Soil parameters including organic matter affecting pretilachlor leaching in different paddy fields.

Finding a method, which may indicate the contribution of soil parameters including organic matter, pH and clay to pretilachlor leaching (persistence) in the soil, with the use of a suitable indicator, which indicates pretilachlor presence in the soil is of significance. Accordingly, using undisturbed soil columns, four paddy fields (A, B, C, D) in the suburbs of Babol city (Mazandaran province, northern Iran) were sampled before the preparation and irrigation of the fields in April 2021. Soil samples were transferred into PVC pipes (divided into 2 cm layers) measuring 12 (height) × 10 cm (diameter), and were injected with pretilachlor at the recommended (1.75 L/ha) and high doses (3.5 L/ha). The surface layers of all fields had a higher concentration of pretilachlor and organic matter with the highest contribution to pretilachlor persistence followed by clay and pH. In the 0-4 cm depth, herbicide concertation was the lowest in field A (139 mg/kg) and the highest in field C (161 mg/kg). The corresponding values for organic matter were equal to 1.88 and 5.68%, respectively. The bioassay of rice (the indicator plant), with a significant correlation with chemical analysis results, indicated field A and field C had the pretilachlor infiltration of 6 and 4 cm, respectively. Accordingly, rice is a suitable plant indicator for measuring the presence of pretilachlor as examining its shoot length is a good criterion for bioassay. Additionally, changes in the amount of organic matter in different soil layers can be used to predict the leaching level of pretilachlor.

Visualization of the distribution of nanoparticle-formulated AZD2811 in mouse tumor model using matrix-assisted laser desorption ionization mass spectrometry imaging.

Penetration of nanoparticles into viable tumor regions is essential for an effective response. Mass spectrometry imaging (MSI) is a novel method for evaluating the intratumoral pharmacokinetics (PK) of a drug in terms of spatial distribution. The application of MSI for analysis of nanomedicine PK remains in its infancy. In this study, we evaluated the applicability of MALDI-MSI for nanoparticle-formulated drug visualization in tumors and biopsies, with an aim toward future application in clinical nanomedicine research. We established an analytic method for the free drug (AZD2811) and then applied it to visualize nanoparticle-formulated AZD2811. MSI analysis demonstrated heterogeneous intratumoral drug distribution in three xenograft tumors. The intensity of MSI signals correlated well with total drug concentration in tumors, indicating that drug distribution can be monitored quantitatively. Analysis of tumor biopsies indicated that MSI is applicable for analyzing the distribution of nanoparticle-formulated drugs in tumor biopsies, suggesting clinical applicability.

Dissipation Dynamics and Residue of Four Herbicides in Paddy Fields Using HPLC-MS/MS and GC-MS.

The dissipation dynamics and residue of pyrazosulfuron-ethyl, bensulfuron-methyl, acetochlor, and butachlor in paddy fields at Good Agricultural Practices (GAP) condition were carefully investigated in this study. The four herbicides' residues were determined based on a quick, easy, cheap, rugged, safe (QuEChERS) method coupled with HPLC-MS/MS and GC-MS. The limit of detection (LOD) for pyrazosulfuron-ethyl, bensulfuron-methyl, acetochlor, and butachlor in all matrices ranged from 0.04⁻1.0 ng. The limit of quantification (LOQ) of the four herbicides ranged from 0.01⁻0.1 mg/kg. Moreover, the average recoveries of the four herbicides ranged from 78.9⁻108% with relative standard deviations (RSDs) less than 15% at three different fortified levels for different matrices. The dissipation results indicated that the average half-lives (t1/2) of the four herbicides in soil were in the range of 3.5⁻17.8 days, and more than 95% of the four herbicides dissipated within 5 days in water. Furthermore, the final residues of the four herbicides were all below the LOQ at harvest time. Such results highlight the dissipation dynamics and residue of the four herbicides in a rice cropping system and contribute to risk assessment as well as scientific guidance on the proper and safe application of herbicides in paddy fields.

Atmospheric CO2 Level and Temperature Affect Degradation of Pretilachlor and Butachlor in Indian Soil.

This study was conducted at ambient (398 ± 10 µmol mol-1), elevated (450 ± 10 µmol mol-1) and elevated (550 ± 10 µmol mol-1) atmospheric CO2 under three moisture regime and also three level of temperature (4, 25, and 40°C) to assess the degradation of pretilachlor and butachlor. Under dry condition at 398 ± 10 µmol mol-1, T1/2 was 28.5 and 59.4 days for pretilachlor and butachlor, respectively; slowly decreased to 18.2 and 44.5 days at 550 ± 10 µmol mol-1 indicated that elevated condition enhanced degradation than ambient condition. Under field capacity with increasing CO2 levels from ambient to elevated, T1/2 decreased from 18.9 to 11.6 days and 39.4 to 16.2 days for of pretilachlor and butachlor, respectively. Similarly, under submerged conditions with increasing CO2 levels T1/2 decreased 14.7-7.1 and 26.3-11.8 days for pretilachlor and butachlor, respectively. Study also revealed that both pretilachlor and butachlor dissipated faster at 40°C (T1/2, 9.7 and 19.4 days) than 25°C (T1/2, 16.2 and 36.7 days). Slower dissipation was recorded at 4°C (T1/2, 87.6 and 182.4 days).

Improvement and application of the PCPF-1@SWAT2012 model for predicting pesticide transport: a case study of the Sakura River watershed.

BACKGROUND: The Soil and Water Assessment Tool combined with Pesticide Concentration in Paddy Field (PCPF-1@SWAT) model was previously developed to simulate the fate and transport of rice pesticides in watersheds. However, the current model is deficient in characterizing the rice paddy area and is incompatible with the ArcSWAT2012 program. In this study, we modified the original PCPF-1@SWAT model to develop a new PCPF-1@SWAT2012 model to address the deficiency in the rice paddy area and utilizing the ArcSWAT2012 program. Next, the new model was applied to the Sakura River watershed, Ibaraki, Japan in order to simulate the transport of four herbicides: mefenacet, pretilachlor, bensulfuron-methyl and imazosulfuron. RESULTS: The results showed that the water flow rate simulated by PCPF1@SWAT2012 was similar with the observed data. The calculated Nash-Sutcliffe efficiency coefficient (NSE) (0.73) and percent bias (PBIAS) (-20.38) suggested satisfactory performance of the model. In addition, the concentrations of herbicides simulated by the PCPF-1@SWAT2012 model were in good agreement with the observed data. The statistical indices NSE and root mean square error (RMSE) estimated for mefenacet (0.69 and 0.18, respectively), pretilachlor (0.86 and 0.18, respectively), bensulfuronmethyl (0.46 and 0.21, respectively) and imazosulfuron (0.64 and 0.28, respectively) indicated satisfactory predictions. CONCLUSION: The PCPF-1@SWAT2012 model is capable of simulating well the water flow rate and transport of herbicides in this watershed, comprising different land use types, including a rice paddy area. © 2018 Society of Chemical Industry.

Measurement of interaction behavior of six biologically important noble metal ions with the iron(III) binding protein, apo-transferrin, using mobility-shift affinity electrophoresis.

Transferrin is iron (III)-binding protein that transports Fe (III) ion to cells in different parts of the body. At saturation level 70% of transferrin remains free from iron (apo-transferrin), suggesting a broader scope of binding capabilities with non-iron (III) metal ions. Our previous work demonstrated that transferrin can effectively coordinate with noble metal ions. Hence to improve our understanding of the in-vitro metal-interaction behavior of the protein and how it correlates with its functions invivo, the interactions between apo-transferrin and medicinally important noble metals, Au (I), Au (III), Os (III), Pt (IV), Ir (III) and Ru (III) were investigated in the mobility shift mode of affinity capillary electrophoresis. The binding interactions were estimated according to the variation in electrophoretic mobility of the protein after coordination with the metal ions at physiological pH 7.4. ΔR/Rf values and confidence intervals were used to express the interaction results, which were calculated by using mobility ratios of protein with and without metal ions (Rf and Ri respectively) with respect to an electrophoretic marker (acetanilide). All the tested metal ions were found to be coordinated well with apo-transferrin, out of those Ir (III) exhibited the strongest interaction followed by the Au (I) ion. Noticeable variations in the shape and intensity of the protein peaks have been observed after interaction with some of the metal ions, especially those showing high binding affinities, which is probably due to conformational changes in the protein structure. The screening results suggest that apo-transferrin can interact with a variety of non-iron (III) metal ions and be the medium of transport for those metal ions into the biological system. This extended binding capability of apo-transferrin can be utilized for the targeted delivery of therapeutically significant metal ions. It can also be helpful in the development of new metal-based drugs for the treatment of a variety of ailments.

Extraction of acetanilides in rice using ionic liquid-based matrix solid phase dispersion-solvent flotation.

Ionic liquid-based matrix solid phase dispersion-solvent flotation coupled with high performance liquid chromatography was developed for the determination of the acetanilide herbicides, including metazachlor, propanil, alachlor, propisochlor, pretilachlor, and butachlor in rice samples. Some experimental parameters, including the type of dispersant, the mass ratio of dispersant to sample, pH of sample solution, the type of extraction solvent, the type of ionic liquid, flotation time, and flow rate of N2 were optimized. The average recoveries of the acetanilide herbicides at spiked concentrations of 50, 125, and 250 µg/kg ranged from 89.4% to 108.7%, and relative standard deviations were equal to or lower than 7.1%, the limits of quantification were in the range of 38.0 to 84.7 µg/kg.

Influence of Long Term Application of Butachlor on its Dissipation and Harvest Residues in Soil and Rice.

The study delineates the effect of repeated application of butachlor to rice crop from 1997 onwards. Additionally, in 2014 and 2015, dissipation kinetics of butachlor in soil was studied under field and laboratory conditions. The average recovery of butachlor for soil, rice grain and rice straw ranged between 80.3%-93.2% and 82.8%-96.5% with quantification limit of 0.01 and 0.003 µg g-1 for HPLC and GC-MS/MS, respectively. The dissipation of butachlor followed first order kinetics and half-life under long term field trials in rice soil varied from 15.2 to 19.29 days and 25.94 to 29.79 days under field and laboratory conditions, respectively. The residue of butachlor in soil, rice grain and straw samples at harvest over the years was below the quantification limit and no quantifiable amount of metabolites were present in soil at harvest suggestive of its safe application.

Effect of Pretilachlor on Soil Enzyme Activities in Tropical Rice Soil.

Pretilachlor treatments, namely, recommended dose at 600 g a.i. ha-1 (RD), double the recommended dose at 1200 g a.i. ha-1 (2RD), ten times of the recommended dose at 6000 g a.i. ha-1 (10RD) along with control, were used to study the effects of pretilachlor on soil enzymes in tropical rice soil. Pretilachlor, at recommended dose completely dissipated 30 days after herbicide application. Twenty days after herbicide application, the dehydrogenase activity was inhibited up to 27 %, 28 % and 40 % of initial values of RD, 2RD and 10RD treatments, respectively. Increase in fluorescein diacetate hydrolase activity was observed during the first 25 days post herbicide application up to 29 %, 36 % and 10 % of initial values of RD, 2RD and 10RD treatments, respectively. ß-Glucosidase activity in the experiment did not provide a specific trend. In general, urease and acid phosphatase activities were not influenced by pretilachlor application. There were significant differences in alkaline phosphatase activities among the treatments until 25 days after herbicide application. Hence, pretilachlor may cause short term transitory changes in soil enzyme parameters. However, it has negative impact on soil enzymes at very high dose.

Effect of long-term application of pretilachlor on its persistence and residues in paddy crop.

The effect of long-term application of pretilachlor to paddy in rice-wheat cropping system was investigated from 1997 to 2015. Additionally, in 2013, field experiment was also conducted where pretilachlor was applied to paddy field having no background of its application. The residues of pretilachlor were quantified using high-performance liquid chromatography (HPLC). The average recoveries of pretilachlor from paddy soil, paddy grain and straw samples ranged from 80.7% to 93.8% using HPLC with standard deviation less than 10%. The dissipation rate of pretilachlor in paddy soil followed first-order kinetics and half-life ranged from 9.58 to 21.19 days. In 2015, HPLC was compared with gas chromatography-tandem mass spectrometry (GC-MS/MS) for quantification of residues. Average recoveries of pretilachlor using GC-MS/MS from paddy soil, paddy grain and straw samples ranged from 81.4% to 98.3% with standard deviation less than 10%. Both HPLC and GC-MS/MS offered high reproducibility; however GC-MS/MS was more sensitive and the limit of detection was 3.0 and 1.0 ng g-1 for HPLC and GC-MS/MS, respectively. At harvest, the residues of pretilachlor in the paddy soil and crop were below the maximum residue limit and no dangerous accumulation was observed after its prolonged application.

Potential effects of rainwater-borne H2O2 on competitive degradation of herbicides and in the presence of humic acid.

In a previous piece of work, we reported some preliminary experimental results showing that hydrogen peroxide at a concentration range frequently encountered in rainwater could lead to degradation of three common herbicides (diuron, butachlor and glyphosate). However, the work was limited to the observation on the effects of Fenton process on the individual herbicides. In field conditions, different types of herbicides along with other organic molecules may occur concurrently. It is unclear how different herbicides and various organic molecules compete for the available hydroxyl radical. In this study, further laboratory experiments were conducted to observe the changes in the herbicides in the scenarios where multiple herbicides or humic acid are present. The results show that humic acid impeded hydroxyl radical-driven degradation of the diuron and butachlor. However, humic acid had no significant effects on reducing glyphosate removal rate. Glyphosate could compete strongly with the humic acid for the available hydroxyl radical in the reaction systems. The reactivity of glyphosate with hydroxyl radical was much higher than those of diuron and butachlor due possibly to its relatively simpler chemical structure, as compared to either diuron or butachlor, which are aromatic compounds that have higher chemical stability. Butachlor degradation was much weaker in the combined diuron and butachlor system than in the combined glyphosate and butachlor system. In the glyphosate-butachlor system, the opposite was observed. The findings have moved another step forward to understanding the potential role of rainwater-borne H2O2 in degrading herbicides in open water environments.

Efficient sample preparation method based on solvent-assisted dispersive solid-phase extraction for the trace detection of butachlor in urine and waste water samples.

In this work, an efficient sample preparation method termed solvent-assisted dispersive solid-phase extraction was applied. The used sample preparation method was based on the dispersion of the sorbent (benzophenone) into the aqueous sample to maximize the interaction surface. In this approach, the dispersion of the sorbent at a very low milligram level was achieved by inserting a solution of the sorbent and disperser solvent into the aqueous sample. The cloudy solution created from the dispersion of the sorbent in the bulk aqueous sample. After pre-concentration of the butachlor, the cloudy solution was centrifuged and butachlor in the sediment phase dissolved in ethanol and determined by gas chromatography with flame ionization detection. Under the optimized conditions (solution pH = 7.0, sorbent: benzophenone, 2%, disperser solvent: ethanol, 500 µL, centrifuged at 4000 rpm for 3 min), the method detection limit for butachlor was 2, 3 and 3 µg/L for distilled water, waste water, and urine sample, respectively. Furthermore, the preconcentration factor was 198.8, 175.0, and 174.2 in distilled water, waste water, and urine sample, respectively. Solvent-assisted dispersive solid-phase extraction was successfully used for the trace monitoring of butachlor in urine and waste water samples.

Frontally eluted components procedure with thin layer chromatography as a mode of sample preparation for high performance liquid chromatography quantitation of acetaminophen in biological matrix.

A new concept of using thin-layer chromatography to sample preparation for the quantitative determination of solute/s followed by instrumental techniques is presented Thin-layer chromatography (TLC) is used to completely separate acetaminophen and its internal standard from other components (matrix) and to form a single spot/zone containing them at the solvent front position (after the final stage of the thin-layer chromatogram development). The location of the analytes and internal standard in the solvent front zone allows their easy extraction followed by quantitation by HPLC. The exctraction procedure of the solute/s and internal standard can proceed from whole solute frontal zone or its part without lowering in accuracy of quantitative analysis.

High performance liquid chromatography of substituted aromatics with the metal-organic framework MIL-100(Fe): Mechanism analysis and model-based prediction.

Metal-organic framework (MOF) MIL-100(Fe) with well-defined thickness was homogenously coated onto the outer surface of magnetic microparticles via a liquid-phase epitaxy method. The as-synthesized MIL-100(Fe) was used as stationary phase for high-performance liquid chromatography (HPLC) and separations of two groups of mixed aromatic hydrocarbons (toluene, styrene and p-xylene; acetanilide, 2-nirtoaniline and 1-naphthylamine) using methanol/water as mobile phase were performed to evaluate its performance. Increasing water content of the mobile phase composition can greatly improve the separations on the expense of a longer elution time. Stepwise elution significantly shortens the elution time of acetanilide, 2-nirtoaniline and 1-naphthylamine mixtures, while still achieving a baseline separation. Combining the experimental results and in-depth modeling using a recently developed chromatographic software (ChromX), adsorption equilibrium parameters, including the affinities and maximum capacities, for each analyte toward the MIL-100(Fe) are obtained. In addition, the pore diffusivity of aromatic hydrocarbons within MIL-100(Fe) was determined to be 5×10(-12)m(2)s(-1). While the affinities of MIL-100(Fe) toward the analyte molecules differs much, the maximum capacities of the analytes are in a narrow range with q*MOFmax,toluene=3.55molL(-1), q*MOFmax,styrene or p-xylene=3.53molL(-1), and q*MOFmax,anilines=3.12molL(-1) corresponding to approximately 842 toluene and 838 styrene or p-xylene, and 740 aniline molecules per MIL-100(Fe) unit cell, respectively.

Persistence behaviour of pretilachlor in puddled paddy fields under subtropical humid climate.

The paper delineates the field trials conducted to investigate the persistence behaviour and dissipation kinetics of pretilachlor in puddled paddy fields under subtropical humid climatic region. Matrix solid phase dispersion (MSPD) method was used for extraction of the pretilachlor from paddy grain and paddy soil samples collected from the experimental field. Pretilachlor residues were quantified using high-performance liquid chromatography (HPLC) with UV/Vis detector at 210 nm. The average recoveries of pretilachlor extracted from matrix ranged from 80.3 to 103.3% with standard deviation less than 10% and sensitivity of 0.01 µg g(-1). The dissipation rate of pretilachlor in paddy field soil and paddy field water followed first-order kinetics with decrease in pretilachlor residues as a function of time. Faster dissipation of pretilachlor was observed in paddy field water than in paddy field soil with half life of 1.89-2.97 days and 7.52-9.58 days, respectively. At harvest, the residues of pretilachlor in the paddy soil and paddy crop samples were below the detection limit.

Liquid Chromatographic Separation and Thermodynamic Investigation of Mirabegron Enantiomers on a Chiralpak AY-H Column.

Liquid chromatographic separation of mirabegron enantiomers on Chiralpak AY-H, a column coated with amylose tris-(5-chloro-2-methylphenylcarbamate) as a chiral stationary phase, was studied under normal phase conditions. The influence of ethanol content (30-45%) and column temperature (20-40°C) on retention, resolution and separation were evaluated. Apparent thermodynamic parameters deduced from Van't Hoff plots were used to understand chiral separation mechanisms, and the chiral separation was enthalpy driven. The optimized chromatographic conditions were using a mixture solution of n-hexane, ethanol and diethyl amine (55 : 45 : 0.1, v/v/v) as a mobile phase at a flow rate of 1.0 mL/min. The column temperature and UV detector were set at 35°C and 254 nm, respectively. The method was validated to be simple, accuracy, sensitive and robust according to the ICH guidelines, and it was suitable for the routine quality control of mirabegron enantiomers for pharmaceutical industries.

Effect of rice husk gasification residue application on herbicide behavior in micro paddy lysimeter.

Effects of rice husk gasification residues (RHGR) application on the fate of herbicides, butachlor and pyrazosulfuron-ethyl, in paddy water were investigated using micro paddy lysimeters (MPLs). The dissipation of both herbicides in paddy water was faster in the RHGR treated MPL than in the control MPL. The average concentrations of butachlor and pyrazosulfuron-ethyl in paddy water in the lysimeter treated with RHGR during 21 days were significantly reduced by 51% and 48%, respectively, as compared to those in the lysimeter without RHGR application. The half-lives (DT50) of butachlor in paddy water for control and treatment were 3.1 and 2.3 days respectively, and these values of pyrazosulfuron-ethyl were 3.0 and 2.2 days, respectively. Based on this study, RHGR application in rice paddy environment is an alternative method to reduce the concentration of herbicide in paddy field water and consequently to reduce potential pollution to aquatic environment.

Activation of human brown adipose tissue by a ß3-adrenergic receptor agonist.

Increasing energy expenditure through activation of endogenous brown adipose tissue (BAT) is a potential approach to treat obesity and diabetes. The class of ß3-adrenergic receptor (AR) agonists stimulates rodent BAT, but this activity has never been demonstrated in humans. Here we determined the ability of 200 mg oral mirabegron (Myrbetriq, Astellas Pharma, Inc.), a ß3-AR agonist currently approved to treat overactive bladder, to stimulate BAT as compared to placebo. Mirabegron led to higher BAT metabolic activity as measured via (18)F-fluorodeoxyglucose ((18)F-FDG) using positron emission tomography (PET) combined with computed tomography (CT) in all twelve healthy male subjects (p = 0.001), and it increased resting metabolic rate (RMR) by 203 ± 40 kcal/day (+13%; p = 0.001). BAT metabolic activity was also a significant predictor of the changes in RMR (p = 0.006). Therefore, a ß3-AR agonist can stimulate human BAT thermogenesis and may be a promising treatment for metabolic disease.

Tea bag filter paper as a novel protective membrane for micro-solid phase extraction of butachlor in aqueous samples.

An innovative, cost-effective, simple, and environmental friendly tea bag filter paper protected micro-solid phase extraction (µ-SPE) technique was developed for the first time with the aim to miniaturize and minimize the use of organic solvents for the extraction and determination of butachlor in aqueous samples. The µ-SPE device was produced by packing 3.0 mg of an easily synthesized new sorbent, hydroxyl-functionalized polypyrrole (OH-PPY), inside a small tea bag filter paper sachet (1.0 cm × 0.5 cm) that served as a protective envelope. Both the extraction and desorption procedures were facilitated by sonication. Due to the high porosity and the fast water absorption of the tea bag filter paper, the analyte could easily diffuse through and enhance the interaction with the sorbent. Under the optimized conditions for the GC-ECD and the µ-SPE, the limit of detection (S/N ≥ 3) was 2.0 µg L(-1) while the limit of quantitation (S/N ≥ 10) was 10.0 µg L(-1). The recoveries of the butachlor spiked at 0.050, 0.10, and 0.50 µg mL(-1) ranged from 77.9 ± 3.0 to 112.5 ± 2.9%. The proposed method was successfully applied for the determination of butachlor in water samples from paddy cultivation sites. The levels found were from non-detectable to 24.71 ± 0.37 µg L(-1).

Three-parameter modeling of the soil sorption of acetanilide and triazine herbicide derivatives.

Herbicides have widely variable toxicity and many of them are persistent soil contaminants. Acetanilide and triazine family of herbicides have widespread use, but increasing interest for the development of new herbicides has been rising to increase their effectiveness and to diminish environmental hazard. The environmental risk of new herbicides can be accessed by estimating their soil sorption (logKoc), which is usually correlated to the octanol/water partition coefficient (logKow). However, earlier findings have shown that this correlation is not valid for some acetanilide and triazine herbicides. Thus, easily accessible quantitative structure-property relationship models are required to predict logKoc of analogues of the these compounds. Octanol/water partition coefficient, molecular weight and volume were calculated and then regressed against logKoc for two series of acetanilide and triazine herbicides using multiple linear regression, resulting in predictive and validated models.