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Synthesis and self-assembly of new amphiphilic thermosensitive poly(N-vinylcaprolactam)/poly(ε-caprolactone) block copolymers via the combination of ring-opening polymerization and click chemistry

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Abstract

New amphiphilic thermosensitive poly(N-vinylcaprolactam)/poly(ε-caprolactone) (PNVCL-b-PCL) block copolymers were synthesized by click reaction with alkynyl-terminated poly(N-vinylcaprolactam) (PNVCL-C ≡ CH) and azido-terminated poly(ε-caprolactone) (N3-PCL). The structures of the polymers were determined by proton nuclear magnetic resonance spectroscopy (1H NMR) and gel permeation chromatography (GPC) measurements. The fluorescence technique was used to determine the critical micelle concentrations (CMC) of copolymer solutions. The factors affecting the lower critical solution temperature (LCST) of the copolymers were studied by UV-visible analysis. The diameters and distribution of the micelles were characterized by dynamic light scattering (DLS), and their shapes were observed by transmission electron microscopy (TEM). The results showed that these copolymers could self-assemble into nano-micelles in water. The CMC values of the copolymer solutions and the sizes of micelles reduced with increasing proportion of hydrophobic parts. TEM images demonstrated that the micelles are all spherical. On the other hand, the UV–visible measurements showed that these block copolymers exhibit a reproducible temperature-responsive behavior with a LCST that is tunable by block composition.

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References

  1. Kuramochi H, Andoh Y, Yoshii N, Okazaki S (2009) J Phys Chem B 113:15181

    Article  CAS  Google Scholar 

  2. Zhang JX, Ellsworth K, Ma PX (2010) J Controlled Release 145:116

    Article  CAS  Google Scholar 

  3. Cai CH, Lin JP, Chen T, Tian XH (2010) Langmuir 26:2791

    Article  CAS  Google Scholar 

  4. Peng CL, Shieh MJ, Tsai MH, Chang CC, Lai PS (2008) Biomaterials 29:3599

    Article  CAS  Google Scholar 

  5. Zhang XW, Oddon M, Giani O, Monge S, Robin JJ (2010) Macromolecules 43:2654

    Article  CAS  Google Scholar 

  6. Hu Y, Jiang ZP, Chen R, Wu W, Jiang XQ (2010) Biomacromolecules 11:481

    Article  CAS  Google Scholar 

  7. Yao J, Ruan YL, Zhai T, Guan J, Tang GP, Li HR, Dai S (2011) Polymer 52:3396

    Article  CAS  Google Scholar 

  8. Li YY, Zhang XZ, Cheng H, Zhu JL, Cheng SX, Zhuo RX (2006) Macromol. Rapid Commun 27:1913

    Article  CAS  Google Scholar 

  9. Virtanen J, Tenhu H (2001) J Polym Sci Part A Polym Chem 39:3716

    Article  CAS  Google Scholar 

  10. Wang YC, Tang LY, Li Y, Wang J (2009) Biomacromolecules 10:66

    Article  CAS  Google Scholar 

  11. Bigot J, Charleux B, Cooke G, Delattre F, Fournier D, Lyskawa J, Sambe L, Stoffelbach F, Woisel P (2010) J Am Chem Soc 132:10796

    Article  CAS  Google Scholar 

  12. Kumar A, Srivastava A, Galaev IY, Mattiasson B (2007) Prog Polym Sci 32:1205

    Article  CAS  Google Scholar 

  13. Qu TH, Wang AR, Yuan JF, Shi JH, Gao QY (2009) Colloids Surf. B: Biointerfaces 72:94

    Article  CAS  Google Scholar 

  14. Iwasaki Y, Wachiralarpphaithoon C, Akiyoshi K (2007) Macromolecules 40:8136

    Article  CAS  Google Scholar 

  15. Liu X, Ni PH, He JL, Zhang MZ (2010) Macromolecules 43:4771

    Article  CAS  Google Scholar 

  16. Vihola H, Laukkanen A, Tenhu H, Hirvonen J (2008) J Pharm Sci 97:4783

    Article  CAS  Google Scholar 

  17. Prabaharan SM, Grailer JJ, Steeber DA, Gong SQ (2008) Macromol Biosci 8:843

    Article  CAS  Google Scholar 

  18. Shah S, Pal A, Gude R, Devi S (2010) Eur Polym J 46:958

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  20. Loos W, Verbrugghe S, Goethals EJ, Prez FED, Bakeeva IV, Zubov VP (2003) Macromol Chem Phys 204:98

    Article  CAS  Google Scholar 

  21. Verbrugghe S, Bernaerts K, Prez FED (2003) Macromol Chem Phys 204:1217

    Article  CAS  Google Scholar 

  22. Hurtgen M, Liu J, Debuigne A, Jerome C, Detrembleur C (2012) J Polym Sci Part A Polym Chem 50:400

    Article  CAS  Google Scholar 

  23. Lequieu W, Shtanko NI, Pre FED (2005) J Membr Sci 256:64

    CAS  Google Scholar 

  24. Dimitrov I, Trzebicka B, Müller AHH, Dworak A, Tsvetanov CB (2007) Prog Polym Sci 32:1275

    Article  CAS  Google Scholar 

  25. Castillo RV, Müller AJ, Raquez JM, Dubois P (2010) Macromolecules 43:4149

    Article  CAS  Google Scholar 

  26. Loh XJ, Sng KBC, Li J (2008) Biomaterials 29:3185

    Article  CAS  Google Scholar 

  27. Li JB, Ren J, Cao Y, Yuan WZ (2010) Polymer 51:1301

    Article  CAS  Google Scholar 

  28. Rong GZ, Deng MX, Deng C, Tang ZH, Piao LH, Chen XS, Jing XB (2003) Biomacromolecules 4:1800

    Article  CAS  Google Scholar 

  29. Sahoo S, Sasmal A, Nanda R, Phani AR, Nayak PL (2010) Carbohydr Polym 79:106

    Article  CAS  Google Scholar 

  30. Sarazin P, Li G, Orts WJ, Favis BD (2008) Polymer 49:599

    Article  CAS  Google Scholar 

  31. Loontjens CAM, Vermonden T, Leemhuis M, Van Steenbergen MJ, Van Nostrum CF, Hennink WE (2007) Macromolecules 40:7208

    Article  CAS  Google Scholar 

  32. Zhang XJ, Zhong ZL, Zhuo RX (2011) Macromolecules 44:1755

    Article  CAS  Google Scholar 

  33. Hanni KD, Leigh DA (2010) Chem Soc Rev 39:1240

    Article  Google Scholar 

  34. Kappe CO, Van der Eycken E (2010) Chem Soc Rev 39:1280

    Article  CAS  Google Scholar 

  35. Zhang Y, He HK, Gao C (2008) Macromolecules 41:9581

    Article  CAS  Google Scholar 

  36. Zhang GL, Liang F, Song XM, Liu DL, Li MJ, Wu QH (2010) Carbohydr Polym 80:885

    Article  CAS  Google Scholar 

  37. Deng C, Chen XS, Yu HJ, Sun J, Lu TC, Jing XB (2007) Polymer 48:139

    Article  CAS  Google Scholar 

  38. Wang YC, Tang LY, Sun TM, Li CH, Xiong MH, Wang J (2008) Biomacromolecules 9:388

    Article  CAS  Google Scholar 

  39. Hain J, Schrinner M, Lu Y, Pich A (2008) Small 4:2016

    Article  CAS  Google Scholar 

  40. Maeda Y, Tsubota M, Ikeda I (2003) Macromol. Rapid Commun 24:242

    Article  CAS  Google Scholar 

  41. Kim YS, Gil ES, Lowe TL (2006) Macromolecules 39:7805

    Article  CAS  Google Scholar 

  42. Shao LD, Hu MQ, Chen L, Xu L, Bi YM (2012) React Funct Polym 72:407

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors are grateful for the financial support from the Natural Science Foundation for Education Department of Liaoning Province of China (No. L2012007), Program for Liaoning Innovative Research Team in University (No. LT2011001) and Foundation of 211 Project for Innovative Talents Training, Liaoning University.

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Authors and Affiliations

  1. Liaoning Province Key Laboratory for Green Synthesis and Preparative Chemistry of Advanced Materials, College of Chemistry, Liaoning University, Shenyang, 110036, People’s Republic of China

    Qiuhua Wu, Jie Yi, Ziling Yin, Siyu Wang, Qi Yang, Shuyao Wu, Ximing Song & Guolin Zhang

  2. College of Chemistry, Liaoning University, Shenyang, 110036, People’s Republic of China

    Guolin Zhang

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  1. Qiuhua Wu
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  2. Jie Yi
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  3. Ziling Yin
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  4. Siyu Wang
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  5. Qi Yang
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  6. Shuyao Wu
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  7. Ximing Song
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  8. Guolin Zhang
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Correspondence to Guolin Zhang.

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Wu, Q., Yi, J., Yin, Z. et al. Synthesis and self-assembly of new amphiphilic thermosensitive poly(N-vinylcaprolactam)/poly(ε-caprolactone) block copolymers via the combination of ring-opening polymerization and click chemistry. J Polym Res 20, 262 (2013). https://doi.org/10.1007/s10965-013-0262-x

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  • DOI: https://doi.org/10.1007/s10965-013-0262-x

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