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Structure and crystallization of sub-elementary fibrils of bacterial cellulose isolated by using a fluorescent brightening agent

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Abstract

The structure and crystallization of carefully isolated sub-elementary fibrils (SEFs) of bacterial cellulose have been investigated using TEM, WAXD, and high-resolution solid-state 13C NMR. The addition of a suitable amount of fluorescent brightener (FB) to the incubation medium of Acetobacter xylinum effectively suppressed the aggregation of the SEFs into the microfibrils, as previously reported. However, this study confirmed for the first time that serious structural change in the SEFs occurs during the removal of excess FB by washing with buffer solutions having pH values higher than 6 or with the alkaline aqueous solution that was frequently used in previous studies. In contrast, the isolation of unmodified SEFs was successfully performed by utilizing a washing protocol employing pH 7 citrate–phosphate buffer solution containing 1% sodium dodecyl sulfate. High-resolution solid-state 13C NMR and WAXD measurements revealed that the SEFs thus isolated are in the noncrystalline state in which the pyranose rings of the almost parallel cellulose chains appear to be stacked on each other. The respective CH2OH groups of the SEFs adopt the gt conformation instead of the tg conformation found in cellulose I α and I β crystals, and undergo significantly enhanced molecular motion in the absence of intermolecular hydrogen bonding associated with these groups. The main chains are also subject to rapid motional fluctuations while maintaining the parallel orientation of the respective chains, indicating that the SEFs have a liquid crystal-like structure with high molecular mobility. Moreover, the SEFs crystallize into cellulose I β when the FB molecules that may adhere to the surface of the SEFs are removed by extraction with boiling 70 v/v% ethanol and 0.1N NaOH aqueous solution. On the basis of these results, the crystallization of the SEFs into the I α and I β forms is discussed, including the possible formation of the crystalline-noncrystalline periodic structure in native cellulose.

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Notes

  1. Recent molecular dynamics (MD) simulations by the current authors revealed that the conformational transition from gt to tg is allowed to occur in the modified pseudo-crystal of cellulose I β (Horii et al. 2006). Matthews et al. (2005) also demonstrated the possibility of similar transitions from gt to tg in small crystallites of cellulose Iβ surrounded by water using MD simulations. Moreover, evidence of such a transition being actually induced in the crystal transformation from cellulose IIII to cellulose Iβ has been reported (Chanzy et al. 1987).

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Acknowledgments

We thank Dr. Toshio Kono of Kochi Prefectural Industrial Technology Center and Prof. Kohji Nishida of the Institute for Chemical Research, Kyoto University, for their kind cooperation on the WAXD measurements by the reflection and transmission methods, respectively. We are grateful to Prof. Masaki Tsuji of the Institute for Chemical Research, Kyoto University, for his kind cooperation on the TEM observations. We also thank Prof. Tsunehisa Kimura and Dr. Fumiko Kimura of the Graduate School of Agriculture, Kyoto University, for kindly measuring FT-IR spectra of our cellulose samples.

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Correspondence to Fumitaka Horii.

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Suzuki, S., Suzuki, F., Kanie, Y. et al. Structure and crystallization of sub-elementary fibrils of bacterial cellulose isolated by using a fluorescent brightening agent. Cellulose 19, 713–727 (2012). https://doi.org/10.1007/s10570-012-9678-4

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  • DOI: https://doi.org/10.1007/s10570-012-9678-4

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