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Diclazuril (DIC) is a broad-spectrum anti-coccidiosis drug of the triazine class, widely used in poultry farming. The overuse of DIC may lead to its accumulation in animal bodies, which may enter the food chain and threaten human health. In this work, we fabricated a stable Eu 3+ -doped UiO-66 fluorescence sensor (EuUHIPA-30) for the sensitive detection of DIC. Among 20 veterinary drugs, the fluorescence of EuUHIPA-30 selectively responds to DIC, with a low detection limit (0.19 μM) and fast response (10 s). EuUHIPA-30 is recyclable and can detect DIC in chicken and eggs with good recoveries. Moreover, a smartphone-integrated paper-based sensor enables the instrument-free, rapid, visual, and intelligent detection of DIC in chickens and eggs. This work provides a promising candidate for practical fluorescent DIC sensing in animal-derived food to promote food safety., 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 Elsevier Ltd. All rights reserved.)

4-Hydroxychlorothalonil (4-OH CHT), the main metabolite of chlorothalonil and the most widely used fungicide, has been frequently detected in human samples during monitoring. 4-OH CHT may exhibit higher toxicity and persistence in the environment compared to its prototype. In this study, a total of 540 paired serum and breast milk samples from pregnant women in three provinces in China were monitored for contaminant residues. 4-OH CHT was analyzed in the samples using ultra high-performance liquid chromatography - high-resolution mass spectrometry with a detection limit of 20 ng/L. The study investigated the effects of demographic factors, such as BMI, region of residence, and education level, on the levels of 4-OH CHT residues in serum and breast milk. Among the three provinces, the highest median concentration of 4-OH CHT in serum samples was observed in Hebei (1.04 × 10 3  ng/L), while the highest median concentration of 4-OH CHT in breast milk samples was observed in Hubei and Guangdong (491 ng/L). Multiple linear regression was used to investigate the significant positive correlation between 4-OH CHT in serum and breast milk (p = 0.000) after adjusting for personal characteristics. Based on this, the study further explored the influencing factors of transfer efficiencies (TEs) in conjunction with the individual TEs and the personal characteristics of the participants. Our results demonstrated that the age of the volunteers and their exercise habits had an effect on TEs, but further studies are needed to determine whether exercise leads to an increase in TEs., 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 Elsevier B.V. All rights reserved.)

Rationale: Chlorothalonil (CHT), a broad-spectrum fungicide, has been employed widely to control foliar diseases, whereas with a major metabolite of polar 4-hydroxychlorothalonil (CHT-4-OH), only an acceptable nonpolar CHT residue is allowed by most countries. This study involves the method development for CHT residue in vegetables/fruits using liquid chromatography-tandem mass spectrometry (LC-MS/MS) with a novel modified discharge-adaptor (DA) interface., Methods: CHT residue was analyzed using LC-MS/MS with DA interface (LC-DA-MS/MS), developed in our previous works. A DA was placed on the electrospray tip to switch the ionization modes. A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was applied to extract CHT residue of vegetables/fruits efficiently with less sample preparation time and analysis cost., Results: CHT and CHT-4-OH spiked in four different vegetables/fruits were extracted using the modified QuEChERS method. After LC with isocratic elution, CHT and CHT-4-OH were separated within 3 min. Using LC-DA-MS/MS, the ion signals of CHT were improved two to three times, and the limit of quantification of 5 ng/g and linearity (r 2  > 0.99) in the range of 5-200 ng/g were achieved using 10 g of vegetables/fruits. The precision and accuracy were within 15% each. The modified QuEChERS and LC-DA-MS/MS were applied to examine eight field-grown vegetables/fruits; 9.5 and 2588.9 ng/g of CHT were detected in two vegetables/fruits., Conclusion: LC-DA-MS/MS combined with modified QuEChERS was successfully applied to determine CHT residue <10 ng/g in vegetables/fruits and with satisfied validation results. The developed method could reduce both analysis cost and time, attributing to simplifications in modified QuEChERS, isocratic elution, and DA interface in LC-DA-MS/MS., (© 2024 John Wiley & Sons Ltd.)

Given the growing concern over the deployment of toxic chemicals in warfare, the rapid and accurate removal and detection of cyanogen chloride (CK) as a blood agent has become increasingly critical. However, conventional physisorbents and chemisorbents used in military respirators are insufficient for the effective removal of CK. In this study, we demonstrate the chemisorption and sensing abilities of Co 2 (m-DOBDC) (m-DOBDC 4-  = 4,6-dioxo-1,3-benzenedicarboxylate) for CK via electrophilic aromatic substitution (EAS) in humid environments. Unlike the chemisorption in triethylenediamine (TEDA) impregnated carbon materials, which generates by-products through hydrolysis, the electron-rich C5 sites in m-DOBDC 4- ligands give rise to cyano substitution with CK. This leads to the formation of stable C-C bonds and chloride ions (Cl - ) coordinating with open Co 2+ sites. Such a mechanism prevents the generation of toxic by-products like cyanic acid and hydrochloric acid. Breakthrough experiments conducted in a packed-bed system conclusively demonstrated the superior CK removal capacity of Co 2 (m-DOBDC) (1662 min/g), compared to TEDA-impregnated activated carbon (323 min/g) under humid conditions. Considering that MOF-74 series, isostructural with Co 2 (m-DOBDC), barely adsorb CK under similar conditions, this finding marks a significant advancement in developing novel sorbents for CK removal. Moreover, this chemisorption not only exhibited rapid and highly efficient CK removal but also enabled colorimetric monitoring via the distinctive color change induced by the coordination of Cl - acting as σ donors. These findings facilitate the development of adsorption and sensing equipment to protect military personnel from toxic chemical threats., 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 Elsevier Ltd. All rights reserved.)

Tetracycline (TC) is extensively utilized in livestock breeding, aquaculture, and medical industry. TC residues seriously harm food security, the environment, and human health. There is an urgent need to exploit a highly efficient and sensitive testing method to monitor TC residue levels in aquatic environments. In this study, graphitic carbon nitride quantum dots (g-CNQDs) were successfully synthesized by a one-step microwave-assisted method using citric acid and urea as precursors. The as-prepared g-CNQDs with size of 1.25-3.75 nm exhibited bright yellow fluorescence at 523 nm when excited at 397 nm. Interestingly, this characteristic fluorescence emission of g-CNQDs could be selectively and efficiently quenched by TC. Based on this phenomenon, for TC detection was successfully explored and applied in real water samples. Wide linear scope of 7-100 μM, low detection limit (LOD) of 0.48 μM, satisfactory recovery of 97.77%-103.4%, and good relative standard deviation (RSD) of 1.05-5.87% were obtained. Mechanism investigations revealed that the static quenching and the inner filter effect (IFE) were responsible for this fluorescence quenching between g-CNQDs and TC. This work not only provided a facile approach for g-CNQDs synthesis but also constructed a g-CNQDs-based fluorescent sensor platform for the highly sensitive and selective detection of TC in aquatic environments., 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 Ltd.)

In the last years, issues related to intensive agriculture have been found in protected areas potentially harming wildlife. This study aimed to analyze a wide range of pesticides in water and sediments of two protected areas namely Doñana Natural Park (DNP) and Tablas de Daimiel National Park (TDNP) performing an environmental risk assessment in order to highlight potential risks to living organisms derived from pesticide burden. Higher pesticide load was found in DNP than TDNP with similar distribution profiles, with pyrethroid insecticides (PYRs) the main detected class. Particularly problematic are two PYRs, cyhalothrin and fenvalerate, which were detected at high concentrations that can pose a high risk to aquatic organisms. In addition, despite being detected at lower concentrations, the presence of chlorpyrifos, cypermethrin, and permethrin in water, and of chlorpyrifos, dicofol, and diflufenican in sediments, must be taken into account due to their potential risks for aquatic organisms. Moreover, some banned pesticides such as dimethoate, terbutryn, diazinon, and tricyclazol were detected in water at levels which deserve further investigation to assess their potential sources, including potential illegal practices., 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 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Background: The Centers for Disease Control and Prevention (CDC) bottle bioassay is a commonly used susceptibility test for measuring insect response to insecticide exposure. However, inconsistencies and high variability in insect response when conducting CDC bottle bioassays have been reported in previous publications. We hypothesized that the CDC bottle bioassay results may be compromised when expected and actual insecticide concentrations in the bottles are not equivalent and that inadequate bottle cleaning and/or loss during insecticide introduction and bottle storage steps could be responsible. We explored this hypothesis by quantifying insecticides using gas chromatography tandem mass spectrometry (GC-MS/MS) in bottles that had been cleaned, prepared, and stored according to the CDC guidelines., Methods: We investigated the bottle cleaning, preparation, and storage methods outlined in the CDC bottle bioassay procedure to identify sources of irreproducibility. We also investigated the effectiveness of cleaning bottles by autoclaving because this method is commonly used in insecticide assessment laboratories. The two insecticides used in this study were chlorpyrifos and lambda-cyhalothrin (λ-cyhalothrin). Insecticides were removed from glass bioassay bottles by rinsing with ethyl-acetate and n-hexane and then quantified using GC-MS/MS., Results: The CDC bottle bioassay cleaning methods did not sufficiently remove both insecticides from the glass bottles. The cleaning methods removed chlorpyrifos, which has higher water solubility, more effectively than λ-cyhalothrin. Chlorpyrifos experienced significant loss during the bottle-coating process whereas λ-cyhalothrin did not. As for bottle storage, no significant decreases in insecticide concentrations were observed for 6 h following the initial drying period for either insecticide., Conclusions: The CDC bottle bioassay protocol is susceptible to producing inaccurate results since its recommended bottle cleaning method is not sufficient and semi-volatile insecticides can volatilize from the bottle during the coating process. This can lead to the CDC bottle bioassay producing erroneous LC 50 values. High levels of random variation were also observed in our experiments, as others have previously reported. We have outlined several steps that CDC bottle bioassay users could consider that would lead to improved accuracy and reproducibility when acquiring toxicity data., (© 2024. The Author(s).)

Bell peppers, a globally significant crop, face infestations from various pests. In a study, bell peppers were treated with deltamethrin, ethion, fenazaquin, and fenpropathrin at recommended and double the doses, repeated twice with a 10-day interval. The QuEChERS method underwent validation for linearity, matrix match, accuracy, and precision in bell pepper matrices for residue analysis. The limit of detection for the tested pesticides on bell peppers was 0.01 mg/L, with a quantification limit of 0.05 mg/L. Recovery studies showed a range of 94.80% to 102.80%. Initial deposits of deltamethrin, ethion, fenazaquin, and fenpropathrin on bell peppers at recommended doses were 0.371, 1.237, 0.617, and 0.640 mg/L, respectively, and at double doses were 0.712, 1.945, 1.221, and 1.189 mg/L, respectively. Safe waiting periods of 10, 11, 10, and 8 days were suggested for deltamethrin, ethion, fenazaquin, and fenpropathrin, respectively. The corresponding half-lives for the pesticides were 1.96, 1.79, 2.06, and 1.69 days, all following first-order dissipation kinetics. Dietary risk assessment indicated Hazard Quotients (HQ) below 1 and Theoretical Maximum Daily Intake (TMDI) below Acceptable Daily Intake (ADI) and Maximum Permissible Intake (MPI) levels. Therefore, at their recommended doses, the pesticides were deemed safe for bell pepper cultivation., (© 2024. The Author(s), under exclusive licence to Springer Nature B.V.)

Extensive utilization of pesticides and herbicides to boost agricultural production increased the environmental health risks, which can be mitigate with the aid of highly sensitive detection systems. In this study, an electrochemical sensor for monitoring the carcinogenic pesticides in the environmental samples has been developed based on sulfur-doped graphitic-carbon nitride-gold nanoparticles (SCN-AuNPs) nanohybrid. Thermal polycondensation of melamine with thiourea followed by solvent exfoliation via ultrasonication leads to SCN formation and electroless deposition of AuNPs on SCN leads to SCN-AuNPs nanohybrid synthesis. The chemical composition, S-doping, and the morphology of the nanohybrid were confirmed by various microscopic and spectroscopic tools. The as-synthesized nanohybrid was fabricated with glassy carbon (GC) electrode for determining the carcinogenic hydrazine (HZ) and atrazine (ATZ) in field water samples. The present sensor exhibited superior electrocatalytic activity than GC/SCN and GC/AuNPs electrodes due to the synergism between SCN and AuNPs and the amperometric studies showed the good linear range of detection of 20 nM-0.5 mM and 500 nM-0.5 mM with the limit of detection of 0.22 and 69 nM (S/N = 3) and excellent sensitivity of 1173.5 and 13.96 μA mM -1 cm -2 towards HZ and ATZ, respectively. Ultimately, the present sensor is exploited in environmental samples for monitoring HZ and ATZ and the obtained results are validated with high-performance liquid chromatography (HPLC) technique. The excellent recovery percentage and close agreement with the results of HPLC analysis proved the practicability of the present sensor. In addition, the as-prepared materials were utilized for the photocatalytic degradation of ATZ and the SCN-AuNPs nanohybrid exhibited higher photocatalytic activity with the removal efficiency of 93.6% at 90 min. Finally, the degradation mechanism was investigated and discussed., 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 The Authors. Published by Elsevier Inc. All rights reserved.)

This study aimed to investigate the dissipation pattern, risk assessment, and waiting period of myclobutanil on apple fruit (Malus domestica Borkh.) under temperate conditions in Kashmir, India. The study involved the application of myclobutanil 10 WP at a single recommended dosage (125 g a.i. ha -1 ) and double dosage (250 g a.i. ha -1 ) on Red Velox apple trees, 2 months before harvest. GC equipped with an electron capture detector was used to analyze myclobutanil residues in fruit samples. The study revealed that myclobutanil, at both recommended and double recommended doses, dissipated rapidly and became nondetectable after 55 and 60 days, respectively. The waiting period for myclobutanil application was determined to be 12.41 days for the single dose and 25.58 days for the double dose, respectively. These waiting periods were based on the maximum residue limit of 0.6 ppm as prescribed by the Codex Alimentarius Commission, Food Safety and Standards Authority of India, and European Commission. The study concludes that myclobutanil 10 WP is safe for consumers at both recommended and double recommended doses when applied 2 months before harvest. Risk assessment, considering the average daily apple consumption in India and theoretical maximum residue contributions (TMRCs), indicates negligible health hazards even at double the recommended dosage. The calculated TMRC values at Day 0 were significantly below the maximum permissible intake. For average and maximum myclobutanil residues at single and double doses, the TMRC values were found to be 0.0069 and 0.0070 mg day -1 person -1 and 0.0105 and 0.0106 mg day -1 person -1 , respectively. These results indicate that myclobutanil, when used according to recommended dosages and waiting periods, poses minimal health risks to consumers. The study emphasizes the importance of prudent fungicide use to minimize fungicide residues on fruits, thereby ensuring their safety for consumption., (© 2024 John Wiley & Sons Ltd.)

In this work, a molecularly imprinted electrochemiluminescence (ECL) sensor was developed for selective detection of 4-nitrophenol (4-NP) in drinking water for the first time. By synthesizing velvet-like graphitic carbon nitride (V-g-C 3 N 4 ) via one-step thermal polycondensation and integrating it with a molecularly imprinted polymer (MIP), the ECL sensor was fabricated. The MIP-modified V-g-C 3 N 4 composites (MIP/V-g-C 3 N 4 ) were synthesized using a sol-gel method with 4-NP as the template molecule. Under optimal conditions, the ECL sensor exhibited a wide detection range (5 × 10 -10 -1 × 10 -5  mol/L) and a low detection limit (1.8 × 10 -10  mol/L). In testing with actual drinking water samples, it displayed high accuracy (recoveries for intraday and inter-day: 93.50-106.2% and 97.00-107.3%, separately) and precision (RSDs for intraday and inter-day: 1.54-4.59% and 1.53-4.28%, respectively). The developed MIP-based ECL sensor demonstrated excellent selectivity, stability, and reproducibility, offering a promising and reliable approach for highly sensitive and selective determination of 4-NP in drinking water., 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 Ltd.)

Pesticides are used in vegetable farming to control pests and diseases, reduce crop losses and improve yield. The study examined pesticide residues in irrigation waters and leafy green vegetables grown in some farming areas in Accra, Ghana. Three types of irrigation water sources ( n  = 23) and two exotic and four indigenous Ghanaian leafy vegetables ( n  = 34) from 10 farming areas in Accra, Ghana were collected and examined for 15 organochlorines, 13 organophosphorus and 9 synthetic pyrethroids pesticide residues using the modified QuEChERS procedure. Pesticide residues were detected on 50% (17/34) of the leafy vegetable and 52% (12/23) of the irrigation water samples analysed. Chlorpyrifos and deltamethrin were the most detected pesticide residues in the vegetables and irrigation water. About 26.5% of the vegetables contained pesticide residues exceeding the EU maximum residue limits, so vegetable farmers should be encouraged to comply with appropriate measures on pesticide use to enhance food safety.

In the electrical industry, there are many hazardous gases that pollute the environment and even jeopardize human health, so timely detection and effective control of these hazardous gases is of great significance. In this work, the gas-sensitive properties of Pd-modified g-C 3 N 4 interface for each hazardous gas molecule were investigated from a microscopic viewpoint, taking the hazardous gases (CO, NO x ) that may be generated in the power industry as the detection target. Then, the performance of Pd-modifiedg-C 3 N 4 was evaluated for practical applications as a gas sensor material. Novelly, an unconventional means was designed to briefly predict the effect of humidity on the adsorption properties of this sensor material. The final results found that Pd-modified g-C 3 N 4 is most suitable as a potential gas-sensitizing material for NO 2 gas sensors, followed by CO. Interestingly, Pd-modified g-C 3 N 4 is less suitable as a potential gas-sensitizing material for NO gas sensors, but has the potential to be used as a NO cleaner (adsorbent). Unconventional simulation explorations of humidity effects show that in practical applications Pd-modified g-C 3 N 4 remains a promising material for gas sensing in specific humidity environments. This work reveals the origin of the excellent properties of Pd-modified g-C 3 N 4 as a gas sensor material and provides new ideas for the detection and treatment of these three hazardous gases., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Pengfei Jia reports financial support was provided by Open Research Fund Program of Data Recovery Key Laboratory of Sichuan Province; Changyou Ma reports financial support was provided by Neijiang basic research and applied basic research project; Pengfei Jia reports financial support was provided by National Natural Science Foundation of China; Pengfei Jia reports financial support was provided by Sichuan Province Science and Technology Support Program; Dachang Chen reports financial support was provided by Natural Science Foundation of Hubei Province. 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 Elsevier Ltd. All rights reserved.)

Background: Cassava roots are widely consumed in tropical regions of Asia, Africa, and Latin America. Although the protein, vitamin, carotenoid, and mineral content in the leaves makes them a nutritionally attractive option, their consumption is limited due to their high levels of cyanogenic compounds (CCs). In this study, the CC content in different parts of the plant (leaves, storage root cortex, and parenchyma) was assessed at harvest for 50 landrace genotypes representative of cassava diversity in Latin America. The changes in CC in leaves at different physiological ages (3, 6, 9, and 11 months after planting) were also investigated., Results: The average CC was higher in the cortex (804 ppm) and leaves (655 ppm) than in root parenchyma (305 ppm). Genotypes from different regions of Latin America, as identified by seven genetic diversity groups, differed significantly in CC levels. The Andean and Amazon groups had, respectively, the lowest (P = 0.0008) and highest (P < 0.0001) CC levels in all three parts of the plants. Cyanogenic compound concentrations were higher in leaves from young plants (P < 0.0001) and decreased with increasing physiological age., Conclusion: The results help to guide the selection of parental lines with low CC levels for breeding and to contribute to the expanded use of cassava and its by-products for food and feed. Cassava for fresh consumption, especially, requires varieties with low total CC content, especially in the root cortex and parenchyma. COL1108 (204, 213, and 174 ppm, respectively, in the parenchyma, cortex, and leaves) and PER297 (83, 238, and 299 ppm, respectively, in the parenchyma, cortex, and leaves) can fulfill this requirement. © 2023 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry., (© 2023 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.)

There is growing attention focused toward the problems of ecological sustainability and food safety raised from the abuse of herbicides, which underscores the need for the development of a portable and reliable sensor for simple, rapid, and user-friendly on-site analysis of herbicide residues. Herein, a novel multifunctional hydrogel composite is explored to serve as a portable and flexible sensor for the facile and efficient analysis of atrazine (ATZ) residues. The hydrogel electrode is fabricated by doping graphite-phase carbon nitride (g-C 3 N 4 ) into the aramid nanofiber reinforced poly(vinyl alcohol) hydrogel via a simple solution-casting procedure. Benefiting from the excellent electroactivity and large specific surface area of the solid nanoscale component, the prepared hydrogel sensor is capable of simple, rapid, and sensitive detection of ATZ with a detection limit down to 0.002 ng/mL and per test time less than 1 min. After combination with a smartphone-controlled portable electrochemical analyzer, the flexible sensor exhibited satisfactory analytical performance for the ATZ assay. We further demonstrated the applications of the sensor in the evaluation of the ATZ residues in real water and soil samples as well as the user-friendly on-site point-of-need detection of ATZ residues on various agricultural products. We envision that this flexible and portable sensor will open a new avenue on the development of next-generation analytical tools for herbicide monitoring in the environment and agricultural products.

Background: 4-hydroxychlorothalonil (HCT, R182281), a transformation product of the fungicide chlorothalonil, was recently identified in human serum and breast milk. There are indications that HCT may be more toxic and environmentally persistent than chlorothalonil., Objective: Our aim was to investigate serum concentrations of HCT in pregnant women in Sweden and Costa Rica., Methods: We developed a quantitative analytical method for HCT using liquid chromatography tandem mass spectrometry. We measured HCT in 1808 serum samples from pregnant women from the general population in Sweden (1997-2015) and in 632 samples from 393 pregnant women from an agricultural population in Costa Rica (2010-2011). In Swedish samples, we assessed time trends and investigated seasonality. In the Costa Rican samples, we evaluated variability between and within women and explanatory variables of HCT concentrations., Results: HCT was detected in all serum samples, and the limit of detection was 0.1 µg/L. The median HCT concentration in the Swedish samples was 4.1 µg/L (interquartile range [IQR] of 2.9 - 5.8 µg/L), and 3.9 times higher in the Costa Rican samples (median: 16.1 µg/L; IQR: 10.6 - 25.0 µg/L). We found clear seasonal variation with higher concentrations in the first half of each year among Swedish women. In the Costa Rican study, women working in agriculture and living near banana plantations had higher HCT concentrations, whilst higher parity and having a partner working in agriculture were associated with decreased HCT, and no clear seasonal pattern was observed., Impact Statement: For the first time, this study quantifies human exposure to the fungicide chlorothalonil and/or its transformation product 4-hydroxychlorothalonil (HCT, R182281) and finds higher serum concentrations in women from a tropical agricultural setting as compared with women from the general population in Sweden., (© 2023. The Author(s).)

An analytical method has been proposed and validated to determine seven acaricides (atrazine, chlorpyrifos, chlorfenvinphos, α-endosulfan, bromopropylate, coumaphos, and τ-fluvalinate) in honeys from different botanical origins (multifloral, heather and rosemary) by means of gas chromatography-mass spectrometry. An efficient and simple sample treatment was proposed that involved a solvent extraction with an ethyl acetate and cyclohexane (50:50, v/v) mixture. Chromatographic analysis (<25 min) was performed in a DB-5MS column under programmed temperature conditions. The method was validated in terms of selectivity, limits of detection (0.2-2.0 µg kg -1 ) and quantification (0.5-7.6 µg kg -1 ), linearity (limit of quantification-700 (heather) or 800 (multifloral and rosemary) µg kg -1 ), matrix effect (<20 % in most cases), trueness (recoveries between 81 % and 108 %), and precision (relative standard deviation < 15 %). Finally, of the seven acaricides investigated in several honey samples only τ-fluvalinate residues (-1 ) were found., 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 Ltd. All rights reserved.)

Main Conclusion: Cytochrome P450 CYP77A59 is responsible for the biosynthesis of phenylacetonitrile in loquat flowers. Flowers of some plants emit volatile nitrile compounds, but the biosynthesis of these compounds is unclear. Loquat (Rhaphiolepis bibas) flowers emit characteristic N-containing volatiles, such as phenylacetonitrile (PAN), (E/Z)-phenylacetaldoxime (PAOx), and (2-nitroethyl)benzene (NEB). These volatiles likely play a defense role against pathogens and insects. PAN and NEB are commonly biosynthesized from L-phenylalanine via (E/Z)-PAOx. Two cytochrome P450s-CYP79D80 and "promiscuous fatty acid ω-hydroxylase" CYP94A90, which catalyze the formation of (E/Z)-PAOx from L-phenylalanine and NEB from (E/Z)-PAOx, respectively-are involved in NEB biosynthesis. However, the enzymes catalyzing the formation of PAN from (E/Z)-PAOx in loquat have not been identified. In this study, we aimed to identify candidate cytochrome P450s catalyzing PAN formation in loquat flowers. Yeast whole-cell biocatalyst assays showed that among nine candidate cytochrome P450s, CYP77A58 and CYP77A59 produced PAN from (E/Z)-PAOx. CYP77As catalyzed the dehydration of aldoximes, which is atypical of cytochrome P450; the reaction was NADPH-dependent, with an optimum temperature and pH of 40 °C and 8.0, respectively. CYP77As acted on (E/Z)-PAOx, (E/Z)-4-hydroxyphenylacetaldoxime, and (E/Z)-indole-3-acetaldoxime. Previously characterized CYP77As are known to hydroxylate fatty acids; loquat CYP77As did not act on tested fatty acids. We observed higher expression of CYP77A59 in flowers than in buds; expression of CYP77A58 was remarkably reduced in the flowers. Because the flowers, but not buds, emit PAN, CYP77A59 is likely responsible for the biosynthesis of PAN in loquat flowers. This study will help us understand the biosynthesis of floral nitrile compounds., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

At the base of the food pyramid is vegetables, which should be consumed most often of all food products, especially in raw and unprocessed form. Vegetables and mushrooms are rich sources of bioactive compounds that can fulfill various functions in plants, starting from protection against herbivores and being natural insecticides to pro-health functions in human nutrition. Many of these compounds contain sulfur in their structure. From the point of view of food producers, it is extremely important to know that some of them have flavor properties. Volatile sulfur compounds are often potent odorants, and in many vegetables, belonging mainly to Brassicaeae and Allium ( Amaryllidaceae ), sulfur compounds determine their specific flavor. Interestingly, some of the pathways that form volatile sulfur compounds in vegetables are also found in selected edible mushrooms. The most important odor-active organosulfur compounds can be divided into isothiocyanates, nitriles, epithionitriles, thiols, sulfides, and polysulfides, as well as others, such as sulfur containing carbonyl compounds and esters, R-L-cysteine sulfoxides, and finally heterocyclic sulfur compounds found in shiitake mushrooms or truffles. This review paper summarizes their precursors and biosynthesis, as well as their sensory properties and changes in selected technological processes.

While cassava is one of the most important staple crops worldwide, it has received the least investment per capita consumption of any of the major global crops. This is in part due to cassava being a crop of subsistence farmers that is grown in countries with limited resources for crop improvement. While its starchy roots are rich in calories, they are poor in protein and other essential nutrients. In addition, they contain potentially toxic levels of cyanogenic glycosides which must be reduced to safe levels before consumption. Furthermore, cyanogens compromise the shelf life of harvested roots due to cyanide-induced inhibition of mitochondrial respiration, and associated production of reactive oxygen species that accelerate root deterioration. Over the past two decades, the genetic, biochemical, and developmental factors that control cyanogen synthesis, transport, storage, and turnover have largely been elucidated. It is now apparent that cyanogens contribute substantially to whole-plant nitrogen metabolism and protein synthesis in roots. The essential role of cyanogens in root nitrogen metabolism, however, has confounded efforts to create acyanogenic varieties. This review proposes alternative molecular approaches that integrate accelerated cyanogen turnover with nitrogen reassimilation into root protein that may offer a solution to creating a safer, more nutritious cassava crop., (© The Author(s) 2021. Published by Oxford University Press on behalf of the Society for Experimental Biology. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

The effects of combined treatment (PAL-U) of plasma-activated liquid (PAL) including plasma-activated water (PAW) and plasma-activated buffer solution (PABS) and ultrasound (U) for the degradation of chlorothalonil fungicide on tomato fruit was investigated. Distilled water and buffer solution were activated by radiofrequency plasma jet for durations of 1, 3, 5, and 10 min to obtain PAL 1 to PAL 10 . Fruits were immersed in PAL for 15 min and also in distilled water with sonication for 15 min for individual treatments, and in PAL with sonication for 15 min for combined treatments. The maximum chlorothalonil fungicide residues were reduced by 89.28 and 80.23% for PAW 10 -U and PABS 10 -U, respectively. HPLC-MS characterization revealed chlorothalonil degradation pathway and formation of 2,4,5-trichloroisophthalonitrile, 2,4-dichloroisophthalonitrile, 4-chloroisophthalonitrile, isophthalonitrile and phenylacetonitrile as degradation products. Treatments also showed no negative effects on tomato quality. Therefore, PAL and PAL-U treatments could serve as effective methods for degrading pesticides on tomatoes., (Copyright © 2021 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

The applications of SERS in therapeutic drug monitoring, or other fields of analytical chemistry, require the availability of sensitive sensors and experimental approaches that can be implemented in affordable ways. In this contribution, we show the production of cost-effective SERS sensors obtained by depositing Lee-Meisel Ag colloids on filter paper either by natural sedimentation or centrifugation. We have characterized the morphological and plasmonic features of the sensors by optical microscopy, SEM, and UV-Vis spectroscopy. Such sensors can be used to quantify by SERS the anti-epileptic drug Perampanel (in the concentration range 1 × 10 -4 -5 × 10 -6 M) by spinning them during the micro-Raman measurements on the top of a custom device obtained from spare part hard disk drives. This approach minimizes laser-induced heating effects and allows averaging over the spatial non-uniformity of the sensor.

Carbohydrate analysis has always been a challenging task due to the occurrence of high polarity and multiple isomers. Aldoses are commonly analyzed by gas liquid chromatography (GLC) following aldononitrile acetate derivatization (AND). However, the GLC technique cannot be applied for the simultaneous determination of aldoses, ketoses, and uronic acids. In this study, a new method based on the combination of liquid chromatography-tandem mass spectrometry (LC-MS/MS) and AND is developed for the complete characterization of monosaccharide composition (i.e., aldoses, ketoses, alditols, amino sugars, and uronic acids) in plant-derived polysaccharides. In addition to discussing the possible byproducts, the study optimizes the multiple reaction monitoring (MRM) parameters and LC conditions. The final separation of 17 carbohydrates is performed on a BEH Shield RP18 column (150 mm × 2.1 mm, 1.7 μm) within 25 min, without using any buffer salt. Notably, the complex polysaccharides extracted from Ligusticum chuanxiong, Platycodon grandiflorum, Cyathula officinalis Kuan, Juglans mandshurica Maxim, and Aralia elata (Miq.). Seem bud can be successfully characterized using the developed method. Overall, the results demonstrated that the newly established LC-MS/MS MRM method is more effective and powerful than the GLC-based methods reported previously, and it is more suitable for the analysis of highly complex natural polysaccharides, including complex pectins, fructosans, and glycoproteins., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The ability to anticipate the useful lifetime of an insecticide-treated mosquito net (ITN) would provide a proactive approach for planning net distribution programs. Therefore, we used an exponential decay model of deltamethrin depletion to predict the effective insecticidal lifetime of PermaNet® 2.0 nets used in the Lao PDR. Residual deltamethrin was measured using two nondestructive analytical field methods; X-ray fluorescence (total levels) and a colorimetric field test (surface levels) at 12 and 24 months postdistribution. The model assumes that the 12-month depletion rate can be used to predict future levels. The median total and surface deltamethrin levels for the Lao nets at 12 months were 31.2 and 0.0743 mg/m2, respectively. By defining a failed net as having total deltamethrin levels of less than 15 mg/m2 or a surface level less than 0.0028 mg/m2, it was predicted that 50% of the group of nets will fail at about 27 months after distribution.

Background: Insecticide-treated nets and indoor residual spraying of insecticides are used as the vector control interventions in the fight against malaria. Measuring the actual amount of deposits of insecticides on bed nets and walls is essential for evaluating the quality and effectiveness of the intervention. A colorimetric "Test Kit" designed for use as a screening tool, able to detect the type II pyrethroids on fabrics and sprayed walls, was used for the first time to detect deltamethrin on long-lasting insecticidal nets (LLINs) deployed on Bioko Island, Equatorial Guinea., Methods: LLINs were analysed using the colorimetric Test Kit performed in situ, which leads to the formation of an orange-red solution whose depth of colour indicates the amount of type II pyrethroid on the net. The kit results were validated by measuring the amount of extracted insecticide using high-performance liquid chromatography (HPLC) with diode array detection (DAD)., Results: Deltamethrin concentration was determined for 130 LLINs by HPLC-DAD. The deltamethrin concentration of these nets exhibited a significant decrease with the age of the net from 65 mg/m 2 (< 12 months of use) to 31 mg/m 2 (> 48 months; p < 0.001). Overall, 18% of the nets being used in households had < 15 mg/m 2 of deltamethrin, thus falling into the "Fail" category as assessed by the colorimetric Test Kit. This was supported by determining the bio-efficacy of the nets using the WHO recommended cone bioassays. The Test Kit was field evaluated in situ and found to be rapid, accurate, and easy to use by people without laboratory training. The Test Kit was shown to have a reliable linear relationship between the depth of colour produced and deltamethrin concentration (R 2  = 0.9135)., Conclusion: This study shows that this colorimetric test was a reliable method to assess the insecticidal content of LLINs under operational conditions. The Test Kit provides immediate results and offers a rapid, inexpensive, field-friendly alternative to the complicated and costly methods such as HPLC and WHO cone bioassays which also need specialist staff. Thus, enabling National Malaria Control Programmes to gain access to effective and affordable monitoring tools for use in situ., (© 2021. The Author(s).)

Although cyanogen ion (CN - ) plays important role in industry which also bring acute environmental pollution. More serious, trace CN - enters the human body can cause serious consequences and even death. Therefore, it is of great significance to detect trace CN - with high sensitivity. Herein, a novel aggregation-induced emission (AIE) probe C-BH was synthesized based on coumarin matrix. Probe C-BH showed high selectivity and sensitivity toward CN - by dual channel response due to the excited state intramolecular proton transfer (ESIPT). The low detection limit was calculated to be 0.05 µM. Moreover, probe C-BH was successfully used for imaging CN - in living cells and zebrafish due to its low toxicity and excellent optical properties., (© 2021. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

In this study, the rGO-PEI-AgNPs sensor was designed as a new effective platform to sensitive monitoring of deltamethrin in human plasma samples. For this purpose, reduced graphene oxide (rGO)-supported polyethylenimine (PEI) was used as a suitable substrate for dispersion of silver nanoparticles (AgNPs) as amplification and catalytic element. Therefore, a novel interface (rGO-PEI-AgNPs) was prepared by the fully electrochemical method on the surface of glassy carbon electrodes. The engineered nano-sensor showed a wide dynamic range of 10 nM to 1 mM and low limit of quantification (LLOQ) as 10 nM in human plasma sample, which revealed excellent analytical performance for the recognition of deltamethrin with high sensitivity and reproducibility through differential pulse voltammetry and square wave voltammetry techniques. The results confirm that rGO-PEI-AgNPs as a novel biocompatible interface can provide appropriate, reliable, affordable, rapid, and user-friendly diagnostic tools in the detection of deltamethrin in human real samples., (© 2021 John Wiley & Sons Ltd.)

A valid method based on ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with a chiral stationary phase was established for the determination of myclobutanil enantiomer residue in wheat grain and its processed products (flour, bran, pasta, steamed bun, noodle, and cooking water). The wheat grain and processed product samples were extracted with acetonitrile and purified with primary secondary amine (PSA) and C18. The enantiomers of myclobutanil were separated by Chiral column Lux Cellulose-1 (150 mm×2.0 mm, 3 μm, Phenomenex). The column temperature, sample volume injected, and flow rate were 30 ℃, 5 μL, and 0.25 mL/min, respectively. The mobile phase consisted of phase A (25%), water with 0.1% formic acid and 4 mM ammonium acetate, and phase B (75%), methanol with 0.1% formic acid and 4 mM ammonium acetate. A Waters Xevo TQ-S Micro MS/MS system (Waters, USA) was used for mass spectrometric analysis. An electrospray ionization (ESI) source operating in the positive ionization mode. MS analyses were performed in the multiple reaction monitoring (MRM) mode. The qualitative ions of myclobutanil were m/z 288.9/69.9 and 288.9/124.9, and the quantitative ion of myclobutanil was m/z 288.9/69.9. The source voltage was 3000 V, and the desolvation temperature was 400 ℃. The desolvation gas flow was 800 L/h, and the source temperature was 150 ℃. The matrix effect of wheat grains and their processed products on the determination of myclobutanil enantiomers by UPLC-MS/MS was investigated. S -(+)-myclobutanil and R -(-)-myclobutanil had a mid signal suppression effect on wheat grain, bran, pasta, steamed bun, and noodle, while S -(+)-myclobutanil and R -(-)-myclobutanil had a mid signal enhancement effect on flour and cooking water. Finally, the matrix-matched calibration method was effective in all matrices and was selected for the quantification of the myclobutanil enantiomer residue in the samples. The results showed that the two enantiomers of myclobutanil were well separated by this method. The first and second eluted enantiomers were S -(+)-myclobutanil and R -(-)-myclobutanil, respectively, with the corresponding retention times being 4.34 min and 5.13 min. The limits of detection (LOD) and limits of quantification (LOQ) of S -(+)-myclobutanil and R -(-)-myclobutanil in wheat and its processed products were 0.2 μg/kg and 0.5 μg/kg, respectively. In the linear range of 0.5-25 μg/L, the peak areas of the myclobutanil enantiomers showed a good linear relationship with the concentration, and the R 2 values were all greater than 0.99. At fortification levels of 5, 50, and 100 μg/kg (enantiomer concentration), the average recoveries of S -(+)-myclobutanil in wheat grain and its processed products ranged from 82% to 110%, with RSDs between 0.9% and 6.8%. The average recoveries of R -(-)-myclobutanil in wheat grain and its processed products ranged from 80% to 109%, with RSDs between 0.9% and 6.8%. This method fulfils the requirements for pesticide residue analysis. The established method was applied to analyze five flour samples, two noodle samples, and two steamed bread samples. The results showed that S -(+)-myclobutanil and R -(-)-myclobutanil enantiomers were not detected in the samples. In this study, methods for the enantiomeric separation and residue analysis of myclobutanil in wheat were evaluated at the enantiomeric level, which enriched the methods of enantiomeric separation and residue analysis of chiral pesticide myclobutanil enantiomers in raw agricultural product (wheat grain) and its processed foods. This method is effective for the residue analysis of chiral pesticide myclobutanil enantiomers in raw agricultural commodities and its processed products.

A novel high-performance liquid chromatography-mass spectrometry method was developed to determine the quantities of pyridine, 4-dimethylaminopyridine, and N, N-dimethylaniline impurities in vildagliptin drug material. These impurities are reactive bases that may be used in synthesis of vildagliptin pharmaceutical ingredients. They are considered as potentially genotoxic impurities since they contain electrophilic functional groups. Therefore, these impurities should be monitored at the allowed limits in vildagliptin. Hence a high-performance liquid chromatography-mass spectrometry method was developed to quantify the amounts of these impurities in vildagliptin. The column was KROMASIL CN (250 mm × 3.9 mm, 3.5 μm) in reversed-phase mode. The mobile phase was a mixture of water-methanol (55:45) containing 2.5 mM ammonium acetate and 0.1% formic acid. The mass spectrometer was used to detect the amounts of impurities using selected ionization monitoring mode at m/z = 80, 122, and 123 for pyridine, N, N-dimethylaniline, and 4-dimethylaminopyridine, respectively. The flow rate was 0.5 mL/min. The sensitivity of the method was excellent at levels very less than the allowed limits. The method had excellent linearity in the concentration ranges of limit of quantification-150% of the permitted level with coefficients of determination above 0.9990. The recovery ratios were in the range of 93.70-108.63%. Results showed good linearity, precision, accuracy, sensitivity, selectivity, robustness, and solution stability., (© 2021 Wiley-VCH GmbH.)

A novel ultra-performance liquid chromatographic (UPLC) method has been developed and approved for the quantitative determination of enzalutamide (ENZ) and its impurities in drug product dosage form by applying the quality by design with design of experiments approach. An efficient chromatographic separation was achieved on a Waters ACQUITY CSH C 18 (100 × 2.1 mm × 1.7 μm) column in gradient elution mode. A mixture of potassium phosphate monobasic buffer and acetonitrile (10 mm, adjusted to pH 4.0 with 1% orthophosphoric acid) at a flow rate of 0.2 mL min -1 (column temperature at 40°C) under ultraviolet detection at 270 nm was used for quantitation. The peak resolution among ENZ and its impurities (Impurity-1, Impurity-2, Impurity-3, Impurity-4, Impurity-5, Impurity-6 and Impurity-7) was greater than 2.5. Regression analysis confers an R 2 value (correlation coefficient) higher than 0.999 for the active substance and impurities. The detection level for ENZ impurities was at a level below 0.015% (0.12 μg/mL). The accuracy levels for different compounds were close to 100%. The inter- and intra-day precisions for ENZ and impurities were evaluated and their relative standard deviation (%) values were less than 3.5. Our results show that the UPLC-UV stability-indicating method will be an essential tool that could determine the drug product's impurities and be useful in regular quality control and stability studies of the ENZ drug product dosage form., (© 2021 John Wiley & Sons, Ltd.)

The construction of multifunctional sensors has attracted considerable attention due to their multifunctional properties, such as high sensitivity and rapid detection. Herein, near-infrared multifunctional fluorescent sensing materials based on core-shell upconversion nanoparticle@magnetic nanoparticle and molecularly imprinted polymers were synthesized for rapid detection of deltamethrin. The difunctional core-shell upconversion nanoparticle@magnetic nanoparticle was introduced as the optical signal and rapid separator. Firstly, the difunctional core-shell materials were prepared through solvothermal method. Then, molecularly imprinted polymers (MIPs) as recognition elements for deltamethrin were coated on the surface of upconversion nanoparticle@magnetic nanoparticle through polymerization. The structure and recognition characterizations of multifunctional fluorescent sensing materials were evaluated. Under optimal condition, the imprinting factor of sensing materials was 3.63, and the fluorescence intensity of sensing materials decreased linearly with increasing concentration of deltamethrin from 0.001 to 1 mg L -1 with a detection limit of 0.749 μg L -1 , and a relative standard deviation of 3.10% was obtained with 5 mg L -1 deltamethrin. The sensing materials showed a high selectivity and were successfully utilized for the detection of deltamethrin in grapes and cabbages; the results showed that the recoveries for two samples obtained were 95.6-102% and 91.8-105%.

This work presents a simple, rapid and green chiral analysis method for five triazole fungicides (penconazole, tebuconazole, triadimefon, myclobutanil, and triadimenol) in tobacco, by which the samples were cleaned up by the novel pass-through solid phase extraction and subsequently the stereoisomers were separated and determined by the supercritical fluid chromatography-tandem mass spectrometry (SFC-MS/MS). Optimized separation of the stereoisomers was achieved on an ACQUITY UPC2 Trefoil AMY 1 column within 6 min. Under fortified concentration levels of 0.1, 0.5 and 2.0 mg/kg, the mean recoveries were 82.8-106.6%, the intra-day relative standard deviations (RSDs) were 1.1-6.6%, and the inter-day RSDs were 2.5-5.6%. The correlation coefficient was greater than 0.9926 for all studied analytes within the range of 10-500 ng/mL. The limits of detection (LODs) for all stereoisomers ranged from 0.26 μg/kg to 3.24 μg/kg. The established method was subsequently successfully applied to analyze authentic samples, confirming that this method is a novel, rapid and environmentally friendly method for the stereoselective separation of triazole fungicides in tobacco., Competing Interests: Declaration of Competing Interest The authors have declared no conflict of interest., (Copyright © 2021. Published by Elsevier B.V.)

Deltamethrin, one of the most toxic pyrethroids, is commonly used to inhibit pests in wheat. However, the trace levels of deltamethrin in wheat is alarming to human health. In this study, surface-enhanced Raman spectroscopy (SERS)-active silver nanoparticles-plated-zinc oxide nanoflowers (Ag@ZnO NFs) nano-sensor were employed for rapid and sensitive quantification of deltamethrin in wheat. To sufficiently utilize the chemical-related information in SERS spectra, various spectral pretreatment and chemometric models were studied. The mean centering (MC) coupling successive projection algorithm-partial least squares regression (SPA-PLS) provided optimal predictive performance (correlation coefficient of prediction (Rp) = 0.9736 and residual predictive deviation (RPD) = 4.75). The proposed method achieved the limit of detection (LOD) = 0.16 μg·kg -1 , the recovery of predicted results was in the range of 96.33-109.17% and the relative standard deviation (RSD) was < 5%. The overall results suggested that SERS based Ag@ZnO NFs combined with MC-SPA-PLS could be an easy and efficient method to quantify deltamethrin residue levels in wheat., 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.)

Chlorothalonil (CLT) is a broad spectrum, and non-systemic fungicide applied in foliar structures to prevent and treat pathogens. This compound reaches to aquatic environments and affects the biota. In this context, the main goal of this study was to assess the effects of CLT at biochemical, tissular, and individual levels of biological organization using the invasive bivalve Corbicula largillierti as a bioindicator species. Clams were exposed to different sublethal concentrations (0, 10, 20 and 50 µg. L -1 CLT) for 96 h. At biochemical level, the enzymatic activity (Glutathione-s-Transferase, Catalase, Acetyl-, Butiryl- and Carboxyl-esterases) and lipid peroxidation were measured in gills and the visceral mass. Also, the digestive gland morphometry through quantitative histological indexes was registered at the tissular level. Finally, filtering activity and burial behavior at the individual level were measured. At the highest CLT concentration, the most significant changes were observed in enzymatic activity (except for butyrylcholinesterase), lipid peroxidation and in digestive gland morphometry. It was also registered increases of the filtering activity and the latency time to burial. Most of the biomarkers assessed showed significant responses under CLT exposure. Therefore, taking into account that C. largillierti was affected by CLT, it can be expected that other species could be in a potential risk if this fungicide is present in freshwater systems., (Copyright © 2020 The Authors. Published by Elsevier Inc. All rights reserved.)

Cabbage, one of the most popular vegetables in the world is infested by several insect-pests and diseases. Novaluron, a chitin synthesis inhibitor and lambda-cyhalothrin, a synthetic pyrethroid group insecticide are used to manage insect-pests on cabbage. The dissipation kinetics and risk assessment of combination formulation (novaluron 9.45% + lambda-cyhalothrin 1.9%) with different modes of action has not yet been investigated in cabbage. Multi-location supervised field trials were therefore, conducted in different agro-climatic regions of India for safety evaluation of the combination product. The co-formulation at the recommended (novaluron 750 g a.i. ha -1 + lambda-cyhalothrin 750 g a.i. ha -1 ) and double the recommended (novaluron 1500 g a.i. ha -1 + lambda-cyhalothrin 1500 g a.i. ha -1 ) dose was sprayed on the cabbage crop. The samples were extracted and cleaned up using a modified QuEChERS method, and the residues analyzed by GC-ECD and GC-MS. The half-life (t 1/2 ) varied between 1.77 and 2.51 and 2.00-3.38 days for novaluron and 1.36-2.24 and 1.69-3.82 days for lambda-cyhalothrin in cabbage at respective doses. The Food Safety and Standards Authority of India (FSSAI) has set the MRL of 0.7 mg kg -1 for novaluron at PHI of 5 days, and no MRL is set for lambda-cyhalothrin in cabbage. On the basis of OECD MRL calculator, the MRLs of 0.6 and 1.5 mg kg -1 for novaluron and lambda-cyhalothrin, respectively were calculated at the respective doses at PHI of 3 days. Hazard quotient (HQ) <1, theoretical maximum daily intake (TMDI) < acceptable daily intake (ADI) and < maximum permissible intake (MPI), percent acute hazard index (% aHI) <1, and percent chronic hazard index (% cHI) <1 for both novaluron and lambda-cyhalothrin suggested that the combination formulation is safe and will not pose any dietary risk to the consumers. The study will be helpful to conduct risk assessment of other pesticides/combination pesticides on food crops on which their MRLs have not yet been fixed., (Copyright © 2020. Published by Elsevier Inc.)

Chlorothalonil is a class of 2B carcinogen which is widely used in the prevention and treatment of fungal diseases in food samples. Its residual problem has been increasingly concerned by society. In this paper, a fast and simple colorimetric assay based on Manganese dioxide nanosheets (MnO 2 NSs)-oxidize 3,3',5,5'-tetramethylbenzidine (TMB) platform was used to detect residual pesticide chlorothalonil in food samples. Under optimal conditions, the half maximal inhibitory concentration and the limit of detection of chlorothalonil were 3.27 and 0.024 ng/mL. There were no obvious cross-reactivity between chlorothalonil and interference substances. The recoveries shown the satisfactory results. The results of colorimetric assay for the authentic samples were largely consistent with gas chromatography. Therefore, the proposed method would be convenient and satisfactory analytical methods for the monitoring of chlorothalonil. Furthermore, the MnO 2 - TMB system was used to produce test strips for quick and convenient visual detection of chlorothalonil with good performance., 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.)

A QuEChERS multi-residue GC-MS/MS method was developed for determining 160 pesticides in fresh edible snails. The method was validated according to the EU guidance SANTE/12682/2019. Twenty-seven different pesticides were quantified in the 824 samples analysed. Of these, 22.09% contained pesticide residues; in one case six different pesticides. The most frequently quantified pesticides were chlorpyrifos (108 samples), cypermethrin (50), difenoconazole (24), oxyfluorfen (13), lambda-cyhalothrin (12), tetraconazole and azoxystrobin (7). Other pesticides were found in <5 samples. Of the samples containing residues, 154 exceeded the EU legal limit. However, the estimated daily intake of pesticide residues showed that snail consumption does not represent appreciable risks to consumer health.

Diclazuril, a broad-spectrum anticoccidial drug, may be accumulated in edible tissues of animals through illegal use, which poses potential threats to human health through the food chain. In this study, an innovative hapten was designed and an immunogen of diclazuril was successfully synthesised with keyhole limpet haemocyanin as carrier protein; then a monoclonal antibody with high specificity was obtained. Furthermore, based on the novel antibody, a one-step indirect competitive enzyme-linked immunosorbent assay (icELISA) was established for rapid and specific detection of diclazuril residues. Compared with the traditional icELISA method, this method saves at least 0.5 hours and one washing step. Under the optimal conditions, the one-step icELISA for diclazuril exhibited good performance with a 50% inhibition concentration (IC 50 ) value of 0.952 μg/kg. The average recoveries of the icELISA ranged from 73.1% to 115.5% with the coefficient of variation lower than 12.7%, which was evaluated by detecting spiked animal-origin food samples. Finally, the one-step icELISA shows a good correlation with an ultra-high liquid chromatography-tandem mass spectrometry method. Those results demonstrate that the one-step icELISA developed for diclazuril detection is time-saving, low-cost, specific, sensitive, and reliable. It shows good potential for social, environmental, and economic benefits in future use.

With the increase in demand, artificially planting Chinese medicinal materials (CHMs) has also increased, and the ensuing pesticide residue problems have attracted more and more attention. An optimized quick, easy, cheap, effective, rugged and safe (QuEChERS) method with multi-walled carbon nanotubes as dispersive solid-phase extraction sorbents coupled with surface-enhanced Raman spectroscopy (SERS) was first proposed for the detection of deltamethrin in complex matrix Corydalis yanhusuo . Our results demonstrate that using the optimized QuEChERS method could effectively extract the analyte and reduce background interference from Corydalis . Facile synthesized gold nanoparticles with a large diameter of 75 nm had a strong SERS enhancement for deltamethrin determination. The best prediction model was established with partial least squares regression of the SERS spectra ranges of 545~573 cm -1 and 987~1011 cm -1 with a coefficient of determination ( R 2 ) of 0.9306, a detection limit of 0.484 mg/L and a residual predictive deviation of 3.046. In summary, this article provides a new rapid and effective method for the detection of pesticide residues in CHMs.

Amygdalin, prunasin, total cyanide and free cyanide concentrations in 12 powdered loquat seeds were investigated. Loquat ( Eriobotrya japonica ) is a species of flowering plant in the family Rosaceae , and its fruit is quite popular in Japan. Amygdalin and prunasin were measured using LC-MS/MS. Total cyanide was measured by enzymatic treatment, steam distillation and colorimetric quantification using the pyridine-pyrazolone method. Free cyanide was measured without enzymatic treatment. The mean concentrations of amygdalin, prunasin, total cyanide and free cyanide in powdered loquat seeds were 5900, 760, 410 and 44 mg/kg, respectively. The range of each quantitative value was extensive. Seven out of twelve samples were at risk for exceeding the acute reference dose (ARfD) of cyanide.

An effective analytical method was optimized for residues including chlorpyrifos-methyl, deltamethrin, fenoxanil, thiobencarb and fludioxonil in mealworms, the larval form of Tenebrio molitor . They are listed for pest control during wheat cultivation and can be found in wheat-bran feed for growing mealworms in South Korea. Analytes were extracted using acetonitrile and salt packet. Four clean-up methods ((1) MgSO 4 + 25 mg PSA + 25 mg C18; (2) MgSO 4 + 50 mg PSA + 50 mg C18; (3) EMR-lipid TM tube; and (4) 10 mL n -hexane) were investigated and the method (1) was selected due to its robustness. Low-temperature precipitation of fat and proteins improved the recoveries. Recoveries from the Method (1) were satisfying with 70-120% with <20% relative SD at a spiking level of 0.01 mg/kg. With the simultaneous sample preparation, fenoxanil, thiobencarb and fludioxonil were analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS) and chlorpyrifos-methyl and deltamethrin by gas chromatography tandem mass spectrometry (GC-MS/MS). Quantification limits for LC-MS/MS and GC-MS/MS were 0.5 and 2.5 μg/L, respectively. No pesticides of interest were detected in 30 real samples collected across the nation. However, the data can be provided for establishing maximum residue limits for the pesticides in mealworms in response to the positive list system.

Rationale: A liquid chromatography/tandem mass spectrometry (LC/MS/MS) method has been developed and validated to determine levodopa, carbidopa, entacapone, and corresponding six related substances - levodopa impurity B, levodopa impurity C, methyldopa, methylcarbidopa, entacapone impurity C, and entacapone impurity A - in film-coated tablets for the first time., Methods: Chromatographic separation was achieved with a gradient elution by using a C18 column, a mobile phase containing 0.5% formic acid in water and 0.5% formic acid in methanol. The mobile phase flow rate was 0.5 mL min -1 . The UV detector was set at 280 nm and the triple quadrupole mass spectrometer was used in multiple reaction monitoring (MRM) mode., Results: The limit of detection (LOD) and limit of quantification (LOQ) results were 1.3 and 3.94 ng mL -1 for levodopa impurity B; 5.26 and 15.9 ng mL -1 for levodopa impurity C; 0.833 and 2.53 ng mL -1 for methyldopa; 3.31 and 10.0 ng mL -1 for methylcarbidopa; 1.67 and 5.06 ng mL -1 for entacapone impurity C; and 0.61 and 1.86 ng mL -1 for entacapone impurity A., Conclusions: The method was rapid, linear, accurate, and reproducible. The LC/MS/MS method that was developed to determine the related substances and assay of levodopa, carbidopa, and entacapone can be used to evaluate the quality of regular samples in the pharmaceutical industry. It can be also used to test the stability of samples., (© 2020 John Wiley & Sons, Ltd.)

Evaluation of chiral pesticides remains a frequently neglected matter in routine food control laboratories. This fact is due to the existence of many residue definitions but also due to the lack of robust instrumental methods for the evaluation of these isomeric compounds. However, supercritical fluid chromatography coupled to mass spectrometry (SFC-ESI-MS/MS) has been demonstrated to perform fast and highly efficient separations without the need to change the mobile phase employed in multiresidue pesticide analyses. Regarding chiral stationary phase columns, the polysaccharide-based ones clearly demonstrate the best separation technology. Two polysaccharide-based columns were tested in this study, and the robustness of their combination with SFC was verified. The enantiomers of lambda-cyhalothrin and metalaxyl were studied precisely due to their markedly distinct toxicity and enantioselectivity. Furthermore, the acute reference dose for gamma-cyhalothrin is half in comparison with its enantiomer (0.0025 and 0.005 mg/kg respectively), which is present in the lambda-cyhalothin residue definition. These enantiomers were analyzed in terms of linearity, reproducibility, and matrix effects in four representative matrices (tomato, orange, leek, and cayenne). Additionally, field tests under greenhouse conditions for these compounds were performed. The results obtained after different sample collections revealed a similar degradation in lambda-cyhalothrin enantiomers (R, S, S, and S, R, R) but not in the case of metalaxyl-M (mefenoxam) where the degradation in tomato was 2 to 6 times less in comparison with its S-enantiomer., 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.)

Lambda-cyhalothrin is a pyrethroid widely used in crop, fruit and vegetable production, but has potential health threats to human. Immunoassay is a cheap, rapid and facile method to detect lambda-cyhalothrin, yet wide application of this method still requires improvement in the construction of antigen. In this study, we developed a one-step lambda-cyhalothrin hapten synthesis that transformed the cyanide group in lambda-cyhalothrin to amide. Complete antigen was assembled by coupling the amide with succinic-anhydride-activated carrier proteins, and corresponding polyclonal antibodies were generated using Balb/c mice. Using antibody generated by the method in this paper, the competitive ELISA demonstrated the lowest detection limit of 3.772 μg/L for lambda-cyhalothrin, and no significant cross-reactivity for other pyrethroid pesticides was observed. All the results suggested we have established a more efficient technique of generating lambda-cyhalothrin antibody. Furthermore, since the activated proteins used in this study are highly controllable, we believe these proteins could potentially be the prototype of a series of standardized carrier proteins for the synthesis of complete antigens., Competing Interests: Declaration of competing interest The authors have filed a patent application covering the synthesis of hapten and protein activation: Chinese patent application no. 201911291688.2., (Copyright © 2020 Elsevier Inc. All rights reserved.)

In this study, we produced a sensitive and specific monoclonal antibody (mAb) against diclazuril based on a new hapten. The mAb, which belongs to the IgG2 subclass, had a 50%-inhibitory concentration of 0.36 ng/mL. A cross reactivity test revealed that the mAb had good specificity for diclazuril. A gold nanoparticle-based lateral-flow strip was assembled for the rapid screening of diclazuril in raw chicken breast and thigh samples. The strip assay had a visual limit of detection (LOD) of 2 μg/kg and a cut-off value of 20 μg/kg for diclazuril in chicken samples when evaluated with the naked eye. With the aid of a strip scan reader, the proposed assay obtained a quantitative measurement for diclazuril with an LOD of 1.08 μg/kg. Therefore, this gold nanoparticle-based lateral-flow strip assay represents a potentially useful tool for on-site detection and rapid initial screening of diclazuril in chicken samples., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

A method for the simultaneous determination of three commonly used coccidiostats in chicken liver was developed, comprising a multi-residue QuEChERS (quick, easy, cheap, effective, rugged and safe) extraction step, and a liquid chromatography-ultra violet-fluorescence (HPLC-UV/FL) analysis. The QuEChERS extraction was optimized using an experimental design approach that includes a screening step to obtain the critical variables, an optimization step using multiple response surface analysis and the calculation of a desirability parameter. The optimized method was validated with fortified samples, reaching an average recovery of 91% and an overall precision of 5.5% (mean of three analytes at three levels). Limits of detection calculated on fortified samples were 20 µg kg -1 for lasalocid, 15 µg kg -1 for nicarbazin and 120 µg kg -1 for diclazuril. These values resulted at least one order of magnitude lower than the maximum allowed residue limit (MRL) of the studied coccidiostats for chicken liver., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

An accurate and sensitive dispersive liquid-liquid microextraction method based on binary solvents was used to enrich prothiofos, oxadiargyl, and gamma-cyhalothrin for quantification by GC-MS. The combination of two extraction solvents (binary mixture) resulted in higher extraction efficiencies compared to the single solvent extraction systems. Parameters of the binary extraction method where optimized to enhance the extraction output of the analytes. The limits of detection calculated for the analytes ranged between 0.59 and 1.6 ng/mL. Linear calibration plots of the analytes covered wide concentration ranges with R 2 values greater than 0.9996 and percent relative standard deviation lower than 10%. Spiked recovery experiments were performed well and wastewater at two different concentrations and satisfactory results (89-104%) were obtained. The binary solvent microextraction method was combined with QuEChERS to quantify the analytes in pineapple matrix, using matrix matching method to enhance the accuracy of the method to almost 100%.

A new sensitive sensor for detecting chlorothalonil (CHL) based on the inner-filter effect (IFE) between gold nanoparticles (AuNPs) and ratiometric fluorescent quantum dots (RF-QDs) was developed. Here, RF-QDs were designed by two different color CdTe QDs. Based on the IFE, the AuNPs can quench the fluorescence of the RF-QDs. Because of the electrostatic attraction between protamine (PRO) and the AuNPs, the PRO can restore fluorescence effectively. Papain (PAP) can easily hydrolyze PRO and causes the quench of fluorescence quenching. The addition of CHL can inhibit PAP activity and restore the fluorescent signal. Through the characterization of the structural changes of PAP, the inhibition and mechanism of CHL on PAP activity were studied. The ability of CHL to inhibit PAP activity was evaluated by measuring the fluorescence of the RF-QDs. Under the optimal conditions, this sensing platform shows a response to CHL in the range of 0.34-2320 ng/mL and a detection limit of 0.0017 ng/mL. Based on the CHL inhibition of PAP activity, the RF-QDs showed good selectivity for CHL. The practical application of the proposed system was demonstrated by detecting CHL in food and environmental samples with satisfying results.

The use of plant tissue analysis as a tool for attaining low cyanogenic glucoside levels in cassava roots, has hardly been investigated. Just as the quality of crops is improved through the use of plant tissue analysis, the same can probably be done to consistently attain the lowest possible cyanogenic glucoside levels in cassava roots. High levels of cyanogenic glucosides in consumed fresh cassava roots or in their products have the potential of causing cyanide intoxication, hence the need to lower them. An experiment was thus conducted to assess the occurrence of meaningful relationships between plant nutritional status and cyanogenic glucoside production in cassava roots. Total hydrogen cyanide (HCN) levels in cassava roots were used to assess cyanogenic glucoside production. Using NPK fertiliser application to induce changes in plant nutritional status, the main objective of the study was investigated using the following sub-objectives; (1) to determine the effects of increased NPK fertiliser application on cassava root HCN levels; (2) and to show the occurrence of relationships between changes in nutrient levels in plant 'indicator tissue' and HCN levels in cassava roots. The study was a field experiment laid out as a split-plot in a randomized complete block design with three replicates. It was repeated in two consecutive years, with soil nutrient deficiencies only being corrected in the second year. The varieties Salanga, Kalinda, Supa and Kiroba were used in the experiment, while the NPK fertiliser treatments included; a control with no fertiliser applied; a moderate NPK treatment (50 kg N + 10 kg P + 50 kg K /ha); and a high NPK treatment (100 kg N + 25 kg P + 100 kg K /ha). A potassium only treatment (50 kg K/ha) was also included, but mainly for comparison. The root HCN levels of Salanga, Kalinda and Kiroba were significantly influenced by NPK fertiliser application in at least one of the two field experiments, while those of Supa remained uninfluenced. Changes in plant nutritional status in response to fertiliser application were thus shown to influence cyanogenic glucoside production. The results of the multiple linear regression analysis for the first field experiment, generally showed that the root HCN levels of some cassava varieties could have been 'reduced' by decreasing concentrations of nitrogen, potassium and magnesium in plants, or by improving plant calcium concentrations along with NPK fertiliser application. However, in the second field experiment (with corrected soil nutrient deficiencies) the regression analysis generally showed that the root HCN levels of some cassava varieties could have been 'reduced' by improving either one or a combination of the nutrients phosphorous, zinc and potassium in plants along with NPK fertiliser application. Although the results obtained in the two experiments had been contradicting due to slight differences in how they were conducted, the study had nonetheless demonstrated the occurrence of meaningful relationships between plant nutritional status and cyanogenic glucoside production; confirming the possible use of plant tissue analysis in predicting fertiliser needs for the consistent attainment of low cyanogenic glucosides in cassava roots., Competing Interests: The authors have declared that no competing interests exist.