Investigation of Chlorpyrifos and Its Transformation Products in Fruits and Spices by Combining Electrochemistry and Liquid Chromatography Coupled to Tandem Mass Spectrometry

The identification of transformation products (TPs) of pesticides in food is a crucial task difficult to tackle, due to the lack of standards. In this work, we present a novel methodology to synthesize five main TP standards of the insecticide chlorpyrifos (CPF) and to investigate their occurrence in selected fruits and spices. TPs were electrochemically (EC) synthesized using a boron-doped diamond electrode (BDD) and identified by EC coupled online to mass spectrometry, LC-MS/MS, and high-resolution mass spectrometry. CPF and its TPs were analyzed in the food samples by LC-MS/MS on multiple reaction monitoring (MRM) after dispersive solid-phase extraction. A good recovery of 83–103% for CPF and 65–85% for TPs was obtained. Matrix effects, which cause signal suppression, ranged between 81 to 95% for all targeted analytes. The limit of detection and quantification for CPF were 1.6–1.9 and 4.9–5.7 μg/kg, respectively. Among investigated samples, CPF was determined in fresh lemon (104 μg/kg), fenugreek seed (40 μg/kg), and black pepper (31 μg/kg). CPF content in all samples was lower than the EU maximum residue level (MRL). The most frequently detected TPs were diethylthiophosphate and diethylphosphate. Other TPs, CPF oxon and trichloropyridinol, were also detected. Hence, EC is a versatile tool to synthesize TP standards which enables the determination of contaminants and residues in foodstuffs even if no commercial standards are available.     

Dual-modulator broadband infrared Mueller matrix ellipsometry

A broadband mid-infrared Mueller matrix ellipsometer is described based on two photoelastic modulators and a step-scan interferometer. The data are analyzed using a combination hardware-software double Fourier transformation. Obtaining spectra of the Mueller matrix elements requires that the infrared wavelength-dependent retardation amplitude of the modulators be known through calibration and subsequently incorporated into the data processing. The spectroscopic capability of the instrument is demonstrated in transmission and reflection geometries by the measured Mueller matrices of air, an anisotropic quartz crystal, and the ZnSe-water interface, each from 2500-4000 cm^-1.     

Electron tunneling through ultrathin boron nitride crystalline barriers

We investigate the electronic properties of ultrathin hexagonal boron nitride (h-BN) crystalline layers with different conducting materials (graphite, graphene, and gold) on either side of the barrier layer. The tunnel current depends exponentially on the number of h-BN atomic layers, down to a monolayer thickness. Conductive atomic force microscopy scans across h-BN terraces of different thickness reveal a high level of uniformity in the tunnel current. Our results demonstrate that atomically thin h-BN acts as a defect-free dielectric with a high breakdown field. It offers great potential for applications in tunnel devices and in field-effect transistors with a high carrier density in the conducting channel.     

A multi-objective particle swarm optimisation for filter-based feature selection in classification problems

Feature selection has the two main objectives of minimising the classification error rate and the number of features. Based on binary particle swarm optimisation (BPSO), we develop two novel multi-objective feature selection frameworks for classification, which are multi-objective binary PSO using the idea of non-dominated sorting (NSBPSO) and multi-objective binary PSO using the ideas of crowding, mutation and dominance (CMDBPSO). Four multi-objective feature selection methods are then developed by applying mutual information and entropy as two different filter evaluation criteria in each of the proposed frameworks. The proposed algorithms are examined and compared with a single objective method on eight benchmark data sets. Experimental results show that the proposed multi-objective algorithms can evolve a set of solutions that use a smaller number of features and achieve better classification performance than using all features. In most cases, NSBPSO achieves better results than the single objective algorithm and CMDBPSO outperforms all other methods mentioned above. This work represents the first study on multi-objective BPSO for filter-based feature selection.     

Investigation on the Impact of Seasonally Frozen Soil on Seismic Response of Bridge Columns

This paper presents the development of numerical models that investigated the seismic response of a simple two span prototype bridge system during warm and frozen temperatures. Models from both temperature conditions were subjected to a range of seismic intensities to examine the effect of seasonal freezing on the response of the system. Stiffness characteristics were defined using cyclic models of a bridge pier that were previously developed and validated using results from an experimental program on identical full-scale column-foundation units, which were tested during the summer and winter months. Dynamic characteristics of the seismic models were defined using approaches found in the literature. Frozen conditions increased the maximum bending moment and shear force demands for all seismic intensities, with nonlinearity in the column/foundation reducing the difference between the peak responses at higher intensities. At the depth of maximum foundation shear for the frozen model, demand was three times higher than the unfrozen for the 500-year return period and twice during the 2,500-year event. This is significant as one will assume shear is not critical at this location if the effects of frozen conditions are ignored. Apart from the smallest intensity event, increased peak lateral displacements were developed by the warm model down the length of the column and foundation. However, the displacement demand to capacity ratio was higher at the column top for the frozen model, exceeding the capacity during the 2,500-year return period event.     

Fluorographene: a two-dimensional counterpart of Teflon

A stoichiometric derivative of graphene with a fluorine atom attached to each carbon is reported. Raman, optical, structural, micromechanical, and transport studies show that the material is qualitatively different from the known graphene-based nonstoichiometric derivatives. Fluorographene is a high-quality insulator (resistivity >10(12) Ω) with an optical gap of 3 eV. It inherits the mechanical strength of graphene, exhibiting a Young's modulus of 100 N m(-1) and sustaining strains of 15%. Fluorographene is inert and stable up to 400 °C even in air, similar to Teflon.     

Fluorinated graphene: Fluorographene: A Two‐Dimensional Counterpart of Teflon (Small 24/2010)

A stoichiometric derivative of graphene with a fluorine atom attached to each carbon is reported. Raman, optical, structural, micromechanical, and transport studies show that the material is qualitatively different from the known graphene‐based nonstoichiometric derivatives. Fluorographene is a high‐quality insulator (resistivity >10¹² Ω) with an optical gap of 3 eV. It inherits the mechanical strength of graphene, exhibiting a Young’s modulus of 100 N m^?1 and sustaining strains of 15%. Fluorographene is inert and stable up to 400 °C even in air, similar to Teflon.     

Effect of estrous expression on timing and failure of ovulation of Holstein dairy cows using automated activity monitors

The aim of this study was to determine if estrous expression, as measured by an automated activity monitor (AAM), affects timing and failure of ovulation of lactating Holstein dairy cows. Cows were equipped with 2 AAM, 1 neck-mounted (AAM_C) and 1 leg-mounted (AAM_L), by 10 d postpartum and enrolled into the trial when their activity crossed the alert threshold on the AAM_C. A total of 850 episodes of estrus from 293 different cows were used for this study. When cows were enrolled, their ovaries were scanned by transrectal ultrasonography and gait and body condition scored. Ovaries of cows detected in estrus were scanned twice daily for a maximum of 3 d to determine the disappearance of the preovulatory follicle (ovulation) and the interval from estrus to ovulation was calculated. Physical activity data recorded from the AAM were used to determine estrus behavior using 2 traits: (1) peak activity and (2) duration. Peak activity was only available for the AAM_L. Peak activity was defined as the maximum activity during an estrus episode. Duration of estrus was defined as the time the activity of the cow exceeded threshold values set by the AAM software. The AAM_C correctly identified 87.8% of the estrus alerts, with 12.2% false positives. The average (±standard deviation) intervals from activity alert to ovulation were 25.8 ± 10.2 and 24.7 ± 9.3 h for the AAM_C and AAM_L, respectively. Changes in estrous expression were associated with differences in the interval from alert to ovulation. Cows with short intervals to ovulation were found to have less intense estrous expression than cows with medium and long length intervals to ovulation using the AAM_C, whereas using the AAM_L, cows with short intervals to ovulation exhibited less intense estrous expression than cows with medium but the same as those with long intervals to ovulation. Furthermore, irrespective of the AAM, estrus events with less estrous expression had increased odds of having a short interval to ovulation (below the median of 20 h) when compared with those having greater estrous expression (2.6 and 1.9 increased odds for the AAM_C and AAM_L, respectively). Ovulation failure was affected by estrous expression because estrus events with greater peak activity or longer duration had reduced ovulation failure compared with those with less estrous expression (AAM_C peak activity: 1.9 ± 1.4 vs. 9.5 ± 1.7%; AAM_L peak activity: 2.3 ± 1.4 vs. 6.2 ± 1.5%; AAM_C duration: 2.1 ± 1.4 vs. 8.9 ± 1.7%). In addition, cows with more estrous expression had greater pregnancy per artificial insemination than those with less estrous expression with both the AAM_C (42.3 ± 0.4 vs. 31.7 ± 0.4%) and the AAM_L (43.1 ± 0.4 vs. 36.3 ± 0.4%). Pregnancy per artificial insemination results were consistent even when removing cows that failed to ovulate. In conclusion, expression of estrus was highly associated with ovulation timing, ovulation failure, and fertility when using 2 different AAM. Cows with greater estrous expression have longer intervals from activity alert to ovulation, experience less ovulation failure, and have greater pregnancy per artificial insemination.     

New insights on effects of directionality and duration of near‐field ground motions on seismic response of tall buildings

The effects of ground motion directionality on seismic response of buildings are at the center of ongoing debate among earthquake engineering professionals and researchers. This has prompted a renewed interest to have a better understanding of directionality effects of near‐field pulse‐like ground motions on seismic response of tall buildings to further improve seismic design in this respect. In particular the prediction of the maximum displacement response along the structural axis which is called the critical displacement response. This paper presents the results from parametric studies that investigate the directionality effects on nonlinear dynamic response of simple structures and a tall building. The outcome of these analyses was the development of a method, which relies on the maximum velocity to provide a good approximation to the critical displacement response. The method developed is computationally efficient and involves less calculation than other methods. In addition, it was determined that the building responses to records rotated to fault‐normal can lead to significant underestimation of the maximum response along the structural axis, using the fault‐parallel ground motion also may lead to large response differences and smaller yet significant differences when using the maximum direction ground motion.     

Antioxidant activity,color chromaticity coordinates,and chemical characterization of monofloral honeys from Morocco

The bioprospecting of several monofloral Moroccan honeys was carried out. The antiradical activity expressed as mmol Trolox equivalents/kg of honey and evaluated by 2,2-diphenyl-1-picrylhydrazyl assay, ranged from 0.15 for euphorb honey to 1.08 for citrus honey. The antioxidant activity expressed as mmol Fe²⁺/kg and evaluated by ferric ion reducing antioxidant power assay, ranged from 0.96 for euphorb honey to 4.74 for orange honey. The total phenol content was evaluated by colorimetric assay, while the color attributes were evaluated as transmittance data. Significant Pearson correlation factors were found between total polyphenol amount and antioxidant activity and between color attributes and antioxidant activity. Furthermore the chemical composition of volatile organic compounds was determined. The volatile organic compounds chemical composition of the studied honeys was mainly represented by terpene and benzene derivatives, Maillard reaction products, isoprenoids, and hydrocarbons. The volatiles fingerprint, as well as a targeted high-performance liquid chromatography analysis of the polar components, was used to tentatively confirm the declared botanical origin of the samples studied.