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We conducted a literature review of urinary 2,4-D in populations not associated with a herbicide application. Of the 33 studies identified, the median/mean concentrations were similar for children, adults, and pregnant women regardless of geography. Individuals with highest concentrations may have had opportunities to directly contact 2,4-D outside of an application. Most studies were conducted in populations in North America and did not examine potential sources of 2,4-D, or what factors might influence higher or lower urinary 2,4-D concentrations. In the future, prioritizing the examination of 2,4-D biomonitoring in other regions and collecting information on sources and factors influencing exposures would better our understanding of 2,4-D exposures globally. In all the studies reviewed the concentrations of urinary 2,4-D observed were orders of magnitude below the US regulatory endpoints, suggesting that people are not being exposed to 2,4-D at levels high enough to result in adverse health effects., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: The literature search and data extraction were conducted while one of the authors (DB) was an employee of Corteva AgriScience. CJB is retired from The Dow Chemical Company, a manufacturer of 2,4-D. The writing of the report, which is reflected in the review, synthesis, and conclusions are the exclusive professional work product of the authors and do not necessarily represent the views of the Corteva AgriScience. A courtesy copy of the draft manuscript was provided to Corteva AgriScience., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Herein, 2,4-dichlorophenoxyacetic acid (2,4-D) was used as a model template in a rational design strategy to produce water-compatible noncovalent imprinted microspheres. The proposed approach involved computational modelling for screening functional monomers and a simple method for preparing monodisperse and highly cross-linked microspheres. The fabricated non-imprinted polymer (NIP) and 2,4-d-imprinted polymer (2,4-d-MIP) were characterised, and their adsorption capabilities in an aqueous environment were evaluated. Results reveal that the pseudo-second-order kinetics model was appropriate for representing the adsorption of 2,4-D on NIP and 2,4-d-MIP, with R 2 values of 0.97 and 0.99, respectively. The amount of 2,4-D adsorbed on 2,4-d-MIP (97.75 mg g -1 ) was considerably higher than those of phenoxyacetic acid (35.77 mg g -1 ), chlorogenic acid (9.72 mg g -1 ), spiramycin (1.56 mg g -1 ) and tylosin (1.67 mg g -1 ). Furthermore, it exhibited strong resistance to protein adsorption in an aqueous medium. These findings confirmed the feasibility of the proposed approach, providing a reference for the development of water-compatible noncovalent imprinted polymers., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Objective: Approximately 3 million Americans served in the armed forces during the Vietnam War. Veterans have a higher incidence rate of lung cancer compared with the general population, which may be related to exposures sustained during service. Agent Orange, one of the tactical herbicides used by the armed forces as a means of destroying crops and clearing vegetation, has been linked to the development of several cancers including non-small cell lung cancer. However, traditional risk models of lung cancer survival and recurrence often do not include such exposures. We aimed to examine the relationship between Agent Orange exposure and overall survival and disease recurrence for surgically treated stage I non-small cell lung cancer., Methods: We performed a retrospective cohort study using a uniquely compiled dataset of US Veterans with pathologic I non-small cell lung cancer. We included adult patients who served in the Vietnam War and underwent surgical resection between 2010 and 2016. Our 2 comparison groups included those with identified Agent Orange exposure and those who were unexposed. We used multivariable Cox proportional hazards and Fine and Gray competing risk analyses to examine overall survival and disease recurrence for patients with pathologic stage I disease, respectively., Results: A total of 3958 Vietnam Veterans with pathologic stage I disease were identified (994 who had Agent Orange exposure and 2964 who were unexposed). Those who had Agent Orange exposure were more likely to be male, to be White, and to live a further distance from their treatment facility (P < .05). Tumor size distribution, grade, and histology were similar between cohorts. Multivariable Cox proportional hazards modeling identified similar overall survival between cohorts (Agent Orange exposure hazard ratio, 0.97; 95% CI, 0.86-1.09). Patients who had Agent Orange exposure had a 19% increased risk of disease recurrence (hazard ratio, 1.19; 95% CI, 1.02-1.40)., Conclusions: Veterans with known Agent Orange exposure who undergo surgical treatment for stage I non-small cell lung cancer have an approximately 20% increased risk of disease recurrence compared with their nonexposed counterparts. Agent Orange exposure should be taken into consideration when determining treatment and surveillance regimens for Veteran patients., (Copyright © 2023. Published by Elsevier Inc.)

2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) is the most toxic congener of dioxin and has serious long-term effects on the environment and human health. Pyruvate Kinase L/R (PKLR) gene expression levels and gene variants are associated with pyruvate kinase enzyme deficiency, which has been identified as the cause of several diseases linked to dioxin exposure. In this study, we estimated PKLR gene copy number and gene expression levels using real-time quantitative PCR (RT-qPCR) assays, genotyped PKLR SNP rs3020781 by Sanger sequencing, and quantified plasma pyruvate kinase enzyme activity in 100 individuals exposed to Agent Orange/Dioxin near Bien Hoa and Da Nang airfields in Vietnam and 100 healthy controls. The means of PKLR copy numbers and PKLR gene expression levels were significantly higher, while pyruvate kinase enzyme activity was significantly decreased in Agent Orange/Dioxin-exposed individuals compared to healthy controls (P < 0.0001). Positive correlations of PKLR gene copy number and gene expression with 2,3,7,8-TCDD concentrations were observed (r = 0.2, P = 0.045 and r = 0.54, P < 0.0001, respectively). In contrast, pyruvate kinase enzyme activity was inversely correlated with 2,3,7,8-TCDD concentrations (r = -0.52, P < 0.0001). PKLR gene copy number and gene expression levels were also inversely correlated with pyruvate kinase enzyme activity. Additionally, PKLR SNP rs3020781 was found to be associated with 2,3,7,8-TCDD concentrations and PKLR gene expression. In conclusion, PKLR copy number, gene expression levels, and pyruvate kinase enzyme activity are associated with 2,3,7,8-TCDD exposure in individuals living in Agent Orange/Dioxin-contaminated areas., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Pesticide dust concentrations in homes have been previously associated with occupational and home/garden use of pesticides, hygiene practices, and other factors. This study evaluated the relationship between self-reported use of 2,4-dichlorophenoxyacetic acid (2,4-D) and house dust concentrations and these factors in the Biomarkers of Exposure and Effect in Agriculture (BEEA) Study, a molecular epidemiologic study of farmers in Iowa and North Carolina. The vacuum dust from the homes of 35 BEEA participants was analyzed for the presence of 2,4-D. Participants provided detailed information on occupational and home/garden pesticide use during the past 12 months and reported household characteristics via questionnaires. Linear regression models were used to examine the association between 2,4-D concentrations and four exposure metrics for occupational use in the last 12 months (yes/no, days since last use, days of use, intensity-weighted days of use), home/garden use (yes/no), as well as several household characteristics. 2,4-D was detected in all homes and was used occupationally by 54% of the participants. In a multi-variable model, compared to homes with no occupational or home/garden 2,4-D use reported in the past 12 months, concentrations were 1.6 (95% confidence interval (CI): 0.5, 4.9) times higher in homes with low occupational 2,4-D use (intensity-weighted days < median) and 3.1 (95% CI: 1.0, 9.8) times higher in homes of participants with high use (≥median intensity-weighted days) (p-trend = 0.06). Similar patterns were observed with other occupational metrics. Additionally, 2,4-D dust concentrations were non-significantly elevated (relative difference (RD) = 1.8, 95% CI: 0.5, 6.2) in homes with home/garden use and were significantly lower in homes that did not have carpets (RD = 0.20, 95% CI: 0.04, 0.98). These analyses suggest that elevated 2,4-D dust concentrations were associated with several metrics of recent occupational use and may be influenced by home/garden use and household characteristics.

The present study aims to produce nanocomposites of silica based organosilane as sensitive and selective fluorescent sensor for the recognition of 2,4 dichlorophenoxyacetic acid (2,4-D). Hydrazone tethered triazole functionalized organosilane has been synthesized by the condensation reaction of 4-hydroxybenzaldehyde and phenyl hydrazine followed by Cu(I) catalysed cycloaddition of azide with alkyne. The prepared compound has been further grafted over silica surface and the synthesized materials were characterized by FT-IR, NMR ( 1 H and 13 C), XRD, mass spectrometry and FE-SEM spectral analyses. The prepared organosilane and its HSNPs have been utilized as an effective emission probe for the selective detection of 2,4 D with good linear relationship in the range of 0-160 μM and 0-115 μM and LOD value of 46 nM and 13.5 nM respectively. In the presence of other active species, the sensor shows minimal interference while the comparison with the previously reported techniques suggests it to be more desirable for the sensitive and selective detection of 2,4 D. Further, the real sample application for detection of 2,4 D was analyzed in field water and the HSNPs based sensing system gave recovery percentage of above 98 %., Competing Interests: Declaration of competing interest There is no conflict of interest., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The efficient preparation of ratiometric fluorescent molecularly imprinted polymer (MIP) microspheres that can directly and selectively optosense a herbicide (i.e., 2,4-dichlorophenoxyacetic acid, 2,4-D) in undiluted pure milk is described. The dual fluorescent MIP microparticles were readily obtained through grafting a green 4-nitrobenzo[c][1,2,5]oxadiazole (NBD)-labeled 2,4-D-MIP layer with hydrophilic polymer brushes onto the preformed uniform "living" red CdTe quantum dot (QD)-labeled SiO 2 microspheres via one-pot surface-initiated atom transfer radical polymerization (SI-ATRP) in the presence of a polyethylene glycol macro-ATRP initiator. They proved to be highly promising "turn-on"-type fluorescent chemosensors with red CdTe QD (the maximum emission wavelength λ e,max around 710 nm) and green NBD (λ e,max around 515 nm) as the reference fluorophore and "turn-on"-type responsive fluorophore, respectively. The sensors showed excellent photostability and reusability, high 2,4-D selectivity and sensitivity (the limit of detection = 0.12 μM), and direct visual detection ability (a fluorescent color change occurs from red to blue-green with the concentration of 2,4-D increasing from 0 to 100 μM) in pure bovine milk. The sensors were used for 2,4-D detection with high recoveries (96.0-104.0%) and accuracy (RSD ≤ 4.0%) in pure goat milk at three spiking levels of both 2,4-D and its mixtures with several analogues. This new strategy lays the foundation for efficiently developing diverse complex biological sample-compatible ratiometric fluorescent MIPs highly useful for real-world bioanalyses and diagnostics., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

Surface-enhanced Raman spectroscopy (SERS) has been extensively investigated for rapid and sensitive detection of trace level chemical contaminants in foods. Lack of selectivity to the targeted molecules in food matrices and fairly poor spectral reproducibility remain the main challenges for practical SERS applications. Herein, an ingenious strategy was proposed to hybridize molecularly imprinted polymers (MIPs) with gold nanoparticles as the functional SERS substrate for selective separation and detection of 2,4-dichlorophenoxyacetic acid (2,4-D), a systemic herbicide that has acute toxicity and potential cancer risk. The core-shell AuNPs@MIPs nanoparticles were finely tailored by wrapping an ultrathin layer of MIPs shell on the surface of AuNPs, which allowed selectively separating and enriching 2,4-D to the near surface of AuNPs and ensured the enhancement of Raman scattering signal of the analyte. Embedding an internal standard (i.e., 4-aminothiophenol) inside AuNPs@MIPs for SERS spectral calibration improved the quantification accuracy for 2,4-D. Three-dimensional finite difference time domain (3D-FDTD) simulation demonstrated the maximal electric field enhancement presented in the gap between adjacent AuNPs@MIPs with the theoretical enhancement factor (EF) as high as 5.85 × 10 6 . Chemometric models established using SERS spectra showed accurate differentiation and quantification results for 2,4-D in milk at various contamination levels with a limit of detection (LOD) of 0.011 μg/mL. Our approach to integrate MIPs with noble metallic nanoparticles has great potential for selective and quantitative detection of analytes using SERS for practical agri-food analysis., 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 © 2022 Elsevier B.V. All rights reserved.)

Chromatography combined with mass spectrometry is the most commonly used detection technology, and it offers the advantages of high sensitivity and high selectivity. The quick, easy, inexpensive, effective, rugged, and safe (QuEChERS) method is low-cost, effective, and time efficient. The application of the QuEChERS has now been extended to the analysis of contaminants in food samples. The aim of the study was to identify different concentration levels of multiple harmful drug residues in bean sprouts. In this study, QuEChERS coupled with high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was established for the simultaneous determination of 40 plant growth regulators, fungicides, insecticides, and antibiotics in bean sprouts. In the HPLC-MS/MS experiment, gibberellic acid, 4-fluorophenoxyacetic acid, chloramphenicol, N 6-( δ 2-isopentenyl)-adenine, 6-benzylaminopurine, 4-chlorophenoxyacetic acid, and 2,4-dichlorophenoxyacetic acid (2,4-D) were analyzed by MS/MS with negative electrospray ionization (ESI - ). The other 33 target analytes (chlormequat, ronidazole, metronidazole, pymetrozine, dimetridazole, methomyl, carbendazim, enoxacin, levofloxacin, pefloxacin mesylate, norfloxacin, ciprofloxacin, enrofloxacin, thiabendazole, lomefloxacin, chlorpyrifos, sarafloxacin, imidacloprid, etc.) were analyzed by MS/MS with positive electrospray ionization (ESI + ). Sensitive MS conditions were realized by optimizing the instrumental parameters such as the desolvent temperature, collision energy, spraying needle position, precursor ions, and product ions. Then, the optimal pretreatment method was determined by comparing the recovery rates of the 40 drugs obtained with different extraction solvents (methanol, acetonitrile, acetonitrile containing 0.1% ammonia, acetonitrile with 1% acetic acid), different extraction methods (ultrasonic extraction, shaking extraction), and purification with primary secondary amine (PSA) and C 18 . In this study, the bean sprouts samples were extracted twice by 10 mL acetonitrile with 1% acetic acid, and extracted under ultrasonic conditions. Then, the extracting solution was only cleaned with 100 mg C 18 . The chromatographic separation of the 40 compounds was accomplished on a Waters ACQUITY UPLC BEH C 18 column (100 mm×2.1 mm, 1.7 μm) with gradient elution. Methanol and 0.01% formic acid aqueous solution were used as the mobile phases. The 40 compounds were analyzed in the multiple reaction monitoring (MRM) mode. The matrix matching external standard method was used for quantitative determination. The results showed that the 40 compounds could be analyzed within 15 min. Under the optimized conditions, the calibration curves showed good linearities for the 40 compounds, and the coefficients of determination ( r 2 ) were greater than 0.99 in the range of 2-200 μg/L. The limits of detection (LODs) and limits of quantification (LOQs) were in the range of 0.1-3 μg/kg and 0.3-9 μg/kg, respectively. Using negative bean sprouts as the substrates, the recovery tests were carried out at three spiked levels of 5, 10, and 50 μg/kg. The average recoveries of the 40 drugs were 78.5% to 115.3%, and the corresponding relative standard deviations (RSDs) were 1.3% to 9.7% ( n =6). This method was successfully applied to the analysis of the 40 drug residues in 21 batches of local bean sprouts in Handan city. The results revealed the presence of extensive drug residues in the bean sprouts. The 26 batches were detected to varying degrees, among which 4-chlorophenoxyacetic acid, carbendazim, 6-benzyladenine, 2,4-D, enrofloxacin, and metronidazole were detected at high rates. The detection rates of 4-chlorophenoxyacetic acid, 6-benzyladenine, carbendazim, 2,4-D, gibberellic acid, and enrofloxacin were 28.6%, 19.0%, 9.5%, 9.5%, 4.8%, and 4.8%, respectively. The contents ranged from 37.5-352.4, 32.4-273.1, 28.8-38.7, 316.1-20.2, 19.9 and 13.6 μg/kg, respectively. Given its advantages of simplicity, rapidness, and high sensitivity, the developed method can be used for the rapid and accurate determination of trace levels of the 40 drug residues in large quantities of bean sprouts.

Background: Previous studies have investigated associations between herbicides such as 2,4-Dichlorophenoxyacetic acid (2,4-D) and dyshormonogenesis, specifically low testosterone, in human, rodent, and cell models, but results have been conflicting and inconclusive., Methods: Using data from a cross-sectional study of 456 adult men in the 2013-2014 NHANES survey cycle, we examined the relationship between urinary concentrations of 2,4-D and serum testosterone levels., Results: Multivariable regression models adjusting for potential confounders revealed a significant, negative association between urinary 2,4-D and mean serum testosterone among U.S. adult males (β =  - 11.4 ng/dL, p = 0.02). Multivariable logistic regression models using a cutoff defining abnormally low testosterone (i.e., serum testosterone < 300 ng/dL) revealed no significant associations between 2,4-D and the odds of low testosterone., Conclusion: These findings expand on previous literature implicating a role for 2,4-D in the etiology of low testosterone and dyshormonogenesis. Future studies are warranted to corroborate these findings, determine clinical significance, and to investigate the proposed potential biological mechanisms underlying this association., (© 2021. This is a U.S. government work and not under copyright protection in the U.S.; foreign copyright protection may apply.)

Bark residues of the forest species Cedrela fissilis were physically and chemically modified with zinc chloride (ZnCl 2 ) as an activating agent. The two modified materials were analyzed as adsorbents in removing atrazine and 2,4-D herbicides from effluents. Firstly, the precursor material and the modified ones were characterized by different techniques to identify the structural changes that occurred in the surfaces. Through TGA, it was observed that both modified materials have thermal stability close to each other and are highly superior to the precursor. X-ray diffractions proved that the amorphous structure was not altered, the three materials being highly heterogeneous and irregular. The micrographs showed that the treatments brought new spaces and cavities on the surface, especially for the material carbonized with ZnCl 2 . The pH PZC of the modified materials was close to 7.5. The physically modified material had a surface area of 47.31 m 2 g -1 and pore volume of 0.0095 cm 3 g -1 , whereas the carbonized material had a surface area of 98.12 m 2 g -1 and pore volume of 0.0099 cm 3 g -1 . Initial tests indicated that none of the adsorbents were efficient in removing 2,4-D. However, they showed good potential for removing atrazine. The Koble-Corrigan isothermal model best fits the experimental data, with a maximum capacity of 3.44 mg g -1 and 2.70 mg g -1 for physically modified and with ZnCl 2 , respectively. The kinetic studies showed that the system tends to enter into equilibrium after 120 min, presenting good statistical indicators to the linear driving force model (LDF). The surface diffusion coefficients were 2.18×10 -9 and 2.37×10 -9 cm 2 s -1 for atrazine adsorption on the physically and chemically modified materials. These results showed that the application of residues from the processing of cedar bark is promising. However, new future studies must be carried out to improve the porous development of the material and obtain greater adsorption capacities., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The compound 2,4-dichlorophenoxyacetic acid (2,4-D) is a synthetic plant growth regulator, which is widely used in agricultural production. Consequently, it is necessary to establish a rapid and sensitive detection method to monitor its use and prevent the environmental and human health problems caused by overuse. In this study, a monoclonal antibody (mAb) 2D5 against 2,4-D was prepared, and based on it, an ic-ELISA and an immunochromatographic strip assay (ICA) were developed for rapid detection. The 50% inhibitory concentration (IC 50 ) of the mAb against 2,4-D was 1.7 ng mL -1 and the mAb showed no cross-reactivity with other plant growth regulators with similar structures to 2,4-D. Under optimum conditions, the ICA showed a visual detection limit (vLOD) of 20 ng mL -1 and a cut-off value of 200 ng mL -1 in bean sprouts, and cabbage samples gave the same results. The quantitative detection showed the linear detection ranges for bean sprouts and cabbage samples were 6.3-73.0 and 5.4-132.6 ng mL -1 , respectively. The ICA was successfully applied to detect 2,4-D in bean sprouts and cabbage samples and achieved good recoveries ranging from 94.7% to 104.3% with a coefficient of variation (CV) less than 8.3%. Hence, the ICA provides a sensitive, efficient and reliable detection method, which has broad application prospects in the detection of a large number of samples., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

2,4-Dichlorophenoxyacetic acid (2,4-D) is a systemic conductive herbicide widely used across the world. With the large-scale and continuous use of 2,4-D, its possible harm to the environment and non-target organisms has attracted increasing attention, and the construction of a stable rapid on-site detection method is particularly important. In order to achieve on-site rapid detection of 2,4-D, we developed a gold nanoparticle immunochromatographic strip method with the visual elimination value was 50 ng/mL, and a quantitative detection limit of 11 ng/mL based on a nanobody. By combing with the color snap, the immunochromatographic strip could quantitatively analyze the amounts of 2,4-D. Meanwhile, a colorimetric card based on the true color of the test strips was developed for the qualitative analysis of 2,4-D on-site. The samples (water, fruits and vegetables) with and without 2,4-D were detected by the immunochromatographic strips, and the results showed the accuracy and reliability. Thus, this assay is a rapid and simple on-site analytical tool to detect and quantify 2,4-D levels in environmental samples, and the analytical results can be obtained in about ten minutes. In addition, the nanobody technology used in this study provides an inexhaustible supply of a relatively stable antibodies that can be archived as a nanobody, plasmid or even its sequence.

Food safety is a growing concern in recent years. This work presents the design of a simple and sensitive method for predicting 2,4-D (2,4-dichlorophenoxyacetic acid) residue levels in green tea extract employing surface-enhanced Raman spectroscopy (SERS) coupled uninformative variable elimination-partial least squares (UVE-PLS). Herein, SERS active citrate functionalized silver nanoparticles (AgNPs) with enhancement factor 1.51 × 10 8 was used to prepare cellulose paper (common office) templated SERS sensor for acquiring SERS spectra of 2,4-D. The principle of the work was based on the interaction between 2,4-D and citrate group of AgNPs via chlorine atoms in the concentration range 1.0 × 10 -4 to 1.0 × 10 3 µg/g. Three different wavenumber selection chemometric algorithms were studied comparatively to build an optimum calibration model, among them UVE-PLS showed enhanced performance as evident from the RPD value of 6.01 and Rp = 0.9864. Under optimized experimental condition proposed paper-based SERS sensor exhibited detection limit and RSD of 1.0 × 10 -4 µg/g and <5%, respectively. In addition, the validation results by HPLC method were satisfactory (p > 0.05)., 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 © 2020 Elsevier B.V. All rights reserved.)

Trace detection of toxic chemicals in foodstuffs is of great concern in recent years. Surface-enhanced Raman scattering (SERS) has drawn significant attention in the monitoring of food safety due to its high sensitivity. This study synthesized signal optimized flower-like silver nanoparticle-(AgNP) with EF at 25 °C of 1.39 × 10 6 to extend the SERS application for pesticide sensing in foodstuffs. The synthesized AgNP was deployed as SERS based sensing platform to detect methomyl, acetamiprid-(AC) and 2,4-dichlorophenoxyacetic acid-(2,4-D) residue levels in green tea via solid-phase extraction. A linear correlation was twigged between the SERS signal and the concentration for methomyl, AC and 2,4-D with regression coefficient of 0.9974, 0.9956 and 0.9982 and limit of detection of 5.58 × 10 -4 , 1.88 × 10 -4 and 4.72 × 10 -3 µg/mL, respectively; the RSD value < 5% was recorded for accuracy and precision analysis suggesting that proposed method could be deployed for the monitoring of methomyl, AC and 2,4-D residue levels in green tea., 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 © 2020 Elsevier Ltd. All rights reserved.)

Rapid and accurate detection of pesticide residues in food matrices are of great significance to food safety. This study aimed to characterize the fingerprint peaks of 2,4-dichlorophenoxyacetic acid (2,4-D) and to enhance its detection accuracy in food matrices by using terahertz (THz) time-domain spectroscopy. Density functional theory was used to simulate molecular dynamics of 2,4-D peaks (1.35, 1.60, 2.37 and 3.00 THz). Four baseline correction methods, including asymmetric least squares smoothing (AsLS), adaptive iteratively reweighted penalized least squares (AirPLS), background correction (Backcor), baseline estimation and denoising with sparsity (BEADS) were compared and used to eliminate spectral baselines of Zizania latifolia (ZIZLA), rice and maize containing 2,4-D residues, from 0.1 to 4 THz. Based on the peak information of 1.35 THz, the detection limit and accuracy of 2,4-D residues in these food matrices were significantly improved after THz spectral baseline correction, providing a new feasibility for food safety and agricultural applications., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Studies reported the harmful effects of 2,4-D on body tissues, provoking changes in the anatomy and physiology of the kidneys, liver, and testicles. Thus, the objective was to evaluate if there were alterations in the bone quality of the tibia of rats submitted to feed consumption that were exposed to three different 2,4-D doses. Male Wistar rats were divided into four groups: oral control group (C: feed consumption without 2,4-D contamination); low oral concentration group (G3: contaminated feed with low concentration of 2,4-D); medium concentration group (G6: contaminated feed with medium concentration of 2,4-D); and high concentration group (G9: contaminated feed with high concentration of 2,4-D). The results demonstrated alterations of the mechanical properties and Raman ratios of the tibias of the contaminated groups. The maximum load, maximum stress, elastic modulus, and the cortical area were lower in the G6 and G9 compared to C group. The mineral-to-matrix ratio (relative mineral to organic content) was lower in the G6 and G9 groups compared to C group, but carbonate-to-matrix ratio (indicator of bone turnover) was higher in both groups. Thus, it is possible to suggest that the 2,4-D herbicide performed deleterious effects on the bone quality of male Wistar rats.

On-site quantitative analysis of pesticide is of significant importance for addressing serious public health issues in clinical, food, and environmental settings. Herein, we designed a novel smartphone-assisted sensing platform for on-site monitoring of 2,4-dichlorophenoxyacetic acid (2,4-D) based on carbon dots/cobalt oxyhydroxide nanosheet (CDs/CoOOH) composite. In this work, a red emissive CDs/CoOOH composite was proposed as a signal indicator for shielding background interference, enhancing anti-interference capability. 2,4-D as an inhibitor of alkaline phosphatase could specifically suppress the production of ascorbic acid, which restrained in situ etching of the CDs/CoOOH composite and further triggered the fluorescence response of the biosensor. By employing a lab-on-smartphone based device and self-designed application software, the fluorescence image was directly captured and analyzed with a sensitive detection limit of 100 μg L -1 for 2,4-D. Merging the CDs/CoOOH composite-based fluorometric system with the smartphone-assisted optical reader, such a cost-effective and portable platform provided a new sight for on-site monitoring of pesticide and expanded application prospect in the field of biological analysis.

Primary production (PP) is a key variable to evaluate the quality of the ecological services provided by freshwater bodies because it gives information on the amount of oxygen and organic matter incorporated into the system. We analysed the impact of a mixture of commercial formulations of glyphosate- and 2,4-D-based herbicides (Roundup Max® and AsiMax 50®, respectively) on freshwater primary production. Primary production was studied through the oxygen exchange method. Four measurements were made during a 23-day experiment in outdoor mesocosms using the light and dark bottle method. High and low concentrations of the active ingredients were assayed to evaluate a concentration-dependent effect. Our results indicated that the mixture of Roundup Max® and AsiMax 50® acted mostly additively on gross and net primary production. Moreover, we found a concentration-dependent effect of each herbicide on PP. Thus, AsiMax 50® at low and Roundup Max® at high concentration induced a significant early decrease in respiration and gross primary production 4 h after application, attributable to physiological responses. Besides, significant increases in primary production were simultaneously recorded with increases in chlorophyll a concentration and micro + nano-phytoplankton abundance 7 days after the application of Roundup Max® at high concentration. This study contributes to the knowledge of the impact of widely used herbicides on freshwater ecosystems., 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 © 2020 Elsevier Inc. All rights reserved.)

2,4-Dichlorophenoxyacetic acid (2,4-D) has been widely used as a herbicide for agricultural purposes. Currently, the available methods for detecting 2,4-D require multi-step sample preparations and expensive instruments. The use of a whole cell biosensor is an interesting approach that is straightforward and simple to use. In this study, we constructed a genetic-based Agrobacterium tumefaciens biosensor based on a cadA promoter and cadR regulator from Bradyrhizobium sp. strain HW13 (2,4-D degrader) with a formylglycine generating enzyme (FGE)-sulfatase as the reporter gene. The performance of the biosensor was further improved through direct evolution of the cadR activator. The detection limit of cadR mutants for phenoxyacetic acid herbicides including 2,4-D and 4-Chlorophenoxyacetic acid (4-CPAA) were 1.56 μM (an eight-fold improvement compared to wild-type CadR). The biosensor could detect 2,4-D contamination in environmental samples without encountering interference from other complex compounds. The Agrobacterium biosensor was also stable after storing in a simple Luria-Bertani (LB) medium at 4 °C for 30 days where the activity remained at 82% when exposed to 100 μM of 2,4-D. This novel biosensor, with its high stability under simple storage conditions, exhibits promising potential to be used as an inexpensive and easy-to-use tool to screen for 2,4-D contamination in environmental sources., 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 © 2020 Elsevier B.V. All rights reserved.)

In order to remove the limitations of natural antibodies or enzymes, a nano-magnetic biomimetic platform based on a surface-enhanced Raman scattering (SERS) sensor has been developed for highly sensitive capture and detection of 2,4-dichlorophenoxyacetic acid (2,4-D) in food and water samples. Magnetic-based molecular imprinted polymer nanoparticles (Mag@MIP NPs) were constructed to capture the target 2,4-D molecule via biomimetic recognition, and gold nanoparticles (Au NPs) served as SERS-based probes, which are bound to the Mag@MIP NPs by electrostatic adsorption. The as-prepared SERS-MIP sensor for sensing of 2,4-D achieved a good linear relationship with a low detection limit (LOD) of 0.00147 ng/mL within 2 h and exhibited high sensitivity. The sensor was successfully applied to detect 2,4-D in milk and tap water and achieved good recoveries ranging from 93.5 to 102.2%. Moreover, the designed sensor system exhibited satisfactory results (p > 0.05) compared to HPLC by validation analysis. Hence, the findings demonstrated that the proposed method has significant potential for practical application in food safety and environmental protection. Graphical abstract .

Fixed bed adsorption is widely used for separations and purifications of active components in medicine, and for wastewater treatment. At present, fixed bed adsorption breakthrough curve is generally obtained by manual sampling and off-line detection. In this study, we proposed a method for on-line monitoring of fixed bed adsorption process using a self-assembled fiber-optic sensing (FOS) system. The adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) on the fixed bed packed with molecularly imprinted polymers (MIPs) and non-imprinted polymers (NIPs) were studied. The reproducibility and precision of the system was investigated. The relative standard deviation (RSD) of the system was less than 1.54%, which indicates that the system has a good reproducibility. The effects of initial concentration, flow rate, adsorbent mass and particle size on the breakthrough curves were investigated. Through screening, it was found that adsorption kinetics of the polymer materials fit to Thomas and Yoon-Nelson models. The MIPs showed high binding capacity, good selectivity, fast adsorption rate, indicating a great potential for the treatment of 2,4-D contaminated water. Moreover, this study has identified that the detection method has the advantages of being on-line, realtime, simple, and accurate. The on-line method can facilitate the study of fixed bed adsorption processes and accelerate the understanding of adsorption kinetics., 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 © 2020. Published by Elsevier B.V.)

Molecularly imprinted polymer (MIP)-based optosensing materials capable of direct, reliable, and highly selective detection of small organic analytes in complex aqueous samples hold great promise in many bioanalytical applications, but their development remains a challenging task. Addressing this issue, well-defined hydrophilic "turn-on"-type ratiometric fluorescent MIP microspheres are developed via a versatile and modular strategy based on the controlled/"living" radical polymerization method. Its general principle was demonstrated by the synthesis of red CdTe quantum dot (QD)-labeled silica particles with surface-bound atom transfer radical polymerization (ATRP)-initiating groups via the one-pot sol-gel reaction and their successive grafting of a thin fluorescent 2,4-D (an organic herbicide)-MIP layer (labeled with green organic fluorophores bearing both nitrobenzoxadiazole (NBD) and urea interacting groups) and hydrophilic poly(glyceryl monomethacrylate) (PGMMA) brushes via surface-initiated ATRP. The introduction of PGMMA brushes and rationally selected dual fluorescence labeling (i.e., red CdTe QDs being inert to 2,4-D and green NBD showing fluorescence "light-up" upon binding 2,4-D) onto MIP particles afforded them excellent complex aqueous sample-compatibility (due to their largely enhanced hydrophilicity) and analyte binding-induced "turn-on"-type ratiometric fluorescence changes, respectively. Such advanced MIP particles proved to be promising optosensing materials, which had a detection limit of 0.13 μM and showed obvious fluorescent color change upon binding different concentrations of 2,4-D in the undiluted pure milk. Moreover, they were successfully applied for direct and highly selective quantification of 2,4-D in the undiluted pure goat and bovine milks with good recoveries (97.9%-104.5%), even in the presence of several analogues of 2,4-D., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Since 2,4-dichlorophenoxy acetic acid (2,4-D) was discovered in the 1940s, 2,4-D and its derivatives remain among most commonly used herbicides in the world. There have been recent increases in using 2,4-D products in a combination with other herbicides such as metribuzin and acetochlor to control noxious weeds. However, accurate analysis of 2,4-D isooctyl ester remains to be improved due to long analysis time and rapid conversion of the ester to acid (i.e., under-reporting residues). In this work, a simple hydrolysis procedure was introduced to provide a quantitative hydrolytic rate of the ester (>95%) and did not affect the other pH-sensitive compounds. Analysis parameters and sample pretreatments were optimized for improved selectivity and accuracy. The hydrolysis-QuEChERS (quick, easy, cheap, effective, rugged, and safe) technique for multidetermination of 2,4-D isooctyl ester, metribuzin, acetochlor, and 2-ethyl-6-methylaniline in corn and soybeans via high performance liquid chromatography-tandem mass spectrometry was established. The method had average recoveries of 74-109% with relative standard deviations ≤13.5% and limits of quantifications (LOQs) of 0.05 mg/kg. The terminal residues of these compounds found in real edible matrixes were less than the corresponding LOQs at harvest time. The risk quotients were far below 100%, indicating a low health risk to consumers.

The portable and automated fluorescence microarray biosensing platform (FMB) that employed a compact hybrid optical structure, microfluidics, and microarray biosensors was constructed for on-site parallel detection of multiple analytes. In the FMB, a hybrid optical structure that composed of a 1 × 4 single mode fiber optic coupler, four fiber optic switches, a single-multi mode fiber optic bundle coupler was at the first time developed for the transmission of the excitation light and the collection and transmission of multi-channel fluorescence signals. Through the control of fiber optic switches, the parallel fluorescence assay of four channels could be achieved using only one excitation light and one photodiode detector on the basis of the time-resolved effect. This optical design not only greatly increased the efficiency of light transmission and fluorescence collection and detection sensitivity of the FMB, but also allows the miniaturization and portability of the whole system because of few optical separation elements used and no requirement of rigorous optical alignment. Taking Microcystin-LR (MC-LR), 2,4-D, atrazine (ATZ), and bisphenol A (BPA) for example, the application potential of the FMB to rapidly and parallelly detect four typical pollutants in real water with high sensitivity and specificity was demonstrated. The limits of detection of MC-LR, 2,4-D, ATZ, and BPA were 0.04 μg/L, 0.09 μg/L, 0.02 μg/L, and 0.03 μg/L, respectively. The FMB could also achieve early-warning of pollutants thanks to its ability of rapidity, high-frequency, and multiple-analyte detection. The FMB has significant implications as a multiplexable, portable, rapid, and quantitative detection platform for pollution accidents and water quality management to satisfy the increasing demands of alerting and protecting civilians., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Fluorescent molecularly imprinted polymer (FMIP) optosensor was utilized for the selective identification of 2,4-dichlorophenoxacetic acid (2,4-D) due to worldwide pollution caused by using herbicides in agricultural industry. In this regards, two derivatives of polymerizable 1,8-naphthalimide namely, 1,8-naphthalimide containing thiourea (NI) and diethyl amine tagged 1,8-naphthalimide (NII) were used as the receptors and 2,4-D was applied as a template. Also, precipitation polymerization was applied to prepare the fluorescent molecularly imprinted polymer (FMIP). The morphological, structural and thermal analysis was carried out using SEM, TEM, EDS, BET, FTIR, DSC and TGA for characterizing the fluorescent optosensor. The adsorption efficiency of FMIP and FNIP was studied using Langmuir, Freundlich, BET and Redlich Peterson isotherms. The results represented that the adsorption of 2,4-D on FMIP and FNIP agreed the Freundlich adsorption isotherm with correlation coefficient of 0.9935 and 0.9801, respectively. The prepared sensor was able for the selective determination of 2,4-D salt in the linear range of 5 × 10 -7 -1 × 10 -3  M with a limit of detection of 16.8 nM. The present study revealed that the FMIP prepared by 1,8-naphthalimide derivative (NI) could potentially recognize the trace concentration of 2,4-D. Graphical Abstract Graphical abstract of flourescene switching mechanism in a fluorescent molecularly imprinted polymer sensor.

Phenoxy acid 2,4-D (2,4-dichlorophenoxy acid) is one of the most commonly-used herbicide in agriculture. Biodegradation of 2,4-D can be stimulated by structurally-related plant secondary metabolites such as ferulic acid (FA). The aim of this study is to: (1) assess the potential of indigenous soil bacteria to degrade 2,4-D in the presence of FA by PCR analysis of functional tfdA genes, (2) to determine the influence of 2,4-D and FA on samples ecotoxicity using Phytotoxkit ® and Microtox ® biotests. The detection of tfdA genes varied depending on the enrichment of samples with FA. FA suppressed detection of the tfdA genes, 100 µM 2,4-D induced higher detection of studied amplicons, while 500 µM 2,4-D delayed their detection. The ecotoxicity response was specific and differed between plants (PE% Lepidium sativum >  Sinapis alba >  Sorghum saccharatum) and bacteria (PE% up to 99% for Vibrio fischeri). Our findings confirm that 2,4-D and FA had a toxic influence on the used organisms.

In the present work, dispersive micro-solid phase extraction (D-μ-SPE) method using magnetic graphene oxide tert-butylamine (GO/Fe 3 O 4 /TBA) nanocomposite, as an efficient sorbent, was applied for determining 2,4-dichlorophenoxyacetic acid (2,4-D) in water and food samples. Detection was carried out using high-performance liquid chromatography (HPLC) instrument. Influential parameters of D-μ-SPE such as sorbent and its amount, elution solvent and its volume, adsorption and desorption times and pH of sample solution were investigated and optimized. Under the optimized conditions, limit of detection and quantitation values were 0.007 and 0.02 μg/mL, respectively. Recovery data for several real samples were obtained within the range of 88.0-94.0% with a relative standard deviation (RSD) less than 7.5%. The proposed method was successfully applied to quantitative determination of 2,4-D in several vegetables and water samples.

Enantioselective biodegradation of racemic dichlorprop in two soils was investigated in the laboratory. Chiral separation of racemic dichlorprop was achieved by using HPLC with Phenomenex Lux Amylose-2. The first-order kinetic model fitted well the dissipation data of racemic dichlorprop and its pure R- and S-enantiomers. S-dichlorprop was preferentially degraded in both soils and enantioselectivity was affected by soil pH. The half-lives (DT 50 ) of S-dichlorprop were 8.22 days in soil A and 8.06 days in soil D, while R-dichlorprop was more persistent with DT 50 of 12.93 days in soil A and 12.38 days in soil D, respectively. Dichlorprop dissipated faster in soil D with lower organic matter content. In sterilized soils, neglected dissipation was observed and enantiomer fraction values remained constant, indicating that the enantioselective degradation was mainly controlled by soil microorganisms. Soil microbial community structure and diversity was assessed by Illumina MiSeq sequencing of 16S rRNA genes from dichlorprop and no dichlorprop contaminated microcosms. Compared with controls, dichlorprop application had no significant effect on microbial community structures at phylum level, but increased bacterial diversity and dichlorprop degradation related taxa in both soils. S-dichlorprop preferential degradation might be attributed to the S-enantiomer preferred degraders in the family of Sphingomonadaceae .

Beehive products are considered sentinels for environmental pollutants. The presence of trace elements and pesticides in honey and beeswax may pose a health hazard to consumers. The study's aim was to determine the profile of pesticides and trace elements in Israeli honey and beeswax samples in relation to human risk assessment. At least two pesticides contaminated the honey and beeswax samples simultaneously, in which, amitraz metabolites and coumaphos were frequently detected. The neonicotinoid insecticides and 2,4-dichlorophenoxyacetic acid, were found only in honey samples, whereas the more lipophilic pesticides were predominantly found in beeswax. In honey, chromium displayed the highest mean concentration, followed by zinc, whereas lead and molybdene occurred only in beeswax. Our findings indicate that the daily consumption of honey and beeswax together may compromise children's health. Sucrose-syrup fed honey could not be distinguished from floral honey based on sugar profile, rather by its trace elements levels., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The authors describe an electrochemical method for the determination of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). It is based on the use of a molecularly imprinted polymer (MIP) and of dsDNA as a bio-specific substance. The modified electrode was prepared by electropolymerization of ortho-phenylenediamine (oPD) in the presence of DNA and of 2,4-D (the template). The imprinted MIP was placed on a pencil graphite electrode (PGE) modified with chitosan and multiwalled carbon nanotubes (MWCNTs). The template was removed with 0.4 M NaOH. The interaction of DNA with 2,4-D leads to its adsorption on the electrode, and this increases the sensitivity and selectivity of the method. After rebinding 2,4-D, the decrease in the peak current of oxidation of iron(II) acting as an electrochemical redox probe was measured by differential pulse voltammetry (DPV). The current, typically measured at around 0.5 V, increases linearly in the 0.01 to 10 pM 2,4-D concentration range, and the detection limit is 4.0 fM. The method is highly selective for 2,4-D. The modified electrode was applied to quantify 2,4-D in spiked environmental water and soil samples and gave absolute recoveries varying from 91.5 to 109.0%. Graphical abstractSchematic representation of the fabrication of an electrochemical sensor for determination of 2,4-dichlorophenoxyacetic acid (2,4-D). Initially, the electrode was modified with chitosan and MWCNTs and then a composite was formed on it consisting of ortho-phenylenediamine (oPD), DNA and 2,4-D.

Metal-organic coordination polymer beads (MOCBs) are described for use as a sorbent for solid-phase extraction of chlorophenoxy herbides. By applying regulation of Co(II) ions, micro-sized monodisperse MOCBs were obtained through the microwave heating. The MOCBs-based method displays excellent extraction efficiency towards chlorophenoxy herbicides, specifically of 2-chlorophenoxyacetic acid, 4-chlorophenoxyacetic acid, 4-chloromethylphenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, 2,4,5-trichlorophenoxyacetic acid and 2-(2,4-dichlorophenoxy)propionic acid. Following extraction, the herbicides were eluted with 8% formic acid in methanol and quantified by HPLC. The method, when applied to analyze spiked cereals, exhibits a wide linear range (from 0.6 to 1000 ng g -1 ) and low limits of quantification (ranging from 0.10 to 0.25 ng g -1 ). For a single column, the inter-day and intra-day precisions, expressed as the relative standard deviation are in the range of 2.5-6.8%. The batch-to-batch reproducibility (for n = 3) is <4.6%. For spiked cereal samples, relative recoveries are very good (90.3-102.3%, for n = 4). The extraction efficiency of MOCBs remains unchanged after reusing for 40 times. Graphical abstractSchematic presentation of Co(II)-doped metal-organic coordination polymer beads (Co(II)@MOCB) using for solid-phase extraction (SPE).

This study aims to develop molecularly imprinted based quartz crystal microbalance (QCM) and surface plasmon resonance (SPR) sensors for highly sensitive and selective detection of 2,4-dichlorophenoxyacetic acid (2,4-D) and to determine their accuracy and precision by liquid chromatography-tandem mass spectrometry (LC-MS/MS) as a reference technique. Here, we synthesized non-imprinted (NIP) and 2,4-D-imprinted (MIP) [ethylene glycol dimetacrylate-N-metacryloyl-(l)-tryptophan methyl ester-p(EGDMA-MATrp)] polymeric nanofilms by using molecular imprinting technique. MIP and NIP nanofilms were characterized by fourier transform infrared spectroscopy attenuated total reflectance (FTIR-ATR), atomic force microscope (AFM), contact angle and ellipsometer measurements. The molecular imprinting procedures were successfully carried out and it was found that the prepared polymeric surfaces were highly desirable for sensitive recognition by QCM and SPR sensors. Competitive experiments for the sensors revealed that MIP nanofilms were found to show more sensitivity and selectivity than NIP ones. The sensor responses have a good linear relationship with 2,4-D concentrations in the range of 0.23-8.0 nM with a limit of detection at 20.17 ng/L for QCM and 24.57 ng/L for SPR sensors. In conclusion, both QCM and SPR sensor systems showed good accuracy and precision, with recovery percentages between 90 and 92% and 87-93%, respectively. Furthermore, they have a fast response time, reusability, high selectivity and sensitivity and low limit of detection., (Copyright © 2019 Elsevier B.V. All rights reserved.)

This study analyzed the performance of organophilic clays obtained from the chemical modification of sodium bentonite clay when applied to the adsorption of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). Kinetic curves and equilibrium isotherms were obtained in order to determine time and adsorption capacity of the material, as well as understand the mechanisms involved in this phenomenon. The results showed that the most predictive kinetic model for experimental data was of pseudo-second order (R 2  > 0.98), and that external mass transfer is the dominant factor in the time of operation. Isotherms were obtained at temperatures of 298, 308, and 318 K, under which the Dubinin-Radushkevich model was shown to have a good fit to data (R 2  > 0.96), according to mathematical adjustments. The maximum adsorption capacity obtained experimentally was 50.36 mg g -1 , found at a temperature of 298 K, being higher or compatible with other materials reported in the literature. With help of the thermodynamic studies on the process, it was observed that the adsorption of 2,4-D in organophilic clays refers to a spontaneous (ΔG° ads  < 0), exothermal (ΔH° ads  = - 9.99 kJ mol -1 ) process of physical nature. Lastly, it was observed that the adsorbent can be easily regenerated when subjected to eluents such as mixtures containing fractions of ethanol/water (desorption = 95%).

A new cationic gemini surfactant-resorcinol/formaldehyde resin was designed and synthesized. Cationic gemini surfactant was introduced into the resorcinol/formaldehyde resin for the first time and led to the retention of negatively charged endocrine disrupting compounds (EDCs) through electrostatic interactions, hydrogen bonding and π-π interactions. The synthesized material showed good performance in the dispersive micro-solid phase extraction (D-μ-SPE) of EDCs such as alkylphenol and phenoxy acid herbicides from food packaging migrants. Extraction parameters such as pH, adsorbent dose, extraction time and salting out effect were optimized. The limits of detections were in the range of 0.5-0.8 ng/mL, and the recoveries were in the range of 90-100%. The developed method was applied to the analysis of EDCs from food contacting materials migrants with pentachlorophenol, 2,4-dichlorophenoxyacetic acid and bisphenol A detected in the concentration range of 0.2-1.2 mg/kg. It also showed great potential in the D-μ-SPE of other compounds with negative charge or high hydrophobicity., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Rapid detection of pesticides in fruits is an ongoing challenge. The objective of the present study was to develop novel fluorescent microfluidic paper chips for specific recognition and sensitive detection of the pesticide 2,4-D through the electron-transfer-induced fluorescence quenching mechanism. CdTe quantum dots (QDs) were deposited onto cellulose paper (base material) to yield imprinted paper chips (paper@QDs@MIPs). This method allows the transferability of the molecularly imprinted fluorescence sensor from the liquid phase to the solid phase (paper base) for rapid and portable analysis. The resultant imprinted paper chips were effectively characterized, and they exhibited ideal ordered spatial network structure, chemical stability, and fluorescence property. The paper@QDs@MIPs showed that 2,4-D binding significantly reduced the fluorescence intensity within less than 18 min, and it achieved satisfactory linearity in the range of 0.83-100 μM and high detectability of 90 nM. The recognition specificity for 2,4-D relative to its analogues was shown, and the imprinting factor was 2.13. In addition, the recoveries of the spiked bean sprouts at three concentration levels ranged within 94.2-107.0%, with a relative standard deviation of less than 5.9%. Collectively, the device provided an effective platform for rapid recognition, convenience, and detection of trace food pollutants in complex matrices, thereby ensuring food safety and further promoting surface imprinting studies.

A novel dual-color total internal reflection fluorescence biosensor (DTB) was successfully developed for the simultaneous detection of two small molecules based on a simple optical structure and the time resolved effect of fiber optic switch. The DTB employed a single-multi mode fiber optic coupler instead of a sophisticated confocal optical system for the transmission of two excitation lights and dual-color fluorescence, and a photodiode detector instead of photomultiplier for the simultaneous detection of dual-color fluorescence. The compact optical design of DTB improved its optical transmission efficiency and detection sensitivity because of no requirement of numerous optical separation elements and rigorous optical alignment. The DTB was applied for the simultaneous detection of 2,4-Bisphenol-A (BPA) and 2,4-Dichlorophenoxyacetic acid (2,4-D) using one bifunctional fiber optic bio-probe modified by two hapten-protein conjugates. When the mixture of Cy5.5 labeled anti-2,4-D antibody and Pacific Blue dye labeled anti-BPA antibody was introduced over the surface of the bio-probe, they bound with their respective hapten-protein conjugate immobilized onto the bio-probe. Based on the time-resolved effect of fiber optic switch, two fluorescence dyes were alternatively excited by 635 nm and 405 nm laser lights and simultaneously detected by one photodiode detector. Taking indirect competitive immunoassay principle, BPA and 2,4-D were simultaneously detected using the DTB with high sensitivity, accuracy, and rapidity. The quantitation of affinity constants between small molecules and their antibodies was also achieved based on the proposed theory. The DTB provides a flexible and powerful platform for simultaneously sensitive quantitation of multiple targets and the affinity constants of biomolecular interactions., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The effects measured with in vitro cell-based bioassays are typically reported as nominal effect concentrations ( C nom ), but the freely dissolved concentration in the exposure medium ( C w ) and the total cellular concentration ( C cell ) are considered more quantitative dose metrics that allow extrapolation to the whole-organism level. To predict C w and C cell , the partitioning of the test chemicals to medium proteins and lipids and cells has to be known. In this study, we developed a solid-phase microextraction (SPME) method based on C18-coated fibers to quantify the partitioning of diclofenac, 2,4-dichlorophenoxyacetic acid (2,4-D), ibuprofen, naproxen, torasemide, warfarin, and genistein to bovine serum albumin (BSA), phospholipid liposomes, fetal bovine serum (FBS), and cells. For ibuprofen, 2,4-D, naproxen, and warfarin, the partitioning to the SPME fibers was found to be concentration dependent, which had to be considered for the calculation of distribution ratios to biological materials. The sorption isotherms to FBS were nonlinear for diclofenac, 2,4-D, ibuprofen, naproxen, and warfarin. The FBS isotherms could be described by assuming that the total amount of chemical bound to FBS is the sum of the amount specifically bound to the binding sites of albumin and nonspecifically bound to all medium proteins and lipids. The determined cell-water distribution ratios ( D cell/w ) differed considerably between four different cell lines (up to 1.83 log-units) and also between different batches of the same cell line (up to 0.48 log-units). The relative importance of protein and lipid content for D cell/w was evaluated with a mass balance model and different types of cellular proteins and lipids as input parameters. Existing in vitro mass balance models may underestimate C w because they do not account for saturable protein binding and overestimate C cell for organic acids, if BSA is used as surrogate for cellular proteins.

With increased concerns on milk safety issues, the development of a simple and sensitive method to detect 2,4-dichlorophenoxyacetic acid (2,4-D), a common contaminant in milk, becomes relevant in safeguarding human health threats that results from its consumption. Surface-enhanced Raman spectroscopy (SERS) shows excellent ability for various targets analysis but its usage for rapid and accurate determination of analyte via SERS presents challenges. This study attempted the quantification of 2,4-dichlorophenoxyacetic acid (2,4-D) residue in milk using a novel SERS active substrate- decorated silica films with Au nanoparticles (Au NPs@ silica) coupled to chemometric algorithms. Au NPs@ silica composite was synthesized as a SERS sensor through self-assembly. Thereafter, the SERS spectrum of 2,4-D extract from milk with different concentrations based on the developed SERS sensor was collected and the spectra were analyzed by partial least squares (PLS), and variable selection algorithms - genetic algorithm-PLS (GA-PLS), competitive-adaptive reweighted sampling-PLS (CARS-PLS) and ant colony optimization-PLS (ACO-PLS), to develop quantitative models for 2,4-D prediction. The results obtained showed that the CARS-PLS model gave the optimum result with LOD of 0.01 ng/mL realized and a determination coefficient in the prediction set of (R P ) = 0.9836 within a linear range of 10 -2 to 10 6  ng/mL was achieved. Au NPs@ silica SERS sensor combined with CARS-PLS may be employed for rapid quantification of 2,4-D extract from milk towards its quality and safety monitoring., (Copyright © 2018. Published by Elsevier B.V.)

An integrated multichannel all-fiber optofluidic biosensing platform (M-AOB) has been developed for a sensitive, rapid, and simultaneous detection of up to three trace analytes. The M-AOB platform employs a 1 × 3 fiber optical switch and three single-multimode fiber optic couplers for the transmission of excitation light and fluorescence and one photodiode detector for the simultaneous detection of fluorescence signals of multiple channels based on the time-resolve effect of the fiber optical switch. This design greatly simplified the entire system structure and improved light transmission efficiency. Through an indirect competitive immunoassay mechanism, we detected two highly regulated small molecules, namely, atrazine and 2,4-D, to demonstrate the value of M-AOB to the simultaneous measurement of trace analytes in water samples. The limits of detection of 0.03 μg/L and 0.04 μg/L were obtained for atrazine and 2,4-D, respectively, and were highly comparable with those of other analytical techniques. The high sensitivity of M-AOB benefited from the high light collective efficiency and low light loss of the excellent all-fiber optical structures and from the advantages of the evanescent wave technique. The regeneration of the biosensor surface, 200 assay cycles, were performed without any significant activity loss. Each assay cycle was less than 15 min. The immunoassay performance of the M-AOB, evaluated in several spiked water samples, showed good recovery, accuracy, and precision, indicating that the M-AOB was less susceptible to matrix effects of water samples. All these results illustrated that M-AOB can be readily extended toward the simultaneous and rapid detection of other trace small molecules using different biosensors modified by other analyte conjugates and their respective fluorescence-labeled antibodies., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The objective of this study was to evaluate the potential for non-invasive biomonitoring of 2,4-Dichlorophenoxyacetic acid (2,4-D) in saliva. Using an in vitro rat salivary gland epithelial cell (SGEC) system, a collection of experiments investigating chemical protein binding, temporal and directional transport, as well as competitive transport with para-aminohippuric acid (PAH), a substrate for renal organic anion transporters, was conducted to identify cellular transport parameters required to computationally model salivary transport of 2,4-D. Additionally, a physiological protein gradient was implemented to mimic physiologically relevant concentrations of protein in rat plasma and saliva, and under these conditions the transfer of 2,4-D was markedly slower, driven by increased protein binding (i.e. reduced free 2,4-D species available to cross salivary barrier). The rate of transfer was directly proportional to the amount of unbound 2,4-D and demonstrated no indication of active transport. An in vivo assessment of 2,4-D exposure in rats revealed non-linear protein binding in plasma, indicating saturated protein binding and increased levels of unbound 2,4-D species at higher doses. A strong correlation between 2,4-D concentrations in saliva and unbound 2,4-D in plasma was observed (Pearson correlation coefficient = 0.95). Saliva:plasma 2,4-D ratios measured in vivo (0.0079) were consistent within the linear protein binding range and expected 2,4-D levels from occupational exposures but were significantly different than ratios measured in vitro (physiological conditions) (0.034), possibly due to 2,4-D concentrations in saliva not being at equilibrium with 2,4-D concentrations in blood, as well as physiological features absent in in vitro settings (e.g. blood flow). We demonstrated that 2,4-D is consistently transported into saliva using both in vitro and in vivo models, making 2,4-D a potential candidate for human non-invasive salivary biomonitoring. Further work is needed to understand whether current sensor limits of detection are sufficient to measure occupationally relevant exposures., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The 2,4-dichlorophenoxyacetic acid (2,4-D) herbicide, as an aromatic hydrocarbon, is a dangerous and toxic organic pollutant among the agricultural pesticides. In this research, the performance of the biochar made from rice husk (BRH), granular activated carbon (GAC), and multi-walled carbon nanotubes (MWCNTs) was investigated for adsorption of 2,4-D in a fixed-bed column system. The influence of pH (2, 5, 7, 9), flow rate (0.5, 1, 1.5 mL min -1 ), bed depth (3, 6, 9 cm), and influent 2,4-D concentration (50, 100, 150, 300 mg L -1 ) on the adsorption process was evaluated. The resulting breakthrough curves indicated that the higher removal efficiency of 2,4-D took place at the lower flow rate, lower influent 2,4-D concentration, higher bed depth, and lower pH. While in most cases the removal ability of GAC was better than other adsorbents, generally, this study confirmed that the BRH, as a cheap and sustainable material, can be a viable alternative to GAC and MWCNTs for remediation and treatment scenarios, particularly in developing countries.

An automated on-line solid-phase extraction (SPE) following liquid chromatography tandem mass spectrometry was established for the fast determination of plant growth regulator residues in soybean sprout and mung bean sprout. The crude extracted specimens were directly purified on a poly (2-(dimethylamino) ethyl methacrylate-co-ethylene dimethacrylate) monolithic column which was well-defined as the on-line SPE adsorbent. Under the optimized conditions, the developed method gave the linear range of 0.3-50 ng/mL for gibberellin and 2,4-dichlorophenoxyacetic acid, 0.2-50 ng/mL for 4-chlorophenoxyacetic acid, and 0.5-50 ng/mL for 1-naphthaleneacetic acid (r ≥ 0.998). The detection limits (S/N = 3) ranged from 1.0 to 2.5 μg/kg and the recoveries for spiked soybean sprout samples were in the range of 75.0-93.3%. Besides, the total time for one analysis was 16 min. The reusability of the monolith was up to 600 extractions. The proposed process facilitated fully automated SPE and accurate determination in one step with rapidity, simplicity, and reliability. Graphical abstract ᅟ.

We report the development of a molecularly imprinted polymers-surface-enhanced Raman spectroscopy (MIPs-SERS) method for rapid detection and quantification of a herbicide residue 2,4-dichlorophenoxyacetic acid (2,4-D) in milk. MIPs were synthesized via bulk polymerization and utilized as solid phase extraction sorbent to selectively extract and enrich 2,4-D from milk. Silver nanoparticles were synthesized to facilitate the collection of SERS spectra of the extracts. Based on the characteristic band intensity of 2,4-D (391 cm -1 ), the limit of detection was 0.006 ppm and the limit of quantification was 0.008 ppm. A simple logarithmic working range (0.01-1 ppm) was established, satisfying the sensitivity requirement referring to the maximum residue level of 2,4-D in milk in both Europe and North America. The overall test of 2,4-D for each milk sample required only 20 min including sample preparation. This MIPs-SERS method has potential for practical applications in detecting 2,4-D in agri-foods., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

We investigated an Electrolyte-Gated Organic Field-Effect transistor based on poly(N-alkyldiketopyrrolo-pyrrole dithienylthieno[3,2-b]thiophene) as organic semiconductor whose gate electrode was functionalized by electrografting a functional diazonium salt capable to bind an antibody specific to 2,4-dichlorophenoxyacetic acid (2,4-D), an herbicide well-known to be a soil and water pollutant. Molecular docking computations were performed to design the functional diazonium salt to rationalize the antibody capture on the gate surface. Sensing of 2,4-D was performed through a displacement immunoassay. The limit of detection was estimated at around 2.5 fM., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This research aims to identifying the potential effect of using a hydrogen-producing reactor's effluent as an enrichment amendment for enhancing the degradation rates of 2,4-dichlorophenoxyacetic acid (2,4-D) during the bioremediation of contaminated paddy soils. The results showed that addition of the effluents to 2,4-D- degrading enrichment culture enhanced (up to 1.3-fold) the degradation rate constant of 2,4-D. The enhancement effect most probably resulted from the co-metabolic degradation of 2,4-D facilitated by volatile fatty acids (e.g., acetate, propionate, and butyrate) in the effluents which served as the beneficial substrates. Results from DNA sequencing analysis showed that the effluent additions shifted the bacterial community composition in the enrichment culture. Dechloromonas and Clostridium were two dominant bacterial genera involved in 2,4-D degradation. The findings will make a substantial contribution to remediation of soils contaminated with 2,4-D., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Supercritical fluid chromatography coupled to triple quadrupole mass spectrometry has been evaluated for pesticide residues in food. In order to check its advantages and limitations it was developed a method to identify and quantify 164 pesticides in three different matrices (tomato, orange and leek). A carbon dioxide gradient with methanol (containing 1 mM ammonium formate) was used allowing a flow rate of 1.5 mL/min that made the total run time of 12 min without any problem of overpressure. Addition of a post column flow 150 μL/min of Methanol with ammonium formate/formic acid was necessary to improve the ionization. The matrix effect study revealed that the percentages of pesticides with irrelevant matrix effect (suppression lower than 20%) was 99% in tomato, 87% in orange and 62% in leek, whereas significant suppression (higher than 50%) was not found in tomato and only 1% of the compounds in orange and 3% in leek.These results compare favorably with that typically obtained in LC-MS/MS. The absence of water in the mobile phase, also provided some important advantages regarding LC-MS/MS as (i) higher retention of polar compounds in the column, which elute with high sensitivity and good peak shape and (ii) a general increase of the sensitivity of the analysis, consequence of the high ionization and ion extraction efficiency. Pesticides evaluated were identified following the SANTE/11813/2017. At the spiking concentration of 5 μg/kg, 98% of the pesticides were identified in tomato, 98% in orange and 94% in leek, whereas for the concentration of 10 μg/kg all the compounds were identified in tomato and only spiromesifen was not identified in orange and leek. At the concentration of 20 μg/kg, spiromesifen was also identified in these two matrices. The linearity and reproducibility of the method were evaluated with results which guarantee high quality in the analytical measurements. Even though only 2 μL of final extract were injected, the sensitivity of the SFC method was enough to achieve stringent LOQs.Real samples, including 6 different fruits and vegetables, were analyzed by the SFC-MS/MS proposed method, the results being similar to those obtained by LC-MS/MS. The method was also applied to a proficiency test of fipronil in eggs with good results in all the cases. Carbon dioxide as mobile phase with methanol as modifier can represent a good alternative to LC-MS/MS with reduction of matrix effects and shorter run times., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In this work, a novel molecularly imprinted electrochemical sensor based on the amino-functionalized silica nanoparticles was built for the sensitive and selective detection of 2,4-dichlorophenoxyacetic acid (2,4-D). The hierarchical porous dendrimer-like silica nanoparticles (HPSNs-NH 2 ) were synthesized by an ethyl ether emulsion method. The selective molecularly imprinted polymers (MIP) was prepared on the HPSNs-NH 2 modified electrode via electropolymerization by using 2,4-D as the template and o-phenylenediamine (OPD) as the monomer. The porous structure of HPSNs-NH 2 reduced the diffusion limitations of the analytes, enhanced the accessibility and increased the surface area of the sensor, while the MIP layer offered the ability to recognize and quantify target 2,4-D by using ferro/ferricyanide as probes. Several significant experimental parameters on the analytical performance of the MIP/HPSNs-NH 2 sensor were explored and optimized. Under the optimized condition, the sensor displayed an appreciable selectivity over structurally related compounds and good sensitivity toward 2,4-D. The linear range of 2,4-D detection was from 1.00 × 10 -10 to 2.50 × 10 -8 M and the detection limit was down to 1.17 × 10 -11 M according to the 3S a /b criteria. This method has been applied to detect 2,4-D in bean sprout samples with satisfying results., (Copyright © 2017. Published by Elsevier B.V.)

Paper spray ionization (PSI) has some limitations such as low sensitivity and ionization suppression when complex samples are analyzed. The use of sample preparation devices directly coupled to MS can avoid these restrictions. Molecularly imprinted polymers (MIPs) are materials widely used as adsorbent in sample preparation methods such as solid-phase extraction and solid-phase microextraction, and they can provide specifics cavities with affinity to a target molecule. Here, we introduce a new MIP membrane spray ionization method combining MIP and PSI. MIP was synthesized directly on a cellulose membrane. Monuron and 2,4,5-T (2,4,5-trichlorophenoxyacetic acid) were used as template molecules in MIP synthesis for diuron and 2,4-D (2,4-dichlorophenoxyacetic acid) analyte sequesters, respectively. Apple, banana and grape methanolic extracts were used as matrices. The MIP membrane spray showed signal intensities of diuron and 2,4-D that were much higher compared to those obtained by non-imprinted polymers(NIP). Calibration curves exhibited R 2 > 0.99 for diuron and 2,4-D in all fruit extracts analyzed. LODs were found less than 0.60µgL -1 and LLOQs were found less than 2.00µgL -1 . The coefficients of variation and relative errors were less than 15% for almost all analyses. The apparent recovery test results ranged between 92,5% and 116.9%. Finally, the MIP membrane spray method was employed for the quantification of diuron and 2,4-D in real samples. Diuron contents were only found in three bananas (4.0, 6.5, and 9.9µgL -1 ). The proposed MIP membrane spray ionization method was straightforward, fast to carry out and provided satisfactory results for analyses of diuron and 2,4-D in apple, banana and grape samples., (Copyright © 2017 Elsevier B.V. All rights reserved.)