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Molecular dynamics and structure of polyrotaxane in solution

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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.

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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).

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Correspondence to Koichi Mayumi.

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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

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