Abstract
The local structure on the surface of plate-like cellulose II oligomer crystals (CIIOCs) was investigated by NMR spectroscopy. CIIOCs with reducing ends that were selectively labeled with 13C were enzymatically synthesized using cellodextrin phosphorylase. The solid-state 13C cross polarization/magic angle spinning spectra of the 13C-labeled CIIOCs clearly exhibited two resonance peaks (labeled as C1Rα and C1Rβ) derived from the C1 atoms of the reducing ends. The 2D 13C double quantum/13C single quantum homonuclear correlation spectrum indicated that two magnetically nonequivalent glucopyranose rings (Rα and Rβ units) coexisted at the reducing end units. The 1H/13C heteronuclear correlation spectrum suggested that there was a large difference between the local environments around the anomeric carbons of Rα and Rβ units. The abundance ratio of C1Rβ to C1Rα in the solid state was 4:1, whereas that of C1α and C1β in solution was 1:1. When the oligomer chains are packed in the cellulose II crystal, the reducing end units located on the surface of the plate-like crystal may tend to have β-anomeric structure, which would be more sterically stable than the α-anomeric structure.
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Acknowledgments
This work was partially supported by a research grant for Exploratory Research on Sustainable Humanosphere Science to R.K. from the Research Institute for Sustainable Humanosphere (RISH) of Kyoto University, a Grant-in-Aid for Scientific Research C (No. 17K05882) to R.K. from the Japan Society for the Promotion of Science (JSPS), and the Advanced Low Carbon Technology Research and Development Program (ALCA; No. JPMJAL1502) from the Japan Science and Technology Agency (JST).
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Kita, Y., Kusumi, R., Kimura, T. et al. Surface structural analysis of selectively 13C-labeled cellulose II by solid-state NMR spectroscopy. Cellulose 27, 1899–1907 (2020). https://doi.org/10.1007/s10570-019-02896-x
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DOI: https://doi.org/10.1007/s10570-019-02896-x