Skip to main content
Log in

Molecular dynamics and structure of polyrotaxane in solution

  • Focus Review
  • Published:
Polymer Journal Submit manuscript


Polyrotaxane (PR) is a supramolecular assembly in which ring molecules are threaded onto an axial polymer chain. This paper reviews the molecular structure and dynamics of a PR composed of polyethylene glycol (PEG) and α-cyclodextrin (CD) based on data obtained from X-ray and neutron scattering experiments on PR solutions. The dynamics of CD and the PEG monomers in the PR were evaluated separately by quasielastic neutron scattering with deuterium labeling. Inclusion complex formation with CD increases the stiffness of the PEG backbone and restricts the diffusion of the PEG monomers that are covered by or in close proximity to the CD molecules. The sliding motion of the CD molecules along the PEG axis was explored using full atomistic molecular dynamics (MD) simulations, showing that the sliding dynamics were retarded by the interaction between the CD cavities and PEG.

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


  1. Lehn JM. Supramolecular chemistry: concepts and perspectives. Weinheim: Wiley–VCH; 1995.

  2. Ciferri A. Supramolecular polymers. New York: Marcel Dekker; 2000.

  3. Sauvage JP, Dietrich-Buchecker C. Molecular catenanes, rotaxanes, and Knots. Weinheim: Wiley–VCH; 1999.

  4. Huang F, Gibson HW. Polypseudorotaxanes and polyrotaxanes. Prog Polym Sci. 2005;30:982–1018.

    Article  CAS  Google Scholar 

  5. Nepogodiev SA, Stoddart JF. Cyclodextrin-based catenanes and rotaxanes. Chem Rev. 1998;98:1959–76.

    Article  CAS  Google Scholar 

  6. Raymo FM, Stoddart JF. Interlocked macromolecules. Chem Rev. 1999;99:1643–64.

    Article  CAS  Google Scholar 

  7. Wenz G, Han BH, Muller A. Cyclodextrin rotaxanes and polyrotaxanes. Chem Rev. 2006;106:782–817.

    Article  CAS  Google Scholar 

  8. Harada A, Hashidzume A, Yamaguchi H, Takashima Y. Polymeric rotaxanes. Chem Rev. 2009;109:5974–6023.

    Article  CAS  Google Scholar 

  9. Takata T. Polyrotaxane and polyrotaxane network: supramolecular architectures based on the concept of dynamic covalent bond chemistry. Polym J. 2006;38:1–20.

    Article  CAS  Google Scholar 

  10. Choi HS, Yui N. Design of rapidly assembling supramolecular systems responsive to synchronized stimuli. Prog Polym Sci. 2006;31:121–44.

    Article  CAS  Google Scholar 

  11. Loethen S, Kim JM, Thompson DH. Biomedical applications of cyclodextrin based polyrotaxanes. J Macromol Sci Part C. Polym Rev. 2007;4:383–418.

    Article  Google Scholar 

  12. Tonelli AE. Nanostructuring and functionalizing polymers with cyclodextrins. Polymer. 2008;49:1725–36.

    Article  CAS  Google Scholar 

  13. Ito K, Kato K, Mayumi K. Polyrotaxane and slide-ring materials. Royal Society of Chemistry; Cambridge, 2015.

  14. Ooya T, Yui N. ynthesis of theophylline–polyrotaxane conjugates and their drug release via supramolecular dissociation. J Controlled Release. 1999;58:251–69.

    Article  CAS  Google Scholar 

  15. Yui N, Ooya T. Molecular mobility of interlocked structures exploiting new functions of advanced biomaterials. Chem Eur J. 2006;12:6730–7.

    Article  CAS  Google Scholar 

  16. Okumura Y, Ito K. The polyrotaxane gel: a topological gel by figure‐of‐eight cross‐links. Adv Mater. 2001;13:485–7.

    Article  CAS  Google Scholar 

  17. Ito K. Novel cross-linking concept of polymer network: synthesis, structure, and properties of slide-ring gels with freely movable junctions. Polym J. 2007;39:489–99.

    Article  CAS  Google Scholar 

  18. Liu C, Kadono H, Mayumi K, Kato K, Yokoyama H, Ito K. Unusual fracture behavior of slide-ring gels with movable cross-links. ACS Macro Lett. 2017;6:1409–13.

    Article  CAS  Google Scholar 

  19. Higgins JS, Benoit HC. Polymers and neutron scattering. Oxford: Clarendon Press; 1994.

  20. Sakai VG, Arbe A. Quasielastic neutron scattering in soft matter. Curr Opin Colloid Interf Sci. 2009;14:381–90.

    Article  CAS  Google Scholar 

  21. Kato K, Okabe Y, Okazumi Y, Ito K. A significant impact of host–guest stoichiometry on the extensibility of polyrotaxane gels. Chem Comm. 2015;51:16180–3.

    Article  CAS  Google Scholar 

  22. Mayumi K, Osaka N, Endo H, Yokoyama H, Sakai Y, Shibayama M, et al. Concentration-induced conformational change in linear polymer threaded into cyclic molecules. Macromolecules. 2008;41:6580–5.

    Article  Google Scholar 

  23. Yoshizaki T, Yamakawa H. Scattering functions of wormlike and helical wormlike chains. Macromolecules. 1980;13:1518–25.

    Article  CAS  Google Scholar 

  24. Kume T, Araki J, Sakai Y, Mayumi K, Kidowaki M, Yokoyama H, et al. Static and dynamic light scattering studies on dilute polyrotaxane solutions. J Phys Conf Ser. 2009;184:012018.

    Article  Google Scholar 

  25. Fleury G, Brochon C, Schlatter G, Bonnet G, Lapp A, Hadziioannou G. Synthesis and characterization of high molecular weight polyrotaxanes: towards the control over a wide range of threaded α-cyclodextrins. Soft Matter. 2005;1:378–85.

    Article  CAS  Google Scholar 

  26. Jarroux N, Guegan P, Cheradame H, Auvray L. High conversion synthesis of pyrene end functionalized polyrotaxane based on poly (ethylene oxide) and α-cyclodextrins. J Phys Chem B. 2005;109:23816–22.

    Article  CAS  Google Scholar 

  27. Yamada S, Sanada Y, Tamura A, Yui N, Sakurai K. Chain architecture and flexibility of α-cyclodextrin/PEG polyrotaxanes in dilute solutions. Polym J 2015;47:464–7.

    Article  CAS  Google Scholar 

  28. Mayumi K, Endo H, Osaka N, Yokoyama H, Nagao M, Shibayama M, et al. Mechanically interlocked structure of polyrotaxane investigated by contrast variation small-angle neutron scattering. Macromolecules. 2009;42:6327–9.

    Article  CAS  Google Scholar 

  29. Endo H, Mayumi K, Osaka N, Ito K, Shibayama M. The static structure of polyrotaxane in solution investigated by contrast variation small-angle neutron scattering. Polym J. 2011;43:155–63.

    Article  CAS  Google Scholar 

  30. Yasuda Y, Hidaka Y, Mayumi K, Yamada T, Fujimoto K, Okazaki S, et al. Molecular dynamics of polyrotaxane in solution investigated by quasi-elastic neutron scattering and molecular dynamics simulation: sliding motion of rings on polymer. J Am Chem Soc. 2019;141:9655–63.

    Article  CAS  Google Scholar 

  31. Liu P, Chipot C, Shao X, Cai W. How do α-cyclodextrins self-organize on a polymer chain? J Phys Chem C. 2012;116:17913–8.

    Article  CAS  Google Scholar 

  32. Ewen B, Richter D. Neutron spin echo investigations on the segmental dynamics of polymers in melts, networks and solutions. Adv Polym Sci. 1997;134:1–128.

    Article  CAS  Google Scholar 

  33. Richter D, Monkenbusch M, Arbe A, Colmenero J. Neutron spin echo in polymer systems. Adv Polym Sci. 2005;174:1–221.

    Google Scholar 

  34. Mayumi K, Nagao M, Endo H, Osaka N, Shibayama M, Ito K. Dynamics of polyrotaxane investigated by neutron spin echo. Phys B. 2009;404:2600–2.

    Article  CAS  Google Scholar 

  35. Mayumi K, Ito K. Structure and dynamics of polyrotaxane and slide-ring materials. Polymer. 2010;51:959–67.

    Article  CAS  Google Scholar 

Download references


The author is grateful to Prof. Kohzo Ito and Prof. Hideaki Yokoyama for their continuous support during the course of this study. The author also gratefully acknowledges Dr. Hitoshi Endo, Dr. Michihiro Nagao, Dr. Noboru Osaka, and Prof. Mitsuhiro Shibayama for the SANS and NSE measurements, Mr. Yuta Hidaka and Dr. Takeshi Yamada for the QENS measurements at J-PRAC/MLF, and Dr. Yusuke Yasuda, Prof. Kazushi Fujimoto, and Prof. Susumu Okazaki for the MD simulations. This work was supported by the ImPACT Program of Council for Science, Technology and Innovation (Cabinet Office, Government of Japan), JSPS KAKENHI grant numbers JP15K17905 and JP20K05627, JST-Mirai Program grant number JPMJMI18A2, and JST CREST grant number JPMJCR1992. The work with the NG5-NSE at the National Institute of Standards and Technology (NIST), US Department of Commerce, utilized facilities supported in part by the National Science Foundation under agreement no. DMR-0454672. The author acknowledges the support of NIST in providing the neutron research facilities used in this work. The SANS and NSE experiments using SANS-U and iNSE were performed with the approval of the Institute for Solid State Physics, The University of Tokyo at the Japan Atomic Energy Agency, Tokai, Japan (Proposal no. 7607). The neutron experiment at the Materials and Life Science Experimental Facility of J-PARC was performed under a user program (Proposal no. 2018A0235). The small-angle X-ray scattering experiments were performed at beamline BL-6A at the Photon Factory, High Energy Accelerator Research Organization, KEK with the approval of the Photon Factory Program Advisory Committee (Proposal no. 2015G716).

Author information

Authors and Affiliations


Corresponding author

Correspondence to Koichi Mayumi.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mayumi, K. Molecular dynamics and structure of polyrotaxane in solution. Polym J 53, 581–586 (2021).

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:

  • Springer Nature Limited

This article is cited by