Abstract
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, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Lehn JM. Supramolecular chemistry: concepts and perspectives. Weinheim: Wiley–VCH; 1995.
Ciferri A. Supramolecular polymers. New York: Marcel Dekker; 2000.
Sauvage JP, Dietrich-Buchecker C. Molecular catenanes, rotaxanes, and Knots. Weinheim: Wiley–VCH; 1999.
Huang F, Gibson HW. Polypseudorotaxanes and polyrotaxanes. Prog Polym Sci. 2005;30:982–1018.
Nepogodiev SA, Stoddart JF. Cyclodextrin-based catenanes and rotaxanes. Chem Rev. 1998;98:1959–76.
Raymo FM, Stoddart JF. Interlocked macromolecules. Chem Rev. 1999;99:1643–64.
Wenz G, Han BH, Muller A. Cyclodextrin rotaxanes and polyrotaxanes. Chem Rev. 2006;106:782–817.
Harada A, Hashidzume A, Yamaguchi H, Takashima Y. Polymeric rotaxanes. Chem Rev. 2009;109:5974–6023.
Takata T. Polyrotaxane and polyrotaxane network: supramolecular architectures based on the concept of dynamic covalent bond chemistry. Polym J. 2006;38:1–20.
Choi HS, Yui N. Design of rapidly assembling supramolecular systems responsive to synchronized stimuli. Prog Polym Sci. 2006;31:121–44.
Loethen S, Kim JM, Thompson DH. Biomedical applications of cyclodextrin based polyrotaxanes. J Macromol Sci Part C. Polym Rev. 2007;4:383–418.
Tonelli AE. Nanostructuring and functionalizing polymers with cyclodextrins. Polymer. 2008;49:1725–36.
Ito K, Kato K, Mayumi K. Polyrotaxane and slide-ring materials. Royal Society of Chemistry; Cambridge, 2015.
Ooya T, Yui N. ynthesis of theophylline–polyrotaxane conjugates and their drug release via supramolecular dissociation. J Controlled Release. 1999;58:251–69.
Yui N, Ooya T. Molecular mobility of interlocked structures exploiting new functions of advanced biomaterials. Chem Eur J. 2006;12:6730–7.
Okumura Y, Ito K. The polyrotaxane gel: a topological gel by figure‐of‐eight cross‐links. Adv Mater. 2001;13:485–7.
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.
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.
Higgins JS, Benoit HC. Polymers and neutron scattering. Oxford: Clarendon Press; 1994.
Sakai VG, Arbe A. Quasielastic neutron scattering in soft matter. Curr Opin Colloid Interf Sci. 2009;14:381–90.
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.
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.
Yoshizaki T, Yamakawa H. Scattering functions of wormlike and helical wormlike chains. Macromolecules. 1980;13:1518–25.
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.
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.
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.
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.
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.
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.
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.
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.
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.
Richter D, Monkenbusch M, Arbe A, Colmenero J. Neutron spin echo in polymer systems. Adv Polym Sci. 2005;174:1–221.
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.
Mayumi K, Ito K. Structure and dynamics of polyrotaxane and slide-ring materials. Polymer. 2010;51:959–67.
Acknowledgements
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
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
About this article
Cite this article
Mayumi, K. Molecular dynamics and structure of polyrotaxane in solution. Polym J 53, 581–586 (2021). https://doi.org/10.1038/s41428-020-00457-9
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41428-020-00457-9
This article is cited by
-
Optimal conditions for the use of polyrotaxane as a cross-linker in preparing elastomers with high toughnesses
Polymer Journal (2024)
-
Rheological studies on polymer networks with static and dynamic crosslinks
Polymer Journal (2021)
-
Visualization of judgment regions in convolutional neural networks for X-ray diffraction and scattering images of aliphatic polyesters
Polymer Journal (2021)