Preparation of completely C6-carboxylated curdlan by catalytic oxidation with 4-acetamido-TEMPO.

Erika Watanabe, Naoyuki Tamura, Tsuguyuki Saito, Naoto Habu, Akira Isogai

Index: Carbohydr. Polym. 100 , 74-9, (2014)

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Abstract

Pure (1→3)-β-polyglucuronic acid sodium salt was prepared from curdlan by oxidation with 4-acetamido-TEMPO/NaClO/NaClO₂ in water at pH 4.7 and 35°C. The oxidation conditions, including the reaction time and amounts of reagents added, were optimized for the preparation of (1→3)-β-polyglucuronic acids with high molecular weights. The primary C6 hydroxyl groups of curdlan were completely oxidized to the corresponding C6-carboxylates using a one- or two-step reaction process by controlling the oxidation conditions, thus providing pure (1→3)-β-polyglucuronic acids consisting only of D-glucuronosyl units. Unfortunately, however, the increased amounts of reagents and long reaction time led to significant depolymerization of the curdlan during the oxidation process, and the resulting (1→3)-β-polyglucuronic acids had weight-average degrees of polymerization of 340-360. The (13)C and (1)H NMR chemical shifts of the products were successfully assigned using pure (1→3)-β-polyglucuronic acid.Copyright © 2012 Elsevier Ltd. All rights reserved.