Effect of fulvic acid concentration levels on the cleavage of piperazinyl and defluorination of ciprofloxacin photodegradation in ice.

Ice is an important physical and chemical sink for various pollutants in cold regions. The photodegradation of emerging fluoroquinolone (FQ) antibiotic contaminants with dissolved organic matter (DOM) in ice remains poorly understood. Here, the photodegradation of ciprofloxacin (CIP) and fulvic acid (FA) in different proportions as representative FQ and DOM in ice were investigated. Results suggested that the photodegradation rate constant of CIP in ice was 1.9 times higher than that in water. When CFA/CCIP ≤ 60, promotion was caused by FA sensitization. FA increased the formation rate of cleavage in the piperazine ring and defluorination products. When 60 < CFA/CCIP < 650, the effect of FA on CIP changed from promoting to inhibiting. When 650 ≤ CFA/CCIP ≤ 2600, inhibition was caused by both quenching effects of 143.9%-51.3% and light screening effects of 0%-48.7%. FA inhibited cleavage in the piperazine ring for CIP by the scavenging reaction intermediate of aniline radical cation in ice. When CFA/CCIP > 2600, the light screening effect was greater than the quenching effect. This work provides new insights into how DOM affects the FQ photodegradation with different concentration proportions, which is beneficial for understanding the environmental behaviors of fluorinated pharmaceuticals in cold regions.

Photodegradation of norfloxacin in ice: Role of the fluorine substituent.

Ice is an important medium in cold regions, because it regulates the environmental behaviors and the fate of pollutants. The photodegradation of fluoroquinolone (FQ) antibiotics as emerging contaminants of concern in ice remains poorly understood. Here, the photodegradation of fluorine-containing norfloxacin (NOR) as one model of FQs in ice formed from freezing solutions was investigated. Pipemidic acid (PPA) as a structural analogue of NOR was selected to compare the effect of molecular structure on the antibiotic photodegradation in the ice. Results suggested that the photodegradation rate constant of NOR in ice relative to pure water increased by 40.0%. Both the absorbance in the absorption spectra and quantum yields of NOR in ice over water increased by 1.4 times. Direct photodegradation mainly caused the defluorination of NOR, which was more important than cleavage and oxidation of the piperazine ring by self-sensitized photooxidation in ice. The defluorination rate of NOR in the ice relative to water increased by about 12.7%. The fluorine substituent played a more important role in the NOR photodegradation in the ice, resulting in a 1.6-fold increase in the photodegradation rate constant of NOR relative to PPA. This work provides a new insight into the role of fluorine substituents in the photodegradation of fluorinated pharmaceuticals in cold regions.

Protonation-Induced Enhanced Optical-Light Photochromic Properties of an Inorganic-Organic Phosphomolybdic Acid/Polyaniline Hybrid Thin Film.

A phosphomolybdic acid/polyaniline (PMoA/PANI) optical-light photochromic inorganic/organic hybrid thin film was successfully synthesized by protonation between the the multiprotonic acid phosphomolybdic acid (H3PO4·12MoO3) and the conductive polymer polyaniline. The stable Keggin-type structure of PMoA was maintained throughout the process. Protonation and proton transfer successfully transformed the quinone structure of eigenstate PANI into the benzene structure of single-polarized PANI in the PMoA/PANI hybridized thin film, and proton transfer transformed the benzene structure of single-polarized PANI back to the quinone structure of eigenstate PANI in the PMoA/PANI hybrid thin film, as verified by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The average distribution of PMoA/PANI was observed by atom force microscopy (AFM). Interestingly, protonation of PMoA caused PANI to trigger transformation of the quinone structure into the single-polarized benzene structure, which enhanced the electron delocalization ability and vastly enhanced the maximum light absorption of the PMoA/PANI hybrid thin film as confirmed by density functional theory (DFT), electrochemistry, and ultraviolet-visible spectroscopy (UV-Vis) studies. Under optical-light illumination, the pale-yellow PMoA/PANI hybrid thin film gradually turned deep blue, thus demonstrating a photochromic response, and reversible photochromism was also observed in the presence of hydrogen peroxide (H2O2) or oxygen (O2). After 40 min of optical-light illumination, 36% of the Mo5+ species in PMoA was photoreduced via a protonation-induced proton transfer mechanism, and this proton transfer resulted in a structural change of PANI, as observed by XPS, generating a dominant structure with high maximum light absorption of 3.46, when compared with the literature reports.