Abstract
2,2,6,6-Tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation has been applied to bacterial cellulose (BC). The TEMPO-oxidized BC (TO-BC) gel particles were subjected to ultrasonication in water to prepare mechanically fibrillated TO-BC (TO-BC-U) samples. The carboxy contents of the TO-BC samples were 1.5‒1.6 mmol/g. X-ray diffraction patterns and solid-state 13C-nuclear magnetic resonance (NMR) spectra of the BC, TO-BC, and TO-BC-U samples showed that cellulose Iα was the dominant crystalline structure. The crystallinities of the samples calculated from the carbon signal areas in the NMR spectra were approximately the same between the BC and TO-BC samples, showing that TEMPO-mediated oxidation selectively occurred on the crystalline BC fibril surfaces. However, the crystallinities of the TO-BC-U samples were lower than those of the BC and TO-BC samples, indicating that ultrasonication of the TO-BC samples in water caused partial decreases in crystallinity. The TO-BC-U samples contained both single fibrils and fibril bundles; completely individualized TO-BC-U fibrils with homogeneous widths was not obtained. The average widths of the single TO-BC-U fibrils were ~ 3 nm, which are close to those of TO-cellulose nanofibrils prepared from wood-cellulose samples. Thus, the crystalline BC fibrils with widths of ~ 3 nm were the smallest crystalline elements. The lengths of the TO-BC samples were greater than 2‒3 µm, whereas the weight-average cellulose chain lengths of the cellulose/TEMPO-oxidized cellulose molecules in TO-BC-U samples were < 800 nm. Hence, each TO-BC-U fibril consisted of multiple cellulose and oxidized cellulose molecules, which were packed along the longitudinal direction.
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Ono, Y., Takeuchi, M., Kimura, S. et al. Structures, molar mass distributions, and morphologies of TEMPO-oxidized bacterial cellulose fibrils. Cellulose 29, 4977–4992 (2022). https://doi.org/10.1007/s10570-022-04617-3
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DOI: https://doi.org/10.1007/s10570-022-04617-3