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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., (Copyright © 2022 Elsevier B.V. All rights reserved.)

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 × 10 5 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., 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 © 2021 Elsevier B.V. All rights reserved.)

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 V max and elevated K m 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., (Copyright © 2021 Elsevier B.V. All rights reserved.)

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 EC 50 s and theoretically evaluate the risk in the PRD. The toxicity results (EC 50 = 0.27 mg/L for A. salina; and EC 50 = 0.17 mg/L and LC 50 = 0.26 mg/L for D. magna), together with the 4,4'-DCBP levels quantified, indicated a low environmental risk., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Current-use pesticides (CUPs) are widely used in agriculture, and some are listed as persistent organic pollutants (POPs) due to their bioaccumulative and toxic properties. China is one of the largest producers and users of pesticides in the world. However, very limited data are available about the environmental fates of CUPs. Four CUPs (trifluralin, chlorothalonil, chlorpyrifos, and dicofol) in surface seawater and low atmospheric samples taken during research cruises on the Bohai Sea in August and December 2016 and February 2017 were analyzed, we added the spring data sampled in May 2012 to the discussion of seasonal variation. In our study, chlorpyrifos was the most abundant CUPs in the gas phase with a mean abundance of 59.06±126.94pgm -3 , and dicofol had the highest concentration dissolved in seawater (mean: 115.94±123.16pgL -1 ). The concentrations of all target compounds were higher during May and August due to intensive use and relatively high temperatures in the spring and summer. Backward trajectories indicated that air masses passing through the eastern coast of the Bohai Sea contained high concentrations of pollutants, while the air masses from the Bohai and Yellow Seas were less polluted. The high concentration of pollutants in seawater was not only influenced by high yields from the source region of production or usage, but also by input from polluted rivers. Volatilization from surface water was found to be an important source of trifluralin and chlorpyrifos in the air. Air-sea gas exchange of chlorothalonil underwent strong net deposition (mean FRs: 51.67), which was driven by higher concentrations in air and indicates that the Bohai Sea acted as a sink for chlorothalonil., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A new type of ionic liquid molecularly imprinted polymers (IL-MIPs) synthesized by precipitation polymerization using 1-allyl-3-methylimidazolium bromide as an auxiliary solvent and α-chloro-dichlorodiphenyltrichloroethane (α-chloro-DDT) as the template was applied as a selective sorbent of minimized pipette tip-solid-phase extraction (PT-SPE) for rapid isolation and extraction of dicofol (DCF) from celery samples. The pretreatment procedure of celery samples involved only 2.0mg of IL-MIPs, 0.8 mL of acetonitrile-water (ACN-H2O; 1:1, v/v) (washing solvent), and 1.0 mL of acetone-10% acetic acid (HOAc) (elution solvent). Compared with molecularly imprinted polymers (MIPs), ionic liquid-non-imprinted polymers (IL-NIPs) and conventional sorbents such as C18, Si, NH2, and Al2O3-N, IL-MIPs showed higher adsorption and purification capacity to DCF in aqueous solution. Good linearity for DCF was observed in the range from 2.3 to 232.5 ng g(-1) (r(2)=0.9995). The average recoveries at three spiking levels ranged from 86.6% to 101.9% with relative standard deviations (RSDs) of ≤ 6.5% (n=3). The presented IL-MIPs-PT-SPE-GC/ECD method combines the advantages of MIPs, IL, and PT-SPE, and can be used in aqueous conditions with high affinity and selectivity to analytes of complex samples., (Copyright © 2014 Elsevier B.V. All rights reserved.)

New ionic liquid-mediated molecularly imprinted polymers (IL-MIPs) were prepared by precipitation polymerization using 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM(+)PF6(-)) as the auxiliary solvent, α-chloro-DDT as the dummy template, and they were successfully applied as the sorbents of solid-phase extraction (SPE) for rapid screening of dicofol from cabbage, tomato, and carrot samples. The IL-MIPs were characterized by FTIR, FE-SEM, static adsorption and chromatographic evaluation, and the results revealed that the IL-MIPs had higher adsorption capacity and selectivity to dicofol in aqueous solution than that of ionic liquid-mediated non-imprinted polymers (IL-NIPs) and non-imprinted polymers (NIPs). Under the optimized conditions, the IL-MIPs-SPE-GC method offered good linearity (0.4-40.0ngg(-1), r(2)=0.9995) and the average recoveries of dicofol at three spiked levels were in a range of 84.6-104.1% (n=3) with RSD≤7.6%. The proposed method obviously improved the selectivity and purification effect, and eliminated the effect of template leakage on dicofol quantitative analysis., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Dicofol with high impurity of DDT compounds is still widely used in agricultural practice such as cotton cultivation and becomes an important source of DDT pollution in China. In this study, investigations on the DDT residues in cotton fields from northern Jiangsu province, China were conducted. The results showed that DDTs in cotton soil were much higher than other mode of land use. The DDTs levels ranged from 4.2 to 678.6 ngg(-1), with a mean concentration of 190.4 ngg(-1), of which the most abundant compounds were p,p'-DDE (mean of 129.38 ngg(-1)), p,p'-DDT (mean of 26.57 ngg(-1)) and o,p'-DDT (mean of 16.92 ngg(-1)). The concentrations of o,p'-DDT and o,p'-DDE were significantly higher (p<0.05) in topsoil (0-10 cm) than in subsoil (10-20 cm), while other DDT compounds were not. Source apportionment showed that dicofol-type DDT accounted for up to 80% of the DDTs residue. All the results indicated that dicofol applications resulted in serious DDT pollution in cotton fields. Our work provided implications for reasons why there was no apparent decrease of DDT level in China.