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Methoxyfenozide and metaflumizone are insecticides used on Chinese broccoli to prevent insects and increase yield. However, the residues are potentially harmful to the environment and consumers. In this study, the quick, easy, cheap, effective, rugged, safe method with high-performance liquid chromatography with tandem mass spectrometry was modified and validated for determination of methoxyfenozide and metaflumizone in Chinese broccoli. The clean-up efficiency of different sorbents including C 18 , primary secondary amine, graphitized carbon black, and carbon nanofiber was compared. Recoveries of the validated method were 71.8-94.6% with relative standard deviations of 1.5-3.2% and the limits of quantification were 0.01 and 0.005 mg/kg for methoxyfenozide and metaflumizone, respectively. A storage stability test showed almost no degradation of methoxyfenozide in Chinese broccoli, however, the degradation rate of metaflumizone was 22.9% after 10-wk storage at -20°C. In field trials in four producing regions, the dissipation of both methoxyfenozide and metaflumizone in Chinese broccoli was fast, with half-lives of only 1.0-5.1 and 0.7-2.5 days, respectively. Terminal residues after application of the two pesticides were all below 1.0 mg/kg after 5 days., (© 2021 Wiley-VCH GmbH.)

Application of pesticides in modern agriculture is a powerful permanent risk factor for public health and the natural environment. The aim of the study was a comparative hygienic assessment of soil pollution hazards by the most widely used herbicides of different chemical classes (sulfonylureas, imidazolinones, pyrimidinyl (thio) benzoates, semicarbazones). Hygienic field experiment for studying of the dynamics of residual amounts of the test substances in the soil under different climatic zones of Ukraine was conducted. Half life periods (DT50) or herbicides in soil were calculated using the method of mathematical modeling. Ecotoxicological risk of herbicides on ecosystems and ecological communities was determined. It was established that bispyribac-sodium (pyrimidinyl (thio) benzoates) and imidazolinones are persist the longest time in soil and most rapidly degradable is diflufenzopyr (semicarbazone); ecotoxicological risk of the studied herbicides for terrestrial biocenoses of Ukraine by 4-6 orders of magnitude lower than dihlordifeniltrihlormetilmetan (DDT).

Metaflumizone is a novel sodium channel blocker insecticide of semicarbazone class. It provides good to excellent control of most of the economically important lepidopterous pests and certain pests in the orders Coleoptera, Hemiptera, Hymenoptera, Diptera, Isoptera, and Siphonaptera. Although metaflumizone has been marketed globally for several years and got registered in India in the year 2009, specifically for the control of DBM on cabbage, to our knowledge, no food safety aspects of metaflumizone residue on cabbage have ever been reported in the literature in India or elsewhere. The present study was undertaken to evaluate the persistence of metaflumizone on cabbage and soil, vis-a-vis its risk assessment, following two spray applications of metaflumizone 220 SC (Verismo®), each at recommended and double dose of 200 and 400 g a.i. ha(-1) respectively. Initial residue deposits of metaflumizone on cabbage were 0.46 and 0.51 mg kg(-1) at recommended and 0.76 and 0.85 mg kg(-1) at double the recommended dose following the first spray and second spray application. The residues persisted beyond 5 days from both the treatments and dissipated with the half-life ranging from 1.7-2.1 days. Initial deposits of metaflumizone on soil ranged from 0.23-0.37 mg kg(-1) and degraded with a half life ranging from 4.0-4.8 days. No degradation product of metaflumizone was detected in cabbage and soil at any point of time. Soil samples collected from the treated field after 7 days were free from any residue of metaflumizone or its metabolites. A pre-harvest waiting period of 3 days after application was suggested based on calculation of theoretical maximum daily intake.

A liquid chromatography-mass spectrometry method to detect semicarbazide and lactose semicarbazone in milk was developed as part of a programme to set up methods for detecting the economically motivated adulteration of raw milk with nitrogen-containing compounds. The detection of semicarbazide was hampered by that fact that this compound tended to give broad, poor intensity peaks in the hydrophobic interaction chromatographic method employed. When spiked into milk at levels of 20-200 ppm, semicarbazide either partially or completely reacted with the matrix, which both increased the limit of detection of the method and made the setting of a threshold by using low level spikes almost impossible. Thus using lactose semicarbazone as a marker for semicarbazide addition to milk was investigated. Lactose semicarbazone was detected in semicarbazide-spiked milk, and its identity was confirmed by fragmentation analysis and comparison with the synthesised compound. The level of lactose semicarbazone correlated with the amount of semicarbazide added to the milk, and the acidic conditions employed in the extraction method appeared to enhance the sensitivity of detection by driving the semicarbazone-forming reaction towards completion. Thus lactose semicarbazone can be used as a marker for the addition of semicarbazide to milk; however, both compounds should be monitored during surveys looking for the semicarbazide adulteration of milk., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Soil is a major sink for the bulk of globally used pesticides. Hence, fate of pesticides in soil under the influence of various biotic and abiotic factors becomes important for evaluation of stability and safety. This paper presents the impact of varying moisture, light, temperature, atmospheric CO(2) level, soil type and soil sterilization on degradation of metaflumizone, a newly registered insecticide in India. Degradation of metaflumizone in soil followed the first order reaction kinetics and its half life values varied from ~20 to 150 d. Under anaerobic condition, degradation of metaflumizone was faster (t(½) 33.4 d) compared to aerobic condition (t(½) 50.1 d) and dry soil (t(½) 150.4 d). Under different light exposures, degradation was the fastest under UV light (t(½) 27.3 d) followed by Xenon light (t(½) 43 d) and dark condition (t(½) 50.1 d). Degradation rate of metaflumizone increased with temperature and its half life values ranged from 30.1 to 100.3d. Elevated atmospheric CO(2) level increased the degradation in soil (t(½) 20.1-50.1 d). However, overall degradation rate was the fastest at 550 ppm atmospheric CO(2) level, followed by 750 ppm and ambient level (375 ppm). Degradation of metaflumizone was faster in Oxisol (pH 5.2, Total Organic Carbon 1.2%) compared to Inceptisol (pH 8.15, TOC 0.36%). In sterile soil, only 5% dissipation of initial concentration was observed after 90 d of sampling. Under various conditions, 4-cyanobenzoic acid (0.22-1.86 mg kg(-1)) and 4-trifluoromethoxy aniline (0.21-1.23 mg kg(-1)) were detected as major degradation products., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The degradation behavior of metaflumizone was studied in a rice field ecosystem, and a simple and reliable analytical method was developed for determination of metaflumizone in soil, rice straw, paddy water and brown rice. Metaflumizone residues were extracted from samples with acetonitrile. The extract was cleaned up with QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method, and determined by liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). The average recoveries of metaflumizone were 75.2-105.1 percent from soil, rice straw, paddy water and brown rice. The relative standard deviations were less than 15 percent. The limits of quantitation (LOQs) of metaflumizone were 3.0μg/L for paddy water and 3.0μg/kg for other samples. The results of the kinetic study of metaflumizone residue showed that metaflumizone degradation in soil, water and rice straw coincided with C=0.08564e(-0.0505t), C=0.04984e(-0.1982t), C=2.2572e(-0.1533t), respectively; the half-lives were about 13.7d, 3.5d, and 4.5d, respectively. The final residues of metaflumizone on brown rice were lower than maximum residue limit (MRL) of 0.05mg/kg after 28d Pre-Harvest Interval (PHI) at the recommended dosage. Therefore, a dosage of 450mLa.i.ha(-1) with 28 days before harvest was recommended, which could be considered as safe to human beings and animals., (Copyright © 2012 Elsevier Inc. All rights reserved.)

Two novel photochromic compounds, 1,3-diphenyl-4-benzal-5-hydroxypyrazole 4-phenylsemicarbazone (1 a) and 1,3-diphenyl-4-(4-nitrobenzal)-5-hydroxypyrazole 4-phenylsemicarbazone (2 a), are synthesized and characterized by elemental analysis, mass spectrometry, FTIR spectroscopy, and (1)H NMR spectroscopy. Their properties, including photochromic behavior, fluorescence properties, and thermal bleaching kinetics, are investigated. The results show that the two compounds exhibit improved photochromic performance in coloration and thermal bleaching rates, excellent photostability, high fatigue resistance, and reversible fluorescence switching properties in the solid state in comparison to reported pyrazolone thiosemicarbazones. The thermal bleaching process obeys first-order kinetics. Bleaching of powders at 130 °C is completed within 90 s for 1 b (the colored isomer of 1 a) and 150 s for 2 b (the colored isomer of 2 a). The activation energy for the thermal bleaching process is determined to be 69 and 95 kJ mol(-1) , with frequency factors of 9.5×10(7) and 9.4×10(10) s(-1) for 1 b and 2 b, respectively., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Sphingosine-1-phosphate (S1P) is a sphingolipid signaling molecule crucial for cell survival and proliferation. S1P-mediated signaling is largely controlled through its biosynthesis and degradation, and S1P lyase (S1PL) is the only known enzyme that irreversibly degrades sphingoid base-1-phosphates to phosphoethanolamine and the corresponding fatty aldehydes. S1PL-mediated degradation of S1P results in the formation of (2E)-hexadecenal, whereas hexadecanal is the product of dihydrosphingosine-1-phosphate (DHS1P) degradation. Fatty aldehydes can undergo biotransformation to fatty acids and/or alcohols, making them elusive and rendering the task of fatty aldehyde quantitation challenging. We have developed a simple, highly sensitive, and high-throughput protocol for (2E)-hexadecenal quantitation as a semicarbazone derivative by liquid chromatography-electrospray ionization-tandem mass spectrometry. The approach was applied to determining S1PL activity in vitro with the ability to use as low as 0.25μg of microsomal protein per assay. The method is also applicable to the use of total tissue homogenate as the source of S1PL. A correction for (2E)-hexadecenal disappearance due to its biotransformation during enzymatic reaction is required, especially at higher protein concentrations. The method was applied to confirm FTY720 as the inhibitor of S1PL with an IC₅₀ value of 52.4μM., (Copyright © 2010 Elsevier Inc. All rights reserved.)

Objective: A series of 4-aryl substituted semicarbazones of levulinic acid (4-oxo pentanoic acid) was designed and synthesized to meet the structural requirements essential for anticonvulsant activity., Methods: All the compounds were evaluated for anticonvulsant activity. Anticonvulsant activity was determined after intraperitoneal (i.p.) administration to mice by maximal electroshock (MES) and subcutaneous metrazol (ScMet) induced seizure methods and minimal motor impairment was determined by rotorod test., Results: A majority of the compounds exhibited significant anticonvulsant activity after intraperitoneal administration. In the present study 4-(4'-fluoro phenyl) levulinic acid semicarbazone emerged as the most active molecule, showing broad spectrum of activity with low neurotoxicity. Unsubstituted levulinic acid semicarbazone was found to be inactive in all the screens., Conclusion: The results obtained validate the hypothesis that presence of an aryl group near the semicarbazone moiety is essential for anticonvulsant activity. The results also indicate that the hydrophilic-hydrophobic site can accommodate hydrophilic groups.

The evolution of the insecticidal pyrazoline moiety that was originally discovered in 1972 has led to the discovery of a new crop insecticide, indoxacarb, which is the first commercialized pyrazoline-type sodium-channel blocker. Both monocyclic and fused-tricyclic pyrazolines and pyridazines, as well as structurally related semicarbazones were examined prior to the discovery of analogous tricyclic oxadiazines which had similarly high activity as well as favorable environmental dissipation rates and low toxicity to non-target organisms. The eventual leading candidate, DPX-JW062, was originally obtained as a racemic molecule, but a chiral synthesis was developed which produces material that is 50% ee in the insecticidal (+)-S-enantiomer (DPX-MP062, indoxacarb).

Assays are proposed for sulpiride and other benzamides, vincamine and naftazone in plasma (or blood) and urine with direct UV reflectance spectrophotometry on this are applied directly on TLC along with a calibration curve on each plate. Plasma (or total blood) samples are extracted, and an internal standard is added before aplication; slopes of the obtained calibration curves do not change significantly from plate to plate, thus allowing several determinations on the same plate. The sensitivity is 2 microgram in a 1-ml sample (amount applied 30 ng) for sulpiride and related compounds and about the same for vincamine. Naftazone is determined in plasma with simultaneous reflectance and transmittance spectrophotometric measurements at 520 nm on chromatoplates sprayed with lead acetate, the sensitivity reached is 10 ng in a 1-ml sample (amount applied 0.5 ng). For all drugs studied, the proposed techniques are specific, reliable and sensitive enough and can be used to perform pharmacokinetic studies in human or in animal after administration of doses in the therapeutic range.