A mechanistic study of ciprofloxacin adsorption by goethite in the presence of silver and titanium dioxide nanoparticles.

The adsorption behaviors of ciprofloxacin (CIP), a fluoroquinolone antibiotic, onto goethite (Gt) in the presence of silver and titanium dioxide nanoparticles (AgNPs and TiO2NPs) were investigated. Results showed that CIP adsorption kinetics in Gt with or without NPs both followed the pseudo-second-order kinetic model. The presence of AgNPs or TiO2NPs inhibited the adsorption of CIP by Gt. The amount of inhibition of CIP sorption due to AgNPs was decreased with an increase of solution pH from 5.0 to 9.0. In contrast, in the presence of TiO2NPs, CIP adsorption by Gt was almost unchanged at pHs of 5.0∼6.5 but was decreased with an increase of pH from 6.5 to 9.0. The mechanisms of AgNPs and TiO2NPs in inhibiting CIP adsorption by Gt were different, which was attributed to citrate coating of AgNPs resulting in competition with CIP for adsorption sites on Gt, while TiO2NPs could compete with Gt for CIP adsorption. Additionally, CIP was adsorbed by Gt or TiO2NPs through a tridentate complex involving the bidentate inner-sphere coordination of the deprotonated carboxylic group and hydrogen bonding through the adjacent carbonyl group on the quinoline ring. These findings advance our understanding of the environmental behavior and fate of fluoroquinolone antibiotics in the presence of NPs.

The influence mechanism of the molecular structure on the peak current and peak potential in electrochemical detection of typical quinolone antibiotics.

Antibiotic pollution in water has become an increasingly serious problem, posing a potentially huge threat to human health. Ofloxacin (OFL), norfloxacin (NOR), and enoxacin (ENX) are typical broad-spectrum quinolone antibiotics, which are frequently detected in various water environments. An electrochemical sensor is a rapid and effective tool to detect antibiotics in the aquatic environment. The molecular structure of target pollutants is an important factor affecting the detection performance of electrochemical sensors. Based on the electrochemical detection results of antibiotics (OFL, NOR, and ENX), we first used the molecular structure analysis method based on quantum chemistry to accurately identify the electronegativity and the electrocatalytic degree of the oxidizable (and non-oxidizable) functional groups of pollutants. We also clarified the influence mechanism of the molecular structure on the peak current and peak potential. These results can provide theoretical support for rapidly selecting electrodes with a suitable electrochemical window to efficiently detect trace organic pollutants (such as antibiotics) in water based on the molecular structure of the target pollutant.