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Conformational characteristics of regioselectively PEG/PS-grafted cellulosic bottlebrushes in solution: cross-sectional structure and main-chain stiffness

Polymer Journal volume 54, pages 503–513 (2022)Cite this article

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Abstract

Cellulosic bottlebrushes with polystyrene (PS) and poly(ethylene glycol) (PEG) side chains at the O-6 and O-2,3 positions, respectively (PEG-PS-cellulose), were synthesized and characterized in diluted solution to reveal the second structure of heterografted bottlebrushes. The regioselectivity and degree of substitution were evaluated by 1H- and 13C-nuclear magnetic resonance spectroscopy and size-exclusion chromatography (SEC). The cross-sectional structure of PEG-PS-cellulose was evaluated from the cross-sectional radius of gyration determined by the small angle X-ray scattering technique as a function of the molecular weight of the PS side chain. As a result, PEG-PS-cellulose was found to show a core-shell-corona structure, in which PEG and PS side chains formed a homogeneous shell layer surrounding the cellulosic core and the outer segments of PS chains formed an outer corona layer. The stiffness parameter (λ−1) of the main chain was analyzed by the SEC–multiangle light scattering technique along with the Kratky-Porod wormlike chain model. In comparison with a previously reported cellulosic bottlebrush with a PS side chain at the O-6 position, it is suggested that the observed increase in λ−1 with increasing molecular weight of PS is mainly derived from the interaction among PS side chains located in an outer layer, while the PEG side chains at the O-2,3 position effectively suppressed the internal rotation of the cellulosic main chain.

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Acknowledgements

High-resolution 600 MHz and 800 MHz NMR spectra were acquired with an NMR spectrometer in the Joint Usage/Research Center (JURC) at the Institute for Chemical Research, Kyoto University. Synchrotron SAXS experiments were performed at BL40B2 (Proposal Nos. 2016B1208 and 2017B1727) in SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI). The authors thank Dr. Noboru Ohta (JASRI/SPring-8) for assistance with the experiments carried out using the BL40B2 beamline.

Funding

This work was supported by a Grant-in-Aid for Challenging Exploratory Research (No. 25620175) and a Grant-in-Aid for Young Scientists (B) (No. 16K17914) from the Ministry of Education, Culture, Sports, and Technology (MEXT) in Japan.

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Authors and Affiliations

  1. Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan

    Yuji Kinose & Yoshinobu Tsujii

  2. Research Institute for Sustainable Chemistry, National Institute of Advanced Science and Technology (AIST), 3-11-32 Kagamiyama, Higashihiroshima, Hiroshima, 739-0046, Japan

    Keita Sakakibara

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  1. Yuji Kinose
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Correspondence to Yoshinobu Tsujii.

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Kinose, Y., Sakakibara, K. & Tsujii, Y. Conformational characteristics of regioselectively PEG/PS-grafted cellulosic bottlebrushes in solution: cross-sectional structure and main-chain stiffness. Polym J 54, 503–513 (2022). https://doi.org/10.1038/s41428-021-00594-9

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