RESUMO
Diquat (DQ) has been confirmed to be toxic to humans and responsible for severe health impairment. While to date, very little is known about the toxicological mechanisms of DQ. Thus, investigations to discover the toxic targets and potential biomarkers of DQ poisoning are urgently needed. In this study, a metabolic profiling analysis was conducted to reveal the changes of metabolites of plasma and find out the potential biomarkers of DQ intoxication by GC-MS. First, multivariate statistical analysis demonstrated that acute DQ poisoning can lead to metabolomic changes in human plasma. Then, metabolomics studies showed that 31 of the identified metabolites were significantly altered by DQ. Pathway analysis indicated that three primarily metabolic pathways including phenylalanine, tyrosine and tryptophan biosynthesis, taurine and hypotaurine metabolism, and phenylalanine metabolism were affected by DQ, resulting in the perturbations of phenylalanine, tyrosine, taurine, and cysteine. Finally, the results of receiver operating characteristic analysis showed the above four metabolites could be used as reliable tools for the diagnosis and severity assessments of DQ intoxication. These data provided the theoretical basis for basic research to understand the potential mechanisms of DQ poisoning, and also identified the desirable biomarkers with great potential for clinical applications.
Assuntos
Diquat , Venenos , Humanos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Metabolômica/métodos , Biomarcadores/metabolismo , Fenilalanina , Tirosina , TaurinaRESUMO
Oxidative stress causes damage to macromolecules, including proteins, DNA, and lipid, and has been recognized as a crucial driver of the onset and progression of several intestinal disorders. Pterostilbene, one of the natural antioxidants, has attracted considerable attention owing to its multiple biological activities. In the present study, we established an oxidative stress model in broiler chickens via injection with diquat to investigate whether pterostilbene could attenuate diquat-induced intestinal damage and reveal the underlying mechanisms. We found that diquat-induced decreases in the activities of superoxide dismutase and glutathione peroxidase and the level of reduced glutathione and the increase in hydrogen peroxide content in plasma and jejunum were significantly alleviated by pterostilbene (P < 0.05). Pterostilbene supplementation also decreased intestinal permeability and jejunal apoptosis rate, improved jejunal villus height and the ratio of villus height to crypt depth, and promoted the transcription and translation of jejunal tight junction proteins occludin and zona occludens 1 in diquat-challenged broilers (P < 0.05). Furthermore, pterostilbene reversed diquat-induced mitochondrial injury in the jejunum, as indicated by the decreased reactive oxygen species level and elevated activities of superoxide dismutase 2 and mitochondrial respiratory complexes (P < 0.05). Importantly, administering pterostilbene maintained iron homeostasis, inhibited lipid peroxidation, and regulated the expression of the markers of ferroptosis in the jejunum of diquat-exposed broilers (P < 0.05). The nuclear factor erythroid 2-related factor 2 signaling pathway in the jejunum of diquat-exposed broilers was also activated by pterostilbene (P < 0.05). In conclusion, our study provides evidence that pterostilbene alleviates diquat-induced intestinal mucosa injury and barrier dysfunction by strengthening antioxidant capacity and regulating ferroptosis of broiler chickens.
Assuntos
Diquat , Ferroptose , Animais , Diquat/toxicidade , Galinhas , Suplementos Nutricionais , Antioxidantes/farmacologia , OxirreduçãoRESUMO
Paraquat (PQ) and diquat (DQ), some of the most widely used herbicides in the world, both present a high mortality index after intentional exposure. In this paper, a fluorescence sensing method for PQ and DQ, based on host-guest molecular recognition, is proposed. Calix[6]arene derivatives containing anthracene or naphthalene as pendant fluorophore at their lower rim recognize DQ and PQ in hydroalcoholic solution with a broad linear response range at the µg L-1 level concentration. The linear response ranges were found from 1.0 to 18 µg L-1 with the detection limit of 31 ng L-1 for paraquat, and from 1.0 to 44 µg L-1 with the detection limit of 0.16 µg L-1 for diquat. The recognition process is detected by following the decrease in the fluorescence emission consequent to complexation. The proposed quenching method has been applied to the determination of paraquat in drinking water samples.
Assuntos
Diquat , Herbicidas , Paraquat , Fluorescência , Herbicidas/análiseRESUMO
Rapid detection of diquat (DQ) is essential in clinical diagnosis and rescue. Here, we developed a fast, simple-yet-practical detection strategy for the reliable identification and quantification of DQ in biological fluids. Based on surface-enhanced Raman spectroscopy (SERS), point-of-care detection was realized under the acidic condition with gold nanoparticles as the substrate. Under optimal experimental conditions, the detection limits of the strategy were 17.5 ppb and 1.99 ppm in human urine and gastric juice, respectively. High specificity and selectivity of the SERS strategy were demonstrated using common pesticides and coexisting biological substances. The method was also used to detect biofluids from 5 patients and urine samples from 10 healthy volunteers. The results were in high agreement with spectrophotometric and clinical liquid chromatography-mass spectrometry methods. The volume of urine samples required for this technique is merely 20 µL, and no preparation of the samples is required. Compared to traditional methods used in clinical settings, SERS-based methods are capable of real-time measurements that accurately provide rapid detection and response in non-laboratory settings, with great potential for on-site and point-of-care testing.
Assuntos
Técnicas Biossensoriais , Nanopartículas Metálicas , Praguicidas , Humanos , Diquat , Ouro/química , Nanopartículas Metálicas/química , Análise Espectral Raman/métodosRESUMO
This study was conducted to investigate the protective effects of chlorogenic acid (CGA) on broilers subjected to (DQ)-induced oxidative stress. In experiment 1, one hundred and ninety-two male one-day-old Ross 308 broiler chicks were distributed into 4 groups and fed a basal diet supplemented with 0, 250, 500, or 1,000 mg/kg CGA for 21 d. In experiment 2, an equivalent number of male one-day-old chicks were allocated to 4 treatments for a 21-d trial: 1) Control group, normal birds fed a basal diet; 2) DQ group, DQ-challenged birds fed a basal diet; and 3) and 4) CGA-treated groups: DQ-challenged birds fed a basal diet supplemented with 500 or 1,000 mg/kg CGA. The intraperitoneal DQ challenge was performed at 20 d. In experiment 1, CGA administration linearly increased 21-d body weight, and weight gain and feed intake during 1 to 21 d (P < 0.05). CGA linearly and/or quadratically increased total antioxidant capacity, catalase, superoxide dismutase, and glutathione peroxidase activities, elevated glutathione level, and reduced malondialdehyde accumulation in serum, liver, and/or jejunum (P < 0.05). In experiment 2, compared with the control group, DQ challenge reduced body weight ratio (P < 0.05), which was reversed by CGA administration (P < 0.05). DQ challenge increased serum total protein level, aspartate aminotransferase activity, and total bilirubin concentration (P < 0.05), which were normalized when supplementing 500 mg/kg and/or 1,000 mg/kg CGA (P < 0.05). DQ administration elevated hepatic interleukin-1ß, tumor necrosis factor-α, and interleukin-6 levels (P < 0.05), and the values of interleukin-1ß were normalized to control values when supplementing CGA (P < 0.05). DQ injection decreased serum superoxide dismutase activity, hepatic catalase activity, and serum and hepatic glutathione level, but increased malondialdehyde concentration in serum and liver (P < 0.05), and the values of these parameters (except hepatic catalase activity) were reversed by 500 and/or 1,000 mg/kg CGA. The results suggested that CGA could improve growth performance, alleviate oxidative stress, and ameliorate hepatic inflammation in DQ-challenged broilers.
Assuntos
Antioxidantes , Galinhas , Ácido Clorogênico , Animais , Masculino , Ração Animal/análise , Antioxidantes/metabolismo , Peso Corporal , Catalase/metabolismo , Galinhas/metabolismo , Ácido Clorogênico/farmacologia , Dieta/veterinária , Suplementos Nutricionais , Diquat/toxicidade , Glutationa/metabolismo , Inflamação/induzido quimicamente , Inflamação/veterinária , Interleucina-1beta , Malondialdeído , Estresse Oxidativo , Superóxido Dismutase/metabolismoRESUMO
Paraquat (PQ) and diquat (DQ) are quaternary ammonium herbicides which have been used worldwide for controlling the growth of weeds on land and in water. However, PQ and DQ are well known to be toxic. PQ is especially toxic to humans. Moreover, there is no specific antidote for PQ poisoning. The main treatment for PQ poisoning is hemoperfusion to reduce the PQ concentration in blood. Therefore, it is essential to be able to detect PQ and DQ concentrations in biological samples. This critical review summarizes the articles published from 2010 to 2022 and can help researchers to understand the development of the sample treatment and analytical methods for the determination of PQ and DQ in various types of biological samples. The sample preparation includes liquid-liquid extraction, solid-phase extraction based on different novel materials, microextration methods, and other methods. Analytical methods for quantifying PQ and DQ, such as different chromatography and spectroscopy methods, electrochemical methods, and immunological methods, are illustrated and compared. We focus on the latest advances in PQ and DQ treatment and the application of new technologies for these analyses. In our opinion, tandem mass spectrometry is a good choice for the determination of PQ and DQ, due to its high sensitivity, high selectivity, and high accuracy. As far as we are concerned, the best LOD of 4 pg/mL for PQ in serum can be obtained.
Assuntos
Herbicidas , Paraquat , Humanos , Diquat/análise , Herbicidas/análise , Cromatografia Líquida de Alta Pressão , Espectrometria de Massas em TandemRESUMO
This study was conducted to investigate the antioxidant effects of hydroxytyrosol (HT) administration in diquat (DQ)-challenged mice. The results showed that HT treatment markedly alleviated DQ-induced oxidative stress, which was indicated by the enhanced total antioxidant capacity (T-AOC), increased activities of superoxide dismutase (SOD), glutathione peroxidase (GSH-Px), and catalase and decreased malondialdehyde (MDA) concentration in serum. Additionally, HT increased the mRNA expression levels of NF-E2-related factor 2 (Nrf2) and its downstream genes, including NADPH quinone oxidoreductase 1 (NQO1) and catalase (CAT) in the small intestine of DQ-challenged mice. 16S rRNA gene sequencing results showed that HT treatment increased the relative abundance of Firmicutes and Lactobacillus and decreased the relative abundance of Bacteroidetes. Interestingly, Pearson correlation analysis showed that there were strong association between colonic Firmicutes, Lactobacillus, and Bacteroidetes and the activities of serum antioxidant enzymes. Meanwhile, HT significantly enhanced the colonic butyrate concentration in DQ-challenged mice. Additionally, HT treatment decreased the serum metabolites involving in glycerophospholipid metabolism, pentose, and glucuronate interconversions, which were associated with alleviated oxidative stress. These results indicate that oral administration of 100 mg/kg body weight HT alleviates oxidative stress in DQ-challenged mice, which may involve Nrf2 signaling pathways via modulation of colonic microbiota.
Assuntos
Antioxidantes , Fator 2 Relacionado a NF-E2 , Animais , Camundongos , Antioxidantes/farmacologia , Antioxidantes/metabolismo , Catalase/metabolismo , Fator 2 Relacionado a NF-E2/genética , Fator 2 Relacionado a NF-E2/metabolismo , Diquat/toxicidade , RNA Ribossômico 16S/metabolismo , Estresse OxidativoRESUMO
Benzalkyldimethylammonium (or benzalkonium; BACs), alkyltrimethylammonium (ATMACs), and dialkyldimethylammonium compounds (DDACs) have been widely used for over six decades as disinfectants, especially during the COVID-19 pandemic. Here we describe methods for the determination of 7 BACs, 6 ATMACs, 6 DDACs, 8 BAC metabolites, and the structurally similar quaternary ammonium compound (QAC) herbicides diquat, paraquat, and difenzoquat in human serum and urine using liquid chromatography-tandem mass spectrometry (LC-MS/MS). The methods were optimized using isotopically labelled internal standards and solid-phase extraction with weak cation-exchange cartridges. We separated diquat and paraquat chromatographically using a mixed-mode LC column, and BACs, ATMACs, DDACs, difenzoquat, and BAC metabolites using reversed-phase (C8 and C18) LC columns. Method limits of detection (MLODs) and quantification (MLOQs) were 0.002-0.42 and 0.006-1.40 ng/mL, respectively. Recoveries of all analytes fortified at 1, 5, and 20 ng/mL concentrations in serum and urine matrices were 61-129%, with standard deviations of 0-20%. Repeated analysis of similarly fortified serum and urine samples yielded intra-day and inter-day variations of 0.22-17.4% and 0.35-17.3%, respectively. Matrix effects for analytes spiked into serum and urine matrices ranged from -27% to 15.4%. Analysis of real urine and serum samples revealed the presence of several QACs in human serum. Although no parent BACs were found in urine, we detected, for the first time, several ω-hydroxy and ω-carboxylic acid metabolites of BACs at average concentrations in the range of 0.05-0.35 ng/mL. The developed method is suitable for application in large-scale biomonitoring of human exposure to QACs and their metabolites in human serum and urine.
Assuntos
COVID-19 , Paraquat , Humanos , Paraquat/urina , Cromatografia Líquida/métodos , Diquat/urina , Compostos de Benzalcônio , Compostos de Amônio Quaternário , Espectrometria de Massas em Tandem/métodos , PandemiasRESUMO
PURPOSE: This study aimed to develop and validate an ultraperformance liquid chromatography-tandem mass spectrometry to simultaneously determine diquat (DQ) and its two primary metabolites in rat plasma and its application to the toxicokinetic study. METHOD: The chromatographic separation of DQ and its two primary metabolites was performed with hydrophilic interaction chromatography column by adding formic acid and ammonium acetate in mobile phase in stepwise elution mode. DQ and its two primary metabolites were detected by liquid chromatography-tandem mass spectrometry in positive mode. RESULTS: The lower limit of quantification ranging from 0.3 to 3.0 ng/mL for DQ and its two primary metabolites was achieved by using only 50 µL of rat plasma. The maximum concentration (Cmax) was 977 ng/mL, half-life (t1/2) was 13.1 h, and area under the plasma concentration-time curve (AUC0-t) was 2770 h*ng/mL for DQ, Cmax was 47.1 ng/mL, t1/2 was 25.1 h, and AUC0-t was 180 h·ng/mL for diquat monopyridone (DQ-M) and Cmax was 246 ng/mL, t1/2 was 8.2 h, and AUC0-t was 2430 h·ng/mL for diquat dipyridone (DQ-D), respectively. CONCLUSIONS: The validated method was shown to be suitable for simultaneous determination of diquat and its two primary metabolites in rat plasma. This study is the first to study the toxicokinetics of DQ and its two primary metabolites.
Assuntos
Diquat , Espectrometria de Massas em Tandem , Ratos , Animais , Diquat/toxicidade , Toxicocinética , Cromatografia Líquida , PlasmaRESUMO
PURPOSE: Paraquat and diquat are well-known toxic herbicides, at least responsible for hundreds of fatal poisoning events worldwide. However, the determination of diquat and paraquat in plasma and urine is very challenging because of their high polarity and double charge characteristics. In this study, we aim to develop a rapid and reliable method for the determination of paraquat and diquat in human plasma and urine by ultraperformance liquid chromatography-tandem mass spectrometry. METHOD: The chromatographic separation of paraquat and diquat was tested with different chromatographic columns and different mobile phase conditions. The mass parameters were optimized by product ions, source gas flow, cone flow, desolvation temperature, and capillary voltage. The isocratic elution mode gave rapid appearance of peak of paraquat and diquat. RESULTS: The sharp peak shapes for paraquat and diquat were achieved with CORTECS® UPLC® HILIC (100 × 2.1 mm, 1.6 µm) column by adding formic acid and ammonium acetate in mobile phase in isocratic elution mode. The lower limit of quantification of 1.0 ng/mL for paraquat and diquat were achieved using only 50 µL of human plasma or urine. The running time for analysis of both paraquat and diquat was as short as 3.5 min per sample. CONCLUSIONS: A rapid and reliable method for the determination of paraquat and diquat was developed and applied to 387 clinical poisoning cases and 22 poisoning cases were found to be paraquat or diquat poisoning.
Assuntos
Diquat , Paraquat , Humanos , Espectrometria de Massas em Tandem , Cromatografia Líquida , Cromatografia Líquida de Alta Pressão , Hospitais , Serviço Hospitalar de EmergênciaRESUMO
OBJECTIVE: To investigate the effect of continuous hemoperfusion (HP) on the levels of soluble CD14 isoform (sCD14-st) and neutrophil gelatinase-associated lipocalin (NGAL) on patients with diquat (DQ) poisoning and its significance. METHODS: A total of 86 patients with acute DQ poisoning admitted to the department of emergency medicine, Harrison International Peace Hospital Affiliated to Hebei Medical University from May 2018 to August 2021 were enrolled and divided into the intermittent HP group (40 cases) and the continuous HP group (46 cases) according to the random number table method. All patients received basic treatment and continuous veno-venous hemofiltration (CVVH) within 24 hours after admission. On this basis, the intermittent HP group received HP treatment within 2 hours, lasting 2 hours each time for every 8 hours, 3 times in all; the continuous HP group received continued HP treatment until there was no DQ component in urine samples. Serum NGAL levels were detected in all patients before treatment and at 3 hours, 12 hours, 24 hours, 2 days, 3 days, 5 days, and 7 days after treatment. At the same time, serum sCD14-st, blood lactate (Lac), arterial partial pressure of oxygen (PaO2), serum creatinine (SCr), MB isoenzyme of creatine kinase (CK-MB) and interleukin-18 (IL-18) levels were detected before treatment and at 24 hours, 3 days, and 7 days after treatment. Kaplan-Meier survival curve was drawn to analyze the 28-day survival of patients. RESULTS: Before treatment, there was no significant difference in serum NGAL, sCD14-st, Lac, PaO2, SCr, CK-MB and IL-18 levels between the two groups. With the prolongation of treatment, the serum levels of NGAL, sCD14-st, Lac, SCr, CK-MB and IL-18 in the intermittent HP group increased at first and then decreased. Serum levels of NGAL, sCD14-st, CK-MB and IL-18 reached their peaks at 24 hours after treatment, and the Lac and SCr levels reached their peaks at 3 days after treatment. In addition, the levels of the above indexes at each time point in the continuous HP group were all significantly lower than those in the intermittent HP group [after 24 hours of treatment: NGAL (µg/L) was 345.90±30.75 vs. 404.24±38.79, sCD14-st (ng/L) was 1 941.88±298.02 vs. 2 656.35±347.93, CK-MB (U/L) was 30.67±9.11 vs. 43.28±8.06, IL-18 (ng/L) was 139.49±16.29 vs. 177.98±27.85; 3 days of treatment: Lac (mmol/L) was 2.98±0.26 vs. 3.72±0.49, SCr (µmol/L) was 125.01±24.24 vs. 156.74±28.88; all P < 0.05]. However, there was no significant difference in PaO2 levels between the two groups at each time point after treatment. The Kaplan-Meier survival curve showed that the 28-day mortality of patients in the continuous HP group was significantly lower than that in the intermittent HP group [26.09% (12/46) vs. 52.50% (21/40); Log-Rank test: χ 2 = 7.288, P = 0.007]. CONCLUSIONS: Continuous HP could effectively reduce serum sCD14-st, NGAL levels and 28-day mortality in patients with DQ poisoning, with good curative effect.
Assuntos
Diquat , Hemoperfusão , Lipocalina-2 , Receptores de Lipopolissacarídeos , Intoxicação , Humanos , Diquat/envenenamento , Hemoperfusão/métodos , Interleucina-18/sangue , Lipocalina-2/sangue , Receptores de Lipopolissacarídeos/sangue , Intoxicação/sangue , Intoxicação/mortalidade , Intoxicação/terapia , Terapia de Substituição Renal Contínua/métodosRESUMO
Diquat is a herbicide that can have deleterious effects on the kidneys, liver, heart, lungs, and central nervous system on ingestion. Diquat poisoning-associated rhabdomyolysis has rarely been reported. We describe two cases of diquat poisoning with acute renal failure, myocardial damage, and rhabdomyolysis. Case 1: A 17-year-old man experienced anuria after ingesting ~200 mL of diquat 16 h prior. On admission, his creatinine (400 µmol/L), urea (11.7 mmol/L), creatine kinase (2,534 IU/L), and myohemoglobin (4,425 ng/mL) concentrations were elevated. Case 2: An 18-year-old woman who ingested ~200 mL of diquat 5.5 h prior to admission had normal creatinine, urea, and creatine kinase concentrations. Eleven hours after ingestion, she developed anuria with elevated creatinine (169 µmol/L) concentration; her creatine kinase (13,617 IU/L) and myohemoglobin (>3,811 ng/mL) concentrations were remarkably elevated 24 h after ingestion. Both patients also had elevated aminotransferase and myocardial enzyme concentrations. After undergoing hemoperfusion and hemofiltration, blood diquat concentrations in cases 1 and 2 on admission (16/6 h after ingestion), after hemoperfusion (20/11 h after ingestion), and after 8 h of hemofiltration/8 h of hemofiltration and 2 h of hemoperfusion (29/21 h after ingestion) were 4.9/9.1, 3.4/5.4, and 1.5/1.2 µg/mL, respectively. Severe diquat poisoning can cause acute kidney failure and rhabdomyolysis. Rhabdomyolysis may induce myocardial injury, aggravating kidney damage, and also increase transaminase concentration. Hemoperfusion and hemofiltration could be effective treatments for eliminating diquat in the blood.
Assuntos
Injúria Renal Aguda , Anuria , Rabdomiólise , Humanos , Masculino , Feminino , Adolescente , Diquat , Creatinina , Rabdomiólise/induzido quimicamente , Injúria Renal Aguda/induzido quimicamente , Creatina Quinase , UreiaRESUMO
Determining the presence of paraquat (PQ) and diquat (DQ) in urine samples through physical and chemical testing is challenging. As PQ and DQ have characteristics such as high molecular polarity and good water solubility, they are difficult to be retained by conventional reversed-phase columns. Most of the methods in the literature use hydrophilic interaction chromatography (HILIC) for the retention of PQ and DQ, but they often require high concentrations of buffer salts as the mobile phase, which increase the contamination of the mass spectrometer. In view of the above problems, a rapid and accurate analysis method was developed for the determination of PQ and DQ residuals in urine samples based on weak cation exchange (WCX) solid-phase extraction (SPE) and ultra performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS) in this study. Urine samples were first diluted with phosphate buffer (pH=6.86) and pretreated using the WCX SPE method. Chromatographic separation was performed on a Syncronis HILIC column (100 mm×2.1 mm, 1.7 µm). An electrospray ion source in the positive (ESI+) mode and full mass-data dependent MS2 (full mass-ddMS2) mode was used for quantification by matrix-matched external standard method. In this study, the concentration of ammonium formate in the mobile phase in the HILIC mode was effectively reduced to 10 mmol/L by the continuous optimization of the chromatographic conditions. MS optimization results indicated that the molecular ion (M+·) of PQ and DQ had the strongest response. In addition, sample pretreatment conditions were also optimized. The obtained results indicated that the hydrophobic polytetrafluoroethylene (PTFE) filter membrane, acetonitrile-water (1â¶1, v/v) as a fixing solution, and polypropylene vials were suitable for PQ and DQ analysis. Under the optimal conditions, the linearity of PQ and DQ was good with correlation coefficients (r2) greater than 0.998. The limits of detection (LODs, S/N≥3) and limits of quantification (LOQs, S/N≥10) were 0.2 µg/L and 0.6 µg/L, respectively. Mean spiked recoveries of PQ and DQ at the four spiked levels (1.0, 20.0, 100.0, and 200.0 µg/L) were in the range of 85.8%-101% and 80.3%-86.9%, with the RSDs of 0.8%-5.1% and 0.9%-4.2%. The established method was employed for the analysis and confirmation of PQ and DQ for clinical poisoning cases. In one case, a 23-year-old male who had taken approximately 20 mL of pesticide orally was confirmed as DQ poisoning by the developed method. DQ concentration monitoring of the urine samples was conducted for this case during the clinical treatment process. The patient was successfully discharged from the hospital after five times of blood perfusion and other treatments until the DQ concentration was low in the urine samples. In conclusion, the method developed in this study based on WCX SPE-UPLC-HRMS can be used for the confirmation of poisoning cases and concentration monitoring during clinical treatment, providing strong technical support for clinical precision treatment. The method is rapid, simple, sensitive, and accurate, and it is suitable for the detection of PQ and DQ in urine samples.
Assuntos
Diquat , Paraquat , Masculino , Humanos , Adulto Jovem , Adulto , Cromatografia Líquida , Espectrometria de Massas , Extração em Fase SólidaRESUMO
In terms of the structure of polar pollutants, the design and development of new materials that can interact with target analytes is vital for effective extraction. Diquat is a broad-spectrum herbicide with strong toxicity. It is sprayed during the growing process of vegetables because of its high efficiency and low cost. Furthermore, diquat is a polar and basic cationic organic compound. Therefore, it is necessary to develop adsorbents that can form strong interaction with diquat to extract it from complex vegetable samples. In this study, sulfonic acid-functionalized ionic liquid, 1-vinyl-3-propyl(3'-sulfonate) imidazolium chloride ([VPImi-SO3H][Cl]), was synthesized through the reaction of 1-vinylimidazole and 1,3-propanesultone and characterized using nuclear magnetic-resonance spectroscopy. The resulting [VPImi-SO3H][Cl] was then immobilized on the surface of vinyl-modified magnetic silica to obtain poly-(1-vinyl-3-propyl(3'-sulfonate) imidazolium chloride)-modified magnetic nanoparticles (Poly([VPImi-SO3H][Cl])-MP) via free radical polymerization between vinyl groups. The structure, morphology and magnetism of the obtained Poly([VPImi-SO3H][Cl])-MP were characterized using Fourier transform infrared spectroscopy, scanning electron microscope, vibrating sample magnetometer, and thermogravimetric analysis. The characterization results indicated that the Poly([VPImi-SO3H][Cl])-MP was synthesized with strong magnetic properties. Poly([VPImi-SO3H][Cl])-MP as magnetic adsorbent exhibited a different pH response to anion and cation. With the increase in solution pH, the adsorption efficiency of Poly([VPImi-SO3H][Cl])-MP for anionic dye amaranth decreased; whereas, the adsorption efficiency for cationic dye, methylene blue, increased. Under a high pH condition, sulfonic acid groups on the surface of Poly([VPImi-SO3H][Cl])-MP existed in the form of -SO3-. Thus, the adsorption efficiency of Poly([VPImi-SO3H][Cl])-MP for methylene blue could reach 95.2% due to the strong electrostatic attraction between adsorbent and positively charged methylene blue; whereas, negatively charged amaranth could hardly be adsorbed due to the electrostatic repulsion between adsorbent and amaranth. The above results showed sulfonic acid modification endowed Poly([VPImi-SO3H][Cl])-MP with abundant negative charges at certain pH conditions. Thus, the extraction can be achieved by the strong electrostatic attraction between negatively charged Poly([VPImi-SO3H][Cl])-MP and positively charged diquat. Using green vegetables as the sample matrix and magnetic solid-phase extraction as extraction model, the extraction performance of Poly([VPImi-SO3H][Cl])-MP for diquat was studied. Some extraction parameters affecting the extraction efficiency, such as solution pH, adsorbent amount, adsorption time, desorption solvent and its volume, and desorption time were optimized using the single factor experiment method. Under the optimized extraction conditions (30 mg of adsorbent, 15 min of adsorption time, 40 µL of ammonia, 600 µL of acetonitrile-formic acid (9â¶1, v/v) as desorption solvent, 1 min of desorption time), the performance, and applicability of the proposed method were investigated by combining magnetic solid-phase extraction, high performance liquid chromatography, and UV-visible detector. Good linearity was observed at contents ranging from 0.2 to 20 µg/g with a correlation coefficient (r) of 0.9981. The limit of detection and limit of quantification based on the signal-to-noise ratio of 3â¶1 and 10â¶1 were 0.09 and 0.2 µg/g, respectively. The spiked recoveries at three levels of 0.5, 1.0, and 2.5 µg/g were obtained in the range of 82.7%-97.5% with the relative standard deviations of 2.8%-5.0% (n=3). The results showed that the sulfonic acid-functionalized Poly([VPImi-SO3H][Cl])-MP could be employed as a magnetic adsorbent for the quick and effective extraction of diquat, and the proposed method could be used for the determination of diquat from green vegetable samples. It could be anticipated that Poly([VPImi-SO3H][Cl])-MP could be used as an adsorbent for extracting other cationic polar pollutants by adjusting the solution pH. This work provides a new way to construct adsorbents for extracting polar pollutants.
Assuntos
Poluentes Ambientais , Herbicidas , Líquidos Iônicos , Acetonitrilas , Adsorção , Amônia , Ânions , Cromatografia Líquida de Alta Pressão , Diquat , Líquidos Iônicos/química , Limite de Detecção , Fenômenos Magnéticos , Azul de Metileno , Polímeros/química , Dióxido de Silício , Extração em Fase Sólida/métodos , Solventes , Ácidos Sulfônicos , Verduras/químicaRESUMO
Selenium nanoparticles (SeNPs) with unique biological properties have been suggested as a safer and more effective platform for delivering of Selenium for biological needs. In this study, we investigated the association between gut microbiota altered by SeNPs supplementation and its metabolites under oxidative stress conditions through 16S rDNA gene sequencing analysis and untargeted metabolomics. The results showed that dietary supplementation with SeNPs attenuated diquat-induced acute toxicity in mice, as demonstrated by lower levels of inflammatory effector cells, and biochemical markers in serum such as aspartate aminotransferase (AST), alanine aminotransferase (ALT), blood urea nitrogen (BUN) and lactate dehydrogenase (LDH). SeNPs also reversed the perturbed gut microbiota composition induced by diquat, decreased the Firmicutes/Bacteroidetes ratio, and increased the abundance of beneficial bacteria such as Akkermansia, Muribaculaceae, Bacteroides and Parabacteroides. Untargeted fecal metabolomics showed that SeNPs can regulate the production of steroids and steroid derivatives, organonitrogen compounds, pyridines and derivatives and other metabolites. Microbiome-metabolome correlation analysis suggested that Parabacteroides was the key bacteria for the SeNPs intervention, which might upregulate the levels of metabolites such as trimethaphan, emedastine, berberine, desoxycortone, tetrahydrocortisone. This study demonstrated that dietary SeNPs supplementation can extensively modulate the gut microbiota and its metabolism, thereby alleviating diquat-induced acute toxicity.
Assuntos
Microbioma Gastrointestinal , Nanopartículas , Selênio , Camundongos , Animais , Selênio/farmacologia , Selênio/química , Diquat/toxicidade , Metaboloma , Nanopartículas/toxicidade , Nanopartículas/química , BactériasRESUMO
Paraquat (PQ) is one of the most commonly used herbicides, but it has polluted the environment and threatened human health through extensive and improper usage. Here, a new naked-eye PQ immunochromatographic strip was developed to recognize PQ in domestic water and real human samples within 10 min based on a novel custom-designed anti-PQ antibody. The PQ test strip could recognize PQ at a concentration as low as 10 ng/ml, reaching the high-efficiency time-of-flight mass spectrometry detection level and identifying trace amounts of PQ in samples treated with a diquat (DQ) and PQ mixture. Notably, both the performance evaluation and clinical trial of the proposed PQ strips were validated in multiple hospitals and public health agencies. Taken together, our study firstly provide the clinical PQ-targeted colloidal gold immunochromatographic test strip designed both for environment water and human sample detection with multiple advantages, which are ready for environmental monitoring and clinical practice.
Assuntos
Herbicidas , Paraquat , Humanos , Água , Diquat/análise , Herbicidas/análise , Espectrometria de Massas/métodosRESUMO
In recent years, with the withdrawal of paraquat (PQ) pesticides from the market, the number of poisoning cases caused by its substitute diquat (DQ) has shown an increasing trend year by year. Among the clinical manifestations of DQ poisoning, the damage to the central nervous system is relatively common and serious, but the specific toxicity mechanism is not clear, and there is no clear treatment. This article reviews the nervous system damage caused by DQ poisoning in order to improve the understanding systen of DQ poisoning.
Assuntos
Herbicidas , Intoxicação , Diquat , Humanos , Sistema Nervoso , ParaquatRESUMO
Although diquat is a widely used water-soluble herbicide in the world, its sublethal adverse effects to fish have not been well characterised. In this study, histopathological examination and biochemical assays were applied to assess hepatotoxicity and combined with gas chromatography-mass spectrometry (GC-MS)-based metabolomics analysis to reveal overall metabolic mechanisms in the liver of zebrafish (Danio rerio) after diquat exposure at concentrations of 0.34 and 1.69 mg·L-1 for 21 days. Results indicated that 1.69 mg·L-1 diquat exposure caused cellular vacuolisation and degeneration with nuclear abnormality and led to the disturbance of antioxidative system and dysfunction in the liver. No evident pathological injury was detected, and changes in liver biochemistry were not obvious in the fish exposed to 0.34 mg·L-1 diquat. Multivariate statistical analysis revealed differences between profiles obtained by GC-MS spectrometry from control and two treatment groups. A total of 17 and 22 metabolites belonging to different classes were identified following exposure to 0.34 and 1.69 mg·L-1 diquat, respectively. The metabolic changes in the liver of zebrafish are mainly manifested as inhibition of energy metabolism, disorders of amino acid metabolism and reduction of antioxidant capacity caused by 1.69 mg·L-1 diquat exposure. The energy metabolism of zebrafish exposed to 0.34 mg·L-1 diquat was more inclined to rely on anaerobic glycolysis than that of normal zebrafish, and interference effects on lipid metabolism were observed. The metabolomics approach provided an innovative perspective to explore possible hepatic damages on fish induced by diquat as a basis for further research.
Assuntos
Herbicidas , Poluentes Químicos da Água , Animais , Diquat/metabolismo , Diquat/toxicidade , Embrião não Mamífero/metabolismo , Herbicidas/toxicidade , Fígado/metabolismo , Poluentes Químicos da Água/toxicidade , Peixe-Zebra/metabolismoRESUMO
Mitochondria-associated endoplasmic reticulum (ER) membranes (MAMs) are not only critical for the communication between two organelles but also crucial for cellular processes such as energy metabolism, calcium signaling, and mitochondrial dynamics. The effects of curcumin on jejunal mitochondria, ER, and MAMs in piglets under diquat-induced oxidative stress were assessed. Twenty-four piglets (35 days old, weaned at 21 days, 9.54 ± 0.28 kg, six piglets per group) were used in the study: (1) control group; (2) control + curcumin group; (3) diquat group; and (4) diquat + curcumin group. Curcumin was mixed with the basic diet at 200 mg/kg and fed to piglets. Piglets were administered intraperitoneally of 0.9% saline solution or diquat at 10 mg/kg body weight on the first day. Compared with the diquat group, curcumin improved jejunal morphology and barrier function. Meanwhile, curcumin improved mitochondrial function and ultrastructure, alleviated endoplasmic reticulum stress (ERS), and inhibited apoptosis induced by diquat. Moreover, curcumin prevented excessive MAM formation and alleviated MAM disorder. In conclusion, dietary curcumin ameliorated jejunal damage and mitochondrial dysfunction, attenuated ERS, and alleviated MAM disorder in oxidative stress piglets induced by diquat.
Assuntos
Curcumina , Diquat , Animais , Curcumina/metabolismo , Curcumina/farmacologia , Diquat/toxicidade , Retículo Endoplasmático/metabolismo , Estresse do Retículo Endoplasmático , Jejuno/metabolismo , Mitocôndrias/metabolismo , Estresse Oxidativo , SuínosRESUMO
The objective of this study was to evaluate the use of diquat, glufosinate ammonium, saflufenacil and flumioxazim, positioned alone and/or combined, in the pre-harvest desiccation of soybean crops. For this purpose, a field experiment was conducted, with application of the treatments in the phenological stage R 7.2 of soybean. At 3 DAA, the herbicides diquat and their combinations with flumioxazin and ammonium glufosinate, at all doses, resulted in defoliation and desiccation percentages greater than 90%. At 5 DAA, only the flumioxazin and glufosinate ammonium treatments, alone, did not show indices for harvesting. At 10 DAA, only the control differed from the other treatments in relation to desiccation, demonstrating the need to apply desiccants to enable harvest. The results indicate that the combination of herbicides may represent an alternative to reduce doses and increase the efficacy of isolated products through synergism, in addition to operational gains.
