Skip to main content
Log in

NMR and DSC study of temperature-induced phase transition in aqueous solutions of poly(N-isopropylmethacrylamide-co-acrylamide) copolymers

  • Original Contribution
  • Published:
Colloid and Polymer Science Aims and scope Submit manuscript

Abstract

Combination of 1H NMR spectroscopy and differential scanning calorimetry (DSC) was used to investigate temperature-induced phase transition in D2O solutions of poly(N-isopropylmethacrylamide-co-acrylamide) random copolymers. Both the NMR and DSC data showed dependence on the acrylamide (AAm) content in the copolymer; with increasing AAm content, the phase transition is shifted to higher temperatures, and both phase-separated fractions determined by NMR and change of the enthalpy determined by DSC decrease faster than the content of thermosensitive N-isopropylmethacrylamide (NIPMAm) units in the copolymer. NMR data were used to construct van't Hoff plots, and changes of the enthalpy ΔH and entropy ΔS, characterizing the phase transition, were determined. As it follows from comparison of NMR and DSC thermodynamical parameters (ΔH values), the size of the cooperative units (domains), undergoing the transition as a whole, decreases with increasing AAm content in the copolymer since the NIPMAm collapsed domains are separated by regions with hydrated AAm and surrounding NIPMAm sequences.

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

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Aseyev VO, Tenhu H, Winnik FM (2006) Adv Polym Sci 196:1–85

    Article  CAS  Google Scholar 

  2. Schild HG (1992) Prog Polym Sci 17:163–249

    Article  CAS  Google Scholar 

  3. Fujishige S, Kubota K, Ando I (1989) J Phys Chem 93:3311–3313

    Article  CAS  Google Scholar 

  4. Netopilík M, Bohdanecký M, Chytrý V, Ulbrich K (1997) Macromol Rapid Commun 18:107–111

    Article  Google Scholar 

  5. Idziak I, Avoce D, Lessard D, Gravel D, Zhu XX (1999) Macromolecules 32:1260–1263

    Article  CAS  Google Scholar 

  6. Schäfer-Soenen H, Moerkerke R, Berghmans H, Koningsveld R (1997) Macromolecules 30:410–416

    Article  Google Scholar 

  7. Liu R, Fraylich M, Saunders BR (2009) Colloid Polym Sci 287:627–643

    Article  CAS  Google Scholar 

  8. Simnick AJ, Limm DW, Chow D, Chilkoti A (2007) J Macromol Sci Part C Polym Rev 47:121–154

    CAS  Google Scholar 

  9. Privalov PL (1979) Adv Protein Chem 33:167–241

    Article  CAS  Google Scholar 

  10. Cherkasskaya OV, Anufrieva VV, Krakoviak MG, Ananeva TD, Lushchik VB (1992) Vysokomol Soedin A 34(10):90–98

    CAS  Google Scholar 

  11. Tiktopulo EI, Uversky VN, Lushchik VB, Klenin SI, Bychkova VE, Ptitsyn OB (1995) Macromolecules 28:7519–7524

    Article  CAS  Google Scholar 

  12. Djokpé E, Wogt W (2001) Macromol Chem Phys 202:750–757

    Article  Google Scholar 

  13. Maeda Y, Nakamura T, Ikeda I (2001) Macromolecules 34:8246–8251

    Article  CAS  Google Scholar 

  14. Wu Y, Meersman F, Ozaki Y (2006) Macromolecules 39:1182–1188

    Article  CAS  Google Scholar 

  15. Schmidt P, Dybal J, Trchová M (2006) Vib Spectrosc 42:278–283

    Article  CAS  Google Scholar 

  16. Dybal J, Trchová M, Schmidt P (2009) Vib Spectrosc 51:44–51

    Article  CAS  Google Scholar 

  17. Salmerón SM, Hanyková L, Ilavský M, Monleón PM (2004) Polymer 45:4087–4094

    Article  Google Scholar 

  18. Starovoytova L, Spěváček J, Hanyková L, Ilavský M (2003) Macromol Symp 203:239–246

    Article  CAS  Google Scholar 

  19. Spěváček J (2009) Curr Opin Colloid Interface Sci 14:184–191

    Article  Google Scholar 

  20. Starovoytova L, Spěváček J, Hanyková L, Ilavský M (2004) Polymer 45:5905–5911

    Article  CAS  Google Scholar 

  21. Starovoytova L, Spěváček J, Ilavský M (2005) Polymer 46:677–683

    Article  CAS  Google Scholar 

  22. Starovoytova L, Spěváček J (2006) Polymer 47:7329–7334

    Article  CAS  Google Scholar 

  23. Starovoytova L, Spěváček J, Trchová M (2007) Eur Polym J 43:5001–5009

    Article  CAS  Google Scholar 

  24. Spěváček J, Starovoytova L, Hanyková L, Kouřilová H (2008) Macromol Symp 273:17–24

    Article  Google Scholar 

  25. Kouřilová H, Hanyková L, Spěváček J (2009) Eur Polym J 45:2935–2941

    Article  Google Scholar 

  26. Spěváček J, Hanyková L, Starovoytova L (2004) Macromolecules 37:7710–7718

    Article  Google Scholar 

  27. Tiktopulo ET, Bychkova VE, Rička J, Ptitsyn OB (1994) Macromolecules 27:2879–2882

    Article  CAS  Google Scholar 

  28. Wu S, Shanks RA (2004) J Appl Polym Sci 93:1493–1499

    Article  CAS  Google Scholar 

  29. Tanaka T (1979) Polymer 20:1404–1412

    Article  CAS  Google Scholar 

  30. Freitag R, Garret-Flaudy F (2002) Langmuir 18:3434–3440

    Article  CAS  Google Scholar 

  31. Spěváček J (1990) Makromol Chem Macromol Symp 39:71–83

    Article  Google Scholar 

  32. Rice CV (2006) Biomacromolecules 7:2923–2925

    Article  CAS  Google Scholar 

  33. Spěváček J (2011) Macromol Symp 305:18–25

    Article  Google Scholar 

  34. Kouřilová H, Šťastná J, Hanyková L, Sedláková Z, Spěváček J (2010) Eur Polym J 46:1299–1306

    Article  Google Scholar 

  35. Bovey FA, Mirau PA (1996) NMR of polymers. Academic, San Diego, p 151

    Google Scholar 

  36. Larsson A, Kuckling D, Schönhoff M (2001) Colloid surf A Physicochem Eng Asp 190:185–192

    Article  CAS  Google Scholar 

  37. Hofmann C, Schönhoff M (2009) Colloid Polym Sci 287:1369–1376

    Article  CAS  Google Scholar 

  38. Hamcerencu M, Desbrieres J, Khoukh A, Popa M, Riess G (2011) Polym Int 60:1527–1534

    Article  CAS  Google Scholar 

  39. Schild HG, Tirrell DA (1990) J Phys Chem 94:4352–4356

    Article  CAS  Google Scholar 

  40. Otake K, Inomata H, Konno M, Saito S (1990) Macromolecules 23:283–289

    Article  CAS  Google Scholar 

Download references

Acknowledgments

Supports by the Czech Science Foundation (project 202/09/1281), Ministry of Education, Youth and Sports of the Czech Republic (grant SVV–2012–265305) and the Grant Agency of Charles University (grant 719812) are gratefully acknowledged. Authors would like to thank Dr. Vladimír Šubr for his determination of molecular weights of investigated samples.

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Lenka Hanyková or Jiří Spěváček.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Šťastná, J., Hanyková, L. & Spěváček, J. NMR and DSC study of temperature-induced phase transition in aqueous solutions of poly(N-isopropylmethacrylamide-co-acrylamide) copolymers. Colloid Polym Sci 290, 1811–1817 (2012). https://doi.org/10.1007/s00396-012-2701-3

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00396-012-2701-3

Keywords

Navigation