Plant holocelluloses were prepared from softwood, gymnosperm, hardwood, and herbaceous species, and subjected to TEMPO-mediated oxidation using the TEMPO/NaBr/NaOCl and TEMPO/NaOCl/NaO<inf>2</inf>Cl systems in water at pH 10 and 6.8, respectively. Weight recovery ratios of the water-insoluble TEMPO-oxidized holocellulose (TOH) fractions and their carboxylate contents, sugar compositions, and X-ray diffraction patterns were measured. When the oxidation at pH 10 was used, the carboxylate content of the TOHs increased up to 1.4-1.7 mmol g<sup>-</sup><sup>1</sup>. The oxidation at pH 6.8 resulted in higher weight recovery ratios of TOHs and their lower carboxylate contents (0.8-1.2 mmol g<sup>-</sup><sup>1</sup>) than those prepared by the oxidation at pH 10. Hemicelluloses in plant holocelluloses are preferentially degraded to water-soluble fractions and removed from TOHs in the oxidation at pH 10. In contrast, the TEMPO-mediated oxidation at pH 6.8 provides hemicellulose-rich TOHs in high weight recovery ratios, although their nanofibrillation yields were low. All TEMPO-oxidized holocellulose nanofibrils (TOHNs) obtained by mechanical disintegration treatment of TOHs in water had the same average widths of ∼3 nm, when measured by atomic force microscopy in water, which were consistent with those of TOHs determined from X-ray diffraction patterns. The number-average lengths of TOHNs were 500-600 nm.
Kuramae, R., Saito, T., & Isogai, A. (2014). TEMPO-oxidized cellulose nanofibrils prepared from various plant holocelluloses. Reactive and Functional Polymers, 85, 126–133. https://doi.org/10.1016/j.reactfunctpolym.2014.06.011