Dissipation of Herbicide Methiozolin and Its Metabolites in Aerobic Sediment-Water Systems.

Methiozolin is a novel herbicide for controlling annual bluegrass. After applying 14C labelled methiozolin in two sediment (clay loam and sand)-water systems under aerobic conditions, its distribution, half-life, and metabolites within 300 days were investigated. The mass balance ranged within 92.0%-104.4% of applied radioactivity (AR). Radioactivity in the water declined sharply from 94.4% to 0.5% AR, while in the sediment it increased to 83.9% AR at 14 days before declining to 9.1% AR. The volatiles were minimal (< 0.5% AR), and the evolved labelled CO2 accounted for up to ~ 33.4% AR. From Radio-HPLC analysis, labelled methiozolin in water decreased from 108.9% to 0% AR, while a maximum of 15.1% AR remained in the sediment at the end. Eight metabolites were detected, all at minor levels and accounting for < 5.5% AR. The half-life of labelled methiozolin in the total sediment-water systems were 50.7 and 38.7 days for clay loam and sand, respectively.

Photocatalytic Degradation Effect of µ-Dielectric Barrier Discharge Plasma Treated Titanium Dioxide Nanoparticles on Environmental Contaminant.

This study focused on the photocatalytic degradation effect of the µ-dielectric barrier discharge (µ-DBD) plasma treated titanium dioxide (TiO2) nanoparticles on environmental contaminant such as formaldehyde. TiO2 nanoparticles were treated by a µ-DBD plasma source with nitrogen gas. We analyzed the degradation of formaldehyde with the plasma treated TiO2 nanoparticles by UV-visible spectrophotometer (UV-VIS), and demonstrated that the photocatalytic activity of the µ-DBD plasma-treated TiO2 nanoparticles showed significantly high catalytic efficiency rather than without plasma treated TiO2 nanoparticles. Field emission scanning electron microscopes (FE-SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and water contact angle analyzer were used to measure the effects of photocatalytic degradation for the plasma treated TiO2 nanoparticles.

Developmental toxicity assessment of the new turf herbicide, methiozolin ([5-(2,6-difluorobenzyl)oxymethyl-5-methyl-3,3(3-methylthiophen-2-yl)-1,2-isoxazoline]), in rabbits.

Methiozolin is a new herbicide to control annual bluegrass (Poa annua L.) and large crabgrass (Digitaria sanguinalis (L.) Scop.) in various turfgrasses. The potential of methiozolin to induce maternal and developmental toxicity was investigated in the pregnant New Zealand White Rabbits. Methiozolin was, at dose levels of 0, 125, 250 and 500 mg/kg/day, administered by oral gavage to artificially inseminated rabbits (25 females per group) from days 6 to 28 of gestation. All does were subjected to Cesarean section on day 29 of gestation. At 500 mg/kg/day, treatment-related toxicities including abortion (10/22), decreased mean body weight, weight gain, net body weight change, reduced food consumption and decreased fetal weight were observed. At 125 and 250 mg/kg/day, no signs of maternal and developmental toxicity were observed. There were no treatment-related external, visceral and skeletal abnormalities of fetuses at all doses tested. In the current experimental conditions, the no observed adverse effect levels (NOAELs) of methiozolin are considered to be 250 mg/kg/day for does and prenatal development.

Structuring poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) towards enhancing hole collection efficiency.

To date, organic photovoltaic devices (OPVs) have obtained relatively low power conversion efficiency, mostly because of the low charge carrier mobility of the polymers to be used. This limits the optimal film thickness for efficient absorption of the solar spectrum. The capability of efficient charge carrier collections is a main factor for utilizing thick OPVs, consequently enhancing the power conversion efficiency. In this report, we demonstrate a facile approach for enhancing the hole carrier collection by possibly shortening the hole collection path via structuring poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) ( PEDOT: PSS), which is widely used as a hole collecting intermediate layer in OPVs. For structuring the PEDOT: PSS, the nanosphere lithographic method was used. Furthermore, the effects of the structuring of PEDOT: PSS on optical properties were also investigated.

Bioconcentration and Metabolism of the New Herbicide Methiozolin in Ricefish (Oryzias latipes).

Methiozolin is a novel herbicide used to control annual bluegrass. It has low vapor pressure and high hydrophobicity, which could result in persistence in water and bioaccumulation. We measured the bioconcentration factors (BCFs) of methiozolin in ricefish (Oryzias latipes). Two radiolabels were used to quantify the parent compound and identify its metabolites. Ricefish were exposed to 2.0 and 20.0 ng/L methiozolin for 28 days in the uptake phase with a 96-h LC50 of 2.2 mg/L(95% confidence limit: 2.1-2.5 mg/L) and water solubility of 4.2 mg/L after 48 h was observed. On the basis of total radioactivity residues (TRRs), BCFss and BCFk values of 797.0-851.9 and 992.9-1077.4 were observed, respectively, while BCFss values for methiozolin were 251.9-257.5. Several minor metabolites with TRR < 3.4% were detected. Among them, 4-(2,6-difluorobenzyloxy-methyl)-3-hydroxy-3-methyl-1-(3-methylthiophen-2-yl)butan-1-one, 2,6-difluorobenzyl alcohol, and 4,5-dihydro-5-methyl-3-(3-methylthiophen-2-yl)isoxazol-5-yl)methanol were identified. Methiozolin is metabolized into numerous minor metabolites with potentially low bioaccumulation capacity in ricefish. These findings can facilitate risk assessments regarding methiozolin use, particularly its movements and final stages in aquatic environments.

Anaerobic Degradation of [14C]Methiozolin under Aquatic Sediment Conditions.

The fate of methiozolin under anaerobic conditions was investigated in clay loam with a high organic carbon content and sandy loam with a low carbon content using [dihydroisoxazole ring-14C] and [phenyl-14C] radiolabels. The sediment/water ratio was 1:3 based on the dry weight:volume (w/v) ratio; the incubations lasted up to 355 days after the treatment (DAT) and were performed in the dark at 20.4 ± 0.7 °C. The overlying water flow-through systems consisted of glass vessels containing sediment with traps for [14C]carbon dioxide and [14C]volatiles. The samples were collected and analyzed at 0, 3, 7, 14, 50, 100, 200, and 355 DAT. The water and sediment samples were extracted with solvent systems, centrifuged, concentrated, and analyzed by liquid scintillation counting and a high-performance liquid chromatography (HPLC) system equipped with a flow scintillation analyzer. Following extraction, the sediments were air-dried, and the subsamples were combusted. [14C]Methiozolin was degraded in the water phase and partitioned rapidly into the sediments, where it was further degraded to other metabolites, which were identified by HPLC and liquid chromatography- or gas chromatography-tandem mass spectrometry (MS/MS) with authentic standards. The dissipation of methiozolin from the overlying water was rapid (with half-lives of 1.1-1.8 and 3.6-4.9 days in the clay loam and sandy loam, respectively). However, methiozolin dissipation from the sediment phase and the whole system was much slower than from the water phase (with half-lives of 122.0-220.0 and 110.0-130.0 days in the sediment phase of the clay loam and sandy loam and 116.0-166.0 and 70.8-85.7 days in the whole system of the clay loam and sandy loam, respectively).

Patterned Well-Aligned ZnO Nanorods Assisted with Polystyrene Monolayer by Oxygen Plasma Treatment.

Zinc oxide is known as a promising material for sensing devices due to its piezoelectric properties. In particular, the alignment of ZnO nanostructures into ordered nanoarrays is expected to improve the device sensitivity due to the large surface area which can be utilized to capture significant quantities of gas particles. However, ZnO nanorods are difficult to grow on the quartz substrate with well-ordered shape. So, we investigated nanostructures by adjusting the interval distance of the arranged ZnO nanorods using polystyrene (PS) spheres of various sizes (800 nm, 1300 nm and 1600 nm). In addition, oxygen plasma treatment was used to specify the nucleation site of round, patterned ZnO nanorod growth. Therefore, ZnO nanorods were grown on a quartz substrate with a patterned polystyrene monolayer by the hydrothermal method after oxygen plasma treatment. The obtained ZnO nanostructures were characterized by X-ray diffraction (XRD) and field-emission scanning electron microscope (FE-SEM).

Patterning ITO by Template-Assisted Colloidal-Lithography for Enhancing Power Conversion Efficiency in Organic Photovoltaic.

Highly structured interfaces are very desirable in organic photovoltaic solar cells (OPVs), in order to enhance power conversion efficiency (PCE) by decreasing of the transport path for excited charge carriers in the absorber and increasing the optical path length for photon absorption. Many complicated, high-cost lithographic methods have been attempted to modify the surface of the absorber or substrate. However, solution-based colloidal-lithography processes are scalable and cost-effective, but generally result in non-uniform structured surfaces. In this report, we demonstrated an optimized silica-templated colloidal lithographical approach to create a well-defined and controlled transparent ITO layer for enhancing power conversion efficiency (PCE). Additionally, morphological effects of the patterned ITO on optical properties and PCE were analyzed in detail.

The Effect of Sodium Dodecyl Sulfate on PEDOT:PSS and Its Application to Organic Photovoltaic Solar Cells.

Recently, the use of PEDOT: PSS in flexible device electrodes has been reported. PEDOT: PSS treatment consists of a step in which a small amount of surfactant is added to enhance the adhesion between PEDOT: PSS and the substrate or TCO materials. However, basic research into the effect of the surfactant is lacking. We studied the effects of sodium dodecyl sulfate (SDS) at controlled concentrations in aqueous PEDOT: PSS solution and that it enhanced the conductivity in the mixed thin films with surfactant and PEDOT: PSS. The thin films were prepared by the spin coating method. To study the structural effects on the resulting electrical properties, the thin films were investigated by FE-SEM (Field Emission Scanning Electron Microscopy) and AFM (Atomic Force Microscopy). At the same time, the electrical properties were investigated using a 4-point probe and solar simulator.

Micropatterning of TiO2 thin films by MOCVD and study of their growth tendency.

In this work, we studied the growth tendency of TiO2 thin films deposited on a narrow-stripe area (<10 µm). TiO2 thin films were selectively deposited on OTS patterned Si(100) substrates by MOCVD. The experimental data showed that the film growth tendency was divided into two behaviors above and below a line patterning width of 4 µm. The relationship between the film thickness and the deposited area was obtained as a function of f(x) = a[1 - e((-bx))]c. To find the tendency of the deposition rate of the TiO2 thin films onto the various linewidth areas, the relationship between the thickness of the TiO2 thin film and deposited linewidth was also studied. The thickness of the deposited TiO2 films was measured from the alpha-step profile analyses and cross-sectional SEM images. At the same time, a computer simulation was carried out to reveal the relationship between the TiO2 film thickness and deposited line width. The theoretical results suggest that the mass (velocity) flux in flow direction is directly affected to the film thickness.

Flow Manipulation in Thread-Based Microfluidics by Tuning the Wettability of Wool.

Recent progress in thread-based microfluidic devices has provided portable and inexpensive field-based technologies enabling medical diagnostics, environmental monitoring, and food safety analysis. However, capillary-driven liquid flow in a single thread, a crucial aspect of thread-based microfluidics, is difficult to control. Among potential materials, hydrophobic wool thread is an appropriate candidate for liquid flow control in thread-based microfluidics because its wettability can be readily tuned by the introduction of a natural color pigment, thereby manipulating flow. Thus, utilizing natural wool thread as a channel, we demonstrate here that liquid flow manipulations, such as microselecting and micromixing, can be achieved by coating the complex Al(III) (Alum) brazilein onto wool thread. In addition to enabling flow control, the coated wool channels consisting entirely of naturally occurring substances will be beneficial for biological sensing devices.

Methiozolin [5-(2,6-difluorobenzyl)oxymethyl-5-methyl-3,3(3-methylthiophen-2-yl)-1,2-isoxazoline], a new annual bluegrass (Poa annua L.) herbicide for turfgrasses.

BACKGROUND: Selective control of annual bluegrass (Poa annual L.) has been difficult in turfgrasses. The potential of methiozolin in this area was investigated. RESULTS: Methiozolin was safe on established zoysiagrass (Zoysia japonica Steud.), creeping bentgrass (Agrostis palustris Huds.), Kentucky bluegrass (Poa pratensis L.), and perennial ryegrass (Lolium perenne L.) at 1000 g ha(-1) , and controlled annual bluegrass with GR50 values of 23, 52, 104, and 218 g ha(-1) at PRE, two-, four- and eight-leaf stage, respectively, in the greenhouse. When applied at early flowering, methiozolin suppressed >80% of annual bluegrass seed heads at 2000 g ha(-1) . (14) C-Methiozolin was readily absorbed by both leaves and roots, but translocation was mainly acropetal. No herbicidal activity resulted from application to the leaf only; however, application to the soil surface only showed equivalent herbicidal activity to that of broadcast application to the leaf and soil. Methiozolin at 500 to 1000 g ha(-1) provided 80 to 100% control of annual bluegrass when applied in the fall with acceptable and temporary injury to creeping bentgrass, and about 60% control when applied in the spring with no bentgrass injury in the field. CONCLUSION: Methiozolin is an excellent candidate for annual bluegrass management in turfgrasses.

Soil metabolism of [14C]methiozolin under aerobic and anaerobic flooded conditions.

Methiozolin is a new turf herbicide controlling annual bluegrass in various cool- and warm-season turfgrasses. This study was conducted to investigate the fate of methiozolin in soil under aerobic and anaerobic flooded conditions using two radiolabeled tracers, [benzyl-(14)C]- and [isoxazole-(14)C]methiozolin. The mass balance of applied radioactivity ranged from 91.7 to 104.5% in both soil conditions. In the soil under the aerobic condition, [(14)C]methiozolin degraded with time to remain by 17.9 and 15.9% of the applied in soil at 120 days after treatment (DAT). [(14)C]Carbon dioxide and the nonextractable radioactivity increased as the soil aged to reach up to 41.5 and 35.7% for [benzyl-(14)C]methiozolin at 120 DAT, respectively, but 36.1 and 39.8% for [isoxazole-(14)C]methiozolin, respectively, during the same period. The nonextractable residue was associated more with humin and fulvic acid fractions under the aerobic condition. No significant volatile products or metabolites were detected during this study. The half-life of [(14)C]methiozolin was approximately 49 days in the soil under the aerobic condition; however, it could not be estimated in the soil under the anaerobic flooded condition because [(14)C]methiozolin degradation was limited. On the basis of these results, methiozolin is considered to undergo fast degradation by aerobic microbes, but not by anaerobic microbes in soil.

In vivo absorption, distribution, excretion, and metabolism of a new herbicide, methiozolin, in rats following oral administration.

Methiozolin [5-(2,6-difluorobenzyl)oxymethyl-5-methyl-3-(3-methylthiophen-2-yl)-1,2-isoxazoline] is a new turf herbicide that controls annual bluegrass in various cool- and warm-season turfgrasses. The present study is the first report elucidating absorption, tissue distribution, excretion, and metabolism of methiozolin in rats. The pharmacokinetic parameters in the blood were observed as follows: t(max) = 6 h, C(max) = 168.7 µg equiv/mL, t(½) = 49.4 h, AUC120 = 9921.5 µg equiv·h/mL, and clearance = 39.2 mL/h/kg. Those parameters and the depletion curve for ¹4C in the plasma were very similar to those in the blood. Total excretion through urine and feces was 24.3 and 68.9%, respectively, during 120 h after administration; however, there was no excretion through expired air. The radioactivity excreted through bile was 40.1% of that administered. Excreted radioactivity peaked between 24 and 48 h, showing 51.0% of total excretion within 48 h. The orally administered ¹4C distributed across various tissues within 12 h after administration, showing 14.0% of the dosed, and was eliminated from all tissues without accumulation. Numerous minor metabolites (<4% of the dosed) in urine and fecal extract were detected within 72 h, and two of those were identified. The identified metabolites were Met-1 (glucuronic acid conjugate), 6-[5-(5-((2,6-difluorobenzyloxy)methyl)-4,5-dihydro-5-methylisoxazol-3-yl)-4-methylthiophen-2-yloxy]-tetrahydro-3,4,5-trihydroxy-2H-pyran-2-carboxylic acid, and Met-2, [2-(5-((2,6-difluorobenzyloxy)methyl)-4,5-dihydro-5-methylisoxazol-3-yl)thiophen-3-yl]methanol. Conclusively, methiozolin was shown to be readily absorbed in the gastrointestinal tract, distributed throughout the tissues within 12 h, metabolized extensively, and eliminated through urine and feces mostly within 48 h, without tissue accumulation.