Facial synthesis of fluorine-engineered magnetic covalent organic framework for selective and ultrasensitive determination of fipronil, its metabolites and analogs in food samples.

To improve the adsorption affinity and selectivity of fipronils (FPNs), including fipronil, its metabolites and analogs, a magnetic covalent organic framework (Fe3O4@COF-F) with copious fluorine affinity sites was innovatively designed as an adsorbent of magnetic solid-phase extraction (MSPE). The enhanced surface area, pore size, crystallinity of Fe3O4@COF-F and its exponential adsorption capacities (187.3-231.5 mg g-1) towards fipronils were investigated. Combining MSPE with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), an analytical method was established for the selective determination of fipronils in milk and milk powder samples. This method achieved high sensitivity (LODs: 0.004-0.075 ng g-1), satisfactory repeatability and accuracy with spiked recoveries ranging from 89.9% to 100.3% (RSDs≤5.1%). Overall, the constructed Fe3O4@COF-F displayed great potential for the selective enrichment of fipronils, which could be ascribed to fluorine­fluorine interaction. This method proposed a feasible and promising strategy for the development of functionalized COF and broadened its application in fluorine containing hazards detection.

Plasmonic Au-NPs photodecorated on NiCoLDH nanosheets as a flexible SERS sensor for the real-time detection of fipronil.

Rapid extraction and detection of probe molecules from curved surfaces is critical for on-site and real-time detection. In this study, a flexible platform was developed using carbon cloth (CC) to create honeycomb-like nickel cobalt layered double hydroxides (NiCoLDH) nanosheets via a simple electrodeposition technique, which were then decorated with gold nanoparticles (Au-NPs) via photodeposition process. The Au-NPs/NiCoLDH/CC was designed as a surface-enhanced Raman scattering (SERS) substrate for detecting the broad-spectrum insecticide, Fipronil (FP). The fabricated sensor achieves a superior SERS activity due to the electrodeposited NiCoLDH, which provides the charge-transfer effect, and the photodeposited Au-NPs, which generate efficient SERS hotspots through the electromagnetic effect. The Density Functional Theory (DFT) calculation was used to estimate the optimal geometry and frontier molecular orbital diagrams of the FP molecules. The influence of electrodeposition time on NiCoLDH production and Au-NPs decorating quantity was investigated in detail. Furthermore, the flexible SERS sensor has excellent sensitivity, homogeneity, a low limit of detection (LOD), and high reproducibility for FP detection. Even after 40 cycles of bending and torsion, the SERS substrate maintained excellent mechanical endurance. Through a direct-sampling approach, FP molecules on the surfaces and mesocarp region of grapes and tomatoes were successfully detected with lower LOD. These findings highlight the outstanding potential of the produced flexible SERS sensor for real-time and on-site insecticide detection, making it valuable for food security analysis and monitoring.

Triple jeopardy: The combined effects of viral, chemical, and thermal stress on kuruma prawn (Penaeus japonicus) juveniles.

Growing concerns have emerged over the combined effects of multiple stressors on ecosystems. Empirical evidence shows that the sensitivity of aquatic invertebrates to insecticides varies under thermally fluctuating conditions. Additionally, field surveys in estuarine areas of western Japan confirmed the presence of juvenile kuruma prawns (Penaeus japonicus) carrying the white spot syndrome virus (WSSV). Given the potential of co-exposure to multiple stressors, we performed a combined exposure experiment using a full-factorial design with three stressors: WSSV infection (presence or absence: initial 2 h exposure), fipronil (insecticide) exposure (0 or 0.1 µg/L: 14 d exposure), and temperature (20, 25, or 30 °C). We observed the highest mortality (75 %) in the WSSV + Fipronil treatment at 30 °C, with the associated specimens showing significant changes in the internal load of WSSV and concentrations of fipronil and its metabolite, fipronil sulfone. Severe perturbations of metabolites associated with increased energy expenditure and fatty acid utilization have been identified as potential factors underlying lethality in juvenile kuruma prawns. The results demonstrate that WSSV infection increases the susceptibility of thermally stressed juvenile kuruma prawns to fipronil. Therefore, further studies are required to determine the combined effects of multiple stressors in environmentally relevant scenarios on juvenile kuruma prawns as well as in estuarine ecosystems.

Fipronil-infused sodium polyacrylate gels provide effective management of Argentine ants in conservation areas.

BACKGROUND: Various types of hydrogel compounds have recently been developed for controlling invasive and pest ants in a range of environmental settings including agricultural, urban and natural areas. The current study evaluated the potential of sodium polyacrylate (ACR) hydrogels to effectively deliver liquid baits to Argentine ants. RESULTS: Relative to standard polyacrylamide (PAM) hydrogels, individual ACR hydrogel particles were approximately five-fold heavier; this may affect how ants interact with the bait particles, and further influence bait uptake and efficacy. Additionally, ACR hydrogels had significantly higher water absorption capacity and significantly slower rate of water loss, especially during the first 2 h. The efficacy of ACR hydrogel bait containing 0.005% fipronil and various attractants was evaluated on laboratory colonies. Results demonstrated that ACR hydrogel acceptance is significantly increased by the addition of feeding attractants. In addition, a field trial was performed in a nature reserve invaded by Argentine ants to evaluate the efficacy of ACR hydrogel bait. The field trial demonstrated that ACR hydrogel bait containing 0.005% fipronil with various attractants is highly effective and that ant densities throughout the baited plots declined by >99% within 7 days. CONCLUSIONS: The results of this study demonstrate that: (i) fipronil is highly effective for Argentine ant control in natural areas when used in low concentrations (0.005%); (ii) ACR hydrogels are an effective tool for delivering liquid baits to Argentine ants; and (iii) hydrogel baits augmented with various attractants including salt, protein and pheromone are highly attractive to Argentine ants. © 2024 The Author(s). Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Combined effects of TiO2 nanoparticle and fipronil co-exposure on microbiota in mouse intestine.

Oral exposure to nanoparticles (NPs) may affect intestinal microbiota, and this effect may be further changed by co-contaminates. In the present study, we investigated the combined effects of TiO2 NPs and fipronil (FPN) on microbiota in mouse intestines. Mice were intragastric exposed to 5.74 mg/kg TiO2 NPs, 2.5 mg/kg FPN, or both of them, once a day, for 30 days. The results showed that individual exposure to TiO2 NPs or FPN decreased body weight and induced pathological changes in intestines. The exposure was also associated with increased cleaved caspase-3 protein, oxidative stress and decreased tight junction protein expression. Furthermore, the levels of diamine oxidase (DAO), lipopolysaccharide (LPS) and inflammatory cytokines in serum were also elevated, indicating increased intestinal barrier permeability. As expected, both TiO2 NPs and FPN decreased the diversity and altered the composition of microbiota. However, the observed effects were not further enhanced after the co-exposure to TiO2 NPs and FPN, except that Romboutsia was only significantly increased after the co-exposure to TiO2 NPs + FPN. We concluded that oral exposure to TiO2 NPs and FPN showed minimal synergistic effects on microbiota in mouse intestine.

Cellulase-responsive hydroxypropyl cellulose-anchored hollow mesoporous silica carriers for pesticide delivery.

In this study, a cellulase-responsive controlled-release formulation (FPR-HMS-HPC) was developed by grafting hydroxypropyl cellulose (HPC) onto fipronil (FPR) loaded hollow mesoporous silica (HMS) nanoparticles via ester linkage. The FPR-HMS-HPC formulation was characterized using scanning and transmission electron microscopies, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The results indicated that FPR-HMS-HPC exhibited a high loading capacity of 10.0 % (w/w) and demonstrated favorable responsiveness to cellulase enzyme. Moreover, its insecticidal efficacy against Reticulitermes flaviceps surpassed that of an equivalent dose of FPR. Toxicology studies showed that the mortality and hatching rates of zebrafish exposed to FPR-HMS-HPC nanoparticles were reduced by >6.5 and 8.0 times, respectively. Thus, HPC-anchored HMS nanoparticles as insecticide delivery systems present a sustainable method for pest control significantly reducing harm to non-target organisms and the environment.

Temperature-dependent in vitro hepatocytotoxicity of insecticides in bats.

Heterothermic insectivorous bats are supposed to experience differential adverse effects of insecticidal pollutants depending on their seasonal and/or daily variation of metabolic and detoxification rates. Here, we investigated effects of imidacloprid, cypermethrin and fipronil on Nyctalus noctula bat-derived hepatocytes through cytotoxicity, cell inhibition and death at different concentrations (0.01, 0.1, 1, 10, 100, 1000 µg/ml), exposure times (10, 24, 48 hrs), incubation temperatures simulating hibernation (8 °C), daily torpor (20 °C), normothermy (37 °C) and active flight (40 °C), and cytochrome P450 addition. Toxic effects were significantly influenced by temperature (p < 0.05), with strong cytotoxicity after 10 hour exposure to fipronil or cypermethrin at 37 and 40 °C, cell replication inhibition (all insecticides at 8 °C) and cellular stimulation, with slight culture proliferation after 48 hours (all insecticides at 40 °C). Replacing protected chiropterans with cell cultures is a way to assess and extrapolate risks of insecticides for bats.

Endocrine-disrupting effects of bisphenol-A, thiamethoxam, and fipronil in hormone-naïve transmen compared to cis-women.

BACKGROUND: Current evidence suggests that the etiology of gender dysphoria (GD) is multifactorial: this, however, remains unclear. Endocrine-disrupting chemicals (EDCs) are one of the etiological hypotheses. OBJECTIVES: In this study, we aimed to evaluate the urinary levels of bisphenol A (BPA), thiamethoxam, and fipronil in hormone-naïve transmen compared with case-matched cis-women as well as the relation between sex hormone levels and EDCs. METHODS: Drug-naïve transmen diagnosed with GD and who were referred from the psychiatry outpatient clinic to the outpatient clinic of the Department of Endocrinology, Marmara University Hospital, were included in the study. These individuals were assessed for eligibility; 38 drug-naïve transmen and 22 cis-women were recruited as the control group. After anthropometric evaluation laboratory tests for FSH, LH, total testosterone, and estradiol were carried out, spot urine samples were collected to evaluate the urine metabolic excretion of BPA, thiamethoxam, and fipronil. RESULTS: We found that androgens, total testosterone, androstenedione, and DHEAS levels were significantly higher in transmen than in cis-women. Thiamethoxam was considerably higher in cis-women than in transmen, whereas fipronil and BPA levels were similar in both groups. A negative correlation was found between thiamethoxam and testosterone and between thiamethoxam and BPA levels. CONCLUSION: The available data suggest that the EDCs that we are most exposed to in our lives are not the only factor in GD development. Even transmen who have not taken hormone replacement have high testosterone levels; however, the mechanism has not as yet been elucidated. The challenge is to determine whether this is a factor leading to GD or a condition that develops in common with GD.

Influences of TiO2 nanoparticle and fipronil co-exposure on metabolite profiles in mouse intestines.

Food contaminates, such as insecticide, may influence the toxicity of nanoparticles (NPs) to intestine. The present study investigated the combined toxicity of TiO2 NPs and fipronil to male mouse intestine. Juvenile mice (8 weeks) were orally exposed to 5.74 mg/kg TiO2 NPs, 2.5 mg/kg fipronil, or both, once a day, for 5 days. We found that both TiO2 NPs and fipronil induced some pathological changes in intestines, accompanying with defective autophagy, but these effects were not obviously enhanced after TiO2 NP and fipronil co-exposure. Fipronil promoted Ti accumulation but induced minimal impact on other trace elements in TiO2 NP-exposed intestines. Metabolomics data revealed that the exposure altered metabolite profiles in mouse intestines, and two KEGG pathways, namely, ascorbate and aldarate metabolism (mmu00053) and glutathione metabolism (mmu00480), were only statistically significantly changed after TiO2 NP and fipronil co-exposure. Five metabolites, including 2-deoxy-D-erythro-pentofuranose 5-phosphate, 5alpha-cholestanol, beta-D-glucopyranuronic acid, elaidic acid, and isopentadecanoic acid, and maltotriose, were more significantly up-regulated after the co-exposure, whereas trisaccharide and xylonolactone were only significantly down-regulated by the co-exposure. We concluded that fipronil had minimal impact to enhance the toxicity of TiO2 NPs to mouse intestines but altered metabolite profiles.

Fipronil and (S)-methoprene can lessen the risk of transmission of Bartonella clarridgeiae among cats with exposure to Ctenocephalides felis.

OBJECTIVE: To cohouse cats experimentally infected with Bartonella clarridgeiae (Bc) with naive cats in a flea-free environment or with Ctenocephalides felis, Bartonella henselae (Bh), Mycoplasma haemofelis, and Candidatus Mycoplasma haemominutum to determine which flea could be a vector and to assess whether transmission of the infectious agents could be blocked by fipronil and (S)-methoprene. ANIMALS: Specific pathogen-free cats (n = 34). METHODS: In experiment 1, Bc was inoculated in 1 cat that was housed with 9 naive cats without C felis. In experiment 2, the 2 cats inoculated with Bc were housed with 6 other cats (2 inoculated with Bh, 2 inoculated with M haemofelis, and 2 inoculated with Candidatus M haemominutum) in the center (enclosure 2) of 3 housing enclosures separated by mesh walls that allow passage of fleas but precludes fighting. C felis were placed only on cats in enclosure 2 (5 times). Cats in enclosures 1 (n = 8) and 2 (8) were untreated, and cats in enclosure 3 (8) were administered fipronil and (S)-methoprene. Blood was collected from all cats for PCR assays for the pathogens. RESULTS: None of the cats housed with the cat inoculated with Bc became PCR positive in the absence of C felis. All cats in enclosure 2 became Bc DNA positive. While 2 of 8 cats in enclosure 1 became Bc PCR positive, none of the treated cats in enclosure 3 became infected. CLINICAL RELEVANCE: The study demonstrated that C felis can be a vector for Bc. The results support the recommendation that flea control products can reduce the risk of transmission of flea-borne pathogens.