular weights of PEG in TBAB under microwave irradiation

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Abstract

In this study novel multi block polyurethane (PU) copolymers containing cyclodipeptide were synthesized under microwave irradiation using a quaternary ammonium salt (QAS) as reaction media. For this, L-leucine cyclodipeptide (LC) was prepared and then a new class of poly(ether-urethane-urea)s (PEUUs) was synthesized in tetrabutylammonium bromide (TBAB) via two-step polymerization method. In the first step, 4,4′-methylene-bis-(4-phenylisocyanate) (MDI) was reacted with LC to produce isocyanate-terminated oligo(imide-urea) as hard segment. The reaction of the aforementioned pre-polymer with poly(ethylene glycols) (PEG) with different molecular weights (PEG400, 600, 1000, and 2000) was the second step to furnish a series of new PEUUs. These PEUUs are thermally stable, soluble in amide-type solvents, hydrolysable, and biodegradable. The resulting PEUUs have inherent viscosities in the range of 0.37–0.67 dL/g. The effects of polymerization method and soft segment length on some of the polymers’ properties and their structural characteristics were compared. The protocol presented here has the merits of environmentally benign, simple operation, convenient work-up, short reaction time and good yields without using volatile organic solvents or catalysts. Ammonium type reaction medium was air and water stable, and relatively cheap, which makes it suitable for applications. The results demonstrate that it can be easily separated and reused without losing activity which makes the method cost effective and eco-benign.

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References

  1. M. Delaforge, G. Bouill’e, M. Jaouen, C. K. Jankowski, C. Lamouroux, and C. Bensoussan, Peptides, 22, 557 (2001).

    Article  CAS  Google Scholar 

  2. D. D. Long, R. J. Tennant-Eyles, J. C. Estevez, M. R. Wormald, R. A. Dwek, M. D. Smith, and G. W. J. Fleet, J. Chem. Soc. Perkin Trans., 1, 807 (2001).

    Article  Google Scholar 

  3. A. P. Einholm, K. E. Pedersen, T. Wind, P. Kulig, M. T. Overgaard, J. K. Jensen, J. S. Bodker, and A. Christensen, Biochem. J., 373, 723 (2003).

    Article  CAS  Google Scholar 

  4. B. Nicholson, G. K. Lloyd, B. R. Miller, M. A. Palladino, Y. Kiso, Y. Hayashi, and S. T. C. N. Neuteboom, Anticancer Drugs, 17, 25 (2006).

    Article  CAS  Google Scholar 

  5. D. R. Houston, B. Synstad, V. G. H. Eijsink, M. J. R. Stark, I. M. Eggleston, and D. M. F. Van Aalten, J. Med. Chem., 47, 5713 (2004).

    Article  CAS  Google Scholar 

  6. Y. Sugie, H. Hirai, T. Inagaki, M. Ishiguro, Y. J. Kim, Y. Kojima, T. Sakakibara, S. Sakemi, A. Sugiura, Y. Suzuki, L. Brennan, J. Duignan, L. H. Huang, J. Sutcliffe, and N. Kojima, J. Antibiot., 54, 911 (2001).

    Article  CAS  Google Scholar 

  7. A. G. Kozlovsky, V. P. Zhelifonova, V. M. Adanin, T. V. Antipova, S. M. Ozerskaya, N. E. Ivanushkina, and U. Grafe, Appl. Biochem. Microbiol., 39, 393 (2003).

    Article  CAS  Google Scholar 

  8. M. K. Song, I. K. Hwang, M. J. Rosenthal, D. M. Harris, D. T. Yamaguchi, I. Yip, and V. L. Go, Exp. Biol. Med., 228, 1338 (2003).

    CAS  Google Scholar 

  9. M. Imamura and C. Prasad, Peptides, 24, 445 (2003).

    Article  CAS  Google Scholar 

  10. D. X. Wang, M. T. Liang, G. J. Tian, H. Lin, and H. Q. Liu, Tetrahedron Lett., 43, 865 (2002).

    Article  CAS  Google Scholar 

  11. M. B. Martins and I. Carvalho, Tetrahedron, 63, 9923 (2007).

    Article  CAS  Google Scholar 

  12. M. Rutkowska, K. Krasowska, A. Heimowska, I. Steinka, and H. Janik, Polym. Degrad. Stab., 76, 233 (2002).

    Article  CAS  Google Scholar 

  13. M. Okada, Prog. Polym. Sci., 27, 87 (2002).

    Article  CAS  Google Scholar 

  14. K. Nakano, Y. Sumitomo, and K. Kondo, Macromolecules, 30, 852 (1997).

    Article  CAS  Google Scholar 

  15. S. E. Matthews, C. W. Pouton, and M. D. Threadgill, J. Control. Release, 67, 129 (2000).

    Article  CAS  Google Scholar 

  16. R. Ogawa, J. Watanabe, and K. Ishihara, Sci. Technol. Adv. Mater., 4, 523 (2003).

    Article  CAS  Google Scholar 

  17. A. Vaidya and M. K. Chaudhury, J. Colloid Interface Sci., 249, 235 (2002).

    Article  CAS  Google Scholar 

  18. M. C. Tanzi, M. Resnati, M. G. Lampugnani, R. Anouchinsky, L. Ambrosio, B. Mambrito, and E. Dejana, Clin. Mater., 12, 17 (1993).

    Article  CAS  Google Scholar 

  19. Y. Kimura, Y. Makita, T. Kumagai, H. Yamane, T. Kitao, H. Sasatani, and S. I. Kim, Polymer, 33, 5294 (1992).

    Article  CAS  Google Scholar 

  20. K. D. Kavlock, T. W. Pechar, J. O. Hollinger, S. A. Guelcher, and A. S. Goldstein, Acta Biomater., 3, 475 (2007).

    Article  CAS  Google Scholar 

  21. B. Sharma, L. Ubaghs, H. Keul, H. Hocker, T. Loontjens, and R. van Benthem, Polymer, 46, 1775 (2005).

    Article  CAS  Google Scholar 

  22. D. J. Martin, G. F. Meijs, G. M. Renwick, S. J. McCarthy, and P. A. Gunatillake, J. Appl. Polym. Sci., 62, 1377 (1996).

    Article  CAS  Google Scholar 

  23. J. David, L. Vojtova, K. Bednarik, J. Kucerık, M. Vávrova, and J. Jancar, Environ. Chem. Lett., 8, 381 (2010).

    Article  CAS  Google Scholar 

  24. R. Gedye, F. Smith, K. Westaway, A. Humera, L. Baldsera, L. Laberge, and L. Rousel, Tetrahedron Lett., 27, 279 (1986).

    Article  CAS  Google Scholar 

  25. D. Bogdal and J. Gorczyk, J. Appl. Polym. Sci., 94, 1969 (2004).

    Article  CAS  Google Scholar 

  26. C. Melo-Junior, C. Albuquerque, M. Fortuny, C. Dariva, S. Egues, A. F. Santos, and A. Ramos, Energy Fuels, 23, 580 (2009).

    Article  CAS  Google Scholar 

  27. F. Wiesbroc, R. Hoogenboom, M. A. M. Leenen, M. R. Meier, and U. S. Schubert, Macromolecules, 38, 5025 (2005).

    Article  Google Scholar 

  28. R. Hoogenboom and U. S. Schubert, Macromol. Rapid Commun., 28, 368 (2007).

    Article  CAS  Google Scholar 

  29. S. Mallakpour and A. Zadehnazari, Amino Acids, 38, 1369 (2010).

    Article  CAS  Google Scholar 

  30. P. R. Martinez, Mol. Divers., 14, 3 (2010).

    Article  Google Scholar 

  31. P. Kubisa, Prog. Polym. Sci., 34, 1333 (2009).

    Article  CAS  Google Scholar 

  32. C. G. Sanchez, M. Lobert, R. Hoogenboom, and U. S. Schubert, Macromol. Rapid Commun., 28, 456 (2007).

    Article  Google Scholar 

  33. S. Mallakpour and Z. Rafiee, Polym. Adv. Technol., 21, 817 (2010).

    Article  CAS  Google Scholar 

  34. S. Mallakpour and M. Dinari, J. Polym. Environ., 18, 705 (2010).

    Article  CAS  Google Scholar 

  35. S. Mallakpour and M. Taghavi, Polym. J., 40, 1049 (2008).

    Article  CAS  Google Scholar 

  36. S. Mallakpour and S. Sepehri, React. Funct. Polym., 68, 1459 (2008).

    Article  CAS  Google Scholar 

  37. S. Mallakpour and Z. Rafiee, Eur. Polym. J., 43, 1510 (2007).

    Article  CAS  Google Scholar 

  38. P. Lidstrom, J. Tierney, B. Wathey, and J. Westman, Tetrahedron, 57, 9225 (2001).

    Article  CAS  Google Scholar 

  39. S. Mallakpour and F. Rafiemanzelat, J. Appl. Polym. Sci., 98, 1781 (2005).

    Article  CAS  Google Scholar 

  40. R. M. Palou, Mol. Divers., 14, 3 (2010).

    Article  Google Scholar 

  41. I. Mohammadpoor-Baltork, M. Moghadam, S. Tangestaninejad, V. Mirkhani, A. R. Khosropour, and A. Mirjafari, Monatsh. Chem., 141, 1083 (2010).

    Article  CAS  Google Scholar 

  42. L. Liao, L. Liu, C. Zhang, and S. Gong, Macromol. Rapid Commun., 27, 2060 (2006).

    Article  CAS  Google Scholar 

  43. Y. J. Zhu, W. W. Wang, R. J. Qi, and X. L. Hu, Angew. Chem. Int. Ed., 43, 1410 (2004).

    Article  CAS  Google Scholar 

  44. F. Rafiemanzelat and E. Abdollahi, Polym. Degrad. Stab., 95, 901 (2010).

    Article  CAS  Google Scholar 

  45. F. Rafiemanzelat, A. Fathollahi Zonouz, and G. Emtiazi, Polym. Degrad. Stab., 97, 72 (2012).

    Article  CAS  Google Scholar 

  46. M. van der Schuur, B. Noordover, and R. J. Gaymans Polymer, 47, 1091 (2006).

    Article  Google Scholar 

  47. A. K. Mishra, D. K. Chattopadhyay, B. Sreedhar, and K. V. S. N. Raju, Prog. Org. Coat., 55, 231 (2006).

    Article  CAS  Google Scholar 

  48. S. Mallakpour and F. Rafiemanzelat, Polym. Bull., 58, 339 (2007).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Organic Polymer Chemistry Research Laboratory, Department of Chemistry, University of Isfahan, Isfahan, 81746-73441, I.R. Iran

    Fatemeh Rafiemanzelat, Abolfazl Fathollahi Zonuz & Elahe Abdollahi

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  1. Fatemeh Rafiemanzelat
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  2. Abolfazl Fathollahi Zonuz
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  3. Elahe Abdollahi
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Correspondence to Fatemeh Rafiemanzelat.

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Rafiemanzelat, F., Zonuz, A.F. & Abdollahi, E. Fast and eco-friendly synthesis of new hydrolysable and biodegradable copolyurethanes derived from L-leucine cyclodipeptide and different molecular weights of PEG in TBAB under microwave irradiation. Macromol. Res. 20, 902–911 (2012). https://doi.org/10.1007/s13233-012-0137-8

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  • DOI: https://doi.org/10.1007/s13233-012-0137-8

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