Erbium(III) complexes with fluoroquinolones: Structure and biological properties.

Four erbium(III) complexes with the fluoroquinolones enrofloxacin, levofloxacin, flumequine and sparfloxacin as ligands were synthesized and characterized by a wide range of physicochemical and spectroscopic techniques as well as single-crystal X-ray crystallography. The compounds were evaluated for their activity against the bacterial strains Staphylococcus aureus, Bacillus subtilis, Escherichia coli and Xanthomonas campestris, which was higher than that of the corresponding free quinolones. The interaction mode of the complexes with calf-thymus DNA is via intercalation, as suggested by diverse studies such as UV-vis spectroscopy, DNA-viscosity measurements and competitive studies with ethidium bromide. Fluorescence emission spectroscopy revealed the high affinity of the complexes for bovine and human serum albumin and the determined binding constants suggested a tight and reversible binding of the compounds with both albumins.

The intracellular concentrations of fluoroquinolones determined the antibiotic resistance response of Escherichia coli.

The extensive consumption of antibiotics has been reported to significantly promote the generation of antibiotic resistance (ABR), however, a quantitative causal relationship between antibiotic exposure and ABR response is absent. This study aimed to pinpoint the accurate regulatory concentration of fluoroquinolones (FQs) and to understand the biochemical mechanism of the mutual action between FQ exposure and FQ resistance response. Highly sensitive analytical methods were developed by using UPLC-MS/MS to determine the total residual, extracellular residual, total intracellular, intracellular residual and intracellular degraded concentration of three representative FQs, including ciprofloxacin (CIP), ofloxacin (OFL) and norfloxacin (NOR), with detection limits in the range of 0.002-0.057 µg/L, and recoveries in the range of 80-93%. The MICs of Escherichia coli (E. coli) were 7.0-31.4-fold of the respective MIC0 after 40-day FQ exposure, and significant negative associations were discovered between the intracellular (residual, degraded or the sum) FQ concentrations and FQ resistance. Transcriptional expression and whole-genome sequencing results indicated that reduced membrane permeability and enhanced multi-drug efflux pumps contributed to the decreasing intracellular concentration. These results unveiled the pivotal role of intracellular concentration in triggering FQ resistance, providing important information to understand the dose-response relationship between FQ exposure and FQ resistance response, and ascertain the target dose metric of FQs for eliminating FQ resistance crisis.

Integrating target-responsive microfluidic-based biosensing chip with smartphone for simultaneous quantification of multiple fluoroquinolones.

The presence of fluoroquinolone (FQs) antibiotic residues in the food and environment has become a significant concern for human health and ecosystems. In this study, the background-free properties of upconversion nanoparticles (UCNPs), the high specificity of the target aptamer (Apt), and the high quenching properties of graphene oxide (GO) were integrated into a microfluidic-based fluorescence biosensing chip (MFBC). Interestingly, the microfluidic channels of the MFBC were prepared by laser-printing technology without the need for complex preparation processes and additional specialized equipment. The target-responsive fluorescence biosensing probes loaded on the MFBC were prepared by self-assembly of the UCNPs-Apt complex with GO based on π-π stacking interactions, which can be used for the detection of the two FQs on a large scale without the need for multi-step manipulations and reactions, resulting in excellent multiplexed, automated and simultaneous sensing capabilities with detection limits as low as 1.84 ng/mL (enrofloxacin) and 2.22 ng/mL (ciprofloxacin). In addition, the MFBC was integrated with a smartphone into a portable device to enable the analysis of a wide range of FQs in the field. This research provides a simple-to-prepare biosensing chip with great potential for field applications and large-scale screening of FQs residues in the food and environment.

Photoisomerization and Light-Controlled Antibacterial Activity of Fluoroquinolone-Azoisoxazole Hybrids.

Photopharmacology holds a huge untapped potential to locally treat diseases involving photoswitchable drugs via the elimination of drugs' off-target effects. The growth of this field has created a pressing demand to develop such light-active drugs. We explored the potential for creating photoswitchable antibiotic hybrids by attaching pharmacophores norfloxacin/ciprofloxacin and azoisoxazole (photoswitch). All compounds exhibited a moderate to a high degree of bidirectional photoisomerization, long thermal cis half-lives, and impressive photoresistance. Gram-negative pathogens were found to be insensitive to these hybrids, while against Gram-positive pathogens, all hybrids in their trans states exhibited antibacterial activity that is comparable to that of the parent drugs. Notably, the toxicity of the irradiated hybrid 6 was found to be 2-fold lower than the nonirradiated trans isomer, indicating that the pre-inactivated cis-enriched drug can be employed for the site-specific treatment of bacterial infection using light, which could potentially eliminate the unwanted exposure of toxic antibiotics to both beneficial and untargeted harmful microbes in our body. Molecular docking revealed different binding affinity of the cis and trans isomers with the topoisomerase IV enzyme, due to their different shapes.

Comparing the photodegradation of typical antibiotics in ice and in water: Degradation kinetics, mechanisms, and effects of dissolved substances.

New antibiotic contaminants have been detected in both surface waters and natural ice across cold regions. However, few studies have revealed distinctions between their ice and aqueous photochemistry. In this study, the photodegradation and effects of the main dissolved substances on the photolytic kinetics were investigated for sulfonamides (SAs) and fluoroquinolones (FQs) in ice/water under simulated sunlight. The results showed that the photolysis of sulfamethizole (SMT), sulfachloropyridazine (SCP), enrofloxacin (ENR) and difloxacin (DIF) in ice/water followed the pseudo-first-order kinetics with their quantum yields ranging from 4.93 × 10-3 to 11.15 × 10-2. The individual antibiotics experienced disparate photodegradation rates in ice and in water. This divergence was attributed to the concentration-enhancing effect and the solvent cage effect that occurred in the freezing process. Moreover, the main constituents (Cl-, HASS, NO3- and Fe(III)) exhibited varying degrees of promotion or inhibition on the photodegradation of SAs and FQs in the two phases (p < 0.05), and these effects were dependent on the individual antibiotics and the matrix. Extrapolation of the laboratory data to the field conditions provided a reasonable estimate of environmental photolytic half-lives (t1/2,E) during midsummer and midwinter in cold regions. The estimated t1/2,E values ranged from 0.02 h for ENR to 14 h for SCP, which depended on the reaction phases, latitudes and seasons. These results revealed the similarities and differences between the ice and aqueous photochemistry of antibiotics, which is important for the accurate assessment of the fate and risk of these new pollutants in cold environments.

Genome sequencing of Porostereum spadiceum to study the degradation of levofloxacin.

Despite various plans to rationalize antibiotic use, antibiotic resistance in environmental bacteria is increasing due to the accumulation of antibiotic residues in the environment. This study aimed to test the ability of basidiomycete fungal strains to biotransform the antibiotic levofloxacin, a widely-used third-generation broad-spectrum fluoroquinolone, and to propose enzyme targets potentially involved in this biotransformation. The biotransformation process was performed using fungal strains. Levofloxacin biotransformation reached 100% after 9 days of culture with Porostereum spadiceum BS34. Using genomics and proteomics analyses coupled with activity tests, we showed that P. spadiceum produces several heme-peroxidases together with H2O2-producing enzymes that could be involved in the antibiotic biotransformation process. Using UV and high-resolution mass spectrometry, we were able to detect five levofloxacin degradation products. Their putative identity based on their MS2 fragmentation patterns led to the conclusion that the piperazine moiety was the main target of oxidative modification of levofloxacin by P. spadiceum, leading to a decrease in antibiotic activity.

Schematic-portfolio of potent anti-microbial scaffolds targeting DNA gyrase: Unlocking ways to overcome resistance.

Drug development process demands validation of specific drug target impeding the Multi Drug Resistance (MDR). DNA gyrase, as a bacterial target has been in trend for developing newer antibacterial candidates due to its absence in higher eukaryotes. The fluoroquinolones are the leading molecules in the drug discovery pipeline for gyrase inhibition due to its diversity. The fluoroquinolones like levofloxacin and moxifloxacin have been listed in class A drugs for treating MDR. Gatifloxacin and ciprofloxacin also proved its efficacy against MDR TB and MDR enteric fever in adults, whereas nemonoxacin can induce anti-MDR activity of other antibiotics already suggested by studies. Though fluoroquinolones already proved its effectiveness against gyrase, other molecules viz., benzothiazinone, phenyl pyrrolamide, substituted oxadiazoles, triazolopyrimidine, arylbenzothiazole, coumarinyl amino alcohols and ciprofloxacin uracil, can inhibit the target more precisely. The structure-activity-relationships of the different scaffolds along with their synthetic strategies have been deciphered in the current review. Also, the naturally occurring compounds along with their extraction procedure have also been highlighted as potent DNA gyrase inhibitors. In addition to fluoroquinolone, the natural compounds novobiocin and simocyclinone could also inhibit the gyrase, impressively which has been designed with the gyrase structure for better understanding. Herein, ongoing clinical development of some novel drugs possessing triazaacenaphthylenes, spiropyrimidinetriones, and oxazolidinone-quinolone hybrids have been highlighted which could further assist the future generation antibiotic development corroborating gyrase as a potential target against MDR pathogens.

Predictive binary mixture toxicity modeling of fluoroquinolones (FQs) and the projection of toxicity of hypothetical binary FQ mixtures: a combination of 2D-QSAR and machine-learning approaches.

All sorts of chemicals get degraded under various environmental stresses, and the degradates coexist with the parent compounds as mixtures in the environment. Antibiotics emerge as an additional concern due to the bioactive nature of both the parent compound and degradation products and their combined exposure to the environment. Therefore, environmental risk assessment of antibiotics and their degradation products is very much necessary. In this direction, we made use of in silico new approach methodologies (NAMs) and machine-learning algorithms. In this study, we have developed a robust and predictive mixture-quantitative structure-activity relationship (QSAR) model with promising quality and predictability (internal: MAETrain = 0.085, QLOO2 = 0.849, external: MAETest = 0.090, and QF12 = 0.859) for predicting the toxicity of the mixtures of a class of antibiotics and their degradation products. To obtain the predictive model, toxicity data of 78 binary fluoroquinolone mixtures in E. coli (endpoint: log 1/IC50 in molar) have been utilized. We have used only 0D-2D descriptors to efficiently encode the structural features of mixture components without any additional complexities. The optimization of the class of mixture descriptors has been performed in this study by using three different mixing rules (linear combination of molecular contributions, the squared molecular contributions, and the norm of molecular contributions). Different machine-learning approaches namely, random forest (RF), ada boost, gradient boost (GB), extreme gradient boost (XGB), support vector machine (SVM), linear support vector machine (LSVM), and ridge regression (RR) have been employed here apart from the conventional partial least squares (PLS) regression to optimize the modeling approach. A rigorous validation protocol has been used for assessing the goodness-of-fit, robustness, and external predictability of the models. Finally, the toxicity of possible untested mixtures of different photodegradation products of fluoroquinolones has been predicted using the best model reported in this study.

Environmental pollution of fluoroquinolones and its relationship with nitrogen cycling mediated by microorganisms.

Fluoroquinolone antibiotics (FQs) are one of the most widely used antibiotics, which are new pollutants with 'pseudo persistence' in the environment, causing great ecological risks. FQs could change the structure and function of microbial communities and affect nitrogen cycling mediated by microorganisms. Consequently, FQs would change the composition of various types of nitrogen in the environment and exert a significant impact on the global nitrogen cycling. We encapsulated the distribution of FQs in the environment and its impacts on nitrogen cycling mediated by microorganisms, explained the role of FQs in each key process of nitrogen cycling, aiming to provide an important reference for revealing the ecological effects of FQs. Generally, FQs could be detected in various environmental media, with significant differences in the concentration and types of FQs in different environments. Ofloxacin, norfloxacin, ciprofloxacin, and enrofloxacin are the four types of FQs with the highest detection frequency and concentration. The effect of FQs on nitrogen cycling deeply depends on typical characteristics of concentration and species. FQs mainly inhibit nitrification by reducing the abundance of amoA gene related to ammoxidation process and the abundance and composition of ammoxidation bacteria. FQs inhibits nitrification by reducing the abundance and composition of microbial communities. The denitrification process is mainly inhibited due to the reduction of the activity of related enzymes and the abundance of genes such as narG, nirS, norB, and nosZ genes, as well as the abundance and composition of denitrifying functional microorganisms. The process of anammox is restricted due to the reduction of the abundance, composition and hzo gene abundance of anaerobic anammox bacteria. FQs lead to the reduction of active nitrogen removal and the increase of N2O release in the environment, with further environmental problems such as water eutrophication and greenhouse effect. In the future, we should pay attention to the effects of low concentration FQs and complex antibiotics on the nitrogen cycling, and focus on the effects of FQs on the changes of nitrogen cycle-related microbial monomers and communities.

Refashioning of the drug-properties of fluoroquinolone through the synthesis of a levofloxacin-imidazole cobalt (II) complex and its interaction studies on with DNA and BSA biopolymers, antimicrobial and cytotoxic studies on breast cancer cell lines.

Levofloxacin (HLVX), a quinolone antimicrobial agent, when deprotonated (LVX-) behaves as a bidentate ligand, and it coordinates to Co2+ through the pyridone oxygen and the carboxylate oxygen. Along with two imidazole (ImH) ligands, levofloxacin forms a Co(II)-Levofloxacin-imidazole complex, [CoCl(LVX)(ImH)2(H2O)]·3H2O (abbreviated henceforth as CoLevim) which was isolated and characterized by 1H and 13C NMR spectroscopy, UV-visible and FT-IR spectroscopy, powder X-ray diffraction and thermal analysis methods. CoLevim shows promise in its antimicrobial activities when tested against microorganisms (Bacillus cereus, Bacillus subtilis, Listeria monocytogenes, Staphylococcus aureus, Salmonella typhimurium and Escherichia coli). Fluorescence competitive studies with ethidium bromide (EB) revealed that CoLevim can compete with EB and displace it to bind to CT-DNA through intercalative binding mode. In addition, CoLevim exhibited a good binding propensity to BSA proteins with relatively high binding constants. The antioxidant activities of the free ligands and CoLevim were determined in vitro using ABTS+ radical (TEAC assay). The Co-complex showed a better antioxidant capacity with inhibitory concentrations (IC50) of 40 µM than the free ligands. CoLevim also showed noteworthy apoptotic potential and behaved as an efficient resistant modifying agent when its antiproliferative potential was examined by MTT assay using the breast cancer cell lines (MCF7, MCF7Dox/R and MCF7Pacli/R cells).

Novel Fluoroquinolones with Possible Antibacterial Activity in Gram-Negative Resistant Pathogens: In Silico Drug Discovery.

Antibiotic resistance is a global threat to public health, and the search for new antibacterial therapies is a current research priority. The aim of this in silico study was to test nine new fluoroquinolones previously designed with potential leishmanicidal activity against Campylobacter jejuni, Escherichia coli, Neisseria gonorrhoeae, Pseudomonas aeruginosa, and Salmonella typhi, all of which are considered by the World Health Organization to resistant pathogens of global concern, through molecular docking and molecular dynamics (MD) simulations using wild-type (WT) and mutant-type (MT) DNA gyrases as biological targets. Our results showed that compound 9FQ had the best binding energy with the active site of E. coli in both molecular docking and molecular dynamics simulations. Compound 9FQ interacted with residues of quinolone resistance-determining region (QRDR) in GyrA and GyrB chains, which are important to enzyme activity and through which it could block DNA replication. In addition to compound 9FQ, compound 1FQ also showed a good affinity for DNA gyrase. Thus, these newly designed molecules could have antibacterial activity against Gram-negative microorganisms. These findings represent a promising starting point for further investigation through in vitro assays, which can validate the hypothesis and potentially facilitate the development of novel antibiotic drugs.

Adsorption Behavior of a Ternary Covalent Organic Polymer Anchored with SO3H for Ciprofloxacin.

Owing to the poor treatment efficiency of wastewater containing fluoroquinolones (FQs), effective removal of such pollutants has become a significant issue in waste management. In this study, a ternary covalent organic polymer anchored with SO3H (COP-SO3H) was designed using the Schiff reaction and a multicomponent solvent thermal method. The synthesized COP-SO3H polymer possesses multiple functional binding sites, including amide groups, sulfonic groups, and aromatic frameworks, enabling it to effectively adsorb ciprofloxacin (which belongs to FQs) through mechanisms such as pore-filling effects, electrostatic interactions, hydrogen bonding, π-π electron donor-acceptor (EDA) interactions, and hydrophilic-lipophilic balance. COP-SO3H demonstrated outstanding adsorption performance for ciprofloxacin, exhibiting a high adsorption capacity, broad pH stability, strong resistance to ionic interference, and good regenerability. Moreover, it displayed preferential selectivity toward fluoroquinolone antibiotics. The present study not only investigates the intricate structural and functional design of COP-SO3H materials but also presents potential applications for the efficient adsorption of specific antibiotics.

A magnetic porous carbon material derived from an MIL-101(Fe) complex for efficient magnetic solid phase extraction of fluoroquinolone antibiotics.

Extraction and determination of trace hazardous components from complex matrices continue to attract public attention. In this work, magnetic porous carbon (MPC) was prepared for efficient magnetic solid phase extraction (MSPE) of fluoroquinolone (FQ) antibiotics in food and water samples. To prepare the MPC, an Fe-based metal-organic framework (MIL-101(Fe)) was grown on a network of graphene oxide and multi-walled carbon nanotubes through a hydrothermal method, and then a carbonization process under a nitrogen atmosphere was carried out to obtain the MPC with high specific surface area and good magnetism. Four target FQs including ciprofloxacin (CIP), enrofloxacin (ENO), lomefloxacin (LOM) and ofloxacin (OFX) were enriched using the as-prepared MPC and determined by coupled high-performance liquid chromatography. Under the optimal conditions, the established MSPE-HPLC-UV detection method exhibited a linear range of 0.5-800 µg L-1 and detection limits of 0.11-0.18 µg L-1 with relative standard deviations (RSDs) of 0.5-4.8%. When applied in the determination of the above four FQs in real samples such as lake water, milk and pork, good recoveries between 85.2 and 103.7% were obtained, and the RSDs were less than 4.8%. This work indicates that the MPC material can be a good adsorption material and has good application prospects in antibiotics enrichment and/or removal from complex samples.

Surface imprinted-covalent organic frameworks for efficient solid-phase extraction of fluoroquinolones in food samples.

Molecularly imprinting on covalent organic frameworks (MI-COF) is a promising way to prepare selective adsorbents for effective extraction of fluoroquinolones (FQs). However, the unstable framework structure and complex imprinting process are challenging for the construction of MI-COF. Here, we report a facile surface imprinting approach with dopamine to generate imprinted cavities on the surface of irreversible COF for highly efficient extraction of FQs in food samples. The irreversible-linked COF was fabricated from hexahydroxytriphenylene and tetrafluorophthalonitrile to ensure COF stability. Moreover, the introduction of dopamine surface imprinted polymer into COF provides abundant imprinted sites and endows excellent selectivity for FQs recognition against other antibiotics. Taking enrofloxacin as a template molecule, the prepared MI-COF gave an exceptional adsorption capacity of 581 mg g-1, a 2.2-fold enhancement of adsorption capacity compared with nonimprinted COF. The MI-COF was further explored as adsorbent to develop a novel solid-phase extraction method coupled with high-performance liquid chromatography for the simultaneous determination of enrofloxacin, norfloxacin and ciprofloxacin. The developed method gave the low limits of detection at 0.003-0.05 ng mL-1, high precision with relative standard deviations less than 3.5%. The recoveries of spiked FQs in food samples ranged from 80.4% to 110.7%.

Application of molecular imprinting technology based on new nanomaterials in adsorption and detection of fluoroquinolones.

Irrational use of fluoroquinolones (FQs) can lead to allergic reactions, adverse reactions to the heart and damage of the liver; thus, it is of great significance to establish rapid, sensitive and accurate detection methods for FQs. Molecularly imprinted polymers (MIPs) with specific structures synthesized by molecular imprinting technology (MIT) are widely used for the detection of FQs due to their high specificity, high sensitivity and stable performance. Recently, new functional nanomaterials with different morphologies and sizes, which can provide rich sites for surface chemical reactions, have attracted more and more attention of the researchers. Thus, the application status and development prospects of MIT based on new nanomaterials in the adsorption and detection of FQs were summarized in this study, providing a theoretical basis and technical guarantee for the development of new and efficient food safety analysis strategies based on MIPs.

Single and combined genotoxicity of metals and fluoroquinolones to zebrafish embryos at environmentally relevant concentrations.

Fluoroquinolones (FQs) are known to have genotoxicity to aquatic organisms. However, their genotoxicity mechanisms, individually and in combination with heavy metals, are poorly understood. Here, we investigated the single and joint genotoxicity of FQs, ciprofloxacin (CIP) and enrofloxacin (ENR), and metals (Cd and Cu) at environmentally relevant concentrations (0.2 µM) to zebrafish embryos. We found that FQs or/and metals induced genotoxicity (i.e., DNA damage and cell apoptosis) to zebrafish embryos. Compared with their single exposure, the combined exposure of FQs and metals elicited less ROS overproduction but higher genotoxicity, suggesting other toxicity mechanisms may also act in addition to oxidation stress. The upregulation of nucleic acid metabolites and the dysregulation of proteins confirmed the occurrence of DNA damage and apoptosis, and further revealed the inhibition of DNA repair by Cd and binding of DNA or DNA topoisomerase by FQs. This study deepens the knowledge on the responses of zebrafish embryos to exposure of multiple pollutants, and highlights the genotoxicity of FQs and heavy metals to aquatic organisms.

Antibacterial and antibiofilm activity of permanently ionized quaternary ammonium fluoroquinolones.

A series of quaternary ammonium fluoroquinolones was obtained by exhaustive methylation of the amine groups present at the 7-position of fluoroquinolones, including ciprofloxacin, enoxacin, gatifloxacin, lomefloxacin, and norfloxacin. The synthesized molecules were tested for their antibacterial and antibiofilm activities against Gram-positive and Gram-negative human pathogens, i.e. Staphylococcus aureus and Pseudomonas aeruginosa. The study showed that the synthesized compounds are potent antibacterial agents (MIC values at the lowest 6.25 µM) with low cytotoxicity in vitro as assessed on the BALB 3T3 mouse embryo cell line. Further experiments proved that the tested derivatives are able to bind to the DNA gyrase and topoisomerase IV active sites in a fluoroquinolone-characteristic manner. The most active quaternary ammonium fluoroquinolones, in contrast to ciprofloxacin, reduce the total biomass of P. aeruginosa ATCC 15442 biofilm in post-exposure experiments. The latter effect may be due to the dual mechanism of action of the quaternary fluoroquinolones, which also involves disruption of bacterial cell membranes. IAM-HPLC chromatographic experiments with immobilized artificial membranes (phospholipids) showed that the most active compounds were those with moderate lipophilicity and containing a cyclopropyl group at the N1 nitrogen atom in the fluoroquinolone core.

New Fluoroquinolone-1,2,4-triazoles as Potent Antibacterial Agents: Design, Synthesis, Docking Studies and in Silico ADME Profiles.

Our current work is aimed at synthesizing novel substituted 1,2,4-triazolyl-fluoroquinolone analogs and study of their biological activity to find active promising molecules. The structural elucidation of the products was demonstrated by a variety of spectroscopic methods such as IR, 1 H-NMR, 13 C-NMR, mass and elemental analysis. The newly synthesized 1,2,4-triazole derivatives were tested in vitro for their ability to inhibit the growth of seven different microbes including S. epidermidis, S. pneumoniae, S. aureus, B. subtilis, K. pneumoniae, E. coli, and P. aeruginosa. Five FQ derivatives 5d, 5e, 5h, 5j, and 5b have demonstrated good antibacterial activity against S. pneumoniae with MICs ranging from 2.5-22.0 µg/mL, while 5c, 5g reported comparable activity against P. aeruginosa with respect to the standard drugs moxifloxacin and ciprofloxacin. The possible mechanism of antibacterial activity of fluoroquinolones was investigated via molecular docking by using DNA gyrase of S. pneumoniae (3RAE). The pefloxacin derivatives also tended a good antibacterial ability based on the results of the molecular docking, ligand 5h with good binding affinity (-9.92 Kcal/mol) and binding site interactions via ValA:86, SerA:79, TyrA:82, MetA:116, AspA:78, AlaA:63, ArgA:117, ProA:112, ProA:113, AlaA:115, AlaA:114. These scaffolds were further evaluated for their ADMET and physicochemical properties by using SwissADME, ADMETlab2.0 web server as a good oral bioavailability.

Photo-transformation of acetaminophen sensitized by fluoroquinolones in the presence of bromide.

Fluoroquinolones (FQs) are a class of antibiotics with emerging concern. This study investigated the photochemical properties of two representative FQs, i.e., norfloxacin (NORF) and ofloxacin (OFLO). Results showed that both FQs could sensitize the photo-transformation of acetaminophen under UV-A irradiation, during which excited triplet state (3FQ*) was the main active species. In the presence of 3 mM Br‾, the photolysis rate of acetaminophen increased by 56.3% and 113.5% in the solutions with 10 µM NORF and OFLO, respectively. Such an effect was ascribed to the generation of reactive bromine species (RBS), which was verified by 3,5-dimethyl-1H-pyrazole (DMPZ) probing approach. 3FQ* reacts with acetaminophen through one-electron transfer, producing radical intermediates which then couple to each other. Presence of Br‾ did not lead to the formation of brominated products but the same coupling products, which suggests that radical bromine species, rather than free bromine, were responsible for the accelerated acetaminophen transformation. According to the identified reaction products and assisted with the theoretical computation, the transformation pathways of acetaminophen under UV-A irradiation were proposed. The results reported herein suggest that sunlight-driven reactions of FQs and Br‾ may influence the transformation of coexisting pollutants in surface water environments.

Use of Fluorescence Spectroscopy and Chemometrics to Visualise Fluoroquinolones Photodegradation Major Trends: A Confirmation Study with Mass Spectrometry.

In this work, we employed EEM-PARAFAC (fluorescence excitation-emission matrices-parallel factor analysis) as a low-cost tool to study the oxidation pathways of (fluoro)quinolones. Amounts of 12.5 µM of enrofloxacin (ENR), ciprofloxacin (CIP), ofloxacin (OFL), oxolinic acid (OA), and flumequine (FLU), as individual solutions, were irradiated under UVA light. A 5-component PARAFAC model was obtained, four of them related to the parent pollutants, named as ENR-like (including CIP), OFL-like, OA-like, and FLU-like, and an additional one related to photoproducts, called ENRox-like (with an emission red-shift with respect to the ENR-like component). Mass spectrometry was employed to correlate the five PARAFAC components with their plausible molecular structures. Results indicated that photoproducts presenting: (i) hydroxylation or alkyl cleavages exhibited fingerprints analogous to those of the parent pollutants; (ii) defluorination and hydroxylation emitted within the ENRox-like region; (iii) the aforementioned changes plus piperazine ring cleavage emitted within the OA-like region. Afterwards, the five antibiotics were mixed in a single solution (each at a concentration of 0.25 µM) in seawater, PARAFAC being also able to deconvolute the fingerprint of humic-like substances. This approach could be a potential game changer in the analysis of (fluorescent) contaminants of emerging concern removals in complex matrices, giving rapid visual insights into the degradation pathways.