Skip to main content
SpringerLink
Log in

Perhydroxycucurbit[6]uril-induced self-assembly of a double-hydrophilic block copolymer in aqueous solution

  • Original Article
  • Published:
Journal of Inclusion Phenomena and Macrocyclic Chemistry Aims and scope Submit manuscript

Abstract

We reported the preparation of the poly(N-vinyl pyrrolidone)-b-polyethylene glycol (PVP-b-PEG) double-hydrophilic block copolymer by atom transfer radical polymerization (ATRP). The PVP-b-PEG samples were characterized by nuclear magnetic resonance spectroscopy and Fourier translation infrared spectrum. By taking advantage of its exceptional binding affinity, the perhydroxycucurbit[6]uril ((HO)12CB[6]) was used to interact with PVP-b-PEG by hydrogen bond and constructed micelle-like core–shell aggregates with the physical cross-link PVP segments as the core and the extending PEG chains as the outer palisade. The size of aggregates was about 50–300 nm. The particle size of this type of assemblies could be controlled by the weight content of (HO)12CB[6]. The size distribution was broad at high concentrations. The broad size distribution at high (HO)12CB[6] concentration was due to the coexistence of isolated particles and clusters. These novel micelle-like core–shell aggregates could be controlled by pH value. At pH lower than 6 or pH larger than 13, hydrogen bond interactions were destroyed and the formed (HO)12CB[6]-induced PVP-b-PEG assemblies could be destructed.

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
Fig. 8
Scheme 2
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. Sang, Y.J., Narayanan, S., Dong, H.O., Jin, K.K., Soo, Y.K., Young, J.J., Jae, W.L., Kimoon, K.: Facile synthesis of cucurbit[n]uril derivatives via direct functionalization: expanding utilization of cucurbit[n]uril. J. Am. Chem. Soc. 125(34), 10186–10187 (2003)

    Article  Google Scholar 

  2. Molina, E., Warnant, J., Mathonnat, M., Bathfield, M., In, M., Laurencin, D., Jerome, C., Lacroix-Desmazes, P., Marcotte, N., Gerardin, C.: Drug–polymer electrostatic complexes as new structuring agents for the formation of drug-loaded ordered mesoporous silica. Langmuir 31(47), 12839–12844 (2015)

    Article  CAS  Google Scholar 

  3. Lagona, J., Mukhopadhyay, P., Chakrabarti, S., Isaacs, L.: The cucurbit[n]uril family. Angew. Chem. Int. Ed. 44(31), 4844–4870 (2005)

    Article  CAS  Google Scholar 

  4. Baek, K., Yun, G., Kim, Y., Kim, D., Hota, R., Hwang, I., Xu, D., Ko, Y.H., Gu, G.H., Suh, J.H., Park, C.G., Sung, B.J., Kim, K.: Free-standing, single-monomer-thick two-dimensional polymers through covalent self-assembly in solution. J. Am. Chem. Soc. 135(17), 6523–6528 (2013)

    Article  CAS  Google Scholar 

  5. Huang, X., Zhang, N., Ban, L., Su, H.: Synthesis of star poly(N-isopropylacrylamide) with a core of cucurbit[6]uril via ATRP and controlled thermoresponsivity. Macromol. Rapid Commun. 36(3), 311–318 (2015)

    Article  Google Scholar 

  6. Yang, L., Bai, Y., Tan, X., Wang, Z., Zhang, X.: Controllable supramolecular polymerization through host–guest interaction and photochemistry. ACS Macro Lett. 4(6), 611–615 (2015)

    Article  CAS  Google Scholar 

  7. Hu, C., Lan, Y., West, K.R., Scherman, O.A.: Cucurbit[8]uril-regulated nanopatterning of binary polymer brushes via colloidal templating. Adv. Mater. 27(48), 7957–7962 (2015)

    Article  CAS  Google Scholar 

  8. Jung, H., Park, J.S., Yeom, J., Selvapalam, N., Park, K.M., Oh, K., Yang, J.A., Park, K.H., Hahn, S.K., Kim, K.: 3D tissue engineered supramolecular hydrogels for controlled chondrogenesis of human mesenchymal stem cells. Biomacromolecules 15(3), 707–714 (2014)

    Article  CAS  Google Scholar 

  9. Rowland, M.J., Atgie, M., Hoogland, D., Scherman, O.A.: Preparation and supramolecular recognition of multivalent peptide–polysaccharide conjugates by cucurbit[8]uril in hydrogel formation. Biomacromolecules 16(8), 2436–2443 (2015)

    Article  CAS  Google Scholar 

  10. Xie, Y., Wang, J., Wang, M., Ge, X.: Fabrication of fibrous amidoxime-functionalized mesoporous silica microsphere and its selectively adsorption property for Pb 2+ in aqueous solution. J. Hazard. Mater. 297, 66–73 (2015)

    Article  CAS  Google Scholar 

  11. Kim, K., Selvapalam, N., Ko, Y.H., Park, K.M., Kim, D., Kim, J.: Functionalized cucurbiturils and their applications. Chem. Soc. Rev. 36(2), 267–279 (2007)

    Article  CAS  Google Scholar 

  12. Kim, J., Ahn, Y., Park, K.M., Kim, Y., Ko, Y.H., Oh, D.H., Kim, K.: Carbohydrate wheels: cucurbituril-based carbohydrate clusters. Angew. Chem. Int. Ed. 46(39), 7393–7395 (2007)

    Article  CAS  Google Scholar 

  13. Kim, D., Kim, E., Kim, J., Park, K.M., Baek, K., Jung, M., Ko, Y.H., Sung, W., Kim, H.S., Suh, J.H.: Direct synthesis of polymer nanocapsules with a noncovalently tailorable surface. Angew. Chem. 119(19), 3541–3544 (2007)

    Article  Google Scholar 

  14. Nagarajan, E.R., Oh, D.H., Selvapalam, N., Ko, Y.H., Park, K.M., Kim, K.: Cucurbituril anchored silica gel. Tetrahedron Lett. 47(13), 2073–2075 (2006)

    Article  CAS  Google Scholar 

  15. Jung, H., Park, K.M., Yang, J.-A., Oh, E.J., Lee, D.-W., Park, K., Ryu, S.H., Hahn, S.K., Kim, K.: Theranostic systems assembled in situ on demand by host–guest chemistry. Biomaterials 32(30), 7687–7694 (2011)

    Article  CAS  Google Scholar 

  16. Park, K.M., Suh, K., Jung, H., Lee, D.-W., Ahn, Y., Kim, J., Baek, K., Kim, K.: Cucurbituril-based nanoparticles: a new efficient vehicle for targeted intracellular delivery of hydrophobic drugs. Chem. Commun. 1, 71–73 (2009)

    Article  Google Scholar 

  17. Kim, E., Kim, D., Jung, H., Lee, J., Paul, S., Selvapalam, N., Yang, Y., Lim, N., Park, C.G., Kim, K.: Facile, template-free synthesis of stimuli-responsive polymer nanocapsules for targeted drug delivery. Angew. Chem. 122(26), 4507–4510 (2010)

    Article  Google Scholar 

  18. Zhang, M., Sigwalt, D., Isaacs, L.: Differentially functionalized acyclic cucurbiturils: synthesis, self-assembly and CB[6]-induced allosteric guest binding. Chem. Commun. 51(78), 14620–14623 (2015)

    Article  CAS  Google Scholar 

  19. Park, K.M., Lee, D.W., Sarkar, B., Jung, H., Kim, J., Ko, Y.H., Lee, K.E., Jeon, H., Kim, K.: Reduction-sensitive, robust vesicles with a non-covalently modifiable surface as a multifunctional drug-delivery platform. Small 6(13), 1430–1441 (2010)

    Article  CAS  Google Scholar 

  20. Bathfield, M., Warnant, J., Gérardin, C., Lacroix-Desmazes, P.: Asymmetric neutral, cationic and anionic PEO-based double-hydrophilic block copolymers (DHBCs): synthesis and reversible micellization triggered by temperature or pH. Polym. Chem. 6(8), 1339–1349 (2015)

    Article  CAS  Google Scholar 

  21. Layrac, G., Gérardin, C., Tichit, D., Harrisson, S., Destarac, M.: Hybrid polyion complex micelles from poly(vinylphosphonic acid)-based double hydrophilic block copolymers and divalent transition metal ions. Polymer 72, 292–300 (2015)

    Article  CAS  Google Scholar 

  22. Wu, J., Wang, Z., Yin, Y., Jiang, R., Li, B., Shi, A.-C.: A simulation study of phase behavior of double-hydrophilic block copolymers in aqueous solutions. Macromolecules 48(24), 8897–8906 (2015)

    Article  CAS  Google Scholar 

  23. Zeynep, E.Y., Antoine, D., Brice, C., Frank, B., Christine, J.: Double hydrophilic polyphosphoester containing copolymers as efficient templating agents for calcium carbonate microparticles. J. Mater. Chem. B 3(36), 7227–7236 (2015)

    Article  CAS  Google Scholar 

  24. Liu, X., Sun, K., Wu, Z., Lu, J., Song, B., Tong, W., Shi, X., Chen, H.: Facile synthesis of thermally stable poly(N-vinylpyrrolidone)-modified gold surfaces by surface-initiated atom transfer radical polymerization. Langmuir 28(25), 9451–9459 (2012)

    Article  CAS  Google Scholar 

  25. Lu, X., Gong, S., Meng, L., Li, C., Yang, S., Zhang, L.: Controllable synthesis of poly(N-vinylpyrrolidone) and its block copolymers by atom transfer radical polymerization. Polymer 48(10), 2835–2842 (2007)

    Article  CAS  Google Scholar 

  26. Wu, Z., Tong, W., Jiang, W., Liu, X., Wang, Y., Chen, H.: Poly(N-vinylpyrrolidone)-modified poly(dimethylsiloxane) elastomers as anti-biofouling materials. Colloids Surf. B 96, 37–43 (2012)

    Article  CAS  Google Scholar 

  27. Sugiura, S., Edahiro, J., Sumaru, K., Kanamori, T.: Surface modification of polydimethylsiloxane with photo-grafted poly(ethylene glycol) for micropatterned protein adsorption and cell adhesion. Colloids Surf., B 63(2), 301–305 (2008)

    Article  CAS  Google Scholar 

  28. Yeon, S.H., Ahn, S.H., Kim, J.H., Lee, K.B., Jeong, Y., Hong, S.U.: Synthesis and gas permeation properties of poly(vinyl chloride)-graft-poly(vinyl pyrrolidone) membranes. Polym. Adv. Technol. 23(3), 516–521 (2012)

    Article  CAS  Google Scholar 

  29. Bhopate, D.P., Mahajan, P.G., Garadkar, K.M., Kolekar, G.B., Patil, S.R.: Polyvinyl pyrrolidone capped fluorescent anthracene nanoparticles for sensing fluorescein sodium in aqueous solution and analytical application for ophthalmic samples. Luminescence 30(7), 1055–1063 (2015)

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors are grateful for the financial supports from National Natural Science Foundation of China (No. 21564010) and Inner Mongolia Natural Science Foundation (No. 2015MS0501).

Author information

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, 010021, China

    Zhipeng Wang, Mingrui Li & Xiaoling Huang

Authors
  1. Zhipeng Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mingrui Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Xiaoling Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Xiaoling Huang.

Ethics declarations

Conflict of interest

The authors declare that they have no competing interests.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 73 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, Z., Li, M. & Huang, X. Perhydroxycucurbit[6]uril-induced self-assembly of a double-hydrophilic block copolymer in aqueous solution. J Incl Phenom Macrocycl Chem 87, 67–74 (2017). https://doi.org/10.1007/s10847-016-0676-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10847-016-0676-2

Keywords

Search

Navigation