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Fluoroquinolone antibiotics (FQs), one of the most widely used antibacterials, have been recognized as emerging contaminants with adverse human health concerns. To overcome the adverse effects, a theoretical molecular design and screening approach was developed in this study to improve the removal efficiency of FQs by Chlorella in artificial or natural wetland systems. Among the 189 designed norfloxacin (NOR) derivatives, NOR-140 was screened with significantly improved biosorption, bioaccumulation, and biodegradation removal and functional effects, and reduced human health and ecological risks. The removal mechanism NOR-140 was also analyzed using adsorption kinetics, molecular docking, molecular dynamics simulations and machine learning models. Protein and polysaccharide structures play a major role in the adsorption process, polarizability and molecular volume of NOR-140 affect the bioaccumulation ability, and hydrogen bonding was found as the key force promoting the degradation ability of NOR-140. Modifying specific sites (5, 8, and 13) with functional groups containing highly electronegative atoms (O, F) significantly enhances the biodegradability of FQs alternatives by Chlorella. This study provided theoretical support for designing environmentally friendly FQs alternatives with improved degradation ability and advanced the understanding of how the FQs' molecular structures affect its removal by Chlorella., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Long-term consumption of foods with excessive enrofloxacin (ENRO) residues may cause the accumulation of ENRO in the human body, thus damaging human health. In this study, quantum dot-based biomimetic fluorescence immunoassays were used for enrofloxacin detection in food of animal origin. Under the most suitable conditions, the detection limit (IC 15 ) of the method in standard solution was 0.13 ± 0.02 ng L -1 and the sensitivity (IC 50 ) was 0.13 ± 0.18 μg L -1 . The recoveries for ENRO from four fortified food samples, including chicken, eggs, shrimp, and milk, ranged from 85.74% to 114.19% and the coefficients of variation were 0.01-18.09%. The established method shows good agreement with the results obtained using commercial ELISA kits, with a correlation coefficient of 0.997. The proposed method shows the advantages of high sensitivity, specificity and wide detection range. It can be used as an alternative method for the rapid and sensitive detection of ENRO in food of animal origin.

Fluoroquinolones (FQs) are widely prescribed antibiotics that are commonly detected in aquatic environments, but the persistence, fates, and ecotoxicities of new generation FQs have yet to be fully investigated. We investigated the direct and indirect (hydroxyl radical (·OH), singlet oxygen (O21), and excited stated of organic matter ( 3 CDOM * )) photodegradation of three 3rd generation FQs, moxifloxacin (MOX), gatifloxacin (GAT), and sparfloxacin (SPAR). The photodegradation rates and photolytic quantum yields (Φ FQ ) of the FQs depended on their dissociation species at different pH in a range of 1×10 -4 to 1×10 -3 M mol-photon -1 . Unlike MOX and GAT whose zwitterions had the highest Φ FQ , the anionic form of SPAR had the highest Φ FQ . The k ·OH,FQ values were in the order of: k ·OH,SPAR > k ·OH,GAT ≈ k ·OH,MOX with the 10 10 M -1 s -1 order of magnitude. The k O21,FQ values were in the order of: k O21,SPAR (∼10 8 M -1 s -1 ) > k O21,MOX (∼10 7 M -1 s -1 ) > >> k O21,GAT (insignificant). Higher k LC*3,FQ values were observed for MOX (10 9 to 10 10 M -1 s -1 ) compared to GAT and SPAR (10 8 to 10 9 M -1 s -1 ). The zwitterions had the highest reactivities with ·OH and the lowest reactivities with O21 and 3 CDOM * . Reactions with ·OH enhanced the formation of transformation products (TPs) from decarboxylation and sidechain oxidation pathways, whereas reactions with O21 and 3 CDOM * enhanced the formation of TPs from sidechain oxidation pathways. Some of the TPs were predicted to exhibit aquatic ecotoxicity and environmental persistence. The half-lives of the FQs were estimated to be 0.42 to 0.67 h for MOX and SPAR, and 4.6 to 4.9 h for GAT. Their half-lives and main photochemical fates depended on the surface water pH and water column depth. These results highlight the key roles that photodegradation plays in removing new generation FQs from aquatic environments, though this might lead to the formation of TPs that are harmful to aquatic ecosystems., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests. Theodora Nah reports financial support was provided by City University of Hong Kong State Key Laboratory of Marine Pollution. Theodora Nah reports financial support was provided by Guangdong Basic and Applied Basic Research Fund Committee. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Type II topoisomerase DNA gyrase transduces the energy of ATP hydrolysis into the negative supercoiling of DNA. The postulated catalytic mechanism involves stabilization of a chiral DNA loop followed by the passage of the T-segment through the temporarily cleaved G-segment resulting in sign inversion. The molecular basis for this is poorly understood as the chiral loop has never been directly observed. We have obtained high-resolution cryoEM structures of Escherichia coli gyrase with chirally wrapped 217 bp DNA with and without the fluoroquinolone moxifloxacin (MFX). Each structure constrains a positively supercoiled figure-of-eight DNA loop stabilized by a GyrA β-pinwheel domain which has the structure of a flat disc. By comparing the catalytic site of the native drug-free and MFX-bound gyrase structures both of which contain a single metal ion, we demonstrate that the enzyme is observed in a native precatalytic state. Our data imply that T-segment trapping is not dependent on the dimerization of the ATPase domains which appears to only be possible after strand passage has taken place., Competing Interests: Competing interests statement:The authors declare no competing interest.

Antimicrobial resistance poses a global health concern and develops a need to discover novel antimicrobial agents or targets to tackle this problem. Fluoroquinolone (FN), a DNA gyrase and topoisomerase IV inhibitor, has helped to conquer antimicrobial resistance as it provides flexibility to researchers to rationally modify its structure to increase potency and efficacy. This review provides insights into the rational modification of FNs, the causes of resistance to FNs, and the mechanism of action of FNs. Herein, we have explored the latest advancements in antimicrobial activities of FN analogues and the effect of various substitutions with a focus on utilizing the FN nucleus to search for novel potential antimicrobial candidates. Moreover, this review also provides a comparative analysis of two widely prescribed FNs that are ciprofloxacin and norfloxacin, explaining their rationale for their design, structure-activity relationships (SAR), causes of resistance, and mechanistic studies. These insights will prove advantageous for new researchers by aiding them in designing novel and effective FN-based compounds to combat antimicrobial resistance., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Preet Mohinder Singh Bedi reports financial support was provided by Department of Biotechnology. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

This study utilized computational simulation and surface molecular imprinting technology to develop a magnetic metal-organic framework molecularly imprinted polymer (Fe 3 O 4 @ZIF-8@SMIP) capable of selectively recognizing and detecting multiple fluoroquinolones (FQs). The Fe 3 O 4 @ZIF-8@SMIP material was synthesized using the "common" template-ofloxacin, identified by computational simulation, demonstrating notable adsorption capacity (88.61-212.93 mg g -1 ) and rapid mass-transfer features (equilibration time: 2-3 min) for all tested FQs, consistent with Langmuir adsorption model. Subsequently, this material was employed as a magnetic solid-phase-extraction adsorbent for adsorption and detection of multiple FQs by combining with high performance liquid chromatography. The developed method exhibited good linearity for various FQs within the concentration range of 0.1-500 μg L -1 , with low limit of detection (0.0605-0.1529 μg L -1 ) and limit of quantitation (0.2017-0.5097 μg L -1 ). Satisfactory recoveries (88.38-103.44%) were obtained when applied to spiked food samples, demonstrating the substantial potential of this Fe 3 O 4 @ZIF-8@SMIP material for rapid enrichment and identification for multiple FQs residues., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Fluorescent nanoprobes are widely applied in innovate enzyme-linked immunosorbent assays (ELISA) for detection of fluoroquinolones (FQs) residue in foodstuffs. Nevertheless, the complicated synthesis of nanoprobes hampers their practical applications. Herein, a nanomaterial-independent and fluorescent ELISA for sensitive detection of FQs is developed using the Eu-micelles as signal probe. Non-nanostructured Eu-micelles with high quantum yield and stability are facilely synthesized through the assembly of Eu 3+ and ligands. Alkaline phosphatase catalyzes hydrolysis of 4-nitrophenyl phosphate to 4-nitrophenol. The fluorescent Eu-micelles can be readily quenched by 4-nitrophenol via static quenching. The signal generation mechanism integrates well with conventional ELISA systems. The established fluorescent ELISA achieves sensitive detection of FQs with a limit of detection of 0.03 μg/kg. The validation results from LC-MS show that the fluorescent ELISA exhibits good accuracy and recoveries. Our study presents a nanomaterial-independent strategy for developing the rapid immunoassay for FQs, which holds good promise for practical applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

The study focuses on reactive orange 16 (RO16), a sulfonated dye, and ciprofloxacin (CiP), a fluoroquinolone antibiotic treatment from aquatic surface by adsorption. The functionalized Persea americana seed powder (PASP) was developed by acid hydrolysis technique and investigated for RO16 and CiP removal in batch scale at different concentrations for CiP and RO16, pH (2-8), contact duration and temperature (303-318K). Utilizing a scanning electron microscope (SEM) with energy dispersive X-ray spectroscopy (EDAX), the generated native PASP were assessed for their morphological characteristics. Fourier transform infrared (FTIR) spectroscopy was applied to examine the performing characteristics of PASP. Experimental findings with four kinetic mathematical models allowed the estimation of the process involved in the biosorption. The most effective agreement was explained by the pseudo-second-order model and Sips isotherm (Cip = 34.603 mg/g and RO16 = 30.357 mg/g) at 303K temperature. For Cip Process economics of the biosorbent was done, and it was observed that it was less than the readily market-available activated carbon., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

In this paper, the effect of zero-valent iron (Fe 0 ) activated persulfate (PDS) on the removal of enrofloxacin (ENR) was investigated, and the effect and mechanism were analyzed by exploring the effects of Fe 0 concentration, PDS concentration, pH, and the influence of anion and aqueous matrix on the removal of ENR by the Fe 0 /PDS system. The results showed that when [ENR] = 20 µmol/L, [Fe 0 ] = 0.15 g/L, [PDS] = 0.4 mmol/L, the removal rate of ENR was 85.3% at 90 min, the mainradicals were HO • , SO 4 •- and O 2 •- . At the same time, the system had a good mineralization effect (TOC removal rate > 40%), in addition, the system did not show obvious toxicity to soil microorganisms after the reaction, furthermore the Fe 0 /PDS system had a good removal effect on ENR in a wide pH range (4 ≤ pH ≤ 10). There is basically no difference in the removal rate of Fe 0 /PDS system in ultrapure water and river water. The results of this experiment could provide a reference for the removal of antibiotics based on advanced oxidation techniques based on SO 4 •- ., (© 2024. The Author(s).)

Surface-imprinted polymers (ZIF-67@MIPs) supported by ZIF-67 were prepared by precipitation polymerization using enrofloxacin (ENR) as the template molecule, methacrylic acid as the functional monomer, and ethylene glycol dimethacrylate as the cross-linker. ZIF-67@MIPs were characterized by Fourier transform infrared spectrometry, X-ray diffraction, scanning electron microscopy, and particle size distribution. The adsorption performance of the polymer was studied. The adsorption equilibrium was reached within 30 min. The maximum adsorption was 9.02 μg·mg -1 . The imprinting factor was 2.58. The polymer was then used as a sorbent of a solid-phase extraction column for the separation and purification of ENR in real water samples. The extraction conditions were optimized. The method was established by high-performance liquid chromatography, and the linearity was verified by UPLC-MSMS. The correlation coefficient and limits of detection and quantification were 0.9999, 0.23 ng·mL -1 , and 0.76 ng·mL -1 , respectively. The recoveries were in the range of 83.79-100.68%; the relative standard deviation was 4.46-7.35%. The above data indicated that the method could be used for the separation and enrichment of ENR in real samples.

Mechanism of direct UV photolysis of the zwitterionic and anionic forms of the quinolone antibiotic ciprofloxacin (CIP) was revealed by combination of nanosecond laser flash photolysis, steady-state photolysis coupled with high resolution LC-MS and DFT quantum-chemical calculations. For both forms, the main intermediate is a dissociative triplet state, which loses a fluorine ion to form a triplet carbocation; subsequent solvent attack of the latter leads to the formation of products of hydroxylation both the aromatic ring and the piperazyl substituent. Correspondingly, the quantum yield of photolysis of both CIP forms does not depend on the excitation wavelength, but depends on the concentration of dissolved oxygen. Secondary photolysis leads to a number of products of oxidation of the aromatic system, as well as oxidation, opening and full destruction of the piperazinyl substituent. The results obtained may be important for understanding the fate of quinolone antibiotics in UVC disinfection processes and in natural waters under the action of sunlight., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The application of a synthesized carbon xerogel (RFX) for the adsorptive removal from water of ciprofloxacin (CPX), a widely used fluoroquinolones-group antibiotic for humans and animals, has been reported in this work. The carbon xerogel was characterized by N 2 adsorption-desorption isotherms, FTIR, Raman spectroscopy, TPD studies, elemental analysis, determination of isoelectric point (pH IEP ) and scanning electron microscopy (SEM). CPX adsorption experiments were conducted in batch mode, using results obtained with F400 commercial activated carbon for comparison purposes. CPX adsorption kinetics were well-described by the pseudo-second-order model for both adsorbents and by the Elovich model in the case of F400 activated carbon. Therefore, CPX equilibrium adsorption capacity values were of 457 and 72 mg g -1 for RFX xerogel and F400 activated carbon, respectively. This significant difference can be attributed to the higher specific surface area and micropores volume values of F400 carbon; in this sense, this material led to a slower CPX kinetic adsorption. Also, the Dual-site Langmuir model best-described the experimental CPX adsorption isotherms in both cases. By the adsorption studies at different solution pH, it could be concluded that several mechanisms, e.g., hydrophobic and π-π interactions, and electrostatic forces highly influenced CPX adsorption capacity. Furthermore, adsorption tests using several environmentally relevant aqueous matrices have been accomplished. In this case, a competitive effect between the natural organic matter (NOM) and the target pollutant occurred in all the tested real matrices, decreasing CPX adsorption capacity, especially remarkable for F400 activated carbon. Finally, Density Functional Theory (DFT) has been used to elucidate the interactions between CPX and adsorbents, finding a high relevance of the π-π electron donor-acceptor interactions in which CPX acts as an acceptor., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The increasing presence of fluoroquinolone (FQ) antibiotics in aquatic environments is a growing concern due to their widespread use, negatively impacting aquatic organisms. This paper provides an overview of the environmental distribution, sources, fate, and both single and mixed toxicity of FQ antibiotics in aquatic environments. It also examines the accumulation of FQ antibiotics in aquatic organisms and their transfer into the human body through the food chain. The study identifies critical factors such as metabolism characteristics, physiochemical characteristics, light, temperature, dissolved oxygen, and environmental compatibility that influence the presence of FQ antibiotics in aquatic environments. Mixed pollutants of FQ antibiotics pose significant risks to the ecological environment. Additionally, the paper critically discusses advanced treatment technologies designed to remove FQ antibiotics from wastewater, focusing on advanced oxidation processes (AOPs) and electrochemical advanced oxidation processes (EAOPs). The discussion also includes the benefits and limitations of these technologies in degrading FQ antibiotics in wastewater treatment plants. The paper concludes by proposing new approaches for regulating and controlling FQ antibiotics to aid in the development of ecological protection measures.

Coriolopsis gallica ( Cga ) is a white-rot fungus renowned for its ability to secrete ligninolytic enzymes that are capable of oxidizing phenolic compounds. This study aimed to investigate the biochemical characteristics of a dye-decolorizing peroxidase named CgaDyP1 and test its ability to biotransform antibiotics. CgaDyP1 was cloned and heterologously expressed in Escherichia coli. We fully characterized the biochemical properties of CgaDyP1 and evaluated its dye-decolorizing potential to confirm that it belongs to the DyP class of enzymes. We also tested its fluoroquinolone antibiotic biotransformation potential for possible biotechnological applications. Alignment of the primary amino acid sequence with DyP homolog sequences showed that Cga DyP1 has high similarity with other fungal DyPs. The recombinant Cga DyP1 exhibited activity on substrates such as ABTS and 2,6-dimethoxyphenol (DMP) with optimal performance at a pH of 3, although activity at pH 2.5, pH 4, and pH5 diminished over time. Thermostability tests indicated that the enzyme remains stable at temperatures between 30 °C and 50 °C and retains 70% of its initial activity after 180 min at 50 °C. Tests on the effect of hydrogen peroxide on CgaDyP1 activity found peak activity at 0.25 mM H 2 O 2 . Cga DyP1 decolorized five industrial dyes, and kinetics data confirmed that it belongs to the DyP class of enzymes. Cga DyP1 was shown to biotransform some of the 7 recalcitrant fluoroquinolone antibiotics tested here, including levofloxacin, moxifloxacin, and norfloxacin, and thus holds potential for biotechnological applications.

Background: Carbon quantum dots (CQDs) have gained much interest recently for being efficient probes. Their cost-effectiveness, eco-friendliness, and unique photocatalytic activities made them distinctive alternatives to other luminescent approaches like fluorescent dyes and luminous derivatization. Meanwhile, delafloxacin (DLF) is a recently approved antibacterial medicine. DLF has been authorized for the treatment of soft-tissue and skin infections as well as pneumonia. Therefore, new eco-friendly, cost-effective, and sensitive tools are needed its estimation in different matrices., Results: In the proposed study, green copper and nitrogen carbon dots (Cu-N@CDs) were synthesized from a green source (plum juice with copper sulphate). Cu-N@CQDs were then characterized using multiple tools including X-ray photon spectroscopy (XPS), FTIR and UV-VIS spectroscopy, Zeta potential measurements, High-resolution transmission electron microscopy (HRTEM), and fluorescence spectroscopy. After gradually adding DLF, the developed quantum dots' fluorescence was significantly enhanced within the working range of 0.5-100.0 ng mL -1 . The limits of detection and quantification were 0.08 and 0.27 ng mL -1 , respectively. The accuracy of the proposed method ranged from 96.00 to 99.12 % in recovery%, when recovered from milk and plasma samples., Significance: Cu-N@CDs were utilized and validated for selectively determining DLF in several matrices including pharmaceutical forms, human plasma and in milk samples using spectrofluorimetric technique. The bio-analytical method is simple and could be used in content uniformity testing as well as in therapeutic drug monitoring in human plasma., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The use of supramolecular assemblies in pharmaceuticals has garnered significant interest. Recent studies have shown that the activities of antibacterial agents can be enhanced through complexation with cyclic oligomers and metal ions. Notably, these complexes sometimes possess greater therapeutic properties than the parent drugs. To develop microbiologically potent supramolecular drugs, the complexation of macrocyclic hosts with fluoroquinolone (FQ) antibiotics was investigated. FQs are a successful family of antibiotics that target the bacterial enzymes DNA gyrase and DNA topoisomerase IV, leading to bacterial cell death through the inhibition of DNA synthesis. However, antibiotic resistance resulting from the repeated use of FQs over time has limited their effectiveness against resistant pathogens. To overcome this issue, the encapsulation of FQs in polyphenolic macrocycles was investigated. This study highlights resorcinarene, a polyphenolic host with antibacterial properties, and its ability to chemically interact with FQs. The inclusion complexation process was analyzed using NMR and FTIR techniques. The binding constants determined by 1 H-NMR titration revealed that levofloxacin forms more stable complexes with resorcinarene than with β-cyclodextrin, which aligned with MD simulations. Assessment of the geometric characteristics of the inclusion complexes using 2D NMR analysis confirmed that different moieties of various FQs can fit into a single host cavity and improve activity against gram-negative bacteria. Overall, these findings suggest that encapsulation in polyphenolic macrocycles is a promising strategy for utilizing FQs against antibiotic-resistant bacteria., (© 2024. The Author(s).)

Metal ions have important roles in supporting the catalytic activity of DNA-regulating enzymes such as topoisomerases (topos). Bacterial type II topos, gyrases and topo IV, are primary drug targets for fluoroquinolones, a class of clinically relevant antibacterials requiring metal ions for efficient drug binding. While the presence of metal ions in topos has been elucidated in biochemical studies, accurate location and assignment of metal ions in structural studies have historically posed significant challenges. Recent advances in X-ray crystallography address these limitations by extending the experimental capabilities into the long-wavelength range, exploiting the anomalous contrast from light elements of biological relevance. This breakthrough enables us to confirm experimentally the locations of Mg 2+ in the fluoroquinolone-stabilized Streptococcus pneumoniae topo IV complex. Moreover, we can unambiguously identify the presence of K + and Cl - ions in the complex with one pair of K + ions functioning as an additional intersubunit bridge. Overall, our data extend current knowledge on the functional and structural roles of metal ions in type II topos., Competing Interests: Competing interests statement:The authors declare no competing interest.

Herein, the pharmacokinetic profiles, binding interactions, and molecular properties of fluoroquinolone derivatives as prospective antiviral drugs are examined using a combination of docking, ADME, and DFT simulations. The effectiveness of the ligands is compared with the clinically tested and FDA-authorized medicine remdesivir. The findings demonstrated encouraging binding energies, indicating possible inhibitory effectiveness against SARS-CoV-2 M pro . The fluoroquinolone derivatives also exhibit promising ADME characteristics, although compounds 5, 6, 9, 12-20 possess poor values, suggesting that oral administration may be possible. The potential of the selected compounds as SARS-CoV-2 M pro inhibitors is thoroughly understood because of the integrated analysis of DFT, with compound 11 demonstrating the highest energy gap of 0.2604 eV of, docking with viral targets with docking scores of -7.9 to -5.9 kcal/mol, with compound 18 demonstrating the highest docking score, which is at the 13th position in energy difference in the DFT data. Their favorable electrical properties, robust binding interactions with viral targets, and attractive pharmacokinetic profiles boost their potential as prospective study subjects. These substances have the potential to be transformed into cutting-edge antiviral therapies that specifically target SARS-CoV-2 M pro and related coronaviruses.

We report the design, synthesis, and antimicrobial evaluation of a series of ciprofloxacin (CP) conjugates coupled with nitrogen-containing heterocycles. In vitro screening of these new hybrid compounds (1-13) against a panel of planktonic bacterial strains highlighted thiazolyl homologs 6 and 7 as the most promising candidates for further investigation. These derivatives demonstrated potent growth-inhibitory activity against various standard and clinical isolates, with minimum inhibitory concentrations (MICs) ranging from 0.05 to 0.4 µg/ml, which are higher or comparable to the reference fluoroquinolone. Both compounds effectively inhibited biofilm formation by selected staphylococci across all tested concentrations (1-8 x MIC), displaying greater efficacy at higher doses compared to CP alone. Notably, conjugate 7 also significantly eradicated existing biofilms formed by S. aureus of various origin. Molecular docking studies revealed that conjugate 7 engages in a broader range of interactions with DNA gyrase and DNA topoisomerase IV than CP, suggesting stronger binding affinity and enhanced flexibility. This may contribute to its potential in overcoming bacterial resistance mechanisms. The above findings indicate compound 7 as a promising candidate for clinical development., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper, (Copyright © 2024 The Authors. Published by Elsevier Masson SAS.. All rights reserved.)

Herein, a new, environmentally friendly, and economical magnetic solid-phase extraction method for fluoroquinolones (FQs) from milk samples was developed using novel recyclable zeolitic imidazolate framework functionalized magnetic multiwalled carbon nanotubes (Fe 3 O 4 @MWCNTs@SiO 2 @ZIF-8) as adsorbents. Various characterization techniques, including scanning electron microscopy, N 2 adsorption-desorption analysis, and vibrating sample magnetometry, demonstrated that the adsorbent possessed a remarkable specific surface area, pore volume, and superparamagnetic properties, rendering it an excellent adsorbent. Combined with high-performance liquid chromatography, this method exhibited excellent linearity (R 2  ≥ 0.9991) over the concentration range of 0.5-500 μg L -1 , low limits of detection (0.10-0.34 μg kg -1 ), and low limits of quantification (0.30-1.00 μg kg -1 ). Finally, the developed method was successfully applied to analyze FQs in milk samples with recoveries ranging from 83.3% to 107.7% and relative standard deviations below 4.2%. The high efficiency and sensitivity of this method highlight the potential application of Fe 3 O 4 @MWCNTs@SiO 2 @ZIF-8 for analyzing FQs in complex matrices., Competing Interests: Declaration of competing interest The authors declare that there are no conflicts of interest., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Sensitive and selective detection of fluoroquinolones, especially from different sources, is challenging. This study reported an uncommon three-cage lanthanide metal-organic framework (1-Eu) with a Eu 3+ cluster as its structural primitive using a C 2 -symmetric 5,5-(Pyrazine-2,6-diyl) diisophthalic acid ligand. The 1-Eu probe effectively detected four fluoroquinolones through distinct color changes and spectral emission bands, demonstrating excellent performance with low detection limits: moxifloxacin (LOD: 9.3 nM), danofloxacin (LOD: 33.7 nM), gatifloxacin (LOD: 67.9 nM), and ofloxacin (LOD: 238.6 nM). Mechanistic studies revealed that internal filtration and photoinduced electron transfer (a-PET) effects were key factors. Furthermore, 1-Eu was successfully used to detect fluoroquinolones in food samples. Additionally, portable paper-based sensors were developed to quickly semi-quantify analyte concentrations using a smartphone color recognition app, underscoring the practical potential of this probe. This study introduces a novel methodology for the identification and detection of fluoroquinolones to enhance food safety., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Accurate and rapid diagnosis of drug susceptibility of Mycobacterium tuberculosis is crucial for the successful treatment of tuberculosis, a persistent global public health threat. To shorten diagnosis times and enhance accuracy, this study introduces a fusion model combining laser-induced breakdown spectroscopy (LIBS) and Raman spectroscopy. This model offers a rapid and accurate method for diagnosing drug-resistance. LIBS and Raman spectroscopy provide complementary information, enabling accurate identification of drug resistance in tuberculosis. Although individual use of LIBS or Raman spectroscopy achieved approximately 90% accuracy in identifying drug resistance, the fusion model significantly improved identification accuracy to 98.3%. Given the fast measurement capabilities of both techniques, this fusion approach is expected to markedly decrease the time required for diagnosis.

Fluoroquinolones are a widely used class of antibiotics, with a large variety, which are frequently monitored in the aqueous environment, threatening ecological and human health. To date, effective degradation of fluoroquinolone antibiotics remains a major challenge. Focused on the broad-spectrum degradation of fluoroquinolone antibiotics, a novel biomimetic peroxidase nanozyme named Hemin-His-Fe (HHF)-peroxidase nanozyme was synthesized through a green and rapid "one-pot" method involving hemin, Fmoc-L-His and Fe 2+ as precursors. After systematic optimization of the reaction conditions, fluoroquinolone antibiotics can be degraded by the HHF-peroxidase nanozyme when supplemented with H 2 O 2 in acidic environments. Through validation and analysis, it was proved that the generated strong oxidative hydroxyl radicals are the main active species in the degradation process. In addition, it was verified that this method shows great universal applicability in real water samples.

The increasing use and abuse of antibiotics in agriculture and aquaculture necessitates a more thorough risk assessment. We first advocate a precise assessment that subdivides the assessment scope from interspecies to intraspecific levels. Differences in ENR residues and degradation within the intraspecific category were simultaneously explored. This study chose red and GIFT tilapia, both belonging to the intra-specific category of tilapia, for an enrofloxacin (ENR) exposure experiment. Red tilapia had a lower area under the curve (AUC) representing drug accumulation, indicating a notably shorter withdrawal period (7 days) compared to GIFT tilapia (31.4 days) in the edible parts. While four potential transformation pathways were proposed for ENR in tilapia, red tilapia had fewer detected degradation products (6 items) than GIFT tilapia (10 items), indicating a simpler transformation pathway in red tilapia. Predictive assessments using the Toxtree model revealed that of the four extra degradation products in GIFT tilapia, two may possess carcinogenic and mutagenic properties. Overall, differences were observed in ENR residues and degradation within the intraspecific category, with red tilapia presenting lower risks than GIFT tilapia. This work suggests a new strategy to perfect the methodology for antibiotic risk assessment and facilitate systematic antibiotic administration management in the future., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Fluoroquinolone antibiotics (FQs) have been used worldwide due to their extended antimicrobial spectrum. However, the overuse of FQs leads to frequent detection in the environment and cannot be efficiently removed. Microalgae-based constructed wetland systems have been proven to be a relatively proper method to treat FQs, mainly by microalgae, plants, microorganisms, and sediments. To improve the removal efficiency of microalgae-constructed wetland, a systematic molecular design, screening, functional, and risk evaluation method was developed using three-dimensional quantitative structure-activity relationship models, molecular dynamics simulation, molecular docking, and TOPKAT approaches. Five designed ciprofloxacin alternatives with improved bactericidal effects and lower human health risks were found to be more easily degraded by microalgae (16.11-167.88 %), plants (6.72-58.86 %), microorganisms (9.10-15.02 %), and sediments (435.83 %-1763.51 %) compared with ciprofloxacin. According to the mechanism analysis, the removal effect of the FQs can be affected via changes in the number, bond energy, and molecular descriptors of favorable and unfavorable amino acids. To the best of our knowledge, this is the first comprehensive study of improving the microalgae, plants, microorganisms, and sediment removal efficiency of FQs in constructed wetlands, which provides theoretical support for the treatment of FQ pollution., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Bacteria have evolved resistance to nearly all known antibacterials, emphasizing the need to identify antibiotics that operate via novel mechanisms. Here we report a class of allosteric inhibitors of DNA gyrase with antibacterial activity against fluoroquinolone-resistant clinical isolates of Escherichia coli. Screening of a small-molecule library revealed an initial isoquinoline sulfonamide hit, which was optimized via medicinal chemistry efforts to afford the more potent antibacterial LEI-800. Target identification studies, including whole-genome sequencing of in vitro selected mutants with resistance to isoquinoline sulfonamides, unanimously pointed to the DNA gyrase complex, an essential bacterial topoisomerase and an established antibacterial target. Using single-particle cryogenic electron microscopy, we determined the structure of the gyrase-LEI-800-DNA complex. The compound occupies an allosteric, hydrophobic pocket in the GyrA subunit and has a mode of action that is distinct from the clinically used fluoroquinolones or any other gyrase inhibitor reported to date. LEI-800 provides a chemotype suitable for development to counter the increasingly widespread bacterial resistance to fluoroquinolones., (© 2024. The Author(s).)

A novel fluorinated triazine-based covalent organic frameworks (F-CTFs) was designed and synthesized by using melamine and 2,3,5,6-tetrafluoroterephthalaldehydeas as organic ligands for selective pipette tip solid-phase extraction (PT-SPE) of amphiphilic fluoroquinolones (FQs). The competitive adsorption experiment and mechanism study were carried out and verified that this F-CTFs possesses favorable adsorption affinity for FQs. The abundant fluorine affinity sites endowed the F-CTFs high selectivity to FQs extraction through F-F interactions. The adsorption capacity of F-CTFs can reach up to 109.1 mg g -1 for enrofloxacin. The detailed characterization of the F-CTFs adsorbent involved the application of various techniques to examine its morphology and structure. Under optimized conditions, a method combining F-CTF-based PT-SPE with high-performance liquid chromatography (PT-SPE-HPLC) was established, which exhibited a broad linear range, excellent precision, and an impressively low limit of detection, and could be used for the determination of six FQs in milk, with LODs as low as 0.0010 μg mL -1 . The recovery rates during extraction varied between 92.1% and 111.4%, exhibiting RSDs below 6.8% at different spiked concentrations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In this work, porous polyimide microfibers (PI-μF) were prepared by high-pressure wet spinning method, and successfully applied as adsorbents for solid phase extraction (SPE) of fluoroquinolones (FQs) in water and food samples. The PI-μFs of ∼10, 25, 50, 100 μm in diameter could be controlled by the inner diameter of quartz capillary nozzles. The flow resistance of SPE cartridges packed with 10 μm PI microfiber (10-PI-μF) and 25-PI-μF was comparable to or even lower than that of commercial SPE cartridges, while the flow resistance of 50-PI-μF and 100-PI-μF SPE cartridges was increased obviously due to tiny broken pieces. The 10-PI-μF and 25-PI-μF have a specific surface area of 102 m 2 g -1 and 76 m 2 g -1 , mesopores of 22-32 nm, and large breakthrough volume of 110 mL/5 mg and 85 mL/5 mg for FQs, while the 50-PI-μF and 100-PI-μF had much lower specific surface area and hardly had retention for FQs. FQs from tap water, egg and milk samples were then extracted by PI-μF SPE, and analyzed by high performance liquid chromatography-fluorescence detector (HPLC-FLD). SPE parameters as type of elution solvent, elution solvent volume, pH value of sample solution, flow rate of sample solution, and breakthrough volume were first optimized in detail. Under the optimal conditions, the PI-μF SPE/HPLC-FLD method showed high recoveries (96.8%-107%), wide linearity (0.05-50 μg L -1 , or 0.01-10 μg L -1 ), high determination coefficients (R 2 ≥0.9992), and low limits of detection (LODs, 0.005-0.014 μg L -1 ). For the real tap water, egg and milk samples, the recoveries and RSDs were 81-119% and 0.8-9.8%, respectively. The results show that porous microfiber up to 25 μm in diameter is a promising solid-phase extraction adsorbent with the lowest flow resistance that can be used for trace organic pollutants in water and food samples., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Fluoroquinolone antibiotics have been extensively used in clinical treatments for human and animal diseases. However, their long-term presence in the environment increases the risk of producing resistance genes and creates a potential threat to ecosystems and the health of humans and animals. Batch equilibrium experiments were utilized to investigate the adsorption and retention behavior and mechanism of the quinolone antibiotic enrofloxacin (ENR) in farmland soil in North China. The adsorption and desorption kinetics of ENR in soil were best fitted by pseudo-second-order model (R 2  > 0.999). Both the adsorption and desorption processes of ENR in soil reached equilibrium in 1 h. The desorption amounts of ENR were significantly lower than the adsorption amounts, with the hysteresis coefficient (HI) being less than 0.7. The adsorption thermodynamic process of ENR followed the Linear and Freundlich models (0.965 < R 2  < 0.985). Hydrophobic distribution and heterogeneous multimolecular layer adsorption were identified as critical factors in the adsorption process. The adsorption amount of ENR gradually decreased with increasing temperature and the initial concentration of ENR. The adsorption rate of ENR was above 80%, while the desorption rate remained below 15%, indicating strong retention ability. The adsorption rate of ENR in soil decreased with increasing pH, the adsorption rate reached 98.3% at pH 3.0 but only 31.5% at pH 11. The influence of coexisting ions on adsorption primarily depended on their properties, such as ion radius, ionic strength, and hydrolysis properties, and the inhibition of adsorption increased with increasing ionic strength. These findings contribute to understanding the fate and risk of veterinary antibiotics in loess soil in North China., (© 2024. The Author(s), under exclusive licence to Springer Nature B.V.)

Background: Fluoroquinolones (FQs) are widely used in livestock and poultry industry because of their satisfactory effects in preventing and treating bacterial infection. However, due to irrational use and poor biodegradability, FQs can easily remain in food animals and further enter the human body through the food chain. Therefore, accurate and sensitive detection of FQs residues in animal-origin food is significant. The traditional methods commonly used for FQs detection have some limitations. Ratiometric fluorescence detection technology has the advantages of fast, sensitive, self-correcting, and easy visualization. However, the reports on the use of ratiometric fluorescence probes for FQs detection are limited., Results: In this work, a novel probe was proposed for ratiometric fluorescent analysis of FQs. In this probe, the fluorescence of dithioerythritol stabilized copper nanoclusters (DTE-Cu NCs) was significantly enhanced due to the Tb 3+ triggered aggregation-induced emission effect. FQs bound Tb 3+ in Tb 3+ /DTE-Cu NCs through carboxyl and carbonyl groups, so that Tb 3+ was effectively sensitized to emit green fluorescence. However, the red fluorescence of DTE-Cu NCs was not interfered. The fluorescence of the probe transformed from red to green with the increase of FQs concentration. Using norfloxacin (NOR), difloxacin (DIF), and enrofloxacin (ENR) as FQs simulants, this probe showed a sensitive linear response ranged from 0.025 to 22.5 μM, with the limits of detection of 9.6 nM, 9.3 nM, and 7.7 nM. The application potential for FQs detection was verified via a standard addition assay of egg samples with the recovery rate of 90.4 %-114.7 %., Significant: The fluorescence probe based on Tb 3+ /DTE-Cu NCs is expected to realize the ratiometric fluorescence sensitive detection of FQs. The establishment of this simple, effective, and rapid detection platform opens up a new way for the detection of FQs residues in animal-origin foods, and also provides a new idea for the design of rapid detection platforms for other hazard factors., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The achievement of smart pharmaceuticals whose bioactivity can be spatiotemporally controlled by light stimuli is known as photopharmacology, an emerging area aimed at improving the therapeutic outcome and minimizing side effects. This is especially attractive for antibiotics, for which the inevitable development of multidrug resistance and the dwindling of new clinically approved drugs represent the main drawbacks. Here, we show that nitrosation of the fluoroquinolone norfloxacin (NF), a broad-spectrum antibiotic, leads to the nitrosated bioconjugate NF-NO, which is inactive at the typical minimum inhibitory concentration of NF. Irradiation of NF-NO with visible blue light triggers the simultaneous release of NF and nitric oxide (NO). The photouncaging process is accompanied by the revival of the typical fluorescence emission of NF, quenched in NF-NO, which acts as an optical reporter. This permits the real-time monitoring of the photouncaging process, even within bacteria cells where antibacterial activity is switched on exclusively upon light irradiation. The mechanism of photorelease seems to occur through a two-step hopping electron transfer mediated by the lowest triplet state of NF-NO and the phosphate buffer ions or aminoacids such as tyrosine. Considering the well-known role of NO as an "unconventional" antibacterial, the NF-NO conjugate may represent a potential bimodal antibacterial weapon activatable on demand with high spatio-temporal control.

Garenoxacin (GRNX) is a novel des-F(6)-fluoroquinolone on the horizon; thus, its fate and risk in the aquatic environment deserve attention. This study systematically investigated, for the first time, the phototransformation of GRNX under simulated and natural sunlight and assessed the ecotoxicity of its photodegradation products. Phototransformation of GRNX was observed to depend strongly on its ionization state, with direct photolysis and self-sensitized photolysis having comparable contributions for the cationic and zwitterionic species, while the latter dominated for the anionic species. Singlet oxygen generated via the self-sensitized photolysis of GRNX was the major reactive oxygen species in its photodegradation. Phototransformation of GRNX in different ionization states followed distinct pathways, with defluorination of the difluoromethyl group occurring only for the zwitterionic and anionic species. GRNX photodegradation in natural water could be described by a simple kinetic model based on the measured steady-state concentrations of 1 O 2 and ·OH. Toxicity tests with Vibrio fischeri and Chlorella vulgaris consistently indicate that the generation of hydroxylation and decarboxylation products during photodegradation of GRNX increased the acute toxicity. These findings not only provide insights into the fate of GRNX in sunlit surface water but also reveal the potentially significant risk of its photodegradation products to the aquatic ecosystem.

The effects on the adsorption of fluoroquinolone antibiotics of long-term soil heterogeneity induced by land-use were investigated. Three different land use areas with their two organic matter (OM) pools were tested for the adsorption of three antibiotics widely detected in the environment (ciprofloxacin, norfloxacin, ofloxacin). The soils were separated into two size fractions, > 63 µm fraction and < 63 µm fractions for the fast and slow OM pools, respectively. Any effect of land use on adsorption was only observed in the slow pool in the increasing order: arable land, grassland, and forest. The composition of the soil organic matter (SOM) did influence adsorption in the slow pool, but not in the bulk soilsThis was, because: 1) the ratio of the slow pool was low, as in forest, 2) the ratio of the slow pool was high but its adsorption capacity was low due to its SOM composition, as in arable land and grassland. Soils containing a large slow SOM pool fraction with aliphatic dominance were found to be more likely to adsorb micropollutants. It is our contention that the release of contaminated water, sludge, manure or compost into the environment should only be undertaken after taking this into consideration., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

The literature reveals gaps in the availability of green analytical methods for assessing products containing gatifloxacin (GFX), a fluoroquinolone. Presently, method development is supported by tools such as the National Environmental Methods Index (NEMI) and Eco-Scale Assessment (ESA), which offer objective insights into the environmental friendliness of analytical procedures. The objective of this work was to develop and validate a green method by the NEMI and ESA to quantify GFX in eye drops using HPLC. The method utilized a C 8 column (4.6 × 150 mm, 5 μm), with a mobile phase of purified water containing 2% acetic acid and ethanol (70:30, v/v). The injection volume was 10 μL and the flow rate was 0.7 mL/min in isocratic mode at 25°C, with detection performed at 292 nm. The method demonstrated linearity in the range of 2-20 μg/mL, and precision at intra-day (relative standard deviation [RSD] 1.44%), inter-day (RSD 3.45%), and inter-analyst (RSD 2.04%) levels. It was selective regarding the adjuvants of the final product (eye drops) and under forced degradation conditions. The method was accurate (recovery 101.07%) and robust. The retention time for GFX was approximately 3.5 min. The greenness of the method, as evaluated by the NEMI, showed four green quadrants, and by ESA, it achieved a score of 88., (© 2024 John Wiley & Sons Ltd.)

Cancer is the second leading cause of death in the world following cardiovascular disease. Its treatment, including radiation therapy and surgical removal of the tumour, is based on pharmacotherapy, which prompts a constant search for new and more effective drugs. There are high costs associated with designing, synthesising, and marketing new substances. Drug repositioning is an attractive solution. Fluoroquinolones make up a group of synthetic antibiotics with a broad spectrum of activity in bacterial diseases. Moreover, those compounds are of particular interest to researchers as a result of reports of their antiproliferative effects on the cells of the most lethal cancers. This article presents the current progress in the development of new fluoroquinolone derivatives with potential anticancer and cytotoxic activity, as well as structure-activity relationships, along with possible directions for further development.

The presence of fluoroquinolone (FQ) antibiotics in soils may cause a threat to human health due to overexposure and the generation of antibiotic resistance genes. Understanding their sorption behavior in soils is important to predict subsequent FQ (bio) availability. Here, FQ sorption in pure soil organic (i.e., humic substances) and mineral (i.e., metal oxides; phyllosilicates) components is evaluated through a solid-liquid distribution coefficient (K d (FQ)) dataset consisting of 243 entries originated from 80 different studies, to elucidate their respective contribution to the overall K d (FQ) in bulk soils. First, different factors affecting FQ sorption and desorption in each of these soil phases are critically discussed. The strong role of pH in K d (FQ), due to the simultaneous effect on both FQ speciation and surface charge changes, encouraged the derivation of normalized sorption coefficients for the cationic, zwitterionic and anionic FQ species in humic substances and in different phyllosilicates. K d (FQ) in metal oxides revealed a key role of metal nature and material specific surface area due to complexation sorption mechanisms at neutral pH. Cumulative distribution functions (CDF) were applied to each dataset to establish a sorption affinity range for each phase and to derive best estimate K d (FQ) values for those materials where normalized sorption coefficients to FQ species were unavailable. The data analysis conducted in the different soil phases set the basis for a K d (FQ) prediction model, which combined the respective sorption affinity of each phase for FQ and phase abundance in soil to estimate K d (FQ) in bulk soils. The model was subsequently validated with sorption data in well characterized soils compiled from the literature., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

A new enantioselective open-tubular capillary electrochromatography (OT-CEC) was developed employing β-cyclodextrin covalent organic frameworks (β-CD COFs) conjugated gold-poly glycidyl methacrylate nanoparticles (Au-PGMA NPs) as a stationary phase. The resulting coating layer on the inner wall of the fabricated capillary column was characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), energy dispersive spectroscopy (EDS), and electroosmotic flow (EOF) experiments. The performance of the fabricated capillary column was evaluated by CEC using enantiomers of seven model analytes, including two proton pump inhibitors (PPIs, omeprazole and tenatoprazole), three amino acids (AAs, tyrosine, phenylalanine, and tryptophan), and two fluoroquinolones (FQs, gatifloxacin and sparfloxacin). The influences of coating time, buffer concentration, buffer pH, and applied voltage on enantioseparation were investigated to obtain satisfactory enantioselectivity. In the optimum conditions, the enantiomers of seven analytes were fully resolved within 10 min with high resolutions of 3.03 to 5.25. The inter- to intra-day and column-to-column repeatabilities of the fabricated capillary column were lower than 4.26% RSD. Furthermore, molecular docking studies were performed based on the chiral fabricated column and as ligand isomers of analytes using Auto Dock Tools. The binding energies and interactions acquired from docking results of analytes supported the experimental data., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

The Zn/Zr-MOFs were synthesized via microwave-assisted ball milling and subsequently characterized using Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The thermal stability of the Zn/Zr-MOFs was evaluated through thermogravimetry (TGA). The results demonstrated the exceptional adsorption properties of the Zn/Zr-MOFs towards Lomefloxacin hydrochloride and Levofloxacin hydrochloride. At a concentration of 30 ppm for Lomefloxacin hydrochloride, the addition of 30 mg of Zn/Zr-MOFs material resulted in an adsorption capacity of 179.2 mg•g-1. Similarly, at a concentration of 40 ppm for Levofloxacin hydrochloride, the addition of 30 mg Zn/Zr-MOFs material led to an adsorption capacity of 187.1 mg•g-1. Kinetic analysis revealed that the experimental data aligned well with a pseudo-second order kinetic model. Overall, these findings highlight the significant potential application of Zn/Zr-MOF materials in wastewater treatment., Competing Interests: Declaration of competing interest There is no potential conflict of interest., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Fluoroquinolone (FQ) antibiotics, one of the leading environmental pollutants, have ecotoxic effects that can accumulate through ecosystems and harm human health. The determination of FQs is still difficult due to the complex matrix, many interfering factors, and low concentration. Hence, a magnetic microporous organic network (MON) composite denoted as Fe 3 O 4 @MON-NH 2 @CM-β-CD with excellent FQ adsorption performance was prepared by β-CD covalent modification of a MON. Based on the existence of π-π packing, hydrophobic interaction, and hydrogen bonding between Fe 3 O 4 @MON-NH 2 @CM-β-CD and FQs, a new magnetic solid phase extraction (MSPE) method for the enrichment of FQs was developed. Under optimized MSPE conditions, five FQs were detected by HPLC-UV with good linearity ( R 2 ≥ 0.9989) in the range of 0.02-1 μg mL -1 , and detection limits (S/N = 3) in the range of 0.0014-0.0023 μg mL -1 . The satisfactory recoveries ranged from 93.1 to 116.2% with RSDs lower than 8.39% when applied to actual environmental water samples. These results revealed that Fe 3 O 4 @MON-NH 2 @CM-β-CD as an adsorbent for MSPE had excellent performance for FQ extraction from real samples, and the MON material types were expanded through the functionalization of MONs, which would have great potential for further application in various analytical methods.

This work compares the electroanalytical performance of two electroanalytical systems based on (1) the glassy carbon electrode (GCE), and (2) the electrified liquid-liquid interface (eLLI), for the detection of fluoroquinolone antibiotic-danofloxacin (DANO). Our aim was to define the optimal conditions to detect the chosen analyte with two employed systems, extract a number of electroanalytical parameters, study the mechanism of the charge transfer reactions (oxidation at GCE and ion transfer across the eLLI), and to provide physicochemical constants for DANO. Detection of the chosen analyte was also performed in the spiked milk samples. To the best of our knowledge, this is the first work that directly compares the electroanalytical parameters obtained with solid electrode (in this case GCE) and eLLI. We have found that for DANO the latter provides better electroanalytical parameters (lower LOD and LOQ) as well as good selectivity when the milk was analyzed., (© 2024. The Author(s).)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Bacterial resistance to fluoroquinolone has been increasing at an alarming rate worldwide. In an attempt to find more potent anti-bacterial agents, an efficient, straightforward protocol was performed to obtain a large substrate scope of novel ciprofloxacin and sarafloxacin analogues conjugated with 4-(arylcarbamoyl)benzyl 7a-ab. All prepared compounds were evaluated for their anti-bacterial activities against three gram-positive strains (Methicillin resistant staphylococcus aureus (MRSA), Staphylococcus aureus, and Enterococcus faecalis) as well as three gram-negative strains (Pseudomonas aeruginosa, Klebsiella pneumonia, and Escherichia coli) through three standard methods including broth microdilution, agar-disc diffusion, and agar-well diffusion assays. Most of the compounds exhibited great to excellent anti-bacterial potencies against MRSA and S. aureus. Among the targeted compounds, derivative 7n exhibited great antibacterial potency, which was noticeably more potent than parent ciprofloxacin. Subsequently, a molecular docking study was performed for this compound to find out its probable binding mode with the active site of S. aureus DNA gyrase (PDB ID: 2XCT)., (© 2023. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

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., Competing Interests: Declaration of competing interest There are no conflicts to declare., (Copyright © 2024 Elsevier Inc. All rights reserved.)

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 MIC 0 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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The structural optimization of B14, an antibacterial agent we previously obtained, has led to the discovery of a new class of CH 2 -linked quinolone-aminopyrimidine hybrids with potent anti-MRSA activities. Surprisingly, the hybrids lacking a C-6 fluoro atom at the quinolone nucleus showed equal or even stronger anti-MRSA activities than their corresponding 6-fluoro counterparts, despite the well-established structure-activity relationships (SARs) indicating that the 6-fluoro substituent enhances the antibacterial activity in conventional fluoroquinolone antibiotics. Moreover, these new hybrids, albeit structurally related to conventional fluoroquinolones, showed no cross-resistance with fluoroquinolone drugs. The most active compound, 15m, exhibited excellent activities with a MIC value of 0.39 μg/mL against both fluoroquinolone-sensitive strain USA500 and -resistant MRSA isolate Mu50. Further resistance development studies indicated MRSA is unlikely to acquire resistance against 15m. Moreover, 15m displayed favorable in vivo half-life and safety profiles. These findings suggest a rationale for further evolution of quinolone antibiotics with a high barrier to resistance., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2024 Elsevier Masson SAS. All rights reserved.)

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., (© 2024 Wiley‐VCH GmbH.)

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, NO 3 - 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 (t 1/2,E ) during midsummer and midwinter in cold regions. The estimated t 1/2,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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

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: MAE Train = 0.085, Q LOO 2 = 0.849, external: MAE Test = 0.090, and Q F1 2 = 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.

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 H 2 O 2 -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 MS 2 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., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Ben Ayed Amal reports financial support was provided by Programme Hubert Curien - Utique. Grigoriev Igor V reports financial support was provided by US Department of Energy Office of Science., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Ice is an important medium that regulates the transformation of organic contaminants. Nonetheless, photodegradation of emerging fluoroquinolone (FQ) antibiotics in the ice, particularly those with varying dissociated species, remains inadequately explored. In this study, the photodegradation of norfloxacin (NOR) and ofloxacin (OFL) in different dissociated species in water ice were investigated. Results indicated that the quantum yield of the zwitterion for NOR in the ice was 1.7-5.0 times higher than that of the cation, and 1.3 times higher than that of the anion. The quantum yield of the zwitterion for OFL in the ice was 2.5-3.4 times higher than that of the cation, and 1.4 times higher than that of the anion. The degradation pathways of NOR and OFL with different dissociated species depended on their molecular structure. Most products possessed lower developmental toxicity than parent NOR and OFL, respectively. OFL showed a higher inhibitory rate of Escherichia coli activity at the initial time of photodegradation, which was higher than that of NOR. This study offers novel insights into the impact of dissociated species on the photodegradation of FQs in ice and contributes to understanding the environmental behavior of fluorinated pharmaceuticals in the cryosphere., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)