Investigating the effects of solvent polarity and temperature on the molecular, photophysical, and thermodynamic properties of sinapic acid using DFT and TDDFT

Abstract

Sinapic acid (SA) is widely used in cosmetics, foods, and pharmaceuticals due to its antioxidant, anti-inflammatory, neuroprotective, antimicrobial, antifungal, anticancer, and cardioprotective properties. However, environmental factors such as solvent polarity and temperature can influence its biological activity. This work determined how solvent polarity and temperature affected the molecular, photophysical, and thermodynamic properties of SA in gas and various solvents using semi-empirical (MP6), Hartree-Fock (HF) with the B3LYP method and a 6-311++G(d,p) basis set, and density functional theory (DFT) with various basis sets, such as 3TO-3G*, 3-21G+, 6-31G++G(d,p), 6-311++G(d,p), aug-CC-PVDZ, LanL2DZ, SDD, and DGD2VP. The results indicated that solvent polarity influences molecular and spectroscopic properties, such as bond angles, dihedral angles, bond lengths, FTIR spectra, solvation energy, dipole moments, HOMO–LUMO band gaps, chemical reactivity, and thermodynamic properties, resulting from interactions between the drug and solvent molecules. The findings suggested that increasing the temperature within the range of 100 to 1000 Kelvin leads to an increase in heat capacity, enthalpy, and entropy due to molecular vibrations, ultimately causing degradation and instability in SA. Furthermore, the results showed that SA underwent a redshift in the absorption peak (from 320.18 to 356.26 nm) and a shift in the fluorescence peak (from 381 to 429 nm) in the solvent phase compared to those in the gas phase. Overall, this study provides background knowledge on how solvent polarity and temperature affect the properties of SA molecules.