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Preparation of Responsive Zwitterionic Diblock Copolymers Containing Phosphate and Phosphonate Groups

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Abstract

In this study, novel zwitterionic diblock copolymers, namely poly(2-(N-morpholino)ethyl methacrylate))-block-poly(2-(methacryloyloxy)ethyl phosphate) (PMEMA-b-PMOEP) and poly(2-(N-morpholino)ethyl methacrylate))-block-poly ((methacryloyloxy)methyl phosphonic acid) (PMEMA-b-PMOMP), were synthesized via reversible addition-fragmentation chain transfer controlled radical polymerization. Solution properties of these phosphorus-based diblock copolymers were investigated using dynamic light scattering, transmission electron microscopy and proton nuclear magnetic resonance spectroscopy. Since the PMEMA block has both salt- and thermo-responsive properties, PMEMA-b-PMOEP and PMEMA-b-PMOMP diblock copolymers formed core-shell micelles in basic aqueous media as the PMEMA block formed insoluble micelle core with the addition of Na2SO4 or an increase in temperature in basic solution. Additionally, PMEMA-b-PMOMP diblock copolymers interacted strongly with calcium cations and yielded reverse micellar structures via complexation of phosphate with metal cation in aqueous media.

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References

  1. Y. L. Gefter, in Organophosphorus Monomers and Polymers, Pergamon Press, 1962, pp 265–288.

  2. E. D. Weil, in Encyclopedia of Polymer Science and Technology, 3, 447 (2001).

    Google Scholar 

  3. E. D. Weil, in Encyclopedia of Polymer Science and Engineering, 11, 96 (1988).

    Google Scholar 

  4. J. Kaiser, B. Schied, N. Trautmann, and W. Vogt, Makromol. Chem. Macromol. Chem. Phys., 193, 799 (1992).

    Article  CAS  Google Scholar 

  5. K. Kaluzynski, J. Pretula, G. Lapienis, M. Basko, Z. Bartczak, A. Dworak, and S. Penczek, J. Polym. Sci. Part A: Polym. Chem., 39, 955 (2001).

    Article  CAS  Google Scholar 

  6. S. Monge, B. Canniccioni, A. Graillot, and J. J. Robin, Biomacromolecules, 12, 1973 (2011).

    Article  CAS  PubMed  Google Scholar 

  7. Y. Iwasaki, C. Nakagawa, M. Ohtomi, K. Ishihara, and K. Akiyoshi, Biomacromolecules, 5, 1110 (2004).

    Article  CAS  PubMed  Google Scholar 

  8. J. Wang, H. Q. Mao, and K. W. Leong, J. Am. Chem. Soc., 123, 9480 (2001).

    Article  CAS  PubMed  Google Scholar 

  9. Y. D. Lei, T. X. Wang, J. W. Mitchell, L. Zaidel, J. H. Qiu, and L. Kilpatrick-Liverman, RSC Adv., 4, 49053 (2014).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  10. Y. Kim, D. Priddy, and H. J. Harwood, Polymer, 44, 4165 (2003).

    Article  CAS  Google Scholar 

  11. J. R. Ebdon, D. Price, B. J. Hunt, P. Joseph, F. G. Gao, G. J. Milnes, and L. K. Cunliffe, Polym. Degrad. Stab., 69, 267 (2000).

    Article  CAS  Google Scholar 

  12. E. Bayer, P.-A. Grathwohl, and K. Geckeler, Angew. Makromol. Chem., 113, 141 (1983).

    Article  CAS  Google Scholar 

  13. P.-L. Kuo, J.-S. Wang, P.-C. Chen, and L.-W. Chen, Macromol. Chem. Phys., 202, 2175 (2001).

    Article  CAS  Google Scholar 

  14. D. Derouet, F. Morvan, and J.-C. Brosse, Eur. Polym. J., 37, 1297 (2001).

    Article  CAS  Google Scholar 

  15. G.-N. Wang, P. S. Lau, Y. Li, and X.-S. Ye, Tetrahedron, 68, 9405 (2012).

    Article  CAS  Google Scholar 

  16. J. Wen and R. X. Zhuo, Macromol. Rapid Commun., 19, 641 (1998).

    Article  CAS  Google Scholar 

  17. S. Penczek, J. Polym. Sci. Part C: Polym. Symp., 149 (1980).

  18. G. David, Z. El Asri, S. Rich, P. Castignolles, Y. Guillaneuf, P. Lacroix-Desmazes, and B. Boutevin, Macromol. Chem. Phys., 210, 631 (2009).

    Article  CAS  Google Scholar 

  19. B. Canniccioni, S. Monge, G. David, and J. J. Robin, Polym. Chem., 4, 3676 (2013).

    Article  CAS  Google Scholar 

  20. G. Moad, E. Rizzardo, and S. H. Thang, Polymer, 49, 1079 (2008).

    Article  CAS  Google Scholar 

  21. S. Suzuki, M. R Whittaker, L. Grondahl, M. J. Monteiro, and E. Wentrup-Byrne, Biomacromolecules, 7, 3178 (2006).

    Article  CAS  PubMed  Google Scholar 

  22. R. Menard, C. Negrell-Guirao, L. Ferry, R. Sonnier, and G. David, Eur. Polym. J., 57, 109 (2014).

    Article  CAS  Google Scholar 

  23. Y. Iwasaki, A. Matsumoto, and S.-I. Yusa, ACS Appl. Mater. Interfaces, 4, 3254 (2012).

    Article  CAS  PubMed  Google Scholar 

  24. A. Hanisch, P. Yang, A. N. Kulak, L. A. Fielding, F. C. Meldrum, and S. P. Armes, Macromolecules, 49, 192 (2016).

    Article  CAS  Google Scholar 

  25. B. Canniccioni, S. Monge, G. David, and J.-J. Robin, Polym. Chem., 4, 3676 (2013).

    Article  CAS  Google Scholar 

  26. G. David, C. Negrell, A. Manseri, and B. Boutevin, J. App. Polym. Sci., 114, 2213 (2009).

    Article  CAS  Google Scholar 

  27. J. Y. Huang and K. Matyjaszewski, Macromolecules, 38, 3577 (2005).

    Article  CAS  Google Scholar 

  28. J. C. Tom, R. Brilmayer, J. Schmidt, and A. Andrieu-Brunsen, Polymers (Basel, Switz.), 9, 539/1 (2017).

    CAS  Google Scholar 

  29. H. T. T. Duong, Y. H. Chen, S. A. Tawfik, S. H. Wen, M. Parviz, O. Shimoni, and D. Y. Jin, RSC Adv., 8, 4842 (2018).

    Article  CAS  Google Scholar 

  30. T. Huang, H. Liu, P. Liu, P. Liu, L. Li, and J. Shen, J. Mater. Chem. B, 5, 5380 (2017).

    Article  CAS  PubMed  Google Scholar 

  31. B. Canniccioni, S. Monge, G. David, and J.-J. Robin, Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 52, 645 (2011).

    CAS  Google Scholar 

  32. D. B. Hua, J. Tang, J. L. Jiang, and X. L. Zhu, Polymer, 50, 5701 (2009).

    Article  CAS  Google Scholar 

  33. D. Hua, J. Tang, J. Jiang, X. Zhu, and R. Bai, Macromolecules, 42, 8697 (2009).

    Article  CAS  Google Scholar 

  34. P. G. Falireas, C. Negrell, and G. David, Polymers-Basel, 10 (2018).

  35. M. Jasieniak, S. Suzuki, M. Monteiro, E. Wentrup-Byrne, H. J. Griesser, and L. Grondahl, Langmuir, 25, 1011 (2009).

    Article  CAS  PubMed  Google Scholar 

  36. F. Azemar, D. Gomes-Rodrigues, J. J. Robin, and S. Monge, Dalton T, 45, 1881 (2016).

    Article  CAS  Google Scholar 

  37. M. Douverne, Y. Ning, A. Tatani, F. C. Meldrum, and S. P. Armes, Angew. Chem. Int. Ed., 58, 8692 (2019).

    Article  CAS  Google Scholar 

  38. C. Tian, T. C. Xu, L. F. Zhang, Z. P. Cheng, and X. L. Zhu, RSC Adv., 6, 34659 (2016).

    Article  CAS  Google Scholar 

  39. B. Rixens, R. Severac, B. Boutevin, P. Lacroix-Desmazes, and Y. Hervaud, Macromol. Chem. Phys., 206, 1389 (2005).

    Article  CAS  Google Scholar 

  40. C. Bouilhac, C. Travelet, A. Graillot, S. Monge, R. Borsali, and J. J. Robin, Polym. Chem., 5, 2756 (2014).

    Article  CAS  Google Scholar 

  41. K. H. Markiewicz, L. Seiler, I. Misztalewska, K. Winkler, S. Harrisson, A. Z. Wilczewska, M. Destarac, and J. D. Marty, Polym. Chem., 7, 6391 (2016).

    Article  CAS  Google Scholar 

  42. X. H. Liu, X. Tan, R. Rao, Y. Y. Ren, Y. H. Li, X. L. Yang, and W. Liu, ACS Appl. Mater. Interfaces, 8, 23450 (2016).

    Article  CAS  PubMed  Google Scholar 

  43. Y. Iwasaki, A. Matsumoto, and S. Yusa, ACS Appl. Mater. Interfaces, 4, 3254 (2012).

    Article  CAS  PubMed  Google Scholar 

  44. A. Graillot, S. Monge, C. Faur, D. Bouyer, and J. J. Robin, Polym. Chem., 4, 795 (2013).

    Article  CAS  Google Scholar 

  45. C. Dolan, B. Naysmith, S. F. R. Hinkley, I. M. Sims, M. A. Brimble, D. E. Williams, and J. Y. Jin, Aust. J. Chem., 68, 680 (2015).

    Article  CAS  Google Scholar 

  46. I. Blidi, O. Coutelier, and M. Destarac, J. Polym. Sci. Pol. Chem., 52, 2616 (2014).

    Article  CAS  Google Scholar 

  47. Y. Y. Mai and A. Eisenberg, Chem. Soc. Rev., 41, 5969 (2012).

    Article  CAS  PubMed  Google Scholar 

  48. S. B. Darling, Prog. Polym. Sci., 32, 1152 (2007).

    Article  CAS  Google Scholar 

  49. G. Kocak C. Tuncer, and V. Bütün, Polym. Chem., 8, 144 (2017).

    Article  CAS  Google Scholar 

  50. C. Giacomelli, V. Schmidt, K. Aissou, and R. Borsali, Langmuir, 26, 15734 (2010).

    Article  CAS  PubMed  Google Scholar 

  51. H. C. Kim, S. M. Park, and W. D. Hinsberg, Chem. Rev., 110, 146 (2010).

    Article  CAS  PubMed  Google Scholar 

  52. X. B. Xiong, A. Falamarzian, S. M. Garg, and A. Lavasanifar, J. Control. Release, 155, 248 (2011).

    Article  CAS  PubMed  Google Scholar 

  53. V. Butun, S. P. Armes, and N. C. Billingham, Polymer, 42, 5993 (2001).

    Article  CAS  Google Scholar 

  54. V. Butun, F. F. Taktak, and C. Tuncer, Macromol. Chem. Phys., 212, 1115 (2011).

    Article  CAS  Google Scholar 

  55. V. Butun, A. B. Lowe, N. C. Billingham, and S. P. Armes, J. Am. Chem. Soc., 121, 4288 (1999).

    Article  Google Scholar 

  56. V. Butun, X. S. Wang, M. V. D. Banez, K. L. Robinson, N. C. Billingham, S. P. Armes, and Z. Tuzar, Macromolecules, 33, 1 (2000).

    Article  CAS  Google Scholar 

  57. T. Wang, Y. Lei, J. W. Mitchell, L. Zaidel, J. Qiu, and M. Hassan, US Patent, US 2015/0283061 A1 (2015).

  58. D. J. Phillips, M. Wilde, F. Greco, and M. I. Gibson, Biomacromolecules, 16, 3256 (2015).

    Article  CAS  PubMed  Google Scholar 

  59. C. Chang, H. Wei, J. Feng, Z. C. Wang, X. J. Wu, D. Q. Wu, S. X. Cheng, X. Z. Zhang, and R. X. Zhuo, Macromolecules, 42, 4838 (2009).

    Article  CAS  Google Scholar 

  60. G. Kocak and V. Butun, Colloid. Polym. Sci., 293, 3563 (2015).

    Article  CAS  Google Scholar 

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Correspondence to Vural Bütün.

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Information is available regarding the experimental procedure for the synthesis of monomers and diblock copolymers and their characterizations. The materials are available via the Internet at http://www.springer.com/13233.

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Footnote: The image from this article is used as the cover image of the Volume 28, Issue 12.

Acknowledgments: Y. Samav thanks The Scientific and Technological Research Council of Turkey for the financial support given under its BIDEB 2211-A Domestic Graduate Scholarship Program.

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Samav, Y., Akpinar, B., Kocak, G. et al. Preparation of Responsive Zwitterionic Diblock Copolymers Containing Phosphate and Phosphonate Groups. Macromol. Res. 28, 1134–1141 (2020). https://doi.org/10.1007/s13233-020-8148-3

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