Skip to main content
SpringerLink
Log in

Stimuli-induced gel-sol transition of supramolecular hydrogels based on β-cyclodextrin polymer/ferrocene-containing triblock copolymer inclusion complexes

  • Original Paper
  • Published:
Journal of Polymer Research Aims and scope Submit manuscript

Abstract

A novel kind of host-guest hydrogel possessing gel–sol phase transformation in response to temperature, oxidizing agent and glucose was prepared by ferrocene (Fc)-containing pluronic F127 and β-cyclodextrin (β-CD) linear polymer, which was synthesized in aqueous alkali by using native β-CD and epichlorohydrin in the presence of toluene. Because of the reversible association–dissociation of Fc-β-CD inclusions and F127 micelles, the gel-sol transition was easily observed. Two-dimension nuclear overhauser effect spectroscopy (2D NOESY), nuclear magnetic resonance (NMR), TEM (transmission electron microscopy) and TGA (thermogravimetric analysis) measurements were used to clarify the inclusion complexes of Fc-β-CD. The results showed that the formation of inclusion complexes affected the micelle size and stabilized the hydrogels. The rheological properties of solution and hydrogels were measured. The viscosity of hydrogel was enhanced markedly, to about 90 times higher than that of Fc-F127-Fc solution at the same concentration. Due to the coactions of PPO aggregation and Fc-β-CD inclusion, the gelation temperature of hydrogel was lower than that of Fc-F127-Fc solution. The reversible gel-sol transition and multi-sensitive supramolecular hydrogels may potentially be used in injectable hydrogel for drug delivery.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Scheme 2
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12

Similar content being viewed by others

References

  1. Koopmans C, Ritter H (2007) J Am Chem Soc 129:3502–3503

    Article  CAS  Google Scholar 

  2. Chen GS, Jiang M (2011) Chem Soc Rev 40:2254–2266

    Article  CAS  Google Scholar 

  3. Quan CY, Chen JX, Wang HY, Li C, Chang C, Zhang XZ, Zhuo RX (2010) ACS Nano 4:4211–4219

    Article  CAS  Google Scholar 

  4. Appel EA, Biedermann F, Rauwald U, Jones ST, Zayed JM, Scherman OA (2010) J Am Chem Soc 132:14251–14260

    Article  CAS  Google Scholar 

  5. Liao XJ, Chen GS, Liu XX, Chen WX, Chen F, Jiang M (2010) Angew Chem Int Ed 49:4409–4413

    Article  CAS  Google Scholar 

  6. Chen Y, Pang XH, Dong C (2010) Adv Funct Mater 20:579–586

    Article  CAS  Google Scholar 

  7. Khashab NM, Trabolsi A, Lau YA, Ambrogio MW, Friedman DC, Khatib HA, Zink JI, Stoddart JF (2009) Eur J Org Chem 2009:1669–1673

    Article  Google Scholar 

  8. Zhang HC, An W, Liu ZN, Hao AY, Hao JC, Shen J, Zhao XH, Sun HY, Sun LZ (2010) Carbohydr Res 345:87–96

    Article  CAS  Google Scholar 

  9. Li M, Hui, Keller P (2009) Soft Matter 5:927–937

    Article  CAS  Google Scholar 

  10. Dong HQ, Li YY, Cai SJ, Zhuo RX, Zhang XZ, Liu LJ (2008) Angew Chem Int Ed 47:5573–5576

    Article  CAS  Google Scholar 

  11. Ren SD, Chen DY, Jiang M (2009) J Polym Sci Polym Chem 47:4267–4278

    Article  CAS  Google Scholar 

  12. Böm I, Isenbügel K, Ritter H, Branscheid R, Kolb U (2011) Angew Chem Int Ed 50:7896–7899

    Article  Google Scholar 

  13. Kretschmann O, Choi SW, Miyauchi M, Tomatsu I, Harada A, Ritter H (2006) Angew Chem Int Ed 45:4361–4365

    Article  Google Scholar 

  14. Schmidt BVKJ, Rudolph T, Hetzer M, Ritter H, Schacher FH, Barner-Kowollik C (2012) Polym Chem 3:3139–3145

    Article  CAS  Google Scholar 

  15. Deng W, Chen J, Kulkarnia A, Thompson DH (2012) Soft Matter 8:5843–5846

    Article  CAS  Google Scholar 

  16. Koopmans C, Ritter H (2008) Macromolecules 41:7418–7422

    Article  CAS  Google Scholar 

  17. Nakahata M, Takashima Y, Yamaguchi H, Harada A (2011) Nat Commun 2:511

    Article  Google Scholar 

  18. Zhu LZ, Shangguan YG, Sun YX, Ji J, Zheng Q (2010) Soft Matter 6:5541–5546

    Article  CAS  Google Scholar 

  19. Du P, Liu JH, Chen GS, Jiang M (2011) Langmuir 27:9602–9608

    Article  CAS  Google Scholar 

  20. Guo MY, Jiang M, Pispas S, Yu W, Zhou CX (2008) Macromolecules 41:9744–9749

    Article  CAS  Google Scholar 

  21. Kulkarni A, DeFrees K, Hyun SH, Thompson DH (2012) J Am Chem Soc 134:7596–7599

    Article  CAS  Google Scholar 

  22. van de Manakker F, Loes MJ, Kroon-Batenburg TV, van Nostrum CF, Hennink WE (2010) Soft Matter 6:187–194

    Article  Google Scholar 

  23. Tomatsu I, Hashidzume A, Harada A (2006) J Am Chem Soc 128:2226–2227

    Article  CAS  Google Scholar 

  24. Tamesue S, Takashima Y, Yamaguchi H, Shinkai S, Harada A (2010) Angew Chem Int Ed 49:7461–7464

    Article  CAS  Google Scholar 

  25. Dong RJ, Liu Y, Zhou YF, Yan DY, Zhu XY (2011) Polym Chem 2:2771–2774

    Article  CAS  Google Scholar 

  26. Tan L, Liu Y, Ha W, Ding LS, Peng SL, Zhang S, Li BJ (2012) Soft Matter 8:5746–5749

    Article  CAS  Google Scholar 

  27. Shim WS, Yoo JS, Bae YH, Lee DS (2005) Biomacromolecules 6:2930–2934

    Article  CAS  Google Scholar 

  28. Huynh DP, Im GJ, Chae SY, Lee KC, Lee DS (2009) J Control Release 137:20–24

    Article  CAS  Google Scholar 

  29. Jiang XG, Jin S, Zhong QX, Dadmun MD, Zhao B (2009) Macromolecules 42:8468–8476

    Article  CAS  Google Scholar 

  30. Tomatsu I, Hashidzume A, Harada A (2006) Macromol Rapid Commun 27:238–241

    Article  CAS  Google Scholar 

  31. He CL, Kim SW, Lee DS (2008) J Control Release 127:189–207

    Article  CAS  Google Scholar 

  32. Shachaf Y, Gonen-Wadmany M, Seliktar D (2010) Biomaterials 31:2836–2847

    Article  CAS  Google Scholar 

  33. Nam JA, Al-Nahain A, Hong S, Lee KD, Lee H, Park SY (2011) Macromol Biosci 11:1594–1602

    CAS  Google Scholar 

  34. Simões SMN, Veiga F, Torres-Labandeira JJ, Ribeiro ACF, Sandez-Macho MI, Concheiro A, Alvarez-Lorenzo C (2012) Eur J Pharm Biopharm 80:103–112

    Article  Google Scholar 

  35. Qin J, Meng XW, Li BJ, Ha W, Yu XQ, Zhang S (2010) J Colloid Interface Sci 350:447–452

    Article  CAS  Google Scholar 

  36. Wang J, Gao P, Wang PJ, Ye L, Zhang AY, Feng ZG (2011) Polymer 52:347–355

    Article  CAS  Google Scholar 

  37. Zhou YX, Fan XD, Xue D, Xing JW, Kong J (2013) React Funct Polym 73:508–517

    Article  CAS  Google Scholar 

  38. Renard E, Deratani A, Volet G, Sebille B (1997) Eur Polym J 33:49–57

    Article  CAS  Google Scholar 

  39. Kong J, Schmalz T, Motz G, Müller AHE (2011) Macromolecules 44:1280–1291

    Article  CAS  Google Scholar 

  40. Alexandridis P, Holzwarth JF, Hatton TA (1994) Macromolecules 27:2414–2425

    Article  CAS  Google Scholar 

  41. Park SY, Lee Y, Bae KH, Ahn CH, Park TG (2007) Macromol Rapid Commun 28:1172–1176

    Article  CAS  Google Scholar 

  42. Ding CX, Zhao LL, Liu FY, Cheng J, Gu JX, Dan S, Liu CY, Qu XZ, Yang ZZ (2010) Biomacromolecules 11:1043–1051

    Article  CAS  Google Scholar 

  43. Li J, Ni XP, Zhou ZH, Leong KW (2003) J Am Chem Soc 125:1788–1795

    Article  CAS  Google Scholar 

  44. Kuo WY, Lai HM (2011) Polymer 52:3389–3395

    Article  CAS  Google Scholar 

  45. Dhanarajan AP, Misra GP, Siegel RA (2002) J Phys Chem A 106:8835–8838

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The financial support from National Natural Science Foundation of China (No. 21274116) and Open Program Funded by Key Laboratory of Shaanxi Provincial Science and Technology Department (Program No.NCSA0003) are acknowledged.

Author information

Authors and Affiliations

  1. Department of Polymeric Materials and Engineering, College of Textiles and Materials, Xi’an Polytechnic University, Xi’an, 710048, People’s Republic of China

    Yingxue Zhou

  2. Shaanxi Key Laboratory of Macromolecular Science and Technology, Department of Applied Chemistry, School of Science, Northwestern Polytechnical University, Xi’an, 710072, People’s Republic of China

    Yingxue Zhou, Xiaodong Fan, Wanbin Zhang, Dan Xue & Jie Kong

Authors
  1. Yingxue Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xiaodong Fan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Wanbin Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Dan Xue
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jie Kong
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Xiaodong Fan or Jie Kong.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Zhou, Y., Fan, X., Zhang, W. et al. Stimuli-induced gel-sol transition of supramolecular hydrogels based on β-cyclodextrin polymer/ferrocene-containing triblock copolymer inclusion complexes. J Polym Res 21, 359 (2014). https://doi.org/10.1007/s10965-014-0359-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10965-014-0359-x

Keywords

Search

Navigation