Redox-responsive supramolecular polymer based on β-cyclodextrin and ferrocene-decorated main chain of PAA


Herein, we present a method for introducing β-cyclodextrin (β-CD) and Ferrocene (Fc) into the main chain of poly(acrylic acid) (PAA) to fabricate a novel supramolecular polymer, which was investigated by Fourier transform infrared spectroscopy and 1H Nuclear Magnetic Resonance (1H NMR). This polymer can self-assemble into interesting nanoparticles in aqueous solution. The redox-responsive Fc–CD host–guest interactions endow these nanoparticles with unique self-degradable and self-healable features under redox potential control. This redox behavior of the supramolecular polymer would open up an approach for redox-controlled biological materials with great application potential.

This is a preview of subscription content, access via your institution.

FIG. 1
FIG. 2
FIG. 3
FIG. 4
FIG. 5
FIG. 6
FIG. 7
FIG. 8


  1. 1.

    S.Y. Dong, Y. Luo, X.Z. Yan, B. Zheng, X. Ding, Y.H. Yu, Z. Ma, Q.L. Zhao, and F.H. Huang: A dual-responsive supramolecular polymer gel formed by crown ether based molecular recognition. Angew. Chem., Int. Ed. 50, 1905 (2011).

    CAS  Article  Google Scholar 

  2. 2.

    Q. Yan, J.B. Wang, Y.W. Yin, and J.Y. Yuan: Breathing polymersomes: CO2-tuning membrane permeability for size-selective release, separation, and reaction. Angew. Chem., Int. Ed. 52, 5070 (2013).

    CAS  Article  Google Scholar 

  3. 3.

    M. Nakahata, Y. Takashima, H. Yamaguchi, and A. Harada: Redox-responsive self-healing materials formed from host-guest polymers. Nat. Commun. 2, 511 (2011).

    Article  Google Scholar 

  4. 4.

    Q. Yan, J. Hu, R. Zhou, Y. Ju, Y.W. Yin, and J.Y. Yuan: Visible light-responsive micelles formed from dialkoxyanthracene-containing block copolymers. Chem. Commun. 48, 1913 (2012).

    CAS  Article  Google Scholar 

  5. 5.

    S. Kumar, X. Tong, Y.L. Dory, M. Lepage, and Y. Zhao: A CO2-switchable polymer brush for reversible capture and release of proteins. Chem. Commun. 49, 90 (2013).

    CAS  Article  Google Scholar 

  6. 6.

    A.O. Moughton and R.K. O’Reilly: Thermally induced micelle to vesicle morphology transition for a charged chain end diblock copolymer. Chem. Commun. 46, 1091 (2010).

    CAS  Article  Google Scholar 

  7. 7.

    J. Rodriguez-Hernandez and S. Lecommandoux: Reversible inside-out micellization of pH-responsive and water-soluble vesicles based on polypeptide diblock copolymers. J. Am. Chem. Soc. 127, 2026 (2005).

    CAS  Article  Google Scholar 

  8. 8.

    X.Z. Yan, F. Wang, B. Zheng, and F.H. Huang: Stimuli-responsive supramolecular polymeric materials. Chem. Soc. Rev. 41, 6042 (2012).

    CAS  Article  Google Scholar 

  9. 9.

    S. Mura, J. Nicolas, and P. Couvreur: Stimuli-responsive nanocarriers for drug delivery. Nat. Mater. 12, 991 (2013).

    CAS  Article  Google Scholar 

  10. 10.

    R.L. Sun, L. Wang, H.J. Yu, Y.S. Chen, J. Huang, and R.B. Tong: Molecular recognition and sensing based on ferrocene derivatives and ferrocene-based polymers. Organometallics 33, 4560 (2014).

    CAS  Article  Google Scholar 

  11. 11.

    S.k. Ahn, R.M. Kasi, S.C. Kim, N. Sharma, and Y.X. Zhou: Stimli-responsive polymer gels. Soft Matter 4, 1151 (2008).

    CAS  Article  Google Scholar 

  12. 12.

    R. Shankar, T.K. Ghosh, and R.J. Spontak: Dielectric elastomers as next-generation polymeric actuators. Soft Matter 3, 1116 (2007).

    CAS  Article  Google Scholar 

  13. 13.

    L. Peng, A.C. Feng, M. Huo, and J.Y. Yuan: Ferrocene-based supramolecular structures and their applications in electrochemical responsive systems. Chem. Commun. 50, 13005 (2014).

    CAS  Article  Google Scholar 

  14. 14.

    H.J. Schneider and A.K. Yatsimirsky: Selectivity in supramolecular host-guest complexes. Chem. Soc. Rev. 37, 263 (2008).

    CAS  Article  Google Scholar 

  15. 15.

    E.M. Seward, R.B. Hopkins, W. Sauerer, S.W. Tam, and F. Diederich: Redox-dependent binding ability of a flavin cyclophane in aqueous solution: Hydrophobic stacking versus cavity-inclusion complexation. J. Am. Chem. Soc. 112, 1783 (1990).

    CAS  Article  Google Scholar 

  16. 16.

    Y. Wang, S. Mendoza, and A.E. Kaifer: Electrochemical reduction of cobaltocenium in the presence of β-cyclodextrin. Inorg. Chem. 37, 7 (1998).

    Google Scholar 

  17. 17.

    C.E. Chan-Thaw, A. Villa, L. Prati, and A. Thomas: Triazine-based polymers as nanostructured supports for the liquid-phase oxidation of alcohols. Chem. Eur. J. 3, 1052 (1997).

    Article  Google Scholar 

  18. 18.

    G.R. Whittell, M.D. Hager, U.S. Schubert, and I. Manners: Functional soft materials from metallopolymers and metallosupramolecular polymers. Nat. Mater. 10, 176 (2011).

    CAS  Article  Google Scholar 

  19. 19.

    T. Matsue, D.H. Evans, T. Osa, and N. Kobayashi: Electron-transfer reactions associated with host-guest complexation. Oxidation of ferrocenecarboxylic acid in the presence of beta-cyclodextrin. J. Am. Chem. Soc. 107, 3411 (1985).

    CAS  Article  Google Scholar 

  20. 20.

    M.C. Jones and J.C. Leroux: Polymeric micelles-a new generation of colloidal drug carriers. Eur. J. Pharm. Biopharm. 48, 101 (1999).

    CAS  Article  Google Scholar 

  21. 21.

    V.P. Torchilin: Structure and design of polymeric surfactant-based drug delivery systems. J. Controlled Release 3, 137 (2001).

    Article  Google Scholar 

  22. 22.

    X.Z. Yan, D.H. Xu, X.D. Chi, J.Z. Chen, S.Y. Dong, X. Ding, Y.H. Yu, and F.H. Huang: A multiresponsive, shape-persistent, and elastic supramolecular polymer network gel constructed by orthogonal self-assembly. Adv. Mater. 24, 362 (2012).

    CAS  Article  Google Scholar 

  23. 23.

    G. Groger, W. Meyer-Zaika, C. Bottcher, F. Grohn, C. Ruthard, and C. Schmuck: Switchable supramolecular polymers from the self-assembly of a small monomer with two orthogonal binding interactions. J. Am. Chem. Soc. 133, 8961 (2011).

    Article  Google Scholar 

  24. 24.

    J.R. Kumpfer and S.J. Rowan: Thermo-, photo-, and chemo-responsive shape-memory properties from photo-cross-linked metallo-supramolecular polymers. J. Am. Chem. Soc. 133, 12866 (2011).

    CAS  Article  Google Scholar 

  25. 25.

    Q. Yan, J.Y. Yuan, Z.N. Cai, Y. Xin, Y. Kang, and Y.W. Yin: Voltage-responsive vesicles based on orthogonal assembly of two homopolymers. J. Am. Chem. Soc. 132, 9268 (2010).

    CAS  Article  Google Scholar 

  26. 26.

    L.C. Liu, L.L. Rui, Y. Gao, and W.A. Zhang: Self-assembly and disassembly of a redox-responsive ferrocene-containing amphiphilic block copolymer for controlled release. Polym. Chem. 6, 1817 (2015).

    CAS  Article  Google Scholar 

  27. 27.

    Y.L. Liu and T.W. Chuo: Self-healing polymers based on thermally reversible Diels–Alder chemistry. Polym. Chem. 4, 2194 (2013).

    CAS  Article  Google Scholar 

  28. 28.

    J. Elbert, M. Gallei, C. Rvttiger, A. Brunsen, H. Didzoleit, B. Stvhn, and M. Rehahn: Ferrocene polymers for switchable surface wettability. Organometallics 32, 5873 (2013).

    CAS  Article  Google Scholar 

  29. 29.

    B.V. Schmidt, M. Hetzer, H. Ritter, and C. Barner-Kowollik: Complex macromolecular architecture design via cyclodextrin host/guest complexes. Prog. Polym. Sci. 39, 235 (2014).

    CAS  Article  Google Scholar 

  30. 30.

    K.C. Wei, J. Li, G.S. Chen, and M. Jiang: Dual molecular recognition leading to a protein-polymer conjugate and further self-assembly. ACS Macro Lett. 2, 278 (2013).

    CAS  Article  Google Scholar 

  31. 31.

    F. Zuo, C. Luo, X.B. Ding, Z. Zheng, X. Cheng, and Y. Peng: Redox-responsive inclusion complexation between β-cyclodextrin and ferrocene-functionalized poly(N-isopropylacrylamide) and its effect on the solution properties of this polymer. Supramol. Chem. 20, 559 (2008).

    CAS  Article  Google Scholar 

  32. 32.

    Z.C. Tian, C. Chen, and H.R. Allcock: Synthesis and assembly of novel poly(organophosphazene) structures based on noncovalent “host-guest” inclusion complexation. Macromolecules 47, 1065 (2014).

    CAS  Article  Google Scholar 

Download references

Author information



Corresponding author

Correspondence to Zhongli Lei.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Guo, W., Lei, Z. Redox-responsive supramolecular polymer based on β-cyclodextrin and ferrocene-decorated main chain of PAA. Journal of Materials Research 30, 3201–3210 (2015).

Download citation