Effect of Zn2+ on emodin molecules studied by time-resolved fluorescence spectroscopy and quantum chemical calculations.

Emodin is a natural drug for treating neurodegenerative diseases and plays a vital role in the mitigation of nerve damage. Metal ions can modify the drug properties of emodin, where Zn2+ can synergize with the emodin molecule and enhance the drug effect of emodin. Besides, complex changes can be observed in the fluorescence intensity and fluorescence lifetime of the emodin molecule as the concentration of Zn2+ increases. Herein, the synergistic effects of ligand structural in Zn(II)-Emodin complexes and the electronic effects of metal elements on the antioxidant properties of the complexes are discussed in detail based on UV-vis absorption spectroscopy, fluorescence spectroscopy, time-correlated single photon counting (TCSPC) technique and quantum chemical calculations at the B3LYP/6-31G(d) level. The experimental results confirm that Zn2+ can coordinate with the hydroxyl groups on the emodin to make the molecule structure more rigid, thus inhibiting the non-radiative processes such as high-frequency vibrations of the emodin molecule in solution. The suppression of non-radiative processes leads to an increase in the average fluorescence lifetime of the emodin molecule, and finally results in the enhanced fluorescence intensity. The chemical softness of Zn(II)-Emodin is then confirmed to be higher than that of emodin by Gaussian calculations, indicating its higher chemical reactivity and lower stability. The stronger electron donating ability of Zn(II)-Emodin compared to emodin may explain the higher antioxidant activity of Zn(II)-Emodin, which gives it a stronger pharmacological activity. The results of this study show that emodin can well complex with Zn2+ to remove excess Zn2+ in human body and the resulting complex has better antioxidant properties, which helps to understand the role of Zn2+ in drug-metal coordination and provides guidance for the design of new drugs.