QuEChERS multiresidue method validation and mass spectrometric assessment for the novel anthranilic diamide insecticides chlorantraniliprole and cyantraniliprole

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.     

Post-mortem recovery,in vitro maturation and fertilization of fallow deer (Dama dama,Linnaeus 1758) oocytes collected during reproductive and no reproductive season

Habitat degradation leads to small and fragmented populations, lower genetic variability and fertility overtime. Assisted reproductive techniques represent important tools to cope with the dramatic loss of biodiversity. Fallow deer (Dama dama), beyond its high commercial value and wide distribution, may represent the most suitable model to study endangered cervids. In this study, oocytes were recovered post-mortem from fallow deer during the breeding and no breeding seasons and were in vitro matured (IVM). The ability of cryopreserved thawed sperm samples recovered by electroejaculation from four adult males was tested by in vitro fertilization of IVM oocytes. The number of oocytes collected per ovary did significantly vary across seasons from 6.2 ± 0.92 during breeding season to 10.4 ± 1.26 during no breeding season (p = .006). Oocytes collected during the breeding season showed higher in vitro fertilization rate compared to the no breeding season (p = .045). However, no embryos reached the blastocyst stage. Semen samples obtained by electroejaculation were successfully cryopreserved, although the cryopreservation process negatively affected most kinetic parameters, mainly at 2 hr post-thawing. Moreover, the percentage of rapid spermatozoa significantly decreased between fresh samples and at 2 hr post-thawing, whereas the percentage of slow spermatozoa increased across the same period (p < .05). Our study provides the logistic steps for the application of assisted reproductive techniques in fallow deer and might be of great interest for genetic resource bank planning.     

Use of CLSA and SPME-headspace techniques followed by GC-MS analysis to extract and identify the floral odorants

Flowers of Ziziphus spina christi are known to be attractive for parasitoids and predators. In Y-tube olfactometer experiments, the dried flowers attracted significantly (p < 0.001) the female parasitoids Aphelinus abdominalis. The flower volatile compounds were analyzed to understand which compounds could be specifically responsible for this attractiveness. The volatile compounds of Ziziphus flowers were extracted by closed-loop-stripping-analysis (CLSA) and also by solid phase microextraction (SPME) followed by gas chromatography-mass spectrometry (GC-MS) analysis. The main chemical classes of the volatile compounds are aldehydes, monoterpene-alcohols, ketones and hydrocarbons. Flower extract and some specific compounds will be further tested for their responsiveness to predators and parasitoids in behavioural and electrophysiological experiments.     

Evaluation of the Lime-Cooking and Tortilla Making Properties of Quality Protein Maize Hybrids Grown in Mexico

Eleven experimental and three commercial white quality protein maize (QPM) hybrids and two regular endosperm controls were planted at Celaya, Guanajuato, Mexico with the aim of comparing grain physical characteristics, protein quality, lime-cooking and tortilla making properties. All genotypes were planted under irrigation using a density of 80,000 plants/ha and fertilized with 250 kg N-60 P-60 K per hectare. When compared with the controls these QPM genotypes had lower test (77.4 vs. 76.5 kg/hL) and 1,000 kernel weights (327 vs. 307 g), softer endosperm texture (2.5 vs. 1.8 where 1 = soft, 2 intermediate and 3 hard endosperm), lower protein (10.0 vs. 8.0%), higher nixtamal water uptake after 30 min lime-cooking (50.0 vs. 53.1% moisture) and lower pericarp removal scores. The lower thousand-kernel weight and softer endosperm texture observed in the QPM genotypes lowered the optimum lime-cooking time as estimated with regression equations. Most QPM genotypes had higher amounts of lysine, tryptophan and albumins/globulins when compared with the controls. QPMs HEC 424973, HEC 774986 and HEC 734286 had the best grain traits for nixtamalization and therefore the best potential for industrial utilization. The commercial use of these QPM hybrids should benefit Mexicans who depend on tortillas as the main staple.     

Antiproliferative activity of Citrus juices and HPLC evaluation of their flavonoid composition

The antiproliferative activity of fresh fruit juices extracted from Citrus sinensis (cv. Washington Navel and cv. Sanguinello), C. deliciosa cv. Avana, C. clementina cv. Nules, C. aurantium subsp. myrtifolia , was evaluated against K562 (human chronic myelogenous leukemia), HL-60 (human leukemia) and MCF-7 (human breast adenocarcinoma) cell lines. All the juices tested showed antiproliferative activity. Moreover, the pattern of the main flavanone compounds in the juices has been determined by HPLC analysis.     

Polyphenolics and Antioxidant Capacity of White and Blue Corns Processed into Tortillas and Chips

White and blue corns of Mexican and American origins were lime-cooked to obtain nixtamals with optimal moisture (48–50%) for tortillas and chips. Blue kernels had less bulk density, softer endosperm and, consequently, required less cooking time than the white kernels. The optimum cooking regime for the white kernels was 100°C for 20 min, while the optimum for both pigmented genotypes was 90°C for 0 min (until the lime-cooking solution reached 90°C). Doughs, tortillas, and chips were characterized by total soluble phenolics (TSP), anthocyanins (ACN), and antioxidant capacity (AOX). A dough acidification procedure using fumaric acid (pH 5.2) was assessed as a means to improve TSP, ACN, and AOX retention. The Mexican blue corn had higher AOX (16%) than the American blue genotype, although the latter had a threefold higher TSP content (12.1 g/kg, dwb). Mexican and American blue corns had higher AOX capacity (29.6 and 25.6 μM trolox equivalents [TE]/g dwb), respectively, than the white corn (17.4 μM TE/g). White corns did not have detectable amounts of ACN, while blue Mexican and American kernels contained 342 and 261 mg/kg. Lime cooking had the greatest negative impact on the stability of TSP, ACN, and AOX. However, the acidification reduced ACN, TSP, and AOX losses by 8–23, 3–14, and 4–15%, respectively. Similar ACN losses were observed for both types of blue kernels when processed into nixtamal/dough (47%); however, ACN losses in tortillas and chips manufactured from the American blue genotype were higher (63 and 81%, respectively) than those of Mexican blue corn products (54 and 75%). ACN losses were highly correlated to TSP (r = 0.91) and AOX capacity losses (r = 0.94).     

Physiological responses of Quercus oleoides (Schltdl & Cham) to soils contaminated by diesel

ABSTRACT

Oil pollution is a worldwide threat to the environment that affects the development of plants. The effect of soil contaminated by diesel on the physiological responses of seedlings of Quercus oleoides was investigated in two independent experiments. We proposed that physiological performance will decrease when seedlings are exposed to higher concentration of contamination. At the first experiment, levels of pollution with diesel were of 0%, 5%, 10% and 15%, and 0%, 2% and 3.5% in the second one. In the first experiment, photosynthetic rate, stomatal conductance, transpiration and total chlorophyll of Q. oleoides were higher in the control seedling, and lower in treatments of pollution with 5%, 10% and 15% of diesel during 3 days of treatment. Only, seedlings in soil polluted with 5% of diesel survived up to 16 days; they showed a photosynthetic rate of 5 μmol m^?2 s^?1, which was lower than control seedlings (9 μmol m^?2 s^?1). This pattern was observed in stomatal conductance, transpiration and relative water content. Surprisingly, in the second experiment, seedlings showed a higher photosynthetic rate and growth at 2% of diesel-contaminated soil than control seedlings, a phenomenon known as hormesis. In both experiments, soil respiration was proportional to soils contaminated. We concluded that Q. oleoides is highly vulnerable in soils contaminated with above 5% of diesel, but it maintains its physiological activities in soils contaminated below 2%, suggesting that seedlings can grow under low concentration of diesel contaminant, and may be used in phytoremediation of soils with low concentrations of diesel contamination.     

Phosphorus fractions in Brazilian Cerrado soils as affected by tillage

No-tillage systems lead to physical, chemical and biological changes in soil. Soil fertility is responsive to changes in tillage as it depends on nutrient status, soil water content and biological characteristics. This work aimed to determine long term changes in phosphorus forms and availability in the profile of two tropical soils under conventional and no-till systems, and to discuss the significance of these changes on plant growth and demand for P fertilizers. Undisturbed soil cores with 20 cm in diameter were collected to a depth of 40 cm, accommodated in PVC tubes and taken to a greenhouse, where the experiment was conducted. Two soils were collected in Central Brazil, in areas under Cerrado. Both soils had been cropped for at least 10 years under conventional tillage and no-till. In the greenhouse, pots received phosphorus fertilization or not at 43.7 kg ha⁻¹, and soybean was grown for 60 days, when soil P fractions were determined. Labile P fractions in the soil profile were not affected by management systems, and there was no accumulation of available P under no-till. A large amount of P added as fertilizer was adsorbed in soil and remained in moderately labile fractions, mainly on uppermost soil layers. Therefore, the phosphate fertilizer has promoted P accumulation on less available fractions in soil, remaining P on the soil after crop harvest. Eventually this phosphorus could migrate to more labile fractions and be available for crops grown in succession.     

Evaluation of single and comparative intradermal tuberculin tests for tuberculosis eradication in caprine flocks in Castilla y León (Spain)

Goats can act as reservoirs for tuberculosis (TB) infection. The main etiological agents of TB in goats are Mycobacterium caprae and Mycobacterium bovis and they infect also a wide range of domestic and wild animals and humans. Control programmes based mainly on the application of single and comparative intradermal tuberculin (SIT and SCIT respectively) tests are being implemented in certain regions of Spain with a high density of caprine flocks as Castilla y León, including goats with epidemiological relationship with cattle. The aim of this study was to evaluate the performance of the intradermal tests in naturally TB-infected caprine flocks from this region. The study was performed using data from 17,450 goats in 54 different flocks that were classified as TB-infected in the control programmes executed in 2010 and 2011. Data from 1237 goats from 7 dairy flocks depopulated after the first intradermal testing were used to estimate the sensitivity (Se) using bacteriology as the gold-standard. Overall Se of the SIT test using the severe interpretation was 43.9% (CI 95%, 40.4–47.4) and decreased to 38.8% (CI 95%, 35.5–42.3) using the standard interpretation. Overall Se of the SCIT test ranged between 21.3% (CI 95%, 17.6–25.4) and 7% (CI 95%, 4.9–9.8) depending of the interpretation criteria. A significant weak positive correlation was found between age and skin fold thickness (Spearman’s test p < 0.05). Results from this study yielded, in general, low Se values probably due the systematic detection and slaughter of reactors as a consequence of the eradication programme in previous years or the presence of factors that may interfere in the diagnosis. Therefore, these results suggest the necessity of including ancillary diagnostic tools and/or strict interpretation criteria to maximize detection of positive animals in infected settings.