The pH dependence and role of fluorinated substituent of enoxacin binding to ferrihydrite

Abstract

The sorption of antibiotics on iron (hydr)oxides is an important process that influences their environmental fate. Ferrihydrite (Fh) nanosized iron hydroxide is omnipresent in nature. However, the sorption mechanism of fluoroquinolone (FQ) antibiotics on Fh is unclear. Here, a combined experimental and computational study was conducted to investigate the sorption of enoxacin (ENO) as one model of FQs on Fh. Pipemidic acid (PPA), as a structural analog of ENO, was selected to compare the effect of fluorinated substituent on the sorption mechanism. Results indicated that the average Kd values of ENO at pH = 7.0 and 8.0 were 1.72 and 2.75 times higher than those at pH in the ranges of 4.0–6.0 and 9.0–10.0, respectively. The main sorption mechanisms included electrostatic, hydrophobic interaction, and inner-sphere complexation. The fluorinated substituent of ENO facilitated its sorption on Fh through enhancing its hydrophobicity as well as modifying its dissociation constants and charge distribution. The findings give new insights into the significant influence of active fluorinated substituents on the environmental behaviors of fluorinated pharmaceuticals.