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Thermo- and pH-Sensitive Behavior of Copolymers of N-Vinylcaprolactam with N-Vinylimidazole

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Abstract

Free-radical copolymerization in bulk has afforded copolymers of N-vinylcaprolactam and N‑vinylimidazole (40–60 mol %). Thermosensitive behavior of aqueous solutions of the copolymers has been probed over wide pH range by means of dynamic and static light scattering as well as high-sensitivity differential scanning calorimetry. Three regions of thermally induced conformational behavior have been observed with the change in the medium pH from the alkaline to acidic: phase separation region (I), region of the conformational transition into the mesoglobules state (II), and region of stable molecular solution of the poly-electrolyte (III). Significant polyelectrolyte effects have been revealed for the salt-free solutions of the copolymers, reflected in the presence of fast and slow diffusion modes in the relaxation time distributions. Moderate increase in the ionic strength with the addition of the low-molecular salt has led to shielding of the polyelectrolyte effects, yet the pH-dependent regions of the conformational behavior have not been affected much. The existence of different types of the thermally induced conformational behavior depending on pH has been explained by the balance between hydrophobic interactions involving the N-vinylcaprolactam units and electrostatic interactions of the weakly basic N-vinylimidazole units.

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REFERENCES

  1. S. A. Gore, S. B. Gholve, S. M. Savalsure, K. B. Ghodake, O. G. Bhusnure, and V. M. Thakare, Int. J. Curr. Pharm. Rev. Res. 8 (3), 298 (2017).

    Google Scholar 

  2. Smart Polymers and Their Applications, Ed. by M. R. Aguilar and J. S. Román (Woodhead Publ., 2014).

    Google Scholar 

  3. S. Chatterjee and P. C. Hui, Molecules 24 (14), 2547 (2019).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  4. A. Kyritsis, A. Laschewsky, and C. M. Papadakis, in Thermodynamics and Biophysics of Biomedical Nanosystems, Ed. by C. Demetzos and N. Pippa (Springer, Singapore, 2019), p. 397.

    Google Scholar 

  5. H. G. Schild, Prog. Polym. Sci. 17, 163 (1992).

    Article  CAS  Google Scholar 

  6. S. Lanzalaco and E. Armelin, Gels 3 (4), 36 (2017).

    Article  PubMed  PubMed Central  Google Scholar 

  7. A. C. W. Lau and Ch. Wu, Macromolecules 32 (3), 581 (1999).

    Article  CAS  Google Scholar 

  8. E. E. Makhaeva, H. Tenhu, and A. R. Khokhlov, Macromolecules 31 (9), 6112 (1998).

    Article  CAS  Google Scholar 

  9. V. Kozlovskaya and E. Kharlampieva, ACS Appl. Polym. Mater. 2, 26 (2020).

    Article  CAS  Google Scholar 

  10. H. Vihola, A. Laukkanen, L. Valtola, H. Tenhu, and J. Hirvonen, Biomaterials 26, 3055 (2005).

    Article  CAS  PubMed  Google Scholar 

  11. Y. Maeda, H. Yamamoto, and I. Ikeda, Langmuir 17, 6855 (2001).

    Article  CAS  Google Scholar 

  12. B. Wang, H. J. Liu, T. T. Jiang, Q. H. Li, and Y. Chen, Polymer 55, 6036 (2014).

    Article  CAS  Google Scholar 

  13. I. M. Okhapkin, L. M. Bronstein, E. E. Makhaeva, V. G. Matveeva, E. M. Sulman, M. G. Sulman, and A. R. Khokhlov, Macromolecules 37, 7879 (2004).

    Article  CAS  Google Scholar 

  14. I. M. Okhapkin, E. E. Makhaeva, and A. R. Khokhlov, Adv. Polym. Sci. 195, 177 (2006).

    Article  CAS  Google Scholar 

  15. Z. S. Ge, D. Xie, D. Y. Chen, X. Z. Jiang, Y. F. Zhang, H. W. Liu, and S. Y. Liu, Macromolecules 40, 3538 (2007).

    Article  CAS  Google Scholar 

  16. A. I. Barabanova, I. V. Blagodatskikh, O. V. Vyshivannaya, A. V. Muranov, A. S. Peregudov, and A. R. Khokhlov, Polym. Sci., Ser. A 63 (4), 382 (2021).

    Article  CAS  Google Scholar 

  17. A. I. Barabanova, I. V. Blagodatskikh, O. V. Vyshivannaya, T. P. Klimova, N. V. Grinberg, T. V. Burova, A. V. Muranov, V. I. Lozinskii, V. Ya. Grinberg, A. S. Peregudov, and A. R. Khokhlov, Dokl. Chem. 465 (1), 253 (2015).

    Article  CAS  Google Scholar 

  18. A. Yu. Mitrofanov, A. V. Murashkina, A. I. Barabanova, A. V. Vorozheikina, Ya. V. Zubavichus, A. R. Khokhlov, and I. P. Beletskaya, Molec. Catal. 541, 112915 (2023).

  19. V. I. Lozinskii, I. A. Simenel, and A. R. Khokhlov, Dokl. Chem. 410, 170 (2006).

    Article  CAS  Google Scholar 

  20. V. I. Lozinskii, I. A. Simenel, E. A. Kurskaya, V. K. Kulakova, V. Y. Grinberg, A. S. Dubovik, I. Y. Galaev, B. Mattiasson, and A. R. Khokhlov, Dokl. Chem. 375, 273 (2000).

    Article  Google Scholar 

  21. V. I. Lozinsky, I. A. Simenel, V. K. Kulakova, E. A. Kurskaya, T. A. Babushkina, and T. P. Klimova, Macromolecules 36, 7308 (2003).

    Article  CAS  Google Scholar 

  22. V. I. Lozinsky, A. Simenel, M. G. Semenova, L. E. Belyakova, M. M. Il’in, V. Y. Grinberg, A. S. Dubovik, and A. R. Khokhlov, Polym. Sci., Ser. A 48 (4), 435 (2006).

    Article  Google Scholar 

  23. G. Odian, Principles of Polymerization (Wiley-Interscience, New York, 2004).

    Book  Google Scholar 

  24. S. W. Provencher, Comput. Phys. Commun. 27, 229 (1982).

    Article  Google Scholar 

  25. Light Scattering from Polymer Solutions, Ed. by M. B. Huglin (Acad. Press; London, New York; 1972).

    Google Scholar 

  26. V. Aseyev, S. Hietala, A. Laukkanen, M. Nuopponen, O. Confortini, F. E. Du Prez, and H. Tenhu, Polymer 46, 7118 (2005).

    Article  CAS  Google Scholar 

  27. W. W. Yau, J. J. Kirkland, and D. D. Bly, Modern Size-Exclusion Liquid Chromatography: Practice of Gel Permeation and Gel Filtration Chromatography (Wiley, New York, 1979).

    Google Scholar 

  28. W. Burchard, Adv. Polym. Sci. 143, 113 (1999).

    Article  CAS  Google Scholar 

  29. J. Bodycomb and M. Hara, Macromolecules 27 (25), 7369 (1994).

    Article  CAS  Google Scholar 

  30. M. Sedlac, in Physical Chemistry of Polyelectrolytes, Ed. by T. Radeva (CRC Press, Boca Raton, 2001).

    Google Scholar 

  31. K. A. Dawson, A. V. Gorelov, E. G. Timoshenko, Y. A. Kuznetsov, and A. Du Chesne, Phys. A (Amsterdam, Neth.) 244, 68 (1997).

  32. S. C. Lin, W. I. Lee, and J. M. Schurr, Biopolymers 17, 1041 (1978).

    Article  CAS  Google Scholar 

  33. J. Bodycomb and M. Hara, Macromolecules 28, 8190 (1995).

    Article  CAS  Google Scholar 

  34. B. D. Ermi and E. J. Amis, Macromolecules 29, 2701 (1996).

    Article  CAS  Google Scholar 

  35. R. Cong, E. Temyanko, P. S. Russo, N. Edwin, and R. M. Uppu, Macromolecules 39, 731 (2006).

    Article  CAS  Google Scholar 

  36. K. J. Zhou, J. F. Li, Y. J. Lu, G. Z. Zhang, and C. Wu, Macromolecules 42, 7146 (2009).

    Article  CAS  Google Scholar 

  37. J. Li, T. Ngai, and Ch. Wu, Polym. J. 42, 609 (2010).

    Article  CAS  Google Scholar 

  38. Vinylazoles. https://xumuk.ru/encyklopedia/732.html. Accessed May 16, 2023.

  39. H. Gorjian, H. Fahim, and N. Khaligh Ghaffary, Turk. J. Chem 45, 2007 (2021).

    CAS  Google Scholar 

  40. W. Feng, W. Gu, L. Zhang, X. Tantai, B. Jiang, H. Yang, and H. Zhang, Trans. Tianjin Univ. 25, 226 (2019).

    Article  CAS  Google Scholar 

  41. A. V. Vorozheikina, A. I. Barabanova, and A. R. Khokhlov, in Abstracts of 7 Congress of Federation of Asian Polymer Societies FAPS2021, Vladivostok–Moscow, Russia, 2021, p. 60.

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Funding

This study was financially supported by the Ministry of Science and Higher Education of the Russian Federation (State Task no. 075-00697-22-00).

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Correspondence to O. V. Vyshivannaya.

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Translated by E. Karpushkin

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Vyshivannaya, O.V., Parkhomenko, E.R., Barabanova, A.I. et al. Thermo- and pH-Sensitive Behavior of Copolymers of N-Vinylcaprolactam with N-Vinylimidazole. Polym. Sci. Ser. A 65, 235–245 (2023). https://doi.org/10.1134/S0965545X2370092X

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  • DOI: https://doi.org/10.1134/S0965545X2370092X

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