Molecular structure and spectral characteristics of hyperoside and analysis of its molecular imprinting adsorption properties based on density functional theory

Abstract

The structure of hyperoside was optimized according to the skeletal types of different galactopyranosides in hyperoside at the DFT/B3LYP/6-31++G(d,p) level, and the frequencies were calculated. The accuracy of the theoretical calculations of the ¹H and ¹³C NMR signals was evaluated by linear correlation. The excited state was calculated via time-dependent density functional theory (TD-DFT). The stable conformation, NMR, UV-vis, natural bond orbital (NBO), molecular electrostatic potential (MEP) and thermodynamic information were obtained. In the most stable conformation of hyperoside, seven intramolecular hydrogen bonds are formed, which affect the imprinting efficiency. The theoretical ¹H and ¹³C NMR results are in good agreement with the experimental results. The B3PW91 function is more suitable than B3LYP for TD-DFT calculations. Combining the UV-vis and NBO analyses, the HOMO→LUMO transition mainly results from the n→π^∗ transition of the phenolic hydroxyl groups and the π→π^∗ transition of the benzene ring on the B ring in ethanol. The HOMO-1→LUMO+1 transition mainly results from the n→π^∗ and π→π^∗ transition on the A ring. The MEP and NBO calculations indicate that the imprinted active sites are mainly located on the carbonyl oxygen atom and the hydroxyl hydrogen atoms. As the temperature increases, the molecular heat capacity, entropy, enthalpy, and activity of the imprinting sites increase. The obtained results provide strong theoretical guidance for hyperoside in the synthesis of molecularly imprinted polymers and separation techniques.

Keywords: Density functional theory; Hyperoside; MEP and NBO; Molecular imprinting; Molecular structure; UV–vis.