Benign catalytic oxidation of potato starch using a homogeneous binuclear manganese catalyst and hydrogen peroxide

Oxidation is an excellent way to improve the properties of native starches. After oxidation, products are easier to handle due to a lowered paste viscosity in water, an improved stability and enhanced adhesive properties. Currently, oxidation by sodium hypochlorite (NaOCl) is the dominant commercial process for oxidized starches, which allows for oxidation of hydroxyl groups into carboxylic acids. Here, we show that by using a commercial homogeneous binuclear manganese catalyst ([MnIV 2 (mu-O)(3)(tmtacn)(2)][(CH3COO)(2)] (Mncat), with tmtacn = 1,4,7-trimethyl-1,4,7-triazacyclononane), and H2O2 as oxidant, starch can be oxidised without the cogeneration of ecotoxic chlorinated waste products. Although oxidation with H2O2 and other catalysts (mainly iron-based) has been done, high loadings were needed and the starch pasting properties were not yet on par with NaOCl oxidised starches. Starch granules suspended in water can be oxidized at room temperature with 0.0021 mol% Mncat and 1 wt% H2O2 yielding starch with similar properties (DSCOOH, yield, pasting properties) as those achieved by NaOCl oxidation. This catalytic oxidation of starch with an earth-abundant metal catalyst at ppm loadings, which is widely applied in detergents, highlights the potential for the development of a more sustainable process to produce oxidized starches.