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SEC-MALS analysis of cellouronic acid prepared from regenerated cellulose by TEMPO-mediated oxidation

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Abstract

The 4-amino-2,2,6,6-tetramethylpiperidine-1-oxy radical (4-amino-TEMPO)-mediated oxidation was applied to regenerated cellulose, and the obtained cellouronic acid was analyzed by size-exclusion chromatography attached with a multi-angle laser light scattering detector (SEC-MALS). Although the cellouronic acid filtered with the usual 0.1 μm membrane gave a bimodal SEC-elution pattern, the high-molecular-mass fraction was removed by micro filtration of the cellouronic acid solution with a 0.02 μm membrane. It is likely, therefore, that some colloidal particles formed from regenerated cellulose by the TEMPO-mediated oxidation are present as incompletely oxidized residues in the cellouronic acid sample and behave as the high-molecular-mass fraction in the SEC elution pattern. Then, the SEC-MALS analysis was applied to the 0.02 μm membrane-filtered cellouronic acid, and the accurate DPw value of 36 was obtained for cellouronic acid. This DPw value was far lower than that of carboxymethyl cellulose, hydroxypropyl cellulose or alginic acid, resulting from significant depolymerization of cellulose chains during the TEMPO-mediated oxidation. Because the value of DPw 36 for cellouronic acid is close to the leveling-off DP (about 40) of regenerated celluloses obtained by the dilute and heterogeneous acid hydrolysis, the DPw value of cellouronic acid must reflect the solid-state structure of the original regenerated cellulose used in the TEMPO-mediated oxidation.

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Acknowledgments

The authors express their sincere thanks to Professor Walther Burchard, University of Freiburg, Germany, for valuable suggestions and comments␣made as part of the review process of an earlier manuscript. These suggestions resulted in a re-examination of our findings, and they helped␣produce a significantly improved paper. Mr.␣Masahide Nakamura of Shoko Co., Ltd., Japan kindly arranged the dn/dc measurement of␣samples in 0.1 M NaCl. This research has been␣supported by a Grant-in-Aid for Scientific Research (Grant number 11660160, 13660157 and 15380116) from the Japan Society for the Promotion of Science (JSPS).

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Authors and Affiliations

  1. Graduate School of Agricultural and Life Sciences, The University of Tokyo, 1-1-1 Yayoi, Bunkyo-ku, Tokyo, 113-8657, Japan

    Izumi Shibata, Masahiro Yanagisawa, Tsuguyuki Saito & Akira Isogai

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  1. Izumi Shibata
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  2. Masahiro Yanagisawa
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  3. Tsuguyuki Saito
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  4. Akira Isogai
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Correspondence to Akira Isogai.

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Shibata, I., Yanagisawa, M., Saito, T. et al. SEC-MALS analysis of cellouronic acid prepared from regenerated cellulose by TEMPO-mediated oxidation. Cellulose 13, 73–80 (2006). https://doi.org/10.1007/s10570-005-9021-4

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  • DOI: https://doi.org/10.1007/s10570-005-9021-4

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