Polysaccharide depolymerization from TEMPO-catalysis: Effect of TEMPO concentration

Polysaccharide TEMPO-oxidation was monitored using automatic continuous online monitoring of polymerization reactions (ACOMP). The products of oxidation, obtained at different pHs (9, 7 and 5) and different concentrations of catalyst TEMPO, were evaluated by Automatic Continuous Mixing (ACM) and Size Exclusion Chromatography (SEC). The degree of oxidation was higher at pH 9 and polysaccharide degradation was observed under different pH conditions, but was much higher without catalyst TEMPO. The rate constant (k) was dependent on reaction pH and TEMPO concentration. The amount of -COOH per g of polysaccharide, at pH 9, in the presence and absence of TEMPO was different, 0.215 and 0.395 mmol g(-1), respectively. This suggested a secondary and non-selective polysaccharide oxidation occurring at a lower rate in the absence of catalyst. TEMPO protects the polysaccharide from degradation caused by secondary oxidant species, acting as a catalyst and sacrificial molecule at higher concentrations. (C) 2017 Elsevier Ltd. All rights reserved.