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The chemical profile and the levels of AVNs in oat varieties after germination have been examinated. In the present study, 12 distinct oat varieties were germinated for 0-192 h and a total of 28 AVNs and 3 AVN-hexosides were determined in these samples. Among them, three novel AVNs were synthesized (AVN 1a, AVN 2a, and AVN 2a d ), characterized using NMR techniques (1D- and 2D-NMR), and assessed in real samples for the first time. The most abundant AVNs in the samples were AVN 2c, AVN 2p, AVN 2f, and their long-chained analogues AVN 2 c d , AVN 2p d , AVN 2f d , together representing 75-85 % of the total AVNs content. The highest total AVN level was observed on average after 48-72 h of germination time and it reached a value 1-1.2 mg/g. Out of 12 investigated oat varieties, CDC Boyer, Diadem, and Rozmar have proved to be the most suitable genotypes for germination., 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.)

Background: Tolfenamic acid (TA) belongs to the fenamates class of nonsteroidal anti-inflammatory drugs. Insufficient information is available regarding the availability of a reliable and validated stability-indicating method for the assay of TA., Objective: A relatively simple, rapid, accurate, precise, economical, robust, and stabilityindicating RP-HPLC method has been developed to determine TA in pure and tablet dosage forms., Methods: The method was validated according to the ICH guideline, and parameters like linearity, range, selectivity, accuracy, precision, robustness, specificity, and solution stability were determined. TLC and FTIR spectrometry were used to ascertain the purity of TA. The specificity was determined with known impurities and after performing forced degradation, while the robustness was established by Plackett-Burman's experimental design. The mobile phase used for the analysis was acetonitrile and water (90:10, v/v) at pH 2.5. The detection of the active drug was made at 280 nm using a C18 column (t R = 4.3 min.). The method's applicability was also checked for the yellow polymorphic form of TA., Results: The results indicated that the method is highly accurate (99.39-100.80%), precise (<1.5% RSD), robust (<2% RSD), and statistically comparable to the British Pharmacopoeia method with better sensitivity and specificity., Conclusion: It was observed that the stress degradation studies do not affect the method's accuracy and specificity. Hence the proposed method can be used to assay TA and its tablet dosage form., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

Cyantraniliprole is an anthranilic diamide insecticide used for the effective management of diamondback moth in cabbage. Dietary risk assessment of pesticides in food is a major concern now. This study developed a QuEChERS/HPLC-PDA-based highly efficient and reliable method, registering 89.80-100.11% recoveries of cyantraniliprole and its metabolite IN-J9Z38 from cabbage and soil with a relative standard deviation of 0.43-5.77%. Field experiment was conducted to study the residue dissipation of cyantraniliprole in cabbage and soil. Two foliar treatments of 10.26% formulation (Benevia) at 60 (T 1 ) and 120 (T 2 ) gram active ingredient/hectare were applied. The dissipation half-lives of cyantraniliprole in cabbage and soil were determined to be 3.5-4.2 and 3.8-5.3 days at T 1 and 3.9-4.8 and 4.1-4.7 days at T 2 , respectively. The maximum concentrations of IN-J9Z38 at T 1 and T 2 were 0.819 and 1.061 mg/kg, respectively, on the fifth day. A risk quotient value of <1 indicates no dietary risk to the consumers. The residues in the harvested cabbage were below the tolerance level of 2.0 mg/kg established by the regulatory body in India., (© 2021 John Wiley & Sons, Ltd.)

Plant uptake and metabolism of pesticides are complex and dynamic processes, which contribute to the overall toxicity of the pesticides. We investigated the metabolic fate of cyantraniliprole, a new diamide class of insecticide, during various growth stages of tomato. Cyantraniliprole was the major residue in leaves, flowers, and fruits, with the relative metabolite-to-parent ratios maintained at < 10% up to 28 days after treatment (DAT). Mature leaves contained consistently higher residues of cyantraniliprole than young leaves throughout the study. Flowers contained the highest cyantraniliprole residues up to 21 DAT, then gradually decreased. Immature green fruits had the highest cyantraniliprole residues (5.3 ± 0.7 ng/g; 42 DAT), and decreased toward red ripening stages (1.4 ± 0.2 ng/g; 84 DAT). Metabolism of cyantraniliprole primarily occurred in the foliage, where 21 metabolites were tentatively identified. Flowers and fruits contained 14 and four of these metabolites, respectively. Major transformation pathways were characterized by ring closure, followed by N-demethylation, and glycosylation. Additionally, plant metabolism of cyantraniliprole was also associated with several minor phase-I, phase-II, and breakdown metabolites. The occurrence of these metabolites in plants varied as a function of tissue types and their developmental stages. Our study highlights a tissue-specific biotransformation and accumulation of metabolites of cyantraniliprole in tomato., (© 2021. The Author(s).)

Dissipation and transformation of cyantraniliprole, a new diamide class of insecticides, were investigated under greenhouse conditions, using snapdragon (Antirrhinum majus) as the model plant. Dissipation of cyantraniliprole in treated leaves was found to be dependent upon application methods (foliar spray versus soil drench) and doses (high versus low dose), with the parent insecticide being the major residue at various sampling points. A high-dose foliar application resulted in pesticide residue of 6.7-23.8 μg/g foliar fresh weight over 8 weeks of treatments, while in soil drench treatment the residue varied from 0.8 to 1.4 μg/g. However, the residue contents were similar between the two application methods at a low application dose. The transformation pathways of cyantraniliprole were primarily intramolecular rearrangements, with IN-J9Z38 being the major metabolite across treatments. Several other metabolites were also identified, some of which were unique to the application methods. Out of total 26 metabolites tentatively identified in this study, 10 metabolites were unique to foliar application, while six metabolites were unique to soil drench. In addition to plant-mediated biotransformation, photodegradation of the parent compound was identified as a potential mechanism in foliar application., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Atopic dermatitis is a typical chronic inflammatory skin disease that affects all age groups and requires basic skin care for treatment. Anti-inflammatory and antiallergy steroids are the most frequently used treatments but they are limited due to their side effects caused by a weakening of the immune system. Many consumers focus on performance as a criterion for selecting cosmetics. However, steroids have been illegally used to improve the performance of cosmetics, and consumers have been adversely affected by the corresponding side effects. In this paper, we propose a simple and rapid method using liquid chromatography-tandem mass spectrometry to simultaneously analyze ten non-permitted atopic therapeutic compounds in cosmetic products: chlorpheniramine maleate, ketotifen fumarate, doxepin hydrochloride, azelastine hydrochloride, bufexamac, clotrimazole, tranilast, fusidic acid, tacrolimus, and pimecrolimus. Additionally, the major characteristic fragment ions for tacrolimus, pimecrolimus, and clotrimazole were identified by time-of-flight mass spectrometry. The specificity, linearity, limit of detection, limit of quantification, recovery, precision, accuracy, and stability of the proposed method were validated. The limit of detection and quantification were in the ranges of 5.05-203.30 pg/mL and 15.15-609.90 pg/mL, respectively. The proposed analysis method could help improve the safety management of cosmetics., (© 2021 Wiley-VCH GmbH.)

Spodoptera frugiperda (Lepidoptera: Noctuidae) is a widely distributed pest of corn. Since it invaded China in 2018, it has caused serious damage to local corn production. Chlorantraniliprole, an anthranilic diamide insecticide, has been widely used to control lepidopteran pests. Tetrachloropyramid is a new allosteric modulator insecticide developed based on chlorantraniliprole, so it has a similar mechanism and insecticidal effect. In this study, we investigated resistance levels to chlorantraniliprole and tetrachloropyramid in S. frugiperda from 13 populations in China. Among the populations tested, the relative highest resistance to chlorantraniliprole occurred in the Guangzhou population, and the most susceptible to chlorantraniliprole was found in the Wuhan population. The lethal dosage LD 50 value of the Guangzhou population against chlorantraniliprole was 27.8-fold higher than that of the Wuhan population. Minimal differences were observed among S. frugiperda populations in terms of sensitivity to tetrachloropyramid. Heterozygous mutations at the I4734 site of the ryanodine receptor (RyR) were found, while no mutations were found in the G4891 site. The mutations were detected in only two of the 786 individuals analyzed, one from the Qinzhou population and other from the Anshun population (frequency below 2% in both cases). There were no significant differences in the expression levels of RyR between Guangzhou and Wuhan populations. In summary, our results indicate that: (i) S. frugiperda has low resistance levels to diamide insecticides in China; and (ii) the differences in relative resistance among the 13 populations analyzed are not caused by the mutations in RyR or the expression of RyR., (© 2020 Institute of Zoology, Chinese Academy of Sciences.)

From a mutagenized oat population, produced by ethyl methanesulfonate mutagenesis, hulled grains from 17 lines with elevated avenanthramide (AVN) content were selected and their AVN structures, concentrations and antioxidant potentials were determined by HPLC-MS 2 and HPLC equipped with an on-line ABTS + antioxidant detection system. The data obtained showed qualitative and quantitative differences in the synthesis of AVNs in the different lines, with a total AVN concentration up to 227.5 µg/g oat seed flour in the highest line, compared with 78.2 µg/g seed in the commercial line, SW Belinda. In total, 25 different AVNs were identified with avenanthramide B structures being among the most abundant, and AVN C structures having the highest antioxidant activity. The findings indicate the potential of oat mutagenesis in combination with a high precision biochemical selection method for the generation of stable mutagenized lines with a high concentration of total and/or individual AVNs in the oat seed grain., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Cyantraniliprole and chlorantraniliprole are anthranilic diamide insecticides acting on ryanodine receptors. In this study, two camel-derived nanobodies (Nbs, named C1 and C2) recognizing cyantraniliprole as well as chlorantraniliprole were generated. C1-based enzyme-linked immunosorbent assays (ELISAs) for the detection of the two insecticides were developed. The half-maximum signal inhibition concentrations (IC 50 ) of cyantraniliprole and chlorantraniliprole by ELISA were 1.2 and 1.5 ng mL -1 , respectively. This assay was employed to detect these two insecticides in soil and vegetables. The average recoveries of cyantraniliprole from both bok choy (Brassica chinensis L.) and soil samples were 90-129%, while those of chlorantraniliprole were in a range of 89-120%. The insecticide residues in soil and bok choy, which were collected from plots sprayed with cyantraniliprole and chlorantraniliprole, were simultaneously detected by the resulting ELISA and a high-performance liquid chromatography (HPLC) method, showing a satisfactory correlation. Higher concentrations of chlorantraniliprole than cyantraniliprole were detected in soil and vegetables, which indicates the longer persistence of chlorantraniliprole in the environment.

A photonic sensor based on inversed opal molecular imprinted polymer (MIP) film to detect the presence of chlorantraniliprole (CHL) residue in tomatoes was developed. Acrylic acid was polymerized in the presence of CHL inside the structure of a colloidal crystal, followed by etching of the colloids and CHL elution. Colloidal crystals and MIP films were characterized by scanning electron microscopy and FT-IR, confirming the inner structure and chemical structure of the material. MIP films supported on polymethylmethacrylate (PMMA) slides were incubated in aqueous solutions of the pesticide and in blended tomato samples. The MIP sensor displayed shifts of the peak wavelength of the reflection spectra in the visible range when incubated in CHL concentrations between 0.5 and 10 μg L -1 , while almost no peak displacement was observed for non-imprinted (NIP) films. Whole tomatoes were blended into a liquid and spiked with CHL; the sensor was able to detect CHL residues down to 0.5 μg kg -1 , significantly below the tolerance level established by the US Environmental Protection Agency of 1.4 mg kg -1 . Stable values were reached after about 30-min incubation in test samples. Control samples (unspiked processed tomatoes) produced peak shifts both in MIP and NIP films; however, this matrix effect did not affect the detection of CHL in the spiked samples. These promising results support the application of photonic MIP sensors as an economical and field-deployable screening tool for the detection of CHL in crops.

Hulled Reins and hulless Lamont oats were dehulled and/or sequentially abraded to produce ten pearling fines and corresponding pearled kernels. Contents of nutrients (protein, oil, starch, beta-glucan, ash and other carbohydrates) and avenanthramides (AVA) 2p, 2c, 2f, and 5p in processing fractions and starting grains were measured. Results show that distribution patterns of nutrients varied with individual nutrients, but those of AVAs varied with variety and individual AVAs. In both varieties, from the surface to inner endosperms, protein and oil increased then decreased; ash and other carbohydrates decreased; starch increased; and beta-glucan unchanged except for the surface area. In Lamont oat, the four AVAs decreased, but in Reins oat, AVA 2p decreased while 2c, 2f and 5p increased, then decreased. Compared to whole grain, pearled oats not only contained lower AVAs, protein, oil, ash, and other carbohydrates and higher beta-glucan and starch but also had a different AVA composition., 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., (Published by Elsevier Ltd.)

In this study, a new method for simultaneous determination of cyantraniliprole, chlorantraniliprole, tetrachlorantraniliprole, cyclaniliprole and flubendiamide in edible mushrooms by high-performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS) combined with a modified QuEChERS procedure. The samples were extracted using acetonitrile and then cleaned up by primary secondary amine (PSA) and octadecylsilane (C18). The determination of these insecticides was achieved in less than 5 min using an electrospray ionization source in positive mode (ESI+) for cyantraniliprole and chlorantraniliprole, while negative mode (ESI-) for tetrachlorantraniliprole, cyclaniliprole and flubendiamide. The linearities of the calibrations for all target compounds were acceptable (R 2  ≥ 0.9922). The limits of detection and quantification were 0.05-2 μg kg -1 and 5 μg kg -1 , respectively. Acceptable recoveries (73.5-110.2%) were acquired for these insecticides with RSDs less than 12.7%. The results demonstrated that the proposed method was effective and convenient for the determination of these insecticides in edible mushrooms., 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.)

Chlorantraniliprole (CAP) is extensively used for rice pest management. Lack of information on the role of standing water and amount and timing of rainfall on CAP dissipation in rice ecosystem could hamper its prospective use. Present study was performed to investigate the effects of different water regimes (saturated, 5 and 10 cm standing water) and simulated rainfall (40 and 100 mm occurred at 4, 8 and 24 h after CAP application) on leaching, surface runoff and dissipation of CAP into components of rice ecosystem. The results showed highest concentration of CAP residues in soil and plant under saturated condition followed by 5 and 10 cm standing water conditions. Whereas, the highest concentration of CAP in leachates was detected under 10 cm standing water (12.19 ng mL -1 ). The results revealed large amount of leaching (21.99 ng mL -1 ) and surface runoff (42.25 ng mL -1 ) losses of CAP when 100 mm rainfall occurred at 4 h after pesticide application. The total quantity of CAP residues in soil and plant was highest when rainfall occurred at 24 h after pesticide application under both the rainfall amounts. Water stagnation and high intensity rainfall occurred shortly after pesticide application will contribute to pesticide loss to non-target sites through surface run-off and leaching. There will be less pesticide available in soil for plant uptake which may not be sufficient to kill the target organisms., (Copyright © 2020 Elsevier Inc. All rights reserved.)

The photochemical degradation of chlorantraniliprole (3-bromo-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-1-(3-chloro-2-pyridine-2-yl)-1H-pyrazole-5-carboxamide; CAP) was characterized under simulated solar light with 2-nitrobenzaldehyde (2NB) actinometry. Overall, aqueous CAP degraded quickly via direct photodegradation with no significant difference observed between high-purity water and filtered rice field water. The 24-h average half-life normalized to summer sunlight using 2NB was 34.5 ± 4.0 h (j CAP,env  = 0.020 ± 0.0023 h -1 , n = 3), and the calculated apparent quantum yield in simulated sunlight was 0.0099 ± 0.00060. These new values were used-alongside previously characterized data for air/and soil/water partitioning, degradation in soil, and hydrolysis-in the Pesticides in Flooded Applications Model to simulate CAP dissipation in a model California (USA) rice field. The model estimates an environmental half-life of 26 d in the aqueous phase, but the bulk of applied CAP remains in the benthic zone and degrades, with estimated half-lives of 29 and 92 d in flooded and drained fields, respectively. Environ Toxicol Chem 2020;39:1929-1935. © 2020 SETAC., (© 2020 SETAC.)

As part of a new generation of diamide insecticides, cyantraniliprole has broad application prospects. In the present study, a QuEChERS-UPLC-MS/MS method was established to determine the residues of cyantraniliprole and its main metabolite J9Z38 in soil and earthworms. Moreover, the accumulation and toxicity of cyantraniliprole and J9Z38 in earthworms were evaluated. The present results show that the detection method of cyantraniliprole and J9Z38 has high sensitivity and accuracy, which could be used for the accurate quantification of cyantraniliprole and J9Z38 residues in soil and earthworms. Additionally, cyantraniliprole degraded faster than its main metabolite J9Z38 in the artificial soil. Moreover, the bioenrichment efficiency of cyantraniliprole was higher than J9Z38. The toxicity test result showed that cyantraniliprole and J9Z38 could induce oxidative stress effect in earthworms from 5.0 mg/kg, finally resulting in cellular damage. Moreover, the oxidative damage degree induced by cyantraniliprole was higher than J9Z38. Combining the results of residue test and toxicity test, although cyantraniliprole degraded faster than its main metabolite J9Z38 in the artificial soil, its risk to earthworms was higher than J9Z38., 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.)

Rationale: Avenanthramides (AVNs) are constituents unique to oats and have many outstanding health benefits. AVNs are antioxidants and possess anti-inflammatory, antifungal and antibacterial activity. The number of known AVNs increased recently because of the latest developments in high-resolution tandem mass spectrometry (HRMS/MS) techniques., Methods: Oat seed extract from 10 oat cultivars was analysed using ultra-high-performance liquid chromatography (UHPLC) and Q Exactive hybrid quadrupole-Orbitrap mass spectrometry (HRMS/MS) with positive heated electrospray ionization., Results: Thirty-five AVNs were identified and characterized in seed extracts, and the structures of 10 novel AVNs were tentatively elucidated, among which were AVNs bearing a cinamoyl or sinapoyl moiety. These AVNs are reported in oats for the first time. The method was validated using AVN standards (AVNs 2c, 2f and 2p), with limits of detection and quantitation at low picomole levels. Recovery of AVN standards varied from 83% to 106%, and relative standard deviations ranged from 2% to 9%. The total AVNs in the selected oat varieties ranged from 36.0 to 302.5 μg/g (dry weight), with AVN 2c, AVN 2f and AVN 2p representing approximately 65%-70% of that total., Conclusions: Our comprehensive method for detecting the full avenanthramide spectrum can contribute to better understanding the chemical and biological properties of individual AVNs for utilization in developing new oat cultivars and novel functional foods., (© 2020 John Wiley & Sons, Ltd.)

In the present work, persistence and degradation of cyantraniliprole, a leading anthranilic diamide pesticide against sucking insect pests, in inceptisol soil has been studied. Effect of various factors like light source (UV-light, sunlight and dark), temperature (5, 25 and 37 °C), moisture regime (dry, field capacity and submerged) and carbon dioxide level (415 and 625 µL L -1 ) on dissipation was also evaluated. Formation of IN-J9Z38, a major metabolite of cyantraniliprole, was monitored in different treatments. Samples were processed as per QuEChERS method and analysis was done by HPLC-PDA. Matrix matched calibration curve, prepared in the range 0.001-10 mg L -1 , indicated very good linearity ( R 2 > 0.99) and sensitivity (instrument limit of detection 0.001 mg L -1 ). Cyantraniliprole residues dissipated with time and 47.7%-98.8% dissipation was recorded on 90th day in different treatments. Minimum half-life of cyantraniliprole, i.e. 8.7 days was recorded at elevated CO 2 level (625 ± 5 µL L -1 ) while its maximum half-life of 86.6 days was recorded at 5 °C. Metabolite IN-J9Z38 started forming from zero-day and reached the maximum on 15th to 60th day. Microbial biomass carbon, as an index of microbial activity of soil, correlated well with the degradation of cyantraniliprole.

Background: Breast milk is a natural and unique nutrient for optimum growth and development of the newborn. The aim of this study was to investigate the presence of unpredictable drug residues in mothers' milk and the relationship between drug residues and maternal-infant characteristics., Methods: In a descriptive study, breastfed infants under 3 months of age and their mothers who applied for child health monitoring were enrolled for the study. Information forms were completed for maternal-infant characteristics, breastfeeding problems, crying and sleep characteristics of infants. Maternal and infant anthropometric measurements and maternal milk sample were taken. Edinburgh Postpartum Depression Scale was applied to mothers. RANDOX Infiniplex kit for milk was used for residual analysis., Results: Overall, 90 volunteer mothers and their breastfed infants were taken into the study and the mean age of the mothers and their infants was 31.5 ± 4.2 years and 57.8 ± 18.1 days, respectively. Anti-inflammatory drug residues in breast milk were detected in 30.0% of mothers and all had tolfenamic acid. Overall, 94.4% had quinolone, 93.3% beta-lactam, 31.1% aminoglycoside and 13.3% polymycin residues. Drugs used during pregnancy or lactation period were not affected by the presence of residues. Edinburgh postpartum depression scores of mothers and crying and sleeping problems of infants were similar in cases with and without drug residues in breast milk. When controlling confounding factors, maternal body mass index alterations were detected to be significantly lower in mothers with anti-inflammatory drug residues in breast milk than in their counterparts (p = 0.017)., Conclusions: Our study suggests that there are unpredictable drug residues in the milk of many mothers. Anti-inflammatory drug exposure might affect maternal weight change during the postpartum period. Further studies are required to evaluate the impact of drug residues on maternal and infant health.

An experiment was set up to determine the rate of dissipation of chlorantraniliprole (CTP) from two soils with contrasting properties. The other objective of the study was to find out the effect of CTP on soil microorganisms (population, microbial biomass carbon and soil enzymes) under controlled environment. CTP residues when applied at recommended dose ((RD) (at 40 g a.i./ha)) could not be recovered either from alluvial soil or red soil at 60 days post application of CTP in a microcosm study. Higher clay content led to higher half-life in alluvial soil compared to red soil. CTP could not be recovered from RD treatment at 30 days after pesticide application under controlled environment. Faster dissipation of CTP was observed in rice rhizosphere soil with 23.89 and 34.65 days dissipation half-lives for RD and double the recommended dose (DRD) treatments, respectively. Different doses of chlorantraniliprole did not have considerable negative effect on actinomycetes, fungi, biological nitrogen fixers and phospahte solubilising bacteria except the bacteria population. Among the treatments, DRD recorded the lowest activity of dehyrodeganse, fluoresein diacetate hydrolase, acid and alkaline phosphatases followed by RD treatment. Microbial biomass carbon, β -glycosidase and urease did not vary significantly among the different doses of CTP. In general, RD did not have negative effcts on soil microbes. Hence, CTP can be recommeded in rice pest managment maintaining existing soil microbes and soil enzymes activity., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Citri Reticulatae Pericarpium (CRP), the dried pericarp of Citrus reticulata Blanco, can be divided into "Guangchenpi" (GCP, the dried pericarps derived from Citrus reticulata 'Chachi') and "Chenpi" (CP, the dried pericarps derived from other cultivars of Citrus reticulata Blanco). To discriminate between GCP and CP, a simple and reliable high-performance thin-layer chromatography (HPTLC) method was firstly developed to analyze the volatile compound dimethyl anthranilate, and a high-performance liquid chromatography (HPLC) method was established to simultaneously quantify dimethyl anthranilate and three predominant flavonoids (hesperidin, nobiletin and tangeretin) in CRP samples. Both the HPTLC analysis and HPLC-orthogonal partial least squares discrimination analysis (OPLS-DA) indicated that GCP can be effectively distinguished from CP based on analysis of dimethyl anthranilate. Our results indicated that dimethyl anthranilate can be used as a marker compound for discrimination of GCP and CP. This work provided a convenient approach which might be applied for quality evaluation of CRP., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Rice-crab (Chinese mitten crab, Eriocheir sinensis) coculture system has become one of the most important agricultural activities practiced in China. However, the effect of pesticide usage on the survival and edible safety of crab species living in the coculture system has not been investigated. In the present study, we created a field simulation experiment and discovered that the amount of pesticide chlorantraniliprole (CAP) entering the rice-crab coculture system accounted for 82.22% of the total CAP content present in the spray barrel. When CAP residues found in the soil leached into nearby areas, we observed an increase in the CAP concentration in the water and sediment. Specifically, peak CAP concentration (1.35 μg/L) was detected in water within 1 day, and a steady CAP concentration in the sediment (2.55 μg/kg) was detected within 3 days. Additionally, an extensive field sampling experiment conducted in the basin of the lower reaches of the Yangtze River revealed that CAP was routinely used in rice-crab coculture systems. Although detected CAP concentrations were below 1 μg/L in ditch water and below 1 μg/kg in ditch sediment, there was still a potential risk associated with the crab growth. Importantly, there was no risk associated with crab consumption, given the low detection frequency of CAP in the collected samples. Our analysis suggests that an increase in usage ratio and a decrease in the total CAP content will likely promote safe application of CAP in the rice-crab coculture systems., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The dissipation patterns of cyantraniliprole and its metabolite IN-J9Z38 were investigated using proso millet (Panicum miliaceum) under open-field conditions to establish a pre-harvest interval. A simple and sensitive analytical method was developed for analyzing residues using ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) for multiple reaction monitoring of target compounds. The analytical method was validated in terms of the instrumental limit of quantitation, method limit of quantitation, linearity, accuracy, and precision. The method was successfully applied to the analysis of cyantraniliprole and IN-J9Z38 residues in the field samples of four plots, which were treated twice with an oil dispersion formulation, according to the date of pesticide treatment before harvest. In the case of cyantraniliprole in grain and straw, there was a 91.1 and 89.1% decrease, respectively, from the initial residues (14-7 days) to the final plot (40-30 days before harvest). However, IN-J9Z38 gradually increased over time, indicating that cyantraniliprole transformed into IN-J9Z38 during cultivation. The biological half-lives of total cyantraniliprole were 11.3 and 9.4 days for grain and straw, respectively. The results obtained in this study will inform regulation and management of pesticide use for the minor crop proso millet.

The dissipation behaviors of acetamiprid and chlorantraniliprole in kimchi cabbages were studied under open-field conditions. A simple and rapid analytical method was developed using ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS). The multiple reaction monitoring (MRM) conditions of two pesticides were optimized to quantify and identify the pesticide residues. Sample preparation was performed by the QuEChERS (quick, easy, cheap, effective, rugged, and safe) method. Average recovery rates at the different spiked levels (0.05 and 0.25 mg/kg) were in the range of 103.6-113.9% (acetamiprid) and 80.8-91.2% (chlorantraniliprole), and the relative standard deviations were ≤4.3% for all. The dissipation kinetics were assessed using first-order equations after spraying acetamiprid and chlorantraniliprole individually on kimchi cabbages. The biological half-lives in field 1 and 2 were 5.2 and 6.3 days (acetamiprid) and 10.0 and 15.2 days (chlorantraniliprole), respectively. Based on the dissipation equations, the pre-harvest residue limits (PHRLs) corresponding to each day before harvest were suggested as the guidelines to meet the MRL on harvest day. It was also predicted that the terminal residues observed after multiple sprayings (three and seven days) would be below the MRL when harvested, in compliance with the established pre-harvest intervals.

Power ultrasound as an emerging processing technology has been investigated for stimulating seeds to enhance germination and accumulation of health-promoting metabolites, such as γ-aminobutyric acid (GABA) and phenolic compounds. This work was undertaken to evaluate the effects of power ultrasound (25 kHz) on the nutritional properties of germinated oats, and the microstructure of oat groats after treatment. The changes in the external and internal microstructures of the ultrasound-treated oats kernel were investigated using Environmental Scanning Electron Microscopy (ESEM) and 3D X-ray Micro Computed Tomography (Micro-CT). Physicochemical properties of oats including GABA, free sugars, avenanthramides, total phenolic content, and antioxidant capacities were enhanced after germination. Furthermore, the power ultrasound treatment for 5 min after soaking significantly enhanced the GABA (48-96 h), alanine (24-96 h), succinic acid (48-72 h), total phenolic content (24 h), and total avenanthramides (24 h) in the germinated oats., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Oat is the nutritious crop containing various compounds with antioxidant properties, such as polyphenols. In this study, we investigated the effect of germination and ultrafiltration process on polyphenol and avenanthramide contents in oat as well as their cytoprotective effect. Germination of oat for 48 hr significantly increased avenanthramide (5.5 to 11.3 mg/g) and polyphenol (115 to 155 mg GAE/g) contents. The compounds were more concentrated after ultrafiltration using 10 kDa membranes (polyphenol, 206 GAE/g; avenanthramide, 18 mg/g). In addition, oat extracts significantly reduced the cellular ROS level against tert-butyl hydroperoxide (t-BHP) stimulation in HepG2 cells. In the mechanistic study, oat extracts induced Nrf2 translocation to the nucleus by inhibition of Keap1 expression, resulting into upregulation of γ-GCS and NQO1. In conclusion, oat germination and ultrafiltration processes increased the polyphenol content, including that of avenanthramide. These extracts protected cells from t-BHP by radical scavenging activities and induced Nrf2 pathway activation. PRACTICAL APPLICATIONS: This study presents the method for avenanthramide-concentrated extract which is unique bioactive compounds in oat. In addition, antioxidant activity and their mechanisms of the avenanthramide-enriched extracts were evaluated. The polyphenol compounds including avenanthramide were found to increase after germination and ultrafiltration, thereby improving the radical scavenging ability. These results can be utilized as data for the development of health-promoting materials using oats., (© 2019 Wiley Periodicals, Inc.)

Avenanthramides are amides, with a phenylalkenoic acid (PA) and an anthranilic acid (AA) subunit, which are secondary metabolites of oat. Oat seeds were germinated, extracted, and the avenanthramides analysed by a combination of UHPLC with ion trap and high resolution ESI-MS. Typical fragmentation pathways with corresponding diagnostic fragments belonging to the PA and AA subunits were identified and summarised in a decision guideline. Based on these findings 28 unique avenanthramides were annotated in the oat seed(ling) extracts, including the new avenanthramide 6f (with a 4/5-methoxy AA subunit). Avenanthramide content increased by 25 times from seed to seedling. Avenanthramides 2p, 2c, and 2f, which are commonly described as the major avenanthramides, represented less than 20% of the total content in the seedlings. Future quantitative analyses should, therefore, include a wider range of avenanthramides to avoid underestimation of the total avenanthramide content., (Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Avenanthramides are phenolic compounds found only in oats, and are of interest due to suggested bioactivities, including anti-inflammatory effects and induction of apoptosis. The objective of this work was to optimise a high performance liquid chromatography (HPLC) method for analysis of avenanthramides in food, and analyse the avenanthramide content in 45 oat fractions and products. The optimised HPLC method was based on triplicate extraction of 100 mg sample with 1 ml 80% ethanol in phosphate buffer (pH 2.8) and used gallacetophenone as an internal standard. Avenalumic acid-derived avenanthramide homologues 2f d and 2p d were also present, making up to 20% of the total avenanthramides detected in oats. The amounts of avenanthramides detected in oat products was 2-82 µg/g. It was estimated that mean avenanthramide intake among oat consumers ranges from 0.3 to 2.1 mg/day, considerably lower than the amount used in studies that have investigated biological effects of avenanthramides in humans., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

A methodology for the rapid determination of the aromatic compounds methyl anthranilate (MA), 2'-aminoacetophenone (2-AAP) and furaneol by GC-MS was validated and used to characterize grape juice and wine elaborated with the new Brazilian grape varieties cultivated in northeastern Brazil, and Brazilian grape nectars. The method presented linearity (R 2  ˃ 0.9952), good accuracy (CV < 12.9%), recovery (76.6% to 106.3%), limit of detection (23 μg L -1 to 94 μg L -1 ) and limit of quantification (96 μg L -1 to 277 μg L -1 ) acceptable in only 20 min of running. The methodology was considered satisfactory for the purpose, being a simple and rapid method for the determination of these compounds in grape derivatives drinks. In the characterization of the nectars the compound that stood out was the MA, being its presence attributed to the addition of flavorings in these products. It was evidenced a significant contribution of furaneol in the aroma of grape juice and wines elaborated with the new Brazilian grape varieties., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Diamide insecticides have become the fourth most commonly used insecticide class in the world. Chlorantraniliprole (CAP) is a first-generation diamide insecticide with broad application potential. In this experiment, the eco-toxicity of CAP in soil at 0.1, 1.0, 5.0 and 10.0mg/kg on earthworms (Eisenia fetida) was evaluated during a 42 d exposure. More specifically, the environmental fate and transport of CAP between soil and earthworms was monitored during the exposure period. The present results indicated that the CAP contents of 0.1, 1.0, 5.0 and 10.0mg/kg treatments decreased to no more than 20% in the soil after 42 d of exposure. The accumulation of CAP in earthworms was 0.03, 0.58, 4.28 and 7.21mg/kg earthworm (FW) at 0.1, 1.0, 5.0 and 10.0mg/kg after 42 d of exposure. At 0.1mg/kg and 1.0mg/kg, CAP had no effect on earthworms during the exposure period. The weight of earthworms was significantly reduced at 5.0 and 10.0mg/kg at 28 and 42 days after CAP application. After the 14th day, CAP induced excess production of reactive oxygen species (ROS) at 5.0 and 10.0mg/kg, resulting in oxidative damage to biomacromolecules. We believe that CAP has a high risk potential for earthworms when used at 5.0 and 10.0mg/kg., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Background: Chlorantraniliprole is widely used as a pesticide. It is only soluble in dimethyl formamide. However, most of the reported methods used acetonitrile and other solvents., Aim: To develop rapid, accurate, precise, and sensitive HPLC method for chlorantraniliprole., Materials and Methods: 10 μG/mL of chlorantraniliprole containing solution was injected into the HPLC system and run in different solvent systems. 10 μG/mL solutions of chlorantraniprole was injected in a column with 20 μL microsyringe. The chromatogram was run for appropriate minutes with mobile phase water. The flow rate was set to 1 mL/min and detection was carried out at wavelength 270 nm. The method is validated by measuring the limit of quantitation, limit of detection, repeatability, intraday precision, inter-day precision, and accuracy. Analysis of marketed formulation, bringle, and tomato for chlorantraniprole content was also made for the developed analytical method., Results: There was linearity of chlorantraniliprole for calibration curve in between 1 and 5 μG/mL concentration. The perfect sharp peak observed in water at a retention time of 6.28 min. The limit of detection and the limit of quantitation were 0.0050 μG/mL and 0.0152 μG/mL, respectively. The study reported 99.55% repeatability, 99.49% intraday precision, 99.65% interday precision, and 99.27% accuracy., Conclusion: The rapid, accurate, precise, and sensitive HPLC method for the detection of chlorantraniliprole using dimethyl formamide was developed.

A novel method, mid-infrared (MIR) spectroscopy, which enables the determination of Chlorantraniliprole in Abamectin within minutes, is proposed. We further evaluate the prediction ability of four wavelength selection methods, including bootstrapping soft shrinkage approach (BOSS), Monte Carlo uninformative variable elimination (MCUVE), genetic algorithm partial least squares (GA-PLS) and competitive adaptive reweighted sampling (CARS) respectively. The results showed that BOSS method obtained the lowest root mean squared error of cross validation (RMSECV) (0.0245) and root mean squared error of prediction (RMSEP) (0.0271), as well as the highest coefficient of determination of cross-validation (Q cv 2 ) (0.9998) and the coefficient of determination of test set (Q 2 test ) (0.9989), which demonstrated that the mid infrared spectroscopy can be used to detect Chlorantraniliprole in Abamectin conveniently. Meanwhile, a suitable wavelength selection method (BOSS) is essential to conducting a component spectral analysis., (Copyright © 2017. Published by Elsevier B.V.)

Cyantraniliprole is an anthranilic diamide insecticide, belonging to the ryanoid class, with a broad range of applications against several pests. In the presented work, a reliable analytical technique employing high-performance liquid chromatography coupled with photodiode array detector (HPLC-DAD) for analyzing cyantraniliprole residues in tomato was developed. The method was then applied to field-incurred tomato samples collected after applications under open field conditions. The latter aimed to ensure the safe application of cyantraniliprole to tomato and contribute the derived residue data to the risk assessment under field conditions. Sample preparation involved a single step extraction with acetonitrile and sodium chloride for partitioning. The extract was purified utilizing florisil as cleanup reagent. The developed method was further evaluated by comparing the analytical results with those obtained using the QuEChERS technique. The novel method outbalanced QuEChERS regarding matrix interferences in the analysis, while it met all guideline criteria. Hence, it showed excellent linearity over the assayed concentration and yielded satisfactory recovery rate in the range of 88.9 to 96.5%. The half-life of degradation of cyantraniliprole was determined at 2.6 days. Based on the Codex MRL, the pre-harvest interval (PHI) for cyantraniliprole on tomato was 3 days, after treatment at the recommended dose. To our knowledge, the present work provides the first record on PHI determination of cyantraniliprole in tomato under open field conditions in Egypt and the broad Mediterranean region.

Oats, in addition to cholesterol-lowering properties, contain unique antioxidants called avenanthramides (Avns), which inhibit both inflammatory cytokines and adhesion molecules in endothelial cells in culture. This study evaluated the effects of Avns of oats on atherosclerosis in Ldlr -/- mice, one of the most commonly used atherosclerosis mouse models with their similar cholesterol distributions to humans. The Ldlr -/- mice were fed a low fat, high fat, high fat containing regular oat brans with low levels of Avns (HFLA), or high fat containing regular oat brans with high levels of Avns (HFHA) diet. After 16 weeks of intervention, blood cholesterol and extent of aortic lesions were evaluated. We found that both oat-based diets reduced high fat diet-induced atheroma lesions in the aortic valve (p < 0.01). Furthermore, the effects of oat-based diets are more profound in HFHA mice than mice fed HFLA. Total plasma cholesterol levels were similarly reduced in both oat-supplemented mice. We concluded that oat bran diets reduce atheroma lesions and higher levels of Avns further reduce aortic lesions compared to regular oat bran. These preliminary in vivo data indicate that consumption of oats bran, with high Avns, has demonstrable beneficial effects on prevention of cardiovascular disease.

The ability to recover to original states after disturbances makes macroinvertebrates useful tools for assessing the impacts of pesticides. Many studies showed that direct exposure to pesticides decreases macroinvertebrate richness and alters their composition. The main objective of this study was to assess recovery patterns in macroinvertebrate communities after pesticide application in irrigated rice fields. We analyzed short-term temporal dynamics of macroinvertebrate communities after application of the herbicides bispyribac-sodium and clomazone and the insecticide chlorantraniliprole, over the rice-growing season in southern Brazil. We selected three conventional rice fields and the recovery of macroinvertebrate communities was also compared with three adjacent natural ponds. The study was developed from November 2011 to February 2012 (rice-growing season). Five macroinvertebrate collections were carried out 3, 7, 14, 38, and 60 days after pesticide application (November 25). Rice fields showed lower richness and abundance than ponds in the period immediately after pesticide application, and recovery rates in the richness of macroinvertebrate communities were more conspicuous as pesticide residuals dissipated from the fields. Macroinvertebrate community structure in rice fields also became more similar to natural ponds as pesticide traces were scarcer. However, macroinvertebrate abundance patterns were not related to pesticide concentrations in the fields. Our results supported the general hypothesis on the negative effects of pesticide application on macroinvertebrate community in irrigated rice fields, although other environmental features (e.g., length of the flooded period) also contributed to explain temporal dynamics in the macroinvertebrate communities from irrigated rice fields.

As a potent drug used to improve the neurodegenerative conditions, there is few information about the brain tissue distribution of tranilast by now. In this study, a novel sensitive LC-MS/MS method has been developed and validated to determine tranilast in rat brain tissue samples. The calibration curve showed good linearity ranged from 2.140 to 428.0ng·mL -1 . The method was fully validated and successfully applied in the brain tissue distribution study of tranilast in rats, which had never been reported in detail by now. Furthermore, a rapid LC-MS/MS method with a short run time of 3min was developed and validated for the determination of tranilast in rat plasma and the application to a pharmacokinetic study of tranilast in rats. After oral dosage of 10.5mg·kg -1 tranilast, the maximum plasma concentration (C max 1 ) of tranilast was (18.59±5.40) μg·mL -1 at (0.667±0.408) h while the area under the curve (AUC 0-24 ) was (54.87±14.13) μg·h·mL -1 with the elimination half-life of (2.93±0.41) h. The ratio calculated by dividing the concentration of tranilast in brain with the concentration of tranilast in the plasma, was (0.6042%±0.0572%), (0.7484%±0.0883%), (0.5914%±0.0416%) and (0.3830%±0.1632%) at 0.167, 0.5, 2 and 8h, respectively. The results showed that tranilast with fast absorption could penetrate the rat brain blood barrier after oral gavage. The obtained data also showed that tranilast could be quickly distributed and eliminated in brain tissue., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Effective, selective, precise and accurate liquid chromatographic analytical methods for the analysis of a novel chlorantraniliprole insecticide in technical and formulation (coragen, 20% SC) have been optimized and validated. Eight methods were designed based on different mobile phases, temperature and two HPLC columns. The mobile phase consists of two mixtures (acetonitrile:water, 70:30 and methanol:water, 70:30) with 25 or 40ºC. HPLC analysis of chlorantraniliprole was carried out at a wavelength of 260 nm, with a flow rate of 0.8 mL/min. The calibration curves showed a good linear relationship (R 2 ˃ 0.99) in the injected quantities ranged from 0.0125 to 1.00 μg. Limit of detection (LOD) was found to be 3.94 to 14.56 ng and from 5.95 to 12.93 ng using the analytical methods I to IV by MicroPack CN-10 and V-VIII by ZORBAX Eclips Plus C18 columns, respectively, based on SDslope values. ZORBAX Eclips Plus C18 column with method VI was the best one (R 2 = 1.00 and RSD = 0.30), short retention time (4.936 min), high theoretical plates per column (65457.15) compared to others and LOD = 6.49 ng. The accuracy of the best method was demonstrated by recovery rates of 83.04% to 98.50% for grape samples supplemented with 5, 10 and 50 mg chlorantraniliprole/kg.

We measured the residual amounts of chlorantraniliprole in various vegetables and fruits. Sample solutions were prepared according to our routine procedure based on the QuEChERS method and analyzed by LC-MS/MS. Performance characteristics were evaluated for 8 kinds of food samples by means of recovery tests of 5 replicates at the concentration of 10 ng/g. Recoveries and RSDs (％) ranged from 50.2 to 93.4％ and from 2.1 to 9.7％, respectively. Application of this method to survey 207 vegetables and 163 fruits gave detection rates of 8.2 and 1.2％, respectively. In vegetables, detection rates were high in okra (4 out of 10 samples), paprika (4 out of 23 samples) and tomato (2 out of 6 samples), and leaf vegetables such as lettuce, mizuna, spinach and wrinkled greens also contained high concentrations of chlorantraniliprole. The highest residual concentration was 571 ng/g in mizuna. The samples containing chlorantraniliprole seemed to be mainly from Asian countries, including samples of domestic Japanese origin. However, none of them contained more than the MRL, which suggests that the use of chlorantraniliprole has been properly controlled.

Four simple, accurate, sensitive and economic Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopic (ATR-FTIR) methods have been developed for the quantitative estimation of some non-steroidal anti-inflammatory drugs. The first method involves the determination of Etodolac by direct measurement of the absorbance at 1716cm -1 . In the second method, the second derivative of the IR spectra of Tolfenamic acid and its reported degradation product (2-chlorobenzoic acid) was used and the amplitudes were measured at 1084.27cm -1 and 1056.02cm -1 for Tolfenamic acid and 2-chlorobenzoic acid, respectively. The third method used the first derivative of the IR spectra of Bumadizone and its reported degradation product, N,N-diphenylhydrazine and the amplitudes were measured at 2874.98cm -1 and 2160.32cm -1 for Bumadizone and N,N-diphenylhydrazine, respectively. The fourth method depends on measuring the amplitude of Diacerein at 1059.18cm -1 and of rhein, its reported degradation product, at 1079.32cm -1 in their first derivative spectra. The four methods were successfully applied on the pharmaceutical formulations by extracting the active constituent in chloroform and the extract was directly measured in liquid phase mode using a specific cell. Moreover, validation of these methods was carried out following International Conference of Harmonisation (ICH) guidelines., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Ginseng is a valuable herb, the roots of which have been consumed for medicinal use since ancient times in Asian countries. Currently, its cultivation in China is conducted in either forests or non-forest areas. In this study, we investigated the dissipation and residues of the diamide insecticide chlorantraniliprole (CAP) in ginseng ecosystems in these two cultivation environments. The half-life of CAP in ginseng leaves was calculated to be 16.5 days in non-forest areas and 23.9 days in forests, while the half-life of CAP in the soil under non-forest and forest cultivation was 33.0 and 53.3 days, respectively. The relatively long persistence of CAP in ginseng leaves and soil could be attributed to the unique cultivation techniques of ginseng, which prevents exposure to direct sunlight irradiation and rainfall. The residual amounts of CAP in ginseng leaves, roots, and soil in non-forest areas were 0.168, 0.011, and 0.013 mg kg -1 21 days after CAP application at the maximum label-allowed dosage and frequency versus 0.564, 0.013, and < 0.005 mg kg -1 in forests. CAP application strategies for the control of Lepidoptera pests such as armyworms, and the safety of harvested ginseng roots are recommended for ginseng cultivated in forests and non-forest areas based on the results of the CAP residue experiments.

Chlorantraniliprole (CAP) is a newly developed insecticide widely used in rice fields in China. There has been few studies evaluating the toxicological effects of CAP on soil-associated microbes. An 85-day microcosm experiment was performed to reveal the dissipation dynamics of CAP in three types of paddy soils in subtropical China. The effects of CAP on microbial activities (microbial biomass carbon-MBC, basal soil respiration-BSR, microbial metabolic quotient-qCO 2 , acid phosphatase and sucrose invertase activities) in the soils were periodically evaluated. Microbial phospholipid fatty acid (PLFA) analysis was used to evaluate the change of soil microbial community composition on day 14 and 50 of the experiment. CAP residues were extracted using the quick, easy, cheap, effective, rugged, and safe (QuChERS) method and quantification was measured by high performance liquid chromatography (HPLC). The half-lives (DT 50 ) of CAP were in the range of 41.0-53.0 days in the three soils. The results showed that CAP did not impart negative effects on MBC during the incubation. CAP inhibited BSR, qCO 2 , acid phosphatase and sucrose invertase activities in the first 14 days of incubation in all the soils. After day 14, the soil microbial parameters of CAP-treated soils became statistically at par with their controls. Principal component analysis (PCA) determining abundance of biomarker PLFAs indicated that the application of CAP significantly changed the compositions of microbial communities in all three paddy soils on day 14 but the compositions of soil microbial communities recovered by day 50. This study indicates that CAP does not ultimately impair microbial activities and microbial compositions of these three paddy soil types., (Copyright © 2017 Elsevier Inc. All rights reserved.)

The mobility of two relatively new antranilic diamide insecticides, cyanantraniliprole (CY) and cholantraniliprole (CH) in soil was examined, by means of disturbed columns loaded with a typical semiarid Mediterranean soil (Calcaric fluvisol) under laboratory conditions. Both insecticides appeared in leachates, with 52% of CY and 41% of CH of the initial mass added (1 µg g -1 ) present. For CY, 21% and 19% were recovered from the upper and bottom layers of the soil, respectively, while for CH, 33% and 22% were recovered from the upper and bottom layers respectively. Based on the calculated half-lives (29 and 27 days for CY and CH, respectively) and their log K OC (about 2.5 for both), the calculated Groundwater Ubiquity Score (GUS) index was higher than 5 for both, indicating they have the potential to leach. Two transformation products, C 13 H 9 Cl 2 N 2 O (IN-ECD73) and C 19 H 12 BrClN 6 O (IN-J9Z38) corresponding to the degradation of CH and CY, respectively were also identified and detected in leachates and soil.

Yersiniabactin (Ybt) is a mixed nonribosomal peptide-polyketide natural product that binds a wide range of metals with the potential to impact processes requiring metal retrieval and removal. In this work, we substantially improved upon the heterologous production of Ybt and an associated anthranilate analog through systematic screening and optimization of culture medium components. Specifically, a Plackett-Burman design-of-experiments methodology was used to screen 22 components and to determine those contributing most to siderophore production. L-cysteine, L-serine, glucose, and casamino acids significantly contributed to the production of both compounds. Using this approach together with metabolic engineering of the base biosynthetic process, Ybt and the anthranilate analog titers were increased to 867 ± 121 mg/L and 16.6 ± 0.3 mg/L, respectively, an increase of ∼38 and ∼79-fold relative to production in M9 medium. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:1193-1200, 2017., (© 2017 American Institute of Chemical Engineers.)

Chlorantraniliprole (CAP) 0.03% granule insecticide-fertilizer is a novel formulation that can not only improve the yield of sugarcane, but can also effectively control sugarcane borer for a long period. The present study was carried out to study the persistence pattern of CAP on sugarcane, sugarcane plants, and soil. The residues of CAP were estimated using liquid chromatography with tandem mass spectrometry (LC-MS/MS). Following application of CAP 0.03% granule insecticide-fertilizer at 112.5 and 168.75 g active ingredient (a.i.)/ha, the final residues of CAP in soil were 0.008-0.053 mg/kg at sites in Guizhou and Guangxi; residual tests of CAP at both sites after 2 years showed that the final residue of CAP in sugarcane was lower than 0.011 mg/kg, which was lower than the maximum residue levels (MRL) set by China (0.05 mg/kg). The half-lives of CAP in soil were from 8.89 to 12.38 days at the recommended dose of 168.75 g a.i./ha at sites in Guizhou and Guangxi. The maximum CAP residues in sugarcane plants in Guizhou were obtained on the seventh day; the residual concentrations were 0.222 and 0.156 mg/kg in 2015 and 2016, respectively. The maximum CAP residues in sugarcane plants in Guangxi were obtained on the fifth day and the residual concentrations were 0.041 and 0.020 mg/kg in 2015 and 2016, respectively.

Herein is reported the separation and identification of a previously unknown imidazoline by-product originating from the fluorescent labeling procedure when applied to enzymatically released N-linked glycans of a human IgG1. The imidazoline by-product was generated via the reductive amination procedure with either sodium cyanoborohydride or 2-picoline borane. Using ultra performance liquid chromatography (UPLC) in conjunction with hydrophilic interaction-based chromatography (HILIC), the 2-aminobenzoic acid (2-AA)-labeled glycans were well-resolved from imidazoline by-products to facilitate direct identification utilizing electrospray ionization mass spectrometry (ESI-MS) with fragmentation. It was found that this minor species (∼2%) was 18.0105u less than the neighboring peak GlcNAc 2 Man 3 GlcNAc 2 Fuc peak, abbreviated as A2G0F at 1582.5899u. While this mass loss corresponds to the mass of a water molecule, the molecular location of loss of water was not straightforward in consideration of the biantennary A2G0F structure. Model studies were carried out using A2G0F standard and N-acetyllactosamine to identify the impurity as an imidazoline ring structure located at the reducing end of the glycan as confirmed by high resolution mass fragment ions. Imidazoline content decreased when the reductant concentration was increased. To conclude, evidence for the imidazoline structure was accomplished through high resolution, high accuracy mass spectrometry (HRAM), and experiments showing chemical susceptibility and isotopically labeled tracers. This study is the first to identify these minor species which likely impact all N-acetylglucosamine-type N-linked glycans from biologics., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Avenanthramides (AVNs) are a family of nitrogen-containing phenolic compounds produced in oat; AVN 2c, 2p, and 2f are the three major members. An LC-MS/MS method was developed, with the limit of detection (LOD) and the limit of quantitation (LOQ) being, respectively, 0.29ng/mL and 1.96ng/mL for AVN 2c, 0.24ng/mL and 0.60ng/mL for AVE 2p, and 0.42ng/mL and 2.2ng/mL for AVN 2f. The method was validated in oat-containing hot cereal and snack bar samples. The recovery of AVN 2c, 2p, and 2f from these two oat products was 95-113%, and the relative standard deviations ranged from 5% to 9%. This method was used to evaluate oat products and raw oat samples. The effects of location and variety on AVN composition were investigated. The method presented here provides a novel and rapid tool to quantitate the abundance of AVN 2c, 2p, and 2f in oat-containing products., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Whole grains are a rich source of several classes of phytochemicals, such as alkylresorcinols, benzoxazinoids, flavonoids, lignans, and phytosterols. A high intake of whole grains has been linked to a reduced risk of some major noncommunicable diseases, and it has been postulated that a complex mixture of phytochemicals works in synergy to generate beneficial health effects. Mass spectrometry, especially when coupled with liquid chromatography, is a widely used method for the analysis of phytochemicals owing to its high sensitivity and dynamic range. In this review, the current knowledge of the mass spectral properties of the most important classes of phytochemicals found in cereals of common wheat, barley, oats, and rye is discussed.

The Poaceae is a large taxonomic group consisting of approximately 12,000 species and is classified into 12 subfamilies. Gramine and benzoxazinones (Bxs), which are biosynthesized from the tryptophan pathway, are well-known defensive secondary metabolites in the Poaceae. We analyzed the presence or absence of garamine and Bxs in 64 species in the Poaceae by LC-MS/MS. We found that Hordeum brachyantherum and Hakonechloa macra accumulated gramine, but the presence of gramine was limited to small groups of species. We also detected Bxs in four species in the Pooideae and six species in the Panicoideae. In particular, four species in the Paniceae tribe in Panicoideae accumulaed Bxs, indicating that this tribe is a center of the Bx distribution. Bxs were absent in the subfamilies other than Pooideae and Panicoideae. These findings provide an overview of biased distribution of gramine and Bxs in Poaceae species.

Analysis of pesticide residues in irrigated rice grains is important for food security. In this study, we analyzed accelerated solvent extraction (ASE) conditions for the extraction of thiamethoxam and chlorantraniliprole insecticides from rice hulls, rice bran, and polished rice grains. Several variables, including extraction solvent, extraction temperature, extraction pressure, cell size, static extraction time, and sample concentration, were investigated. The average recoveries of the three matrixes were between 89.7 and 109.7% at the fortification level of 0.75 mg/kg. The optimum ASE operating conditions were acetonitrile (100%) as extraction solvent, extraction temperature of 75°C for rice hulls and 100°C for rice bran and polished rice grains, extraction cell pressure of 10.3 MPa, 22 mL cell size, and two extraction cycles. The total extraction time was approximately 25 min. The extracted volume was evaporated to dryness and the residues were redissolved in 2 mL acetonitrile after 1 min of vortex-shaking. Thiamethoxam and chlorantraniliprole were analyzed by ultra-HPLC with tandem MS. In conclusion, ASE in rice hulls, rice bran, and polished rice grains offers the possibility of a fast and simple method for obtaining a quantitative extraction of the studied pesticides.

This paper shows that the aging and death of nematodes, accompanied by the ignition of a blue glow under fluorescent microscopy, are not directly linked to any lipofuscin (aging pigment), nor with the anthranilic acid (a product of degradation of tryptophan residues of proteins). The main contribution in the blue flash of the dying nematodes belongs to parasitic light, scattered on the cuticle and bodies of the worm. The main contribution in the blue region at spectrofluorometry of homogenates, obtained from nematodes, really gives anthranilic acid. However, the content of anthranilic acid, measured by spectrofluorimetry, in adult nematodes is lower than that in the young ones. Artificial aging of nematodes by moderate heating revealed no accumulation of anthranilate and no loss of tryptophan, from which it must be formed. Thus, it is hardly lipofuscin or anthranilic acid. The cause of aging and death of nematodes is the formation of strong cross-links between proteins. This is supported by data on tryptophan fluorescence and light scattering of homogenates: the old worms show a large number of denaturated proteins and large protein particles with a strong cross-links, which are not destroyed be detergent.

Oats (A. sativa L.) have an important and positive role in human diet and health. The health benefits of oats are attributed to its multifunctional characteristic and nutritional profile, being an important source of soluble dietary fiber, well-balanced proteins, unsaturated fatty acids, vitamins, essential minerals, and a good source of natural antioxidants. These antioxidants include the avenanthramides (Avns) and avenalumic acids, which are unique to oats among cereals. High-performance liquid chromatography allows a simultaneous quantification of free amino acids and biogenic amines in oat samples as their OPA/FMOC-CL (o-phthalaldehyde/9-fluorenylmethoxycarbonyl chloride) derivatives. In addition, an ultra-performance liquid chromatography/mass spectrometry method was developed to quantify and characterize avenanthramides contained in oat samples.