Combining Computational and Experimental Studies for Synthesis of Oxidative Derivatives of Glycogen Using Kinetics and Mechanism of Oxidation of Glycogen by Alkaline Permanganate: Homogenous Catalysis

Glycogen is a glucose polymer that plays a crucial role in glucose homeostasis by functioning as a short-term energy storage reservoir in animals and bacteria. Knowing the conditions of glycogen reaction and type of electron transfer is crucial for enhancing production efficiency, ensuring product quality, and exploring new applications in various industries. Glycogen (Gly) oxidation kinetics has been studied by using spectrophotometric analysis utilizing alkaline permanganate. The influence of variable factors on the oxidation rates has been examined for both formation and decomposition, which are approximately the same. The reaction was studied under pseudo-first-order conditions, the experimental results showed a first-order dependence in [MnO₄^–], fractional first-order kinetics in [Gly], and fractional second order in [OH^–] concentrations. The oxidation rates were increased with increasing alkali concentration; therefore, the oxidation process was of base-catalyzed nature. The oxidation product of Gly was applied for chelation with Ca²⁺and Mg²⁺ ions providing potential applications of Gly in different fields, especially in drug delivery. The time-dependent density-functional theory (TD-DFT) calculations regarding the isolated molecule of glycogen [Gly]^Iso and the isolated molecule of keto-glycogen molecule [Keto-Gly]^Iso are 6.212 and 2.057 eV, respectively, for DMol³/CASTEP methods. The experimental values of [Gly]^Poly and [Keto-Gly]^Poly for the isolated particles of [Gly]^Iso and [Keto-Gly]^Iso are almost identical to the simulated optical parameter values produced by DMol³/CASTEP in TD-DFT.