Oxidation-induced starch molecular degradation: A comprehensive kinetic investigation using NaClO/NaBr/TEMPO system

Starch degradation often coincides with its chemical modification, and understanding how chemical modification influences starch degradation is vital for determining the properties of the resultant modified products. This work investigates the effect of oxidation on starch molecular degradation, examining factors such as oxidation degree, reaction kinetics, and degradation patterns during 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated starch oxidation under varying conditions, including reaction time, pH, temperature, and concentrations of NaBr, TEMPO, and NaClO. Results emphasize that extended reaction durations primarily lead to β-elimination, causing α-1,4 linkage cleavages. pH 8.5 favored non-selective oxidation, while pH 11 enhanced β-elimination, both slowing the reaction rate and severely damaging starch chains (M_w of 8.8 × 10⁵ g/mol and 7.2 × 10⁵ g/mol, respectively). Elevated temperature from 0 to 30 °C significantly expedited both selective and non-selective oxidation, dramatically reducing molecular mass to 8.1 × 10⁵ g/mol. Increasing concentrations of NaBr and TEMPO boost the reaction rate with minimal impact on molecular mass. Meanwhile, increasing NaClO concentration from 0.2 to 2.2 mmol/g-starch not only affects the reaction rate but also reinforces β-elimination, enhancing molecular degradation. This study is insightful for starch modification to achieve desired oxidation levels and chain lengths by controlling reaction conditions, offering potential advancements in oxidized starch-based materials like nano micelles.