chlorantranilipole and cyantraniliprole

The CncC pathway regulates the expression of multiple detoxification genes and contributes to the detoxification and antioxidation in insects. Many studies have focused on the impacts of plant allelochemicals on the CncC pathway, whereas studies on the effects of pesticides on key genes involved in this pathway are very limited. In this study, the effects of different types of commonly used insecticides on the transcripts of CncC, Keap1, and Maf and multiple detoxification genes of Helicoverpa armigera were evaluated using real-time quantitative polymerase chain reaction. The results showed that 8 insecticides (bifenthrin, λ-cyhalothrin, chlorantraniliprole, cyantraniliprole, spinosad, indoxacarb, chlorfenapyr, tolfenpyrad, and thiacloprid) significantly induced the expression of CncC and 4 insecticides (cypermethrin, acetamiprid, thiacloprid, and indoxacarb) suppressed the expression of Keap1 both at 24 h and 48 h; meanwhile, the expression levels of Maf were induced by 5 insecticides (fenvalerate, chlorantraniliprole, cyantraniliprole, lufenuron, and tolfenpyrad) at 24 h or 48 h. Multiple detoxification genes, especially cytochrome P450s genes, showed different up-regulation after bifenthrin, λ-cyhalothrin, chlorantraniliprole, cyantraniliprole, indoxacarb, and spinosad treatment for 48 h. Our results suggest that the CncC pathway and detoxification genes can be activated by different insecticides in H. armigera. These results establish a foundation for further studies on the relationship between the CncC pathway and the detoxification genes in H. armigera.

Topics: Animals; Insecticides; Kelch-Like ECH-Associated Protein 1; Moths; NF-E2-Related Factor 2

The common armyworm Mythimna convecta is an important pest of pastures and graminaceous crops in Australia, but materials currently registered for its control are limited to broad-spectrum compounds incompatible with integrated pest management (IPM) systems. In this study we assessed the response of M. convecta larvae to four alternative compounds using topical and dietary bioassays.. Emamectin benzoate [LC. Both emamectin benzoate and chlorantraniliprole are suitable for use against M. convecta. The decision as to which of these compounds should be prioritized for further development should be based on their potential effects on beneficial species once their optimal field rates have been determined.

Topics: Animals; Australia; Insecticide Resistance; Insecticides; Ivermectin; Larva; Moths; ortho-Aminobenzoates; Oxazines; Pyrazoles; Spodoptera

Anthranilic diamide insecticides, including chlorantraniliprole (CHL), cyantraniliprole (CYA), cyclaniliprole (CYC), and tetrachlorantraniliprole (TEA), are widely used in agricultural production, resulting in potential risk to human health. In this study, we designed novel haptens for the preparation of a broad-specific monoclonal antibody (mAb) against CHL, CYA, CYC, and TEA simultaneously. The mAb 4F5 we produced belonged to the IgG1 subtype and had 50% inhibition concentration (IC

Topics: Antibodies, Monoclonal; Diamide; Fruit; Humans; Immunoassay; Vegetables

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

Topics: Brassica; Enzyme-Linked Immunosorbent Assay; Insecticides; ortho-Aminobenzoates; Pyrazoles; Soil; Soil Pollutants; Vegetables

As for developing effective integrated pest management (IPM), it is necessary to understand the sublethal effects of common insecticides on the non-target beneficial arthropods. In this lab-scale study, the sublethal effects of two anthranilic diamide insecticides chlorantraniliprole and cyantraniliprole on the populations of 7-spot ladybird Coccinella septempunctata (Coleoptera: Coccinellidae) were determined and compared using an age-stage, TWO-SEX life table and CONSUME-MSChart computer program. Cyantraniliprole at low-lethal concentrations of 1 and 10 mg L

Topics: Animals; Aphids; Coleoptera; Insecticides; Larva; ortho-Aminobenzoates; Predatory Behavior; Pyrazoles

The translocation of chemical insecticides in corn plants could enhance the control of Spodoptera frugiperda, based on their application form. Chlorantraniliprole and cyantraniliprole were applied via seed treatment and foliar spray in corn (VE and V3) to characterize the systemic action of both molecules in leaves that appeared after application. Bioassays with S. frugiperda and chemical quantification in LC-MS/MS confirmed the absorption and upward translocation of chlorantraniliprole and cyantraniliprole by xylem to new leaves. Both insecticides caused the mortality of larvae up to stage V6 (57.5±9.5% for chlorantraniliprole and 40±8.1% for cyantraniliprole), indicating the translocation of insecticides into leaves of corn plants when applied via seed treatment. However, the translocation of chlorantraniliprole and cyantraniliprole from sprayed leaves to new leaves was not observed, regardless of the stage of application plus the next first, second and third stages. An increased dosage of cyantraniliprole did not influence on its translocation in plant tissues, however, it influenced on the present amount of active ingredient. The application of chlorantraniliprole and cyantraniliprole in seed treatment is an important alternative for integrated pest management. The absorption and redistribution capacity of chlorantraniliprole and cyantraniliprole throughout the plant confer a prolonged residual action with satisfactory control of S. frugiperda.

Topics: Animals; Insect Control; Insecticides; Larva; ortho-Aminobenzoates; Plant Leaves; Pyrazoles; Seeds; Spodoptera; Zea mays

Diamide resistant phenotypes have evolved in the field and the resistance has been attributed to target-site mutations in some lepidopteran pests. In this study, we documented the resistance status of Chilo suppressalis to chlorantraniliprole during 2016-2018 in seven provinces of China. To investigate the possible role of target-site mutations as known from lepidopterans, we sequenced respective domains of the RyR gene of C. suppressalis with different levels of diamide resistance. The results revealed that I4758M (corresponding to I4790M in P. xylostella), Y4667D/C (numbered according to C. suppressalis), G4915E (corresponding to G4946E in P. xylostella), and one novel Y4891F (numbered according to C. suppressalis) RyR target-site mutations were present. The contribution of these mutations was further investigated by diamide toxicity bioassays with eight genome modified Drosophila melanogaster lines. The study showed that genome modified flies bearing the Y4667D mutation (corresponding to the Y4667D and I4758M simultaneous mutation in C. suppressalis) exhibited high resistance ratios to chlorantraniliprole (1542.8-fold), cyantraniliprole (487.9-fold) and tetrachlorantraniliprole (290.1-fold). The M4758I and G4915E simultaneous mutations (corresponding to single G4915E mutation in C. suppressalis) showed high resistance ratios to chlorantraniliprole (153.1-fold) and cyantraniliprole (323.5-fold), and relatively low resistance to flubendiamide (28.9-fold) and tetrachlorantraniliprole (25.2-fold). These findings suggest that multiple point mutations in RyR confer diamide resistance of C. suppressalis. The results contribute to a better understanding of insect diamide resistance mechanisms and provide insights on the impact of RyR target-site mutations in insects.

Topics: Amino Acid Sequence; Animals; Benzamides; CRISPR-Cas Systems; Drosophila melanogaster; Insect Proteins; Insecticide Resistance; Insecticides; Moths; Mutation; ortho-Aminobenzoates; Pyrazoles; Ryanodine Receptor Calcium Release Channel; Sequence Alignment; Sulfones

The effect of temperature on the toxicities of four diamide insecticides (chlorantraniliprole, cyantraniliprole, flubendiamide, tetraniliprole) against three lepidopteran insects (Helicoverpa armigera, Plutella xylostella, Athetis lepigone) were determined from 15 to 35 °C by exposing third-instar larvae to dip-treated cabbage leaf. The results indicated that increase in temperature led to an increase significantly and regularly in the toxicities of the four diamide insecticides against P. xylostella and H. armigera, but not for A. lepigone. The temperature coefficients (TCs) of the four diamide insecticides increased from 15 to 35 °C. Tetraniliprole for H. armigera (+825.83), chlorantraniliprole for P. xylostella (+315.65) and cyantraniliprole for H. armigera (+225.77) exhibited high positive TCs. For A. lepigone, temperature had a positively weak or no effect on the toxicities of most of the diamide insecticides from 20 to 30 °C, but a higher effect from 30 to 35 °C. In addition, the toxicities of chlorantraniliprole, cyantraniliprole and tetraniliprole all decreased from 15 to 20 °C. This study can guide pest managers in choosing suitable ambient field temperature when spraying diamide insecticides against lepidopteran insects.

Topics: Animals; Benzamides; Diamide; Insecta; Insecticides; Larva; Moths; ortho-Aminobenzoates; Pyrazoles; Sulfones; Temperature; Toxicity Tests

Topics: Animals; Benzamides; Binding Sites; Biological Assay; Fluorescent Dyes; Kinetics; Moths; ortho-Aminobenzoates; Pyrazoles; Reproducibility of Results; Ryanodine Receptor Calcium Release Channel; Sulfones

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

Topics: Agaricales; Benzamides; Chromatography, High Pressure Liquid; Diamide; Food Analysis; Insecticides; ortho-Aminobenzoates; Pyrazoles; Sulfones; Tandem Mass Spectrometry

The diamondback moth Plutella xylostella is a major destructive pest of Brassica worldwide. P. xylostella has evolved resistance to nearly all commercial insecticides used for its control, including the most recent chemical class, diamide insecticides. Several studies show that the G4946E and I4790M mutations of ryanodine receptor (RyR) are strongly associated with diamide resistance in insects. While the pivotal functional role of G4946E in conferring diamide resistance phenotype has confirmed by several studies in different species, no direct evidence has unambiguously confirmed the functional significance of the single I4790M mutation in diamide resistance. Here, we successfully constructed a knockin homozygous strain (I4790M-KI) of P. xylostella using CRISPR/Cas9 coupled with homology directed repair approach to introduce I4790M into RyR. When compared with the background susceptible IPP-S strain, the manipulated I4790M-KI strain exhibited moderate resistance to the phthalic acid diamide flubendiamide (40.5-fold) and low resistance to anthranilic diamides chlorantraniliprole (6.0-fold) and cyantraniliprole (7.7-fold), with no changes to the toxicities of indoxacarb and β-cypermethrin. Furthermore, the acquired flubendiamide resistance was inherited in an autosomally recessive mode and significantly linked with the I4790M mutation of RyR in this I4790M-KI strain. Our findings provide in vivo functional evidence for the causality of I4790M mutation of PxRyR with moderate levels of resistance to flubendiamide in P. xylostella, and support the hypothesis that the diamide classes have different interactions with RyRs.

Topics: Animals; Benzamides; Calcium Signaling; CRISPR-Cas Systems; Diamide; Gene Silencing; Genes, Insect; Insect Control; Insecticide Resistance; Insecticides; Moths; Mutation; ortho-Aminobenzoates; Pest Control; Pyrazoles; Ryanodine Receptor Calcium Release Channel; Sulfones

Insecticide resistance is a paradigm of microevolution, and insecticides are responsible for the strongest cases of recent selection in the genome of

Topics: Alleles; Animals; Animals, Genetically Modified; Chromosome Mapping; DNA Copy Number Variations; Drosophila melanogaster; Drosophila Proteins; Genome-Wide Association Study; Insecticide Resistance; Insecticides; Myosin-Light-Chain Kinase; ortho-Aminobenzoates; Phenotype; Pyrazoles; Survivorship; Trans-Activators; Transcriptome

Diamide insecticides are used widely against lepidopteran pests, acting as potent activators of insect Ryanodine Receptors (RyRs) and thus inducing muscle contraction and eventually death. However, resistant phenotypes have recently evolved in the field, associated with the emergence of target site resistance mutations (G4946E/V and I4790M). We investigated the frequency of the mutations found in a resistant population of Tuta absoluta from Greece (G4946V ~79% and I4790M ~21%) and the associated diamide resistance profile: there are very high levels of resistance against chlorantraniliprole (9329-fold) and flubendiamide (4969-fold), but moderate levels against cyantraniliprole (191-fold). To further investigate functionally the contribution of each mutation in the resistant phenotype, we used CRISPR/Cas9 to generate genome modified Drosophila carrying alternative allele combinations, and performed toxicity bioassays against all three diamides. Genome modified flies bearing the G4946V mutation exhibited high resistance ratios to flubendiamide (91.3-fold) and chlorantraniliprole (194.7-fold) when compared to cyantraniliprole (5.4-fold). Flies naturally wildtype for the I4790M mutation were moderately resistant to flubendiamide (15.3-fold) but significantly less resistant to chlorantraniliprole (7.5-fold), and cyantraniliprole (2.3-fold). These findings provide in vivo functional genetic confirmation for the role and relative contribution of RyR mutations in diamide resistance and suggest that the mutations confer subtle differences on the relative binding affinities of the three diamides at an overlapping binding site on the RyR protein.

Topics: Amides; Animals; Benzamides; CRISPR-Cas Systems; Drosophila melanogaster; Greece; Insecticide Resistance; Insecticides; Moths; Mutation; ortho-Aminobenzoates; Pyrazoles; Ryanodine Receptor Calcium Release Channel; Sulfones

Anthranilic diamides are an important commercial synthetic class of insecticides (IRAC Group 28) that bind to the ryanodine receptor with selective potency against insect versus mammalian forms of the receptor. The first commercialized diamide, chlorantraniliprole, has exceptional activity against lepidopteran pests. The second anthranilamide product, cyantraniliprole, has excellent cross-spectrum activity against a range of insect orders, including both lepidopteran and hemipteran pests. Here, a retrospective look is presented on the discovery of the class, along with chemistry highlights of the lead evolution to both products. © 2016 Society of Chemical Industry.

Topics: Animals; Hemiptera; Insecticides; Moths; ortho-Aminobenzoates; Pyrazoles; Ryanodine Receptor Calcium Release Channel

The diamondback moth (DBM), Plutella xylostella (L.) (Lepidoptera: Plutellidae), is a globally distributed and important economic pest. Chemical control is the primary approach to regulate populations of this pest. However, resistance to insecticides evolves following heavy and frequent use. Therefore, the insecticide resistance in field populations of P. xylostella collected from Central China from 2013 to 2014 was determined with a leaf-dipping method. Based on the results of the monitoring, P. xylostella has developed high levels of resistance to beta-cypermethrin (resistance ratio=69.76-335.76-fold), Bt (WG-001) (RR=35.43-167.36), and chlorfluazuron (RR=13.60-104.95) and medium levels of resistance to chlorantraniliprole (RR=1.19-14.26), chlorfenapyr (RR=4.22-13.44), spinosad (RR=5.89-21.45), indoxacarb (RR=4.01-34.45), and abamectin (RR=23.88-95.15). By contrast, the field populations of P. xylostella remained susceptible to or developed low levels of resistance to diafenthiuron (RR=1.61-8.05), spinetoram (RR=0.88-2.35), and cyantraniliprole (RR=0.4-2.15). Moreover, the LC50 values of field populations of P. xylostella were highly positively correlated between chlorantraniliprole and cyantraniliprole (r=0.88, P=0.045), chlorantraniliprole and spinosad (r=0.66, P=0.039), spinosad and diafenthiuron (r=0.57, P=0.0060), and chlorfenapyr and diafenthiuron (r=0.51, P=0.016). Additionally, the activities of detoxification enzymes in field populations of P. xylostella were significantly positively correlated with the log LC50 values of chlorantraniliprole and spinosad. The results of this study provide an important base for developing effective and successful strategies to manage insecticide resistance in P. xylostella.

Topics: Animals; Bacillus thuringiensis; China; Drug Combinations; Insecticide Resistance; Insecticides; Ivermectin; Macrolides; Moths; ortho-Aminobenzoates; Oxazines; Phenylthiourea; Phenylurea Compounds; Pyrazoles; Pyrethrins; Pyridines

Many vegetable insect pests are managed using neonicotinoid and pyrethroid insecticides. Unfortunately, these insecticides are toxic to many bees and natural enemies and no longer control some pests that have developed resistance. Anthranilic diamide insecticides provide systemic control of many herbivorous arthropod pests, but exhibit low toxicity to beneficial arthropods and mammals, and may be a promising alternative to neonicotinoids and pyrethroids. Anthranilic diamides may be delivered to vegetable crops via seed, in-furrow, or foliar treatments; therefore, it would be desirable to identify which application method provides high levels of pest control while minimizing the amount of active ingredient. As a case study, chlorantraniliprole and cyantraniliprole applied via the methods listed above were evaluated for managing seedcorn maggot, Delia platura (Meigen) (Diptera: Anthomyiidae), and European corn borer, Ostrinia nubilalis (Hübner) (Lepidoptera: Crambidae), in snap bean. Chlorantraniliprole and cyantraniliprole delivered as seed and in-furrow treatments reduced D. platura damage to the same level as the standard neonicotinoid seed treatment. Both diamides applied via all three methods significantly reduced O. nubilalis damage, but only the foliar application provided similar control as the standard pyrethroid spray. Results from laboratory bioassays revealed that both diamides applied as seed and in-furrow treatments caused high O. nubilalis neonate mortality up to 44 d after application. While the diamides provided equivalent control of these pests as the neonicotinoid and pyrethroid standards when applied in the same manner, chlorantraniliprole delivered as a seed treatment showed the most promise for managing both pests.

Topics: Animals; Diptera; Insect Control; Insecticides; Larva; Moths; ortho-Aminobenzoates; Phaseolus; Pyrazoles

A survey of insecticide resistance in over 150 Canadian populations of Colorado potato beetle was completed between 2008 and 2011. Three neonicotinoid and two anthranilic diamide insecticides were tested at a discriminating concentration (DC) with second-instar larvae in a leaf-disc bioassay.. The mean mortality for the imidacloprid (Admire) DC was 46-67% between 2008 and 2011 respectively. Over the 4 years, 10-46% and 26-40% of the populations were classified as resistant or showed reduced susceptibility to imidacloprid. The mean mortality for thiamethoxam (Actara) and clothianidin (Poncho/Titan) ranged from 56-76% in 2008 to 81-84% in 2010 for each insecticide respectively, indicating continuous susceptibility to clothianidin but reduced susceptibility to thiamethoxam. In 2008 and 2009, susceptibility to chlorantraniliprole (Coragen) was observed in 85% of populations. Similarly, cyantraniliprole (Cyazypyr) affected 93% of the 2009 and 74% of the 2010 populations. There was a significant (P < 0.05) and high positive correlation (R = 0.4-0.84) between the three neonicotinoids, indicating the potential for cross-resistance.. The trend observed in decreasing susceptibility for thiamethoxam and clothianidin will continue unless resistance management practices are followed.

Topics: Animals; Canada; Coleoptera; Guanidines; Imidazoles; Insecticide Resistance; Insecticides; Larva; Neonicotinoids; Nitro Compounds; ortho-Aminobenzoates; Oxazines; Pyrazoles; Thiamethoxam; Thiazoles

A reliable and sensitive isotope-labelled internal standard method for simultaneous determination of chlorantraniliprole and cyantraniliprole in fruits (apple and grape), vegetables (cucumber and tomato) and cereals (rice and wheat) using ultra-high-performance liquid chromatography-tandem mass spectrometry was developed. Isotope-labelled internal standards were effective in compensating for the loss in the pretreatment and overcoming the matrix effect. The analytes were extracted with acetonitrile and cleaned up with different kinds of sorbents. The determination of the target compounds was achieved in less than 4 min using a T3 column combined with an electrospray ionization source in positive mode. The overall average relative recoveries in all matrices at three spiking levels (10, 20 and 50 μg kg(-1)) ranged from 95.5 to 106.2 %, with all relative standard deviations being less than 14.4 % for all analytes. The limits of detection did not exceed 0.085 μg kg(-1) and the limits of quantification were below 0.28 μg kg(-1) in all matrices. The method was demonstrated to be convenient and accurate for the routine monitoring of chlorantraniliprole and cyantraniliprole in fruits, vegetables and cereals.

Topics: Chromatography, Liquid; Food Analysis; Fruit; Isotope Labeling; Molecular Structure; ortho-Aminobenzoates; Pyrazoles; Reproducibility of Results; Sensitivity and Specificity; Tandem Mass Spectrometry; Vegetables; Whole Grains

The hydrolysis reactions of [(14)C]-chlorantraniliprole (CLAP) and cyantraniliprole (CNAP) were investigated in sterile buffer solutions at pH 4, 7, and 9. Both compounds displayed similar degradation reactions. The reactions observed were intramolecular cyclizations and rearrangements instead of the anticipated amide hydrolysis to carboxylic acids. Despite a minor difference in their structures, the degradation rates for the two compounds were substantially different. The reaction rates were examined at multiple temperatures to understand the mechanistic aspects of the underlying transformations. Similarities and differences in the hydrolysis behavior of these compounds in various pH values and temperatures are described.

Topics: Hydrogen-Ion Concentration; Hydrolysis; Insecticides; Kinetics; ortho-Aminobenzoates; Pyrazoles

Diamide insecticides with high efficacy against pests and good environmental safety are broadly applied in crop protection. They act at a poorly-defined site in the very complex ryanodine (Ry) receptor (RyR) potentially accessible to a fluorescent probe. Two N-propynyl analogs of the major anthranilic diamide insecticides chlorantraniliprole (Chlo) and cyantraniliprole (Cyan) were accordingly synthesized and converted into two fluorescent ligands by click reaction coupling with 3-azido-7-hydroxy-2H-chromen-2-one. The new diamide analogs and fluorescent ligands were shown to be nearly as potent as Chlo and Cyan in inhibition of [3H]Chlo binding and stimulation of [3H]Ry binding in house fly thoracic muscle RyR. Although the newly synthesized compounds had only moderate activity in insect larvicidal activity assays, their high in vitro potency in a validated insect RyR binding assay encourages further development of fluorescent probes for insect RyRs.

Topics: Animals; Benzopyrans; Click Chemistry; Fluorescent Dyes; Inhibitory Concentration 50; Insect Proteins; Insecticides; Kinetics; Larva; Lepidoptera; Muscles; ortho-Aminobenzoates; Pyrazoles; Ryanodine Receptor Calcium Release Channel

Photodegradation of [(14)C]-chlorantraniliprole (CLAP) and [(14)C]-cyantraniliprole (CNAP) was investigated in sterile buffer solutions, in natural water, and on soil surfaces. Both compounds displayed rapid degradation in aqueous buffers when exposed to light at concentrations which could result from direct overspray to a shallow water body. While the main products observed had analogous structures, a substantial difference was noted in the rate of degradation of the two compounds despite minimal differences in their structures. Transformations observed were primarily intramolecular rearrangements and degradations resulting from addition of hydroxyl radicals leading to molecular cleavage. Some of the degradation products were transient, and several degradates had isomeric molecular compositions. The sequence of transformations was established definitively with the help of kinetics modeling. Utility of kinetics analysis in verification of the proposed pathways is illustrated.

Topics: Insecticides; Kinetics; ortho-Aminobenzoates; Photolysis; Pyrazoles; Soil; Soil Pollutants; Solubility; Water; Water Pollutants, Chemical

The gas-phase dissociation reactions of chlorantraniliprole (Rynaxypyr) and cyantraniliprole (Cyazypyr) have been studied in triple-quadrupole, ion trap, and orbitrap mass spectrometers equipped with electrospray and desorption electrospray ion sources, revealing the formation of odd-electron fragment ions, the structures of which were elucidated. The odd-electron fragments were unusually abundant, and their formation is proposed to occur via a tricyclic intermediate. The applicability of the QuEChERS multiresidue method for the quantitation of chlorantraniliprole and cyantraniliprole was also assessed in this study. Four matrices representative of oily, watery, acidic, and dry crop groups were tested, with a targeted limit of quantitation (LOQ) of 0.01 mg/kg. Average recoveries ranged between 87 and 107%, with relative standard deviations (RSD) of ≤ 8%. Linear calibration functions with correlation coefficients r > 0.99 were obtained. The study provides an expansion of the QuEChERS method to include anthranilic diamides and a mass spectrometric assessment for these two novel agrochemical active ingredients.

Topics: Chromatography, High Pressure Liquid; Food Analysis; Mass Spectrometry; ortho-Aminobenzoates; Pesticide Residues; Pyrazoles; Spectrometry, Mass, Electrospray Ionization; Tandem Mass Spectrometry