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1.
Molecules ; 28(14)2023 Jul 08.
Artigo em Inglês | MEDLINE | ID: mdl-37513164

RESUMO

Dicofol is a highly toxic residual pesticide in tea, which seriously endangers human health. A method for detecting dicofol in tea by combining stoichiometry with surface-enhanced Raman spectroscopy (SERS) technology was proposed in this study. AuNPs were prepared, and silver shells were grown on the surface of AuNPs to obtain core-shell Au@AgNPs. Then, the core-shell Au@AgNPs were attached to the surface of a PDMS membrane by physical deposition to obtain a Au@AgNPs/PDMS substrate. The limit of detection (LOD) of this substrate for 4-ATP is as low as 0.28 × 10-11 mol/L, and the LOD of dicofol in tea is 0.32 ng/kg, showing high sensitivity. By comparing the modeling effects of preprocessing and variable selection algorithms, it is concluded that the modeling effect of Savitzky-Golay combined with competitive adaptive reweighted sampling-partial least squares regression is the best (Rp = 0.9964, RPD = 10.6145). SERS technology combined with stoichiometry is expected to rapidly detect dicofol in tea without labels.


Assuntos
Nanopartículas Metálicas , Análise Espectral Raman , Humanos , Análise Espectral Raman/métodos , Dicofol , Ouro/química , Quimiometria , Nanopartículas Metálicas/química , Chá/química
2.
Molecules ; 28(9)2023 Apr 27.
Artigo em Inglês | MEDLINE | ID: mdl-37175171

RESUMO

Although dicofol has been widely banned all over the world as a kind of organochlorine contaminant, it still exists in the environment. This study developed a high-performance liquid chromatography coupled with mass spectrometry (HPLC-MS/MS) detection technique for dicofol, an environmental pollutant, for the first time using in-source fragmentation. The results confirmed that m/z 251 was the only precursor ion of dicofol after in-source fragmentation, and m/z 139 and m/z 111 were reasonable product ions. The main factors triggering the in-source fragmentation were the H+ content and solution conductivity when dicofol entered the mass spectrometer. Density functional theory can be used to analyze and interpret the mechanism of dicofol fragmentation reaction in ESI source. Dicofol reduced the molecular energy from 8.8 ± 0.05 kcal/mol to 1.0 ± 0.05 kcal/mol, indicating that the internal energy release from high to low was the key driving force of in-source fragmentation. A method based on HPLC-MS/MS was developed to analyze dicofol residues in environmental water. The LOQ was 0.1 µg/L, which was better than the previous GC or GC-MS methods. This study not only proposed an HPLC-MS/MS analysis method for dicofol for the first time but also explained the in-source fragmentation mechanism of compounds in ESI source, which has positive significance for the study of compounds with unconventional mass spectrometry behavior in the field of organic pollutant analysis and metabonomics.

3.
Ecotoxicol Environ Saf ; 171: 1-11, 2019 Apr 30.
Artigo em Inglês | MEDLINE | ID: mdl-30583221

RESUMO

The Pearl River Delta (PRD) is one of the areas with higher environmental concentration of organochlorine pesticides (OCPs), being DDT one of the most abundant. In this work, 4,4'-dichlorobenzophenone (4,4'-DCBP), a common metabolite of dicofol (DDT related) and DDT, was quantified in surface waters of Hong Kong and Macao, together with the analysis of physicochemical and nutrients parameters. Hong Kong presented higher 4,4'-DCBP mean levels (12.50 ng/L) than Macao (4.05 ng/L), which may be due to the use of dicofol as a pesticide and DDT as antifouling-paint for ships. The region presented a possible eutrophication state due to the high nutrients' concentration. For the first time, toxicity evaluation of this metabolite in Artemia salina and Daphnia magna was done, in order to compute valid EC50s and theoretically evaluate the risk in the PRD. The toxicity results (EC50 = 0.27 mg/L for A. salina; and EC50 = 0.17 mg/L and LC50 = 0.26 mg/L for D. magna), together with the 4,4'-DCBP levels quantified, indicated a low environmental risk.


Assuntos
Artemia/efeitos dos fármacos , Benzofenonas/análise , Benzofenonas/toxicidade , Daphnia/efeitos dos fármacos , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidade , Animais , Monitoramento Ambiental , Hong Kong , Hidrocarbonetos Clorados/análise , Hidrocarbonetos Clorados/toxicidade , Macau , Resíduos de Praguicidas/análise , Resíduos de Praguicidas/toxicidade , Rios/química , Qualidade da Água
4.
Pestic Biochem Physiol ; 143: 127-134, 2017 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-29183581

RESUMO

Organochlorine pesticides have generated growing concern owing to their diverse toxicities. In this connection, we have evaluated toxic potential of an acaricide, dicofol (DCF) and its harmful effects on human RBCs and lymphocytes. DCF caused hemolysis and rupture of human erythrocytes as confirmed by scanning electron microscopy (SEM). Significant increase in protein oxidation, lipid peroxidation, ROS production, methemoglobin formation with enhanced activities of superoxide dismutase and catalase but decreased level of reduced glutathione were observed as a result of DCF exposure to human erythrocytes. SEM showed significant DCF induced alterations in RBCs from normal discoid shape to echinocytes. Similarly, lymphocytes showed membrane damage, formation of membrane blebs and distorted cell morphology. In vitro comet assay indicated a significant DNA fragmentation in human lymphocytes upon DCF exposure. These results strongly suggest that DCF induces oxidative stress in RBCs via generation of ROS and alters the cellular architecture directly and indirectly.


Assuntos
Dicofol/toxicidade , Eritrócitos/efeitos dos fármacos , Inseticidas/toxicidade , Linfócitos/efeitos dos fármacos , Adulto , Catalase/metabolismo , Células Cultivadas , Ensaio Cometa , Dano ao DNA , Eritrócitos/metabolismo , Eritrócitos/patologia , Eritrócitos/ultraestrutura , Glutationa/metabolismo , Hemólise/efeitos dos fármacos , Humanos , Linfócitos/metabolismo , Linfócitos/patologia , Linfócitos/ultraestrutura , Malondialdeído/metabolismo , Metemoglobina/metabolismo , Microscopia Eletrônica de Varredura , Superóxido Dismutase/metabolismo
5.
J Sep Sci ; 39(12): 2388-95, 2016 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-27119595

RESUMO

In this work, a novel dual-template magnetic molecularly imprinted polymer particle for dicofol and chlorpyrifos-methyl was prepared through oil-in-water emulsifier-free emulsion technology. The resulting magnetic particles were characterized with electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. It was found that as-prepared particles were well-shaped spheres with multi-hollow structures and of a size around 125 µm. Meanwhile it showed a good magnetic sensitivity. The results testified that multi-hollow magnetic molecularly imprinted polymers possessed excellent recognition capacity and fast kinetic binding behavior to the objective molecules. The maximum binding amounts toward dicofol and chlorpyrifos-methyl were 31.46 and 25.23 mg/g, respectively. The feasibility of the use of the particles as a solid-phase extraction sorbent was evaluated. Satisfactory recoveries ranging from 90.62 to 111.47 and 91.07 to 94.03% were obtained for dicofol and chlorpyrifos-methyl, respectively, spiked at three concentration levels from real samples. The Langmuir isotherm equation provided an excellent fit to the equilibrium sorption data of either dicofol or chlorpyrifos-methyl. It provided a novel way to advise dual-template magnetic molecularly imprinted polymer particles to adsorb pesticides with high selectivity.

6.
J Environ Sci (China) ; 36: 22-8, 2015 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-26456602

RESUMO

It remains unclear whether dicofol should be defined as a persistent organic pollutant. Its environmental persistence has gained attention. This study focused on its degradation by cellulase. Cellulase was separated using a gel chromatogram, and its degradation activity towards dicofol involved its endoglucanase activity. By analyzing the kinetic parameters of cellulase reacting with mixed substrates, it was shown that cellulase reacted on dicofol and carboxyl methyl cellulose through two different active centers. Thus, the degradation of dicofol was shown to be an oxidative process by cellulase. Next, by comparing the impacts of tert-butyl alcohol (a typical OH free-radical inhibitor) on the removal efficiencies of dicofol under both cellulase and Fenton reagent systems, it was shown that the removal of dicofol was initiated by OH free radicals produced by cellulase. Finally, 4,4'-dichloro-dibenzophenone and chloride were detected using gas chromatography mass spectrometry and ion chromatography analysis, which supported our hypothesis. The reaction mechanism was analyzed and involved an attack by OH free radicals at the orthocarbon of dicofol, resulting in the degradation product 4,4'-dichloro-dibenzophenone.


Assuntos
Celulase/metabolismo , Dicofol/metabolismo , Inseticidas/metabolismo , Poluentes Químicos da Água/metabolismo , Cromatografia por Troca Iônica , Dicofol/química , Cromatografia Gasosa-Espectrometria de Massas , Peróxido de Hidrogênio/química , Inseticidas/química , Ferro/química , Cinética , Poluentes Químicos da Água/química
7.
J Environ Sci (China) ; 33: 163-8, 2015 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-26141889

RESUMO

A new technique whereby cellulase immobilized on aminated silica was applied to catalyze the degradation of dicofol, an organochlorine pesticide. In order to evaluate the performance of free and immobilized cellulase, experiments were carried out to measure the degradation efficiency. The Michaelis constant, Km, of the reaction catalyzed by immobilized cellulase was 9.16 mg/L, and the maximum reaction rate, Vmax, was 0.40 mg/L/min, while that of free cellulase was Km=8.18 mg/L, and Vmax=0.79 mg/L/min, respectively. The kinetic constants of catalytic degradation were calculated to estimate substrate affinity. Considering that metal ions may affect enzyme activity, the effects of different metal ions on the catalytic degradation efficiency were explored. The results showed that the substrate affinity decreased after immobilization. Monovalent metal ions had no effect on the reaction, while divalent metal ions had either positive or inhibitory effects, including activation by Mn2+, reversible competition with Cd2+, and irreversible inhibition by Pb2+. Ca2+ promoted the catalytic degradation of dicofol at low concentrations, but inhibited it at high concentrations. Compared with free cellulase, immobilized cellulase was affected less by metal ions. This work provided a basis for further studies on the co-occurrence of endocrine-disrupting chemicals and heavy metal ions in the environment.


Assuntos
Celulase/metabolismo , Dicofol/metabolismo , Metais/farmacologia , Praguicidas/metabolismo , Celulase/química , Dicofol/química , Poluentes Ambientais/química , Enzimas Imobilizadas/química , Enzimas Imobilizadas/metabolismo , Cinética , Praguicidas/química
8.
Chemosphere ; 341: 139997, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37648173

RESUMO

BACKGROUND: Environmental exposure to dicofol (DCF), one of common organochlorine pesticides (OCPs) widely used for controlling agricultural pests, elicits a potential risk for human health due to its toxicity. However, potential physiological hazards of oral DCF exposure remain largely unknown. METHODS: Mice were exposed to relatively chronic and subacute DCF at different doses (5, 20 and 100 mg/kg) by gavage for 2 weeks. 1H NMR-based metabolomics was used to explore alterations of metabolic profiling induced by DCF exposure. Targeted metabolomics was subsequently employed to investigate the dose-dependent effects of oral DCF exposure on lipid metabolism and the gut microbiota-derived metabolites of mice. 16S rRNA gene sequencing was further employed to evaluate the changes of gut community of mice exposed to DCF. RESULTS: Oral exposure to DCF dose-dependently induced liver injury, manifested by hepatic lipogenesis, inflammation and liver dysfunction of mice. Typically, DCF exposure disrupted host fatty acids metabolism that were confirmed by marked alteration in the levels of related genes. DCF exposure also dose-dependently caused dysbiosis of the gut bacteria and its metabolites including altered microbial composition accompanied by inhibition of bacterial fermentation. CONCLUSION: These results provide metabolic evidence that DCF exposure dose-dependently induces liver lipidosis and disruption of the gut microbiota in mice, which enrich our views of molecular mechanism of DCF hepatoxicity.


Assuntos
Microbioma Gastrointestinal , Humanos , Camundongos , Animais , Dicofol , RNA Ribossômico 16S/genética , Multiômica , Homeostase , Bactérias/genética , Disbiose/induzido quimicamente
9.
Environ Sci Pollut Res Int ; 30(4): 8732-8745, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-35404035

RESUMO

The residues of pesticides that reach water resources from agricultural activities in several ways contaminate drinking water resources and threaten aquatic life. This study aimed to investigate the performance of three reverse osmosis (RO) membranes (BW30-LE, SW30-XLE, and GE-AD) in rejecting four different pesticides (tributyl phosphate, flutriafol, dicofol, and irgarol) from secondary treated urban wastewater and also to elucidate the mechanisms underlying the rejection of these pesticides. RO experiments were conducted using pesticide-spiked wastewater samples under 10 and 20 bar transmembrane pressures (TMP) and membrane performances were evaluated. Overall, all the membranes tested exhibited over 95% rejection performances for all pesticides at both TMPs. The highest rejections for tributyl phosphate (99.0%) and irgarol (98.3%) were obtained with the BW30-LE membrane, while for flutriafol (99.9%) and dicofol (99.1%) with the GE-AD membrane. The increase in TMP from 10 to 20 bar did not significantly affect the rejections of all pesticides. The rejection performances of RO membranes were found to be governed by projection area as well as molecular weight and hydrophobicity/hydrophilicity of pesticides. Among the membranes tested, the SW30-XLE membrane was the most prone to fouling due to the higher roughness.


Assuntos
Praguicidas , Purificação da Água , Águas Residuárias , Dicofol , Osmose , Filtração , Membranas Artificiais
10.
Chemosphere ; 311(Pt 1): 137002, 2023 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-36419270

RESUMO

Human exposure to persistent organic pollutants (POPs) is reflected by POP concentrations in breast milk. Many studies of POPs in breast milk have been performed in Japan, but insufficient information is available about some legacy POPs (e.g., mirex and toxaphenes, included in the Stockholm Convention in 2001) and novel POPs (e.g., dicofol and endosulfans, included in the Stockholm Convention in 2019 and 2011, respectively). In this study, dicofol, endosulfan, mirex, and toxaphene concentrations in breast milk from 10 prefectures in Japan were determined. The samples were collected between 2005 and 2010, before Stockholm Convention restrictions on endosulfans and mirex were implemented. Common POPs (e.g., polychlorinated biphenyls) were also analyzed to allow the contamination statuses to be compared. The α-endosulfan and ß-endosulfan concentrations were 0.26-13 and 0.012-0.82 ng/g lipid, respectively. The toxaphene #26 and #50 concentrations were <0.08-5.6 and < 0.1-8.5 ng/g lipid, respectively. The dicofol concentrations were <0.01-4.8 ng/g lipid. The mirex concentrations were <0.2-3.5 ng/g lipid. The α- and ß-endosulfan concentrations on a lipid weight basis negatively correlated with the lipid contents of the milk samples (ρ = -0.65, p < 0.01 for α-endosulfan; ρ = -0.58, p < 0.01 for ß-endosulfan). The toxaphene concentrations positively correlated with the lipid contents. The mirex concentrations positively correlated with the maternal age but negatively correlated with the maternal body mass index. No correlations between the dicofol concentrations and the factors were found. Principal component analysis divided the data into four groups, (1) chlordanes, dichlorodiphenyltrichloroethanes and related compounds, hexachlorobenzene, hexachlorocyclohexanes, hexachloroethane, and polychlorinated biphenyls, (2) endosulfans, (3) dicofol, dieldrin, and toxaphenes, and (4) bromodiphenyl ether 47. This indicated that bromodiphenyl ether 47, dicofol, endosulfans, and toxaphenes have different exposure routes or different kinetics to the other legacy POPs.


Assuntos
Poluentes Ambientais , Bifenilos Policlorados , Toxafeno , Feminino , Humanos , Dicofol/análise , Endossulfano/análise , Mirex/análise , Leite Humano/química , Bifenilos Policlorados/análise , Japão , Monitoramento Ambiental , Poluentes Ambientais/análise , Éteres , Lipídeos
11.
EFSA J ; 21(11): e08425, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-38027437

RESUMO

In accordance with Article 43 of Regulation (EC) 396/2005, EFSA received a request from the European Commission to review the existing maximum residue levels (MRLs) for the non-approved active substance dicofol in view of the possible lowering of the MRL. EFSA investigated the origin of the current EU MRLs. All existing EU MRLs reflect previously authorised uses in the EU or are based on obsolete Codex Maximum Residue Limits. Furthermore, in view of the limitations of the toxicological dataset and related uncertainties, the existing toxicological reference values derived at the EU level cannot be confirmed for dicofol. EFSA therefore proposed lowering all existing EU MRLs for dicofol to the limit of quantification.

12.
Spectrochim Acta A Mol Biomol Spectrosc ; 264: 120277, 2022 Jan 05.
Artigo em Inglês | MEDLINE | ID: mdl-34455384

RESUMO

Dicofol, a broad-spectrum acaricide, has garnered considerable attention because of the potential harm to the environment and various organisms. Herein, this study applied spectroscopic and in silico methods to understand the interaction between human serum albumin (HSA) and dicofol. Fluorescence experiments demonstrated that dicofol formed a stable complex and the binding process occurred in Suldow's site I of HSA. Its binding constant was 2.26 × 105 M-1 at 298 K. Van der Waals forces and hydrogen bond were primarily facilitated the interaction between dicofol and HSA (ΔH < 0, ΔS < 0) according to thermodynamic experiments. Additionally, 3D fluorescence and circular dichroism (CD) spectra revealed a few conformational changes in HSA due to dicofol. Molecular docking analysis indicated that dicofol interacted with Ser192, Gln196, Leu481, Arg218, Leu238, and Phe211 via van der Waals forces and formed a hydrogen bond with His242. Molecular dynamics (MD) simulation showed that Lys195 and Arg218 residues contributed greater energy for forming the HSA-dicofol complex. MD simulation analysis also showed that dicofol can affect the HSA structure with a reduction in α-helix. This research is desired to facilitate a new perspective on the toxicity mechanism of dicofol in the human body.


Assuntos
Dicofol , Albumina Sérica Humana , Sítios de Ligação , Dicroísmo Circular , Humanos , Simulação de Acoplamento Molecular , Ligação Proteica , Albumina Sérica Humana/metabolismo , Espectrometria de Fluorescência , Termodinâmica
13.
Food Chem ; 370: 131033, 2022 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-34509146

RESUMO

Dicofol is an organochlorine pesticide, which is widely used in fruits, tea and other crops, and is moderately toxic to humans. Therefore, the monitoring of organochlorine pesticide-dicofol is critical for food safety. In this work, a fluorometric chemosensor based on mercaptoethanol and boron dipyrromethene (BODIPY) was first constructed to detect the dicofol. The chemosensor displayed turn-off fluorescence behavior upon dicofol with a detection limit of 200 ppb. The nucleophilicity of the glutathione and other biological thiols was studied to evaluate the reactivity of thiols with dicofol. In practical applications, an obvious color difference was observed on a paper based microfluidic device modified by phenyltriethoxysilane (PTES). We designed an integrated device for pretreatment and paper-based detection, and successfully used for the detection of dicofol in tea. The applicability was demonstrated by detection of dicofol in real tea samples with good recovery ranging from 86% to 109%. The apparatus was convenient and could be used for on-site evaluation of dicofol.


Assuntos
Dicofol , Praguicidas , Boro , Humanos , Porfobilinogênio/análogos & derivados
14.
Artigo em Inglês | MEDLINE | ID: mdl-35329028

RESUMO

To identify bioaccumulation patterns of α-, ß- hexachlorocyclohexane (HCH) and dicofol in relation to sociodemographic, dietary, and lifestyle factors, adipose tissue samples of 387 subjects from GraMo cohort in Southern Spain were analyzed. Potential predictors of these organochlorine pesticides (OCP) levels were collected by face-to-face interviews and assessed by multivariable linear and logistic regression. OCPs were detected in 84.2% (ß-HCH), 21.7% (α-HCH), and 19.6% (dicofol) of the population. ß-HCH levels were positively related to age, body mass index (BMI), mother's occupation in agriculture during pregnancy, living in Poniente and Alpujarras, white fish, milk and water consumption, and negatively related to being male, living near to an agricultural area, working ≥10 years in agriculture, and beer consumption. Detectable α-HCH levels were positively related to age, BMI, milk consumption, mother's occupation in agriculture during pregnancy, and negatively with residence in Poniente and Alpujarras, Granada city, and Granada Metropolitan Area. Residence near to an agricultural area, smoking habit, white fish and water consumption, and living in Poniente and Alpujarras, Granada city and Granada Metropolitan Area were negatively associated with detectable dicofol levels. Our study revealed different bioaccumulation patterns of α, ß-HCH and dicofol, probably due to their dissimilar period of use, and emphasize the need for assessing the exposure to frequently overlooked pollutants.


Assuntos
Hidrocarbonetos Clorados , Praguicidas , Tecido Adiposo/química , Animais , Bioacumulação , Dicofol , Feminino , Hexaclorocicloexano/análise , Humanos , Hidrocarbonetos Clorados/análise , Masculino , Praguicidas/análise , Gravidez , Espanha
15.
Anal Chim Acta ; 1224: 340235, 2022 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-35998992

RESUMO

To minimize the need of complex testing procedures, accurate, rapid and selective on-site determination of dicofol (DICO) is of vital importance. Herein, fluorescence immunosensing platforms based on the Förster resonance energy transfer (FRET) between Au-Ag bimetallic nanoclusters (Au-Ag NCs) and Au nanoflowers (Au NFs) were developed for the rapid detection of DICO in both liquid system and paper-based analytical devices (PADs). Conjugations of Au-Ag NCs and antigen (NCs-Agen) and Au-Ag NCs were regarded as energy donors in liquid system and PADs, respectively, while conjugations of Au NFs and antibody (NFs-Ab) were synthesized as energy acceptors. The overlapping spectrum and decrease of fluorescence lifetime of NCs-Agen proved that the fluorescence quenching mechanism was FRET effect. When DICO was captured by NFs-Ab, FRET effect was inhibited due to the long distance between NFs-Ab and NCs/NCs-Agen. Under optimal conditions, the FRET-based fluorescent immunosensors allowed for a rapid response toward DICO with considerable sensitivities of 0.185 ng/mL and 0.170 ng/mL in liquid system and PADs, respectively. Excellent specificity and satisfactory recovery in three kinds of tea samples were confirmed as well. This study opens an avenue for on-site, portable and sensitive detection methods.


Assuntos
Técnicas Biossensoriais , Nanopartículas Metálicas , Técnicas Biossensoriais/métodos , Dicofol , Transferência Ressonante de Energia de Fluorescência/métodos , Ouro , Imunoensaio , Prata
16.
Biosens Bioelectron ; 194: 113611, 2021 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-34500229

RESUMO

The high toxicity of dicofol (DICO) to nontarget organisms has resulted in the contamination of food materials and caused a threat to human health. Developing a rapid and sensitive detection method of DICO in food samples is essential and still pursued. Fluorescent nanomaterials have been widely applied in biosensors to improve the sensitivity of detection. Herein, glutathione-capped Au-Ag bimetallic nanoclusters (Au-Ag NCs) exhibited the outstanding fluorescence characteristic with the average fluorescence lifetime of 1971.08 ns and photoluminescence quantum yield of 9.84% when the molar ratio of Au to Ag was 5:1. Polyethyleneimine modified gold nanoparticles (PEI-Au NPs) with the positive charge were prepared to generate a strong colorimetric signal. A dual-model colorimetric/fluorescent immune probe based on the Au-Ag NCs and PEI-Au NPs was successfully constructed by electrostatic force, and could be applied in both ic-ELISA and LFIA methods for rapid and ultrasensitive detection of DICO. In the ic-ELISA method, the introduction of fluorescence signal significantly increased the sensitivity of detection with the limit of detection (LOD) of 0.62 ng/mL and exhibited an excellent linear relationship within the range of 1.36 ng/mL-19.92 ng/mL. In the LFIA method, the fluorescence signal of Au-Ag NCs was accumulated on the test line and control line for the fluorescence model detection with a quantitative LOD at the level of 1.59 ng/mL. Such a dual-model colorimetric/fluorescent immunoassay serves as a promising candidate to develop new approaches in field detection.


Assuntos
Técnicas Biossensoriais , Nanopartículas Metálicas , Colorimetria , Dicofol , Ouro , Humanos , Imunoensaio , Prata
17.
Chem Biol Interact ; 350: 109707, 2021 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-34656558

RESUMO

The organochlorine pesticide dicofol (DCF), a persistent organic pollutant, is used as acaricide worldwide. Considering its large consumption in the agriculture sector and potential toxic effects such as endocrine disruption, carcinogenicity, and environmental persistence are detrimental to human health. To take an extensive evaluation of its potential toxicity, the current study was aimed to explore the binding mechanism and adverse effect of DCF on human serum albumin (HSA) by using an array of biophysical techniques (UV-visible, fluorescence, 3D fluorescence, and circular dichroism spectroscopy), isothermal titration calorimetric (ITC), computational methods and biochemical approaches. Fluorescence quenching and UV-Visible spectra of the HSA-DCF system confirmed static quenching mechanism and complex formation between HSA and DCF. The thermodynamics results from ITC revealed DCF-HSA interaction was exothermic and spontaneous and involved hydrophobic interactions and hydrogen bonding. The esterase activity of HSA displayed constant Vmax and elevated Km values confirming DCF-HSA competitive interaction. Circular dichroism spectra results revealed structural changes in HSA protein on interaction with DCF. Furthermore, molecular-specific site marker and molecular modelling results affirmed that the binding Site of DCF is Site I of HSA. A significant carbonyl content level in DCF-HSA system suggested protein structure damage. This work is likely to add a better understanding of DCF toxicity in human health and helpful in fortifying the check on food safety.


Assuntos
Dicofol/farmacocinética , Dicofol/toxicidade , Poluentes Orgânicos Persistentes/farmacocinética , Poluentes Orgânicos Persistentes/toxicidade , Praguicidas/farmacocinética , Praguicidas/toxicidade , Albumina Sérica Humana/efeitos dos fármacos , Albumina Sérica Humana/metabolismo , Sítios de Ligação , Dicroísmo Circular , Dicofol/química , Humanos , Ligação de Hidrogênio , Interações Hidrofóbicas e Hidrofílicas , Técnicas In Vitro , Cinética , Simulação de Acoplamento Molecular , Poluentes Orgânicos Persistentes/química , Praguicidas/química , Ligação Proteica , Albumina Sérica Humana/química , Espectrometria de Fluorescência , Análise Espectral , Termodinâmica
18.
Ultrason Sonochem ; 51: 526-532, 2019 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-30224289

RESUMO

Dicofol, a recommended Stockholm convention persistent organic pollutants (POPs) candidate is well known for its endocrine disruptive properties and has been extensively used as an organochlorine pesticide worldwide. The hydrodynamic cavitation (HC) treatment of Dicofol in aqueous media induced by a liquid whistle hydrodynamic cavitaion reactor (LWHCR) has been investigated while considering important parameters such as inlet pressure, initial concentration of Dicofol, solution temperature, pH, addition of H2O2 and radical scavenger for the extent of degradation. The pseudo-first-order degradation rate constant (k) was determined to be 0.073 min-1 with a cavitational yield of 1.26 × 10-5 mg/J at optimum operating conditions and a complete removal of Dicofol was achieved within 1 h of treatment. Considering the removal rate and energy efficiency, the optimal inlet pressure was found to be 7 bar, resulting in a cavitation number of 0.17. High performance liquid chromatography (HPLC) and Gas chromatography mass spectroscopy (GC-MS) analyses indicated a sharp decline in the concentration of Dicofol with treatment time and indicated the presence of degraded products. An 85% total organic carbon (TOC) removal was achieved within 1 h of treatment time, demonstrating successful mineralization of Dicofol. The obtained results suggest that the degradation of Dicofol followed thermal decomposition and successive recombination reactions at bubble-vapor interface. Overall, the attempted hydrodynamic cavitation demonstrated successful and rapid removal of endocrine disruptive chemicals such as Dicofol and is expected to provide efficient solution for wastewater treatment.


Assuntos
Dicofol/química , Disruptores Endócrinos/química , Hidrodinâmica , Resíduos de Praguicidas/química , Acústica , Sequestradores de Radicais Livres/química , Peróxido de Hidrogênio/química , Concentração de Íons de Hidrogênio , Pressão , Temperatura
19.
Chemosphere ; 219: 645-654, 2019 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-30557720

RESUMO

As an effective organochlorine pesticide, Dicofol has been extensively applied in more than 30 countries for protecting over 60 different crops. Considering its large consumption and potential adverse effect on human health (endocrine disrupting and carcinogenicity), the fate of Dicofol sprayed into the air is of public concern. In this study, we conducted a comprehensive study on the reaction mechanisms of p,p'-Dicofol with OH and NO3 radicals using DFT method. Comparing the abstrations by OH and NO3 radical, OH and NO3 radical addition reactions are predominant due to the lower potential barriers and stronger heat release. The phenolic substances (P1P5), epoxides (P11 and P15), dialdehyde (P13) and other species (P8, P9, P10 and P14) are generated by OH additions and their subsequent reactions while OH abstraction reactions produce DCBP, P7 and chlorphenyl radical. Particularly, NO3 additions and their subsequent reactions yield dialdehydes (P16 and P17) and 2,8-DCDD, which is the first report of the generation of dioxin from atmospheric oxidation of p,p'-Dicofol. Additionally, based on the structure optimization and energy calculation, rate constants and Arrhenius formulas of the elementary reactions of p,p'-Dicofol with OH and NO3 radicals were obtained over the temperature range of 280-380 K and at 1 atm. The rate constants for the reactions of p,p'-Dicofol with OH and NO3 radicals are 1.51 × 10-12 and 8.88 × 10-14 cm3 molecule-1 s-1, respectively. The lifetime (τTotal) of p,p'-Dicofol determined by the reactions of OH and NO3 radical is 5.86 h, indicating a potential long-range transport in the atmosphere.


Assuntos
Poluentes Atmosféricos/química , Atmosfera/química , Dicofol/química , Radicais Livres/química , Radical Hidroxila/química , Inseticidas/química , Cinética , Nitratos/química , Oxirredução , Temperatura
20.
Braz J Microbiol ; 39(2): 311-3, 2008 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-24031222

RESUMO

The fate of organochlorine (14)C-dicofol in activated sludge process was investigated. Results showed that the major part of radioactivity remained adsorbed on biological sludge. Consequently, its final disposal deserves special attention. The small amounts of dicofol, biotransformed or not, which remained in the treated effluent could contaminate receiving bodies.

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