A Highly Selective Analytical Method Based on Salt-Assisted Liquid-Liquid Extraction for Trace-Level Enrichment of Multiclass Pesticide Residues in Cow Milk for Quantitative Liquid Chromatographic Analysis.

In this study, a simple, inexpensive, selective, and fast salting-out assisted liquid-liquid extraction (SALLE) technique coupled with high-pressure liquid chromatography-diode array detection (HPLC-DAD) was developed for the extraction, preconcentration, and analysis of trace level seven multiclass pesticide residues in pasteurized and raw cow milk samples. The significant factors that affect the extent to which the target analytes are extracted, such as the type of extraction solvent and its volume, the type and concentration of salting-out salts, the pH of the solution, and the extraction time, have been investigated. Under optimum conditions, the correlation coefficient (r2) was obtained within a range of 0.9982-0.9997 for a broad linear range concentration of 2-1500 ng·mL-1. Reliable sensitivity was achieved with limits of detection (LODs) and limits of quantification (LOQs) ranging from 0.58-2.56 ng·mL-1 and 1.95-8.51 ng·mL-1, respectively. While precision with interday and intraday in terms of relative standard deviations (RSDs) was observed in the range of 1.97 - 7.88% and 4.52 - 8.04%, respectively. The results of the precision studies reveal that good repeatability and reproducibility (RSDs <9) were achieved, thus showing a low variability extraction of the developed method. Finally, the proposed and validated approach was effectively used to extract and determine pesticide residues in real milk matrices; however, the target analytes were not detected in all samples.

Effect of Processing Methods on Antinutritional Factors (Oxalate, Phytate, and Tannin) and Their Interaction with Minerals (Calcium, Iron, and Zinc) in Red, White, and Black Kidney Beans.

The purpose of this study was to assess how different processing techniques affected mineral compositions, antinutritional factors, and their interactions in red, white, and black kidney beans consumed in Ethiopia. Mineral contents were found to be 41-44, 58-78, and 112-126 mg Ca/100 g in the raw, soaked, and cooked samples, respectively. Iron content in the raw, soaked and cooked samples were found to be 2.77-2.97, 1.94-2.20 and 2.87-3.28 mg Fe/100 g, respectively, showing 26-30% loss on soaking followed by 33-48% increase on cooking. While Zn content in the raw, soaked and cooked samples were found to be 2.47-3.26, 3.34-4.68 and 2.83-3.31 mg Zn/100 g, respectively, showing 35-43% increase on soaking followed by 15-29% decrease on cooking. In the case of antinutrients, both treatments showed incredible decrements. Phytate in the raw samples was 178-179 mg/100 g and showed a 12-16% decrement on soaking and a 37-38% decrement up on cooking, oxalate was 1.5-1.8 mg/100 g in the raw samples and showed a 4.4-13% decrement during treatments, and tannin in the raw samples was 102-160 mg/100 g and showed a 23-30% decrement on soaking, followed by 21-41% during cooking. Phytate : Ca and oxalate : Ca molar ratios in soaked and cooked samples were within the critical values in the raw samples. In contrast, phytate : Zn and Ca × phytate : Zn in all treatments were found to be within the critical value, confirming the good bioavailability of zinc in all the samples, while phytate : Fe was found over the critical value, showing its poor availability.

Pyridinic-Type N-Doped Graphene on Cobalt Substrate as Efficient Electrocatalyst for Oxygen Reduction Reaction in Acidic Solution in Fuel Cell.

In this study, we use density functional theory to investigate the catalytic activity of graphene (G), single vacancy defective graphene (GSV), quaternary N-doped graphene (NGQ), and pyridinic N-doped graphene (NGpy, 3NGpy, and 4NGpy) on Co(0001) substrate for an oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). The results show pyridinic N-doped graphene on a Co support exhibited better performance than the NGQ on a Co support and free-standing systems. According to the results, ORR intermediates (*OOH, *O, and *OH) become more stable due to the presence of a Co substrate. The single pyridinic (3NGpy) layer placed on Co(0001) is the most active site. The overpotential for Co/3NGpy is rather higher compared to pure Pt(111) catalyst (0.65 V). Therefore, pyridinic N-doped graphene with a cobalt support could be a promising strategy to enhance the ORR activity of N-doped graphene in PEMFCs.

Oxygen reduction reaction on Pt-skin Pt3V(111) fuel cell cathode: a density functional theory study.

Pt-non-precious transition metals (Pt-NPTMs) alloy electrocatalysts have gained considerable attention to develop cheaper and efficient electrocatalysts for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs). In this report, density functional theory (DFT) has been applied to study the catalytic activity of Pt-skin Pt3V(111) electrocatalyst for ORR in PEMFCs. The results revealed that the ORR intermediates (O, OH and OOH) have lower binding energies on Pt-skin Pt3V(111) compared to pure Pt(111) surface. The ORR on Pt-skin Pt3V(111) surface proceed via OOH dissociation with an activation energy of 0.33 eV. The formation of OH is found to be the rate determining step with an activation energy of 0.64 eV, which is even lower than in pure Pt(111) surface (0.72 eV). This indicates a better performance of Pt-skin Pt3V(111) for ORR compared to pure Pt(111) surface. Moreover, the DFT results revealed that the negative formation energy of the Pt3V alloy and the positive dissolution potential shift of the surface Pt atoms revealed the better stability of Pt-skin Pt3V(111) surface over pristine Pt(111) surface. Due to the improved activity and better stability, the new Pt3V alloy electrocatalyst is very promising for the development of low-cost and efficient PEMFCs.

Iron-/Nitrogen-Doped Electrocatalytically Active Carbons for the Oxygen Reduction Reaction with Low Amounts of Cobalt.

Transition-metal-doped carbon catalysts are promising Pt-free alternatives for low-temperature fuel cells. They are frequently obtained from sacrificial N-rich zeolitic imidazolate frameworks (ZIFs) doped with Co and Fe. The optimal low loading of metals has to be achieved to guarantee the competitive efficiency and facilitate an inquiry into the mechanism of their catalytic activity. We report on microwave-assisted solvothermal synthesis of Zn,Co-ZIFs with a relatively low (1-15 mol %) Co loading, which were further enriched with Fe(II). Materials were pyrolyzed at 700 °C to form catalytically active carbons bearing metal nanoparticles confined in structured carbon. The electrochemistry test of carbons for the oxygen reduction reaction (ORR) in perchloric acid demonstrated their high efficiency even at low cobalt contents. The initial loading of 10 mol % was found efficient, leading to the production of catalytically active carbons allowing for four-electron path of ORR.