Environmental fate and metabolic transformation of two non-ionic pesticides in soil: Effect of biochar, moisture, and soil sterilization.

Soil moisture, organic matter, and soil microbes are the key considering factors that control the persistence, degradation, and transformation of applied pesticides under varied soil conditions. In this study, underlying influence of these factors was assessed through the fates and metabolic transformation of two non-ionic pesticides (e.g., Phorate and Terbufos) in soils. Concisely, two distinct experiments including a customized batch equilibrium (sorption study), and a lab incubation trial (degradation study) were performed, following the OECD guidelines. As per study findings, biochar (BC) amendment was found to be the most influential factors during sorption study, particularly, 1% BC amendment contributed to achieve the best results. In addition, the non-linearity of sorption isotherm (1/n < 1.0) was revealed through Freundlich isotherm, indicating the strong adsorption of studied pesticides onto the soils. On the other hand, during degradation study, soil moisture initiates the enhanced degradation of parent pesticides and subsequent metabolism. In the presence of 40% water holding capacity (WHC), 1% BC amendment enhances the metabolic transformation, while H2O2 treatment could hinder the process. Additionally, the half-life degradation (t1/2) of phorate and terbufos was controlled by biochar amendment, moisture, and soil sterilization, respectively. Finally, BC can accelerate the metabolic transformation, whereas, phorate underwent a metabolic change into sulfoxide and sulfone while terbufos turned into solely sulfoxide. This pioneering study gathered crucial data for understanding the persistence and metabolic transition of non-ionic pesticides in soils and their patterns of degradation.

Factors Affecting Incurred Pesticide Extraction in Cereals.

This study investigated the effect of milling on the yields of incurred residues extracted from cereals. Rice, wheat, barley, and oat were soaked in nine pesticides (acetamiprid, azoxystrobin, imidacloprid, ferimzone, etofenprox, tebufenozide, clothianidin, hexaconazole, and indoxacarb), dried, milled, and passed through sieves of various sizes. The quick, easy, cheap, effective, rugged, and safe method and liquid chromatography-tandem mass spectrometry extracted and quantified the incurred pesticides, respectively. For rice and oat, the yields were higher for vortexed samples than for soaked samples. For rice, the yields improved as the extraction time increased from 1 to 5 min. The optimized method was validated based on the selectivity, limit of quantitation, linearity, accuracy, precision, and the matrix effect. For rice and barley, the average yields improved as the particle size decreased from <10 mesh to >60 mesh. For 40-60-mesh wheat and oat, all pesticides (except tebufenozide in oat) had the highest yields. For cereals, 0.5 min vortexing, 5 min extraction, and >40-mesh particle size should be used to optimize incurred pesticide extraction.

Validation of a Multi-Residue Analysis Method for 287 Pesticides in Citrus Fruits Mandarin Orange and Grapefruit Using Liquid Chromatography-Tandem Mass Spectrometry.

Since the introduction of the positive list system (PLS) for agricultural products in the Republic of Korea, the demand for a quick, easy multi-residue analysis method increased continuously. Herein, the quick, easy, cheap, effective, rugged, and safe (QuEChERS) technique combined with liquid chromatography−tandem mass spectrometry was employed to optimize a method for the multi-residue analysis of 287 pesticide residues in mandarin orange and grapefruit. Method validation was conducted in terms of selectivity, limit of quantitation (LOQ), linearity, accuracy, precision, and matrix effect. All the compounds at low spiking levels (1, 2.5, 5, or 10 mg/kg) could be quantified at LOQs lower than 0.01 mg/kg (PLS level). The linearity of the matrix-matched calibration curve for each compound is in the range 0.5−50 µg/L, and its coefficient of determination (R2) is >0.990. Satisfactory recovery values of 70−120% with a relative standard deviation of ≤20% are obtained for all compounds in the mandarin orange and grapefruit samples. A negligible matrix effect (−20−20%) is observed for more than 94.8% and 85.4% of the pesticides in mandarin orange and grapefruit, respectively. Therefore, this analytical method can contribute to pesticide residue analyses of citrus fruits for routine laboratory testing.

Activation of the EGFR-PI3K-CaM pathway by PRL-1-overexpressing placenta-derived mesenchymal stem cells ameliorates liver cirrhosis via ER stress-dependent calcium.

BACKGROUND: Cholesterol accumulation and calcium depletion induce hepatic injury via the endoplasmic reticulum (ER) stress response. ER stress regulates the calcium imbalance between the ER and mitochondria. We previously reported that phosphatase of regenerating liver-1 (PRL-1)-overexpressing placenta-derived mesenchymal stem cells (PD-MSCsPRL-1) promoted liver regeneration via mitochondrial dynamics in a cirrhotic rat model. However, the role of PRL-1 in ER stress-dependent calcium is not clear. Therefore, we demonstrated that PD-MSCsPRL-1 improved hepatic functions by regulating ER stress and calcium channels in a rat model of bile duct ligation (BDL). METHODS: Liver cirrhosis was induced in Sprague-Dawley (SD) rats using surgically induced BDL for 10 days. PD-MSCs and PD-MSCsPRL-1 (2 × 106 cells) were intravenously administered to animals, and their therapeutic effects were analyzed. WB-F344 cells exposed to thapsigargin (TG) were cocultured with PD-MSCs or PD-MSCsPRL-1. RESULTS: ER stress markers, e.g., eukaryotic translation initiation factor 2α (eIF2α), activating transcription factor 4 (ATF4), and C/EBP homologous protein (CHOP), were increased in the nontransplantation group (NTx) compared to the control group. PD-MSCsPRL-1 significantly decreased ER stress markers compared to NTx and induced dynamic changes in calcium channel markers, e.g., sarco/endoplasmic reticulum Ca2+ -ATPase 2b (SERCA2b), inositol 1,4,5-trisphosphate receptor (IP3R), mitochondrial calcium uniporter (MCU), and voltage-dependent anion channel 1 (VDAC1) (*p < 0.05). Cocultivation of TG-treated WB-F344 cells with PD-MSCsPRL-1 decreased cytosolic calmodulin (CaM) expression and cytosolic and mitochondrial Ca2+ concentrations. However, the ER Ca2+ concentration was increased compared to PD-MSCs (*p < 0.05). PRL-1 activated phosphatidylinositol-3-kinase (PI3K) signaling via epidermal growth factor receptor (EGFR), which resulted in calcium increase via CaM expression. CONCLUSIONS: These findings suggest that PD-MSCsPRL-1 improved hepatic functions via calcium changes and attenuated ER stress in a BDL-injured rat model. Therefore, these results provide useful data for the development of next-generation MSC-based stem cell therapy for regenerative medicine in chronic liver disease.

Dissipation and Distribution of Picarbutrazox Residue Following Spraying with an Unmanned Aerial Vehicle on Chinese Cabbage (Brassica campestris var. pekinensis).

We assessed the residual distribution and temporal trend of picarbutrazox sprayed by agricultural multicopters on Chinese cabbage and considered fortification levels and flying speeds. In plot 2, 14 days after the last spraying, the residues decreased by ~91.3% compared with those in the samples on day 0. The residues in the crops decreased by ~40.8% of the initial concentration owing to growth (dilution effect) and by ~50.6% after excluding the dilution effect. As the flight speed increased, picarbutrazox residues decreased (p < 0.05, least significant deviation [LSD]). At 2 m s-1 flight speed, the residual distribution differed from the dilution rate of the spraying solution. The average range of picarbutrazox residues at all sampling points was 0.007 to 0.486, below the limit of quantitation -0.395, 0.005-0.316, and 0.005-0.289 mg kg-1 in plots 1, 2, 3, and 4, respectively, showing significant differences (p < 0.05, LSD). These results indicated that the residual distribution of picarbutrazox sprayed by using a multicopter on the Chinese cabbages was not uniform. However, the residues were less than the maximum residue limit in all plots. Accordingly, picarbutrazox was considered to have a low risk to human health if it was sprayed on cabbage according to the recommended spraying conditions.

Taxifolin and Sorghum Ethanol Extract Protect against Hepatic Insulin Resistance via the miR-195/IRS1/PI3K/AKT and AMPK Signalling Pathways.

This study aimed to evaluate the effects of taxifolin and sorghum ethanol extract on free fatty acid (FFA)-induced hepatic insulin resistance. FFA treatment decreased glucose uptake by 16.2% compared with that in the control, whereas taxifolin and sorghum ethanol extract increased the glucose uptake. Additionally, taxifolin and sorghum ethanol extract increased the expression of p-PI3K, p-IRS1, p-AKT, p-AMPK, and p-ACC in FFA-induced hepatocytes. Furthermore, FFA treatment increased the expression of miR-195. However, compared with the FFA treatment, treatment with taxifolin and sorghum ethanol extract decreased miR-195 expression in a dose-dependent manner. Taxifolin and sorghum ethanol extract enhanced p-IRS1, p-PI3K, p-AMPK, p-AKT, and p-ACC expression by suppressing miR-195 levels in miR-195 mimic- or inhibitor-transfected cells. These results indicate that taxifolin and sorghum ethanol extract attenuate insulin resistance by regulating miR-195 expression, which suggests that taxifolin and sorghum ethanol extract may be useful antidiabetic agents.

UPLC-ESI-Q-TOF-MS-Based Metabolite Profiling, Antioxidant and Anti-Inflammatory Properties of Different Organ Extracts of Abeliophyllum distichum.

Plant extracts have gained more attention as natural therapeutic agents against inflammation characterized by an overproduction of several inflammatory mediators such as reactive oxygen species and pro-inflammatory cytokines. Although Abeliophyllum distichum Nakai is generally known for its ornamental value, recent pharmacological research has demonstrated its potential therapeutic properties. Thus, to further evaluate the applicability of A. distichum in the food, cosmetic, and medical industries, we identified the phytochemicals in three organ extracts (fruits: AF, branches: AB, leaves: AL) of A. distichum and determined their antioxidant and anti-inflammatory activities. Using UPLC-ESI-Q-TOF-MS, a total of 19 compounds, including dendromoniliside D, forsythoside B, isoacteoside, isomucronulatol 7-O-Glucoside, plantamajoside, and wighteone were identified in the A. distichum organ extracts. AB exhibited a strong reducing power, an oxygen radical antioxidant capacity, and radical scavenging values compared with other samples, whereas AL exhibited the best anti-inflammatory properties. Gene expression, western blot, and molecular docking analyses suggested that the anti-inflammatory effect of AL was mediated by its ability to suppress lipopolysaccharide (LPS)-induced production of reactive oxygen species and/or inhibit LPS-stimulated activation of extracellular signal-regulated protein kinases (ERK1/2) in RAW264.7 cells. Collectively, these results indicate that AL is a potential source of phytochemicals that could be used to treat inflammation-associated diseases.

Ethyl Acetate Fraction of Aqueous Extract of Lentinula edodes Inhibits Osteoclastogenesis by Suppressing NFATc1 Expression.

Bone tissue is continuously remodeled by the coordinated action of osteoclasts and osteoblasts. Nuclear factor-activated T cells c1 (NFATc1) is a well-known transcription factor for osteoclastogenesis and transcriptionally activated by the c-Fos and nuclear factor-kappa B (NF-κB) signaling pathways in response to receptor activation of NF-κB ligand (RANKL). Since excessive RANKL signaling causes an increase of osteoclast formation and bone resorption, inhibition of RANKL or its signaling pathway is an attractive therapeutic approach to the treatment of pathologic bone loss. In this study, we show that an ethyl acetate fraction (LEA) from the shiitake mushroom, Lentinula edodes, inhibited RANKL-induced osteoclast differentiation by blocking the NFATc1 signaling pathway. We found that the water extract and its subsequent ethyl acetate fraction of L. edodes significantly suppressed osteoclast formation. Comparative transcriptome analysis revealed that LEA specifically downregulated a set of RANKL target genes, including Nfatc1. Next, we found that LEA suppresses Nfatc1 expression mainly through the inhibition of the transactivity of p65 and NFATc1. Moreover, treatment of LEA rescued an osteoporotic phenotype in a zebrafish model of glucocorticoid-induced osteoporosis. Collectively, our findings define an undocumented role of the shiitake mushroom extract in regulating bone development.

A UPLC-ESI-Q-TOF method for rapid and reliable identification and quantification of major indole alkaloids in Catharanthus roseus.

We developed a novel ultra performance liquid chromatography-quadrupole time-of-flight (UPLC-Q-TOF) mass spectrometry method that allows sensitive, rapid, and reliable detection and identification of six representative indole alkaloids (vincristine, vinblastine, ajmalicine, catharanthine, serpentine, and vindoline) that exhibit physiological activity in Catharanthus roseus (C. roseus). The alkaloids were eluted on a C18 column with acetonitrile and water containing 0.1% formic acid and 10 mM ammonium acetate, and separated with good resolution within 13 min. Electrospray ionization-Q-TOF (ESI-Q-TOF) analysis was performed to characterize the molecules and their fragment ions, and the characteristic ions and fragmentation patterns were used as to identify the alkaloids. The proposed analytical method was verified in reference to the ICH guidelines and the results showed excellent linearity (R2 > 0.9988), limit of detection (1 ng/mL to 10 ng/mL), limit of quantification (3 ng/mL to 30 ng/mL), intra-day and inter-day precisions, and extraction recovery rates (92.8% to 104.1%) for all components. The validated UPLC-Q-TOF method was applied to the analysis of extracts from the root, stem, and leaves of C. roseus, allowing the identification of six alkaloids by comparison of retention times, molecular ions, and fragmentation patterns with those of reference compounds. Sixteen additional indole alkaloids were tentatively identified by comparison of chromatograms to chemical databases and literature reports. The contents of bis-indole alkaloids (vincristine and vinblastine) were high in the aerial parts, while the contents of mono-indole alkaloids (ajmalicine, catharanthine, serpentine, and vindoline) were high in the roots. The present results demonstrate that the proposed UPLC-Q-TOF method can be useful for the investigation of phytochemical constituents of medicinal plants.

Comparison of the content of tobacco alkaloids and tobacco-specific nitrosamines in 'heat-not-burn' tobacco products before and after aerosol generation.

Standardized methods for collecting smoke and for measuring smoke components in heat not burn tobacco product (HTP) are yet to be established, and there is a lack of consensus as to whether the content of HTP cigarettes can be assayed in the same manner as for conventional cigarettes. Since HTPcigarettes do not generate ash when smoked, we compared the levels of tobacco alkaloids (TAs) and tobacco-specific nitrosamines (TSNAs) of HTP cigarettes before and after aerosol generation. HTP cigarettes were smoked according to two international standardization methods. The TAs and TSNAs contents of the cigarettes were analyzed by UPLC-Q-TOF and UPLC-MSMS, respectively. Smoking was found to significantly decrease the content of nicotine, nornicotine, anatabine, and anabasine by 53 ∼ 100% in all samples, and the maximum inhalable amounts of these entities were determined to be 4.24 mg/cig, 103.52 µg/cig, 258.72 µg/cig, and 33.03 µg/cig, respectively. By contrast, smoking significantly increased the content of NNK and NAB. we suggested that the reduced nicotine content minus the nicotine content remaining in the filter is an amount that could potentially be inhaled during smoking. The increase of NNK and NAB in HTP cigarette after aerosol generation is expected to be caused by the precursor, but more specific behavioral studies should be performed.

Acoustic transmission analysis on cavity resonance sound in a cylindrical cavity system: application to a Korean bell.

This paper presents an analytical model for acoustic transmission characteristics of a cylindrical cavity system representing the acoustic resonance conditions of a Korean bell. The cylindrical cavity system consists of an internal cavity, a gap, an auxiliary cavity, and a rigid base. Since the internal cavity is connected to the external field through a gap, determination of the acoustic transmission characteristics becomes a coupling problem between the internal cavity and external field. The acoustic field of the internal cavity is considered by expanding the solution method of the mixed boundary problem, and the external field is addressed by modifying the radiation impedance model of a finite cylinder. The analytical model is validated by comparison with both experiment and a boundary element method. Using the analytical model, the resonance conditions are determined to maximize the resonance effect. Thus, the resonance frequencies of the bell cavity system are investigated according to the gap size and auxiliary cavity depth. By adjusting gap size or auxiliary cavity depth, the cavity resonance frequency is tuned to resonate partial tones of the bell sound. Finally, the optimal combination of gap size and auxiliary cavity depth is determined.