Polyglucuronic acids prepared from -(1 3)-glucan by TEMPO-catalytic oxidation

2,2,6,6-Tetramethylpiperidine-1-oxyl radical (TEMPO)-catalytic oxidation was applied to a water-insoluble alpha-(1 -> 3)-glucan in water at pH 10 and room temperature (similar to 24 degrees C), with solid NaOCl5H(2)O as the primary oxidant. Oxidation with NaOCl at 15 mmol/g gave a water-soluble TEMPO-oxidized product at a mass recovery ratio of 97 %. The carboxy content of the TEMPO-oxidized product was 5.3 mmol/g, which corresponds to a degree of C6-oxidation (DO) of 93 %. A new water-soluble alpha-(1 -> 3)-polyglucuronic acid with a nearly homogeneous chemical structure was therefore quantitatively obtained. X-ray diffraction and solid-state C-13 NMR spectroscopic analyses showed that the original alpha-(1 -> 3)-glucan and its TEMPO-oxidized product with a carboxy content of 5.3 mmol/g had crystalline structures, whereas the oxidized products with DOs of 50 % and 66 % had almost disordered structures. The carboxy groups in the oxidized products were regioselectively methyl esterified with trimethylsilyl diazomethane, and analyzed by using size-exclusion chromatography with multi-angle laser-light scattering and refractive index detections. The results show that the original alpha-(1 -> 3)-glucan and its oxidized products with DOs of 50 %, 66 %, and 93 % had weight-average degrees of polymerization of 671, 288, 54, and 45, respectively. Substantial depolymerization of the alpha-(1 -> 3)-glucan molecules therefore occurred during catalytic oxidation, irrespective of the oxidation pH.