Theoretical and Kinetic Study of the Hydrogen Atom Abstraction Reactions of Neu5Gc with Hydroxyl Radical
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Abstract:
The new red meat and it’s products risk factor N-glycolylneuraminic acid (Neu5Gc) can induced inflammation, but the interaction mechanism with the hydroxyl radicals (OH·) that related to the food consumption, metabolism process and inflammation is unclear. The OH· simulation test showed that the optimal rate of Neu5Gc content decrease was 76.23%±2.17% at the conditions bellow, the amount of hydrogen peroxide (H2O2) was 2% and the 254 nm UV lamp was treated for 15 minutes. To explore the reaction mechanism, the density functional theory was used to optimize the station points and enthalpy correction of all one-step hydrogen abstraction channels of OH· on Neu5Gc hydroxyl hydrogen and non-hydroxy hydrogen at the theoretical level of M062X/6-31+G(d, p) in the gas phase, aqueous phase and benzene phase. The energy barrier was calculated at the level M062X/def2TZVP. Reaction rates and kinetic parameters were obtained in the 298 K~453 K range by the transition state theory and the three-parameter Arrhenius equation. Theoretical calculations showed that the minimum hydrogen extraction energy barrier occurred at the H 24 position of Neu5Gc under the gas and benzene phase with 13.20 kJ/mol and 19.54 kJ/mol, respectively, the lowest energy barrier in the aqueous phase was 6.25 kJ/mol at H 29 position. For the lowest activation energy, in the gas phase was 8.09 kJ/mol at the H 39 position, in the benzene phase was 1.78 kJ/mol at the H 38 position, in the aqueous phase was 14.3 kJ/mol at the H 24 position. In the range of 273 to 453 K, the hydrogen extraction rate of the non-hydroxyl hydrogen in the Neu5Gc molecule can be up to 108 times higher than that of the hydroxyl hydrogen. In summary, the interaction mechanism of OH· with Neu5Gc was mainly through the hydrogen extraction of Neu5Gc non-hydroxyl hydrogen atoms.
