Phytase inhibition by insecticides and herbicides

The effect of three herbicides (Linuron, Diuron, and Atrazine) and three vinyl phosphate insecticides (Crotoxyphos, Phosphamidon, and Dichlorvos) on phytase was examined. All the insecticides and Atrazine were competitive inhibitors, with Linuron and Diuron being mixed inhibitors. Some implications of phytase inhibition on inorganic P availability in soil are discussed.     

Immobilization of yeast cells with ionic hydrogel carriers by adhesion-multiplication

The mixture of an ionic monomer, 2-acrylamido 2-methylpropanesulfonic acid (TBAS), and a series of poly(ethylene glycol) dimethacrylate (nG) monomers were copolymerized with 60Co gamma-rays, and the produced ionic hydrogel polymers were used for immobilization of yeast cells. The cells were adhered onto the surface of the hydrogel polymers and intruded into the interior of the polymers with growing. The immobilized yeast cells with these hydrogel polymers had higher ethanol productivity than that of free cells. The yield of ethanol with poly(TBAS-14G) carrier was the highest and increased by 3.5 times compared to the free cells. It was found that the ethanol yield increased with the increase of glycol number in poly(ethylene glycol) dimethacrylate. The state of the immobilized cells was observed with microscope, and it was also found that the difference in the ethanol productivity is mainly due to the difference in the internal structure and properties of polymer carrier, such as surface charge, hydrophilicity, and swelling ability of polymer carrier.     

Effect of soil on urease inhibition by substituted urea herbicides

The effects of some substituted urea herbicides, fenuron, monuron, diuron and linuron, on soil urease were investigated. All herbicides are soil urease mixed inhibitors and the same inhibition mechanism is presumed. A kinetic relationship, which takes into account herbicide adsorption, is developed in order to calculate the inhibition constants of soil urease from adsorption constants. A linear relationship between Hammett sigma values and log K_i for fenuron, monuron and diuron is obtained, from which the formation of a complex between herbicides and enzyme is proposed By comparing kinetic constants for soil urease with those obtained for jack bean, in the presence of the same herbicides, a possible effect of the soil matrix on the enzyme-herbicide complex is also suggested.     

Degradation of chloroacetanilide herbicides by anodic fenton treatment

Anodic Fenton treatment (AFT) is an electrochemical treatment employing the Fenton reaction for the generation of hydroxyl radicals, strong oxidants that can degrade organic compounds via hydrogen abstraction. AFT has potential use for the remediation of aqueous pesticide waste. The degradation rates of chloroacetanilides by AFT were investigated in this work, which demonstrates that AFT can be used to rapidly and completely remove chloroacetanilide herbicides from aqueous solutions. Acetochlor, alachlor, butachlor, metolachlor, and propachlor were treated by AFT, and parent compound concentrations were analyzed over the course of the treatment time. Degradation curves were plotted and fitted by the AFT kinetic model for each herbicide, and AFT model kinetic parameters were used to calculate degradation rate constants. The reactivity order of these five active ingredients toward hydroxyl radical was acetochlor approximately metolachlor > butachlor approximately alachlor > propachlor. Treatment of the chloroacetanilides by AFT removed the parent compounds but did not completely mineralize them. However, AFT did result in an increase in the biodegradability of chloroacetanilide aqueous solutions, as evidenced by an increase in the 5-day biochemical oxygen demand to chemical oxygen demand ratio (BOD5/COD) to >0.3, indicating completely biodegradable solutions. Several degradation products were formed and subsequently degraded, although not always completely. Some of these were identified by mass spectral analyses. Among the products, isomers of phenolic and carbonyl derivatives of parent compounds were common to each of the herbicides analyzed. More extensively oxidized products were not detected. Degradation pathways are proposed for each of the parent compounds and identified products.     

Soy isoflavones protect the intestine from lipid hydroperoxide mediated oxidative damage

The effects of 24 h supplementation of human colon carcinoma cells (Caco-2) with isoflavones, genistein, and daidzein and their activities against oleic acid hydroperoxide mediated oxidative stress were investigated. Genistein, at 25, 50, and 100 microM, and daidzein, at 25 and 50 microM, did not induce cell injury to Caco-2 cells. Both compounds reduced cell injury and DNA damage mediated by 5 microM oleic acid hydroperoxides in Caco-2 cells. The effects of genistein and daidzein on antioxidant enzymes were dependent upon the compound and its concentration.     

Low-temperature alcoholic fermentation by delignified cellulosic material supported cells of kefir yeast.

A novel system for low-temperature alcoholic fermentation of glucose is described. This system consists of kefir yeast immobilized on delignified cellulosic materials. Batch fermentations were carried out at various pH values, and the effect of temperature on kinetic parameters, in the range of 5-30 degrees C, was examined. At pH 4.7 the shortest fermentation time was obtained. The formation of volatiles indicates that the concentration of amyl alcohols (total content of 2-methylbutanol-1 and 3-methylbutanol-1) is reduced as the temperature becomes lower. Propanol-1 and isobutyl alcohol formation drops significantly below 15 degrees C. The percentage of ethyl acetate increases as the temperature is diminished. At 5 degrees C the content of total volatiles in the product was only 38% of the volatiles formed during fermentation at 30 degrees C.     

Reduced tillage techniques for wetland rice as affected by herbicides

Two experiments on land preparation practices, consisting of zero, minimum and conventional tillage treatments, revealed that conventional tillage was the best practice in terms of grain yield, tiller number and weed yield. It was followed by minimum and zero tillage, respectively. A third experiment where zero tillage was associated with dry-seeding with a rolling-injection planter produced yields which were similar to minimum and conventional tillage. Compared to paraquat and SC-0224, glyphosate performed better both in zero and in minimum tillage when followed by harrowing. Application time of paraquat or glyphosate did not affect the grain yield. Butachlor (0.8) application 6 days after seeding significantly increased the grain yield and tiller number. Of the crop establishment methods tested, dry-seeding with a rolling-injection planter in zero tillage, broadcast wet-seeding by hand in minimum tillage and wet-seeding with a low land-seeder in conventional tillage proved to be most suitable. Dry-seeding with a rolling-injection planter proved better in the dry-season, than in the wet-season experiment.     

The antiproliferative and differentiating effects of human leukemic U937 cells are mediated by cytokines from activated mononuclear cells by dietary mushrooms

Proliferation of human leukemic U937 cells was remarkably inhibited by conditioned medium (CM) of human peripheral blood mononuclear cells (MNC-CM) stimulated with cold-water extracts (CWE) (10-800 microg/mL of medium) of dietary mushrooms, Hypsizigus mamoreus (HM), Agrocybe aegerita (AA), Flammulina velutipes (FV), whereas insignificant results were observed when cells were cultured in the presence of CWE at the corresponding level. Water extracts from mushrooms were fractionated by Sephadex G-50 chromatography, and the pooled high molecular weight fraction (F1) (200 microg/mL) of HM (HM1) and AA (AA1) exhibited growth inhibitions >80% on U937 cells. Interestingly, the thus-cultured U937 cells showed high nitroblue tetrazolium (NBT) positive (>68%) and nonspecific esterase (NSE) positive (>47%) percentages, revealing the remarkable differentiation into monocytes/macrophages upon incubation with HM1- and AA1-stimulated MNC-CM. In addition, assays for the expressions of monocyte-associated antigens, CD11b, CD14, and CD68, also evidenced the remarkable differentiation of U937 cells into monocytes/macrophages by presenting high CD maker positive percentages (>50%). Tumor necrosis factor (TNF)-alpha and interleukin (IL)-1beta in CM of HM1-stimulated MNC for 1 day (MNC-CM-1) were 1350 and 1374 pg/mL, respectively, revealing the potent antitumor and differentiation-inducing activities of HM. Of note, MNC-CM-1 appeared to be more effective than day 5 MNC-CM (MNC-CM-5) in both antitumor and differentiation-inducing activities.     

Antioxidative activity of propolis extract in yeast cells

The antioxidative activities of propolis and its main phenolic compounds, caffeic acid, p-coumaric acid, ferulic acid, and caffeic acid phenethyl ester, were investigated in the yeast Saccharomyces cerevisiae. After 1 h of exposure of the yeast cells, their intracellular oxidation was measured using 2',7'-dichlorofluorescein. Yeast cells exposed to 96% ethanolic extracts of propolis in DMSO (EEP) showed decreased intracellular oxidation, with no significant differences seen for the individual phenolic compounds. However, cellular uptake was seen only for a moderately polar fraction of EEP (E2) and caffeic acid phenethyl ester. The EEP antioxidative activity thus resulted from this E2 fraction of EEP. The influence of EEP was also investigated at the mitochondrial proteome level, by analyzing its profile after 1 h of exposure of the yeast cells to EEP and E2. Changes in the levels of antioxidative proteins and proteins involved in ATP synthesis were seen.     

Degradation of phenyl carbamate herbicides by Pseudomonas alcaligenes isolated from soil

A bacterial strain isolated from soil and identified as Pseudomonas alcaligenes, was able to hydrolyze four phenylcarbamate herbicides (CIPC, BIPC, IPC and swep) to corresponding anilines and alcohols by co-metabolism. The pH of the growth medium had little influence on bacterial growth and rate of herbicide transformation. Increase in CIPC and BIPC concentrations resulted in a significant inhibition of bacterial growth and herbicide degradation. Using a range of antibiotics it was shown that the enzyme involved in degradation was inducible.     

Gas chromatography of uracil herbicides by on-column methylation with trimethylanilinium hydroxide

Substituted uracil herbicides injected into a gas chromatograph react with trimethylanilinium hydroxide to give N-methyl derivatives with good gas chromatographic properties. Maximum methylation is obtained when the molar ratio of methylating reagent to herbicide is ca 4:1. This technique for preparing derivatives provides rapid qualitative and quantitative chromatography of the substances examined. Chromatographic response was linear with increased concentration for the synthetic standard and the on-column product of uracil herbicide. The proposed derivatization method was used to analyze herbicides in formulations. The methyl derivatives were identified spectroscopically.     

Effect of some herbicides on microbial activity in soil

The effect of 25 herbicides and herbicide combinations, in amounts comparable to those used in agriculture, on microbial activity in two soil types was determined in the laboratory. Herbicides did not affect respiration, assayed by CO₂ evolution and dehydrogenase activity, in either silty clay loam or loamy sand. Organic matter decomposition, determined by the amount of CO₂ evolved and inorganic N formed from decomposing alfalfa tissue, was also not affected. Alteration in soil pH or moisture content did not affect herbicide action. Addition of herbicides 3 weeks before amendment, or fertilizer application, also did not influence herbicide activity. Selected herbicides (trifluralin, linuron, dinoseb) at concentrations 100-fold higher than the recommended rates did not affect alfalfa decomposition. Solubilization of Ca₃(PO₄)₂ in soil was not affected by herbicides. S oxidation to SO^2?₄ in soil, however, was increased by most herbicides. In silty clay loam, 18 of the 25 herbicides and herbicide combinations increased S oxidation almost up to 3-fold. Results in loamy sand were similar. Dinoseb effectively reduced the algal population in loamy sand by more than 90%. Trifluralin, linuron, and metribuzin did not inhibit algal populations.     

Multiresidue method for determining substituted urea herbicides in foods by liquid chromatography

A method is described for determining substituted urea herbicides in foods. The residues are extracted from the product with methanol, and the food coextractives are removed by using solvent partitioning and Florisil column chromatography. The extract is analyzed using liquid chromatography with postcolumn photodegradation, chemical derivatization with orthophthalaldehyde, and spectrofluorometry. Recoveries were determined by spiking 8 different food products with 6 phenylureas--chlorbromuron, chloroxuron, diuron, fluometuron, linuron, and metobromuron--at 0.05 and 0.5 ppm. Three determinations were made at each level for each product. Average recovery at 0.05 ppm was 95% (with a standard deviation of 7.9%), and at 0.5 ppm, 98% (with a standard deviation of 6.9%).     

Analysis of herbicides in olive oil by liquid chromatography time-of-flight mass spectrometry

The application of liquid chromatography time-of-flight mass spectrometry (LC/TOF-MS) for the identification and quantitation of four herbicides (simazine, atrazine, diuron, and terbuthylazine) in olive oil samples is reported here. The method includes a sample treatment step based on a preliminary liquid-liquid extraction followed by matrix solid-phase dispersion (MSPD) using aminopropyl as a sorbent material. A final cleanup step is performed with florisil using acetonitrile as an eluting solvent. The identification by LC/TOF-MS is accomplished with the accurate mass (and the subsequent generated empirical formula) of the protonated molecules [M + H]+, along with the accurate mass of the main fragment ion and the characteristic chlorine isotope cluster present in all of them. Accurate mass measurements are highly useful in this type of complex sample analyses since they allow us to achieve a high degree of specificity, often needed when other interferents are present in the matrix. The mass accuracy typically obtained is routinely better than 2 ppm. The sensitivity, linearity, precision, mass accuracy, and matrix effects are studied as well, illustrating the potential of this technique for routine quantitative analyses of herbicides in olive oil. Limits of detection (LODs) range from 1 to 5 microg/kg, which are far below the required maximum residue level (MRL) of 100 microg/kg for these herbicides in olive oil.     

Metabolism of nitrodiphenyl ether herbicides by dioxin-degrading bacterium Sphingomonas wittichii RW1

Nitrodiphenyl ether herbicides, including chlomethoxyfen, nitrofen, and oxyfluorfen are potent herbicides. Some metabolites and parent compounds are considered as possible mutagens and endocrine disruptors. Both properties pose serious hygienic and environmental risks. Sphingomonas wittichii RW1 is a well-known degrader of polychlorinated dibenzo- p-dioxins, dibenzofurans, and diphenyl ethers. However, no detailed research of its metabolic activity has been performed against pesticides with a diphenyl ether scaffold. In this study, we report S. wittichii RW1 as a very potent diphenyl ether herbicide-metabolizing bacterium with broad substrate specificity. The structures of metabolites were determined by instrumental analysis and synthetic standards. Most pesticides were rapidly removed from the culture medium in the order of nitrofen > oxyfluorfen > chlomethoxyfen. In general, herbicides were degraded through the initial reduction and N-acetylation of nitro groups, followed by ether bond cleavage. Relatively low concentrations of phenolic and catecholic metabolites throughout the study suggested that these metabolites were rapidly metabolized and incorporated into primary metabolism. These results indicate that strain RW1 has very versatile metabolic activities over a wide range of environmental contaminants.