Department of Biomaterials Sciences, Graduate School of Agricultural and Life Sciences, The University of Tokyo, Tokyo 113-8657, Japan.
Biomacromolecules. 2010 Jun 14;11(6):1593-9. doi: 10.1021/bm1002575.
Curdlan, amylodextrin, and regenerated cellulose fiber were subjected to electromediated oxidation with a 4-acetamido-TEMPO catalyst in a buffer at pH 6.8 without NaClO or NaClO(2). More than 90% of the C6 primary hydroxyls of Curdlan and amylodextrin were converted to sodium carboxylate groups by this method. Molecular mass values of the oxidized products were much higher than those prepared by the TEMPO/NaBr/NaClO system at pH 10. When the regenerate cellulose fiber was treated by the TEMPO electromediated oxidation for 45 h, carboxylate and aldehyde groups of 1.1 and 0.6 mmol/g, respectively, were formed in the oxidized cellulose fiber. The original fibrous and fine surface morphologies were maintained, and nearly no weight losses by the oxidation were observed. Thus, the TEMPO electromediated oxidation is a characteristic and environmentally friendly chemical modification for regenerated cellulose fibers, films, and related forming materials, and ion-exchangeable carboxylate and reactive aldehyde groups can be efficiently introduced into regenerated celluloses.
凝乳多糖、直链淀粉和再生纤维素纤维在没有 NaClO 或 NaClO2 的情况下,在 pH 值为 6.8 的缓冲液中,用 4-乙酰氨基-TEMPO 催化剂进行电介导氧化。该方法将凝乳多糖和直链淀粉的 90%以上的 C6 伯羟基转化为羧酸钠基团。氧化产物的分子量值明显高于在 pH 值为 10 的 TEMPO/NaBr/NaClO 体系中制备的产物。当再生纤维素纤维经 TEMPO 电介导氧化处理 45 小时后,在氧化纤维素纤维中形成了 1.1 和 0.6mmol/g 的羧酸盐和醛基。原始的纤维状和精细的表面形貌得以保持,并且几乎没有观察到氧化导致的重量损失。因此,TEMPO 电介导氧化是一种对再生纤维素纤维、薄膜和相关成型材料具有特色和环保的化学修饰方法,可以有效地将可离子交换的羧酸盐和反应性醛基引入再生纤维素中。