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Phototransformation of metoxuron [3-(3-chloro-4-methoxyphenyl)-1,1-dimethylurea] in aqueous solution.

UV irradiation of metoxuron in aerated aqueous solution at 254 nm or between 300 and 450 nm led initially to an almost specific photohydrolysis of the C-Cl bond, resulting in the formation of 3-(3-hydroxy-4-methoxyphenyl)-1,1-dimethylurea (MX3) and hydrogen chloride. The quantum yield was determined to be 0.020 (+/- 0.005) in solutions irradiated at 254 nm. Five minor photoproducts were also identified, in particular the dihydroxydimethoxybiphenyl derivatives resulting from the phototransformation of MX3. Irradiation increased the toxicity of an aqueous solution of metoxuron to the marine bacterium Vibrio fischeri.

Herbicides↗

Influence of topsoil tilth and soil moisture status on losses of pesticide to drains from a heavy clay soil.

Twelve lysimeters with a surface area of 0.5 m2 and a length of 60 cm were taken over mole drains from a Denchworth heavy clay soil and divided into two groups with either a standard agricultural tilth or a finer topsoil tilth. The influence of topsoil tilth on leaching of the herbicide isoproturon and a bromide tracer was evaluated over a winter season. The effect of variations in soil moisture status in the immediate topsoil on leaching of isoproturon, chlorotoluron and linuron was investigated in the following winter season. Here, water inputs were controlled such that lysimeters received 50 mm at a maximum intensity of 2 mm h-1 over a 4-week period with herbicides applied on day 15. Three treatments received the water either all prior to application, all after application, or evenly spread over the 4-week period. Leaching losses of the three herbicides were monitored for a subsequently drainage event. Analysis of covariance showed a significant effect of topsoil tilth and total flow on both the maximum concentrations (P = 0.034) and total losses (P = 0.012) of isoproturon in drainflow. Both concentrations and losses were c 35% smaller from lysimeters with the finer tilth. However, generation of the fine tilth in the field was restricted by a wet autumn and this is not considered a reliable management option for reducing pesticide losses from heavy clay soils. In the second experiment, variation in soil moisture content prior to and after application did not have any significant effect (P < 0.05) upon subsequent losses of the three herbicides to drains.

Aluminum Silicates↗

Lysimeter study to investigate the effect of rainfall patterns on leaching of isoproturon.

The influence of five rainfall treatments on water and solute leaching through two contrasting soil types was investigated. Undisturbed lysimeters (diameter 0.25 m, length 0.5 m) from a sandy loam (Wick series) and a moderately structured clay loam (Hodnet series) received autumn applications of the radio-labelled pesticide isoproturon and bromide tracer. Target rainfall plus irrigation from the end of November 1997 to May 1998 ranged from drier to wetter than average (235 to 414 mm); monthly rainfall was varied according to a pre-selected pattern or kept constant (triplicate lysimeters per regime). Leachate was collected at intervals and concentrations of the solutes were determined. Total flow (0.27-0.94 pore volumes) and losses of bromide (3-80% of applied) increased with increasing inputs of water and were larger from the Wick sandy loam than from the Hodnet clay loam soil. Matrix flow appeared to be the main mechanism for transport of isoproturon through the Wick soil whereas there was a greater influence of preferential flow for the Hodnet lysimeters. The total leached load of isoproturon from the Wick lysimeters was 0.02-0.26% of that applied. There was no clear variation in transport processes between the rainfall treatments investigated for this soil and there was an approximately linear relationship (r2 = 0.81) between leached load and total flow. Losses of isoproturon from the Hodnet soil were 0.03-0.39% of applied and there was evidence of enhanced preferential flow in the driest and wettest treatments. Leaching of isoproturon was best described by an exponential relationship between load and total flow (r2 = 0.62). A 45% increase in flow between the two wettest treatments gave a 100% increase in leaching of isoproturon from the Wick soil. For the Hodnet lysimeters, a 35% increase in flow between the same treatments increased herbicide loss by 325%.

Aluminum Silicates↗

Climate change and decreasing herbicide persistence.

A herbicide degradation model, using real weather data for the period 1980-2001, has been used to estimate the change in persistence of autumn-applied isoproturon over this period. The results suggest that soil residues fell to the minimum for weed control on average approximately 30 days earlier over the last 5 years of this period than in the first 5 years, equivalent to a reduction of approximately 25% in the duration of weed control. This decline in persistence is attributed to increasing soil temperature. The results are discussed in relation to recent observations and predictions on climate change. The relevance of the findings to other pesticides and future weed control is considered.

Climate↗

DNA damaging effects of pesticides measured by the single cell gel electrophoresis assay (comet assay) and the chromosomal aberration test, in CHOK1 cells.

One herbicide (isoproturon), two fungicides (carbendazim and chlorothalonil) and etoposide (an effective antitumor agent used as a positive control), were tested for their ability to induce cytotoxic and genotoxic effects in Chinese Hamster Ovary (CHOK1) cells. Etoposide induced DNA damage detectable both by the alkaline Single Cell Gel Electrophoresis (SCGE) assay and the chromosomal aberration (CA) test in absence of noticeable cytotoxicity. With the SCGE assay, a clear induction of DNA damage was observed for chlorothalonil within a 0.2 to 1 microM concentration range. In the CA test, chlorothalonil gave also positive results, inducing mainly chromosome breaks. In contrast, no DNA damage was observed with the SCGE assay for carbendazim and isoproturon. In the CA test, carbendazim induced only numerical aberrations in the concentration range of 25 microM to 100 microM, and isoproturon did not induce any significant increase in CA. In conclusion, chlorothalonil appears genotoxic in proliferative CHOK1 cells, and as expected, the aneugenic compound, carbendazim, did not induce DNA strand breaks in the SCGE assay.

Animals↗

Regeneration of the Egyptian medicinal plant Artemisia judaica L.

An in vitro propagation system for Artemisia judaica L., a traditional Egyptian medicinal plant, has been developed. De novo shoot organogenesis was induced by culturing etiolated hypocotyls and intact seedlings on medium supplemented with thidiazuron [N-phenyl-N'-(1,2,3-thidiazol-yl) urea] via callusing at the cotyledonary notch region. Up to 16 shoots formed per seedling cultured on a medium containing 1 micro mol l(-1) thidiazuron for an optimal duration of exposure of 20 days. Regenerated shoots formed roots when subcultured onto a medium containing 1 micromol l(-1) indole-3-butyric acid. The regeneration protocol developed in this study provides a basis for germplasm conservation and for further investigation of medicinally active constituents of A. judaica.

Adenine↗

Fluorosulfonyl- and bis-(beta-chloroethyl)amino-phenylamino functionalized pyrazolo[4,3-e]1,2,4-triazolo[1,5-c]pyrimidine derivatives: irreversible antagonists at the human A3 adenosine receptor and molecular modeling studies.

A series of pyrazolotriazolopyrimidines was previously reported to be highly potent and selective human A(3) adenosine receptor antagonists (Baraldi et al. J. Med. Chem. 2000, 43, 4768-4780). A derivative having a methyl group at the N(8) pyrazole combined with a 4-methoxyphenylcarbamoyl moiety at N(5) position, displayed a K(i) value at the hA(3) receptor of 0.2 nM. We now describe chemically reactive derivatives which act as irreversible inhibitors of this receptor. Electrophilic groups, specifically sulfonyl fluoride and nitrogen mustard (bis-(beta-chloroethyl)amino) moieties, have been incorporated at the 4-position of the aryl urea group. Membranes containing the recombinant hA(3) receptor were preincubated with the compounds and washed exhaustively. The loss of ability to bind radioligand following this treatment indicated irreversible binding. The most potent compound in irreversibly binding to the receptor was 14, which contained a sulfonyl fluoride moiety and a propyl group at the N(8) pyrazole nitrogen. The bis-(beta-chloroethyl)amino derivatives displayed a much smaller degree of irreversible binding than the sulfonyl fluoride derivatives. A computer-generated model of the human A(3) receptor was built and analyzed to help interpret these results. The model of the A(3) transmembrane region was derived using primary sequence comparison, secondary structure predictions, and three-dimensional homology building, using the recently published crystal structure of rhodopsin as a template. According to our model, sulfonyl fluoride derivatives could dock within the hypothetical TM binding domain, adopting two different energetically favorable conformations. We have identified two amino acids, Ser247 and Cys251, both in TM6, as potential nucleophilic partners of the irreversible binding to the receptor.

Aniline Compounds↗

Probing the reorganization of the nicotinic acetylcholine receptor during desensitization by time-resolved covalent labeling using [3H]AC5, a photoactivatable agonist.

The structural reorganizations occurring on the nicotinic acetylcholine receptor (nAChR) during activation and subsequent desensitization have been investigated through time-resolved photoaffinity labeling using a photoactivatable nicotinic agonist. [(3)H]AC5 is a photosensitive nicotinic probe with high affinity for the desensitized state of the Torpedo marmorata receptor (K(D) = 5 nM) that displays full agonist activity on the Torpedo californica receptor expressed in oocytes (EC(50) = 1.2 microM). Photoaffinity labeling of this receptor in the desensitized state showed a predominant specific labeling of gamma and delta subunits, whereas the alpha subunit was barely labeled. Using a stopped-flow device combined with a flash photolysis quenching system, we investigated the covalent mapping of the subunits as a function of incubation time of the receptor with [(3)H]AC5 (17 ms-1.25 h). During agonist-induced desensitization, specific labeling increased substantially, with similar time constants for gamma and delta subunits (0.016 s(-1)), whereas labeling of the alpha subunit remained relatively low. Therefore, the repartition of radioactivity shifted during desensitization from a weak but predominant labeling of the alpha and gamma subunits toward a substantial labeling of gamma and delta subunits. The observed time-dependent labeling pattern together with AC5 docking into a homology model of the T. californica nAChR suggest a subunit reorganization during agonist-induced desensitization, leading to a tightly packed arrangement that corresponds to a stable high affinity state for agonists.

Animals↗

Enrichment and molecular characterization of a bacterial culture that degrades methoxy-methyl urea herbicides and their aniline derivatives.

Soil treated with linuron for more than 10 years showed high biodegradation activity towards methoxy-methyl urea herbicides. Untreated control soil samples taken from the same location did not express any linuron degradation activity, even after 40 days of incubation. Hence, the occurrence in the field of a microbiota having the capacity to degrade a specific herbicide was related to the long-term treatment of the soil. The enrichment culture isolated from treated soil showed specific degradation activity towards methoxy-methyl urea herbicides, such as linuron and metobromuron, while dimethyl urea herbicides, such as diuron, chlorotoluron, and isoproturon, were not transformed. The putative metabolic intermediates of linuron and metobromuron, the aniline derivatives 3, 4-dichloroaniline and 4-bromoaniline, were also degraded. The temperature of incubation drastically affected degradation of the aniline derivatives. Whereas linuron was transformed at 28 and 37 degrees C, 3,4-dichloroaniline was transformed only at 28 degrees C. Monitoring the enrichment process by reverse transcription-PCR and denaturing gradient gel electrophoresis (DGGE) showed that a mixture of bacterial species under adequate physiological conditions was required to completely transform linuron. This research indicates that for biodegradation of linuron, several years of adaptation have led to selection of a bacterial consortium capable of completely transforming linuron. Moreover, several of the putative species appear to be difficult to culture since they were detectable by DGGE but were not culturable on agar plates.

Aniline Compounds↗

[Effect of cytokinin preparations on the pools of pigments and proteins of wheat cultivars differing in their tolerance to water stress].

Contents of chlorophylls, carotenoids, soluble leaf proteins, and the key enzyme of carbon metabolism--ribulose bisphosphate carboxylase/oxygenase (RuBisCO; EC 4.1.1.39)--in young seedlings and adult leaves of the wheat Triticum aestivum L. cultivars Mironovskaya 808 and Lyutestsens 758, contrasting in their water stress tolerances, were compared under conditions of normal available water supply, water deficiency, and subsequent rehydration. It was discovered that compounds displaying a cytokinin activity (6-benzylaminopurine, thidiazuron, cartolin-2, and cartolin-4) reduced the decreases in contents of chlorophylls, carotenoids, soluble leaf proteins, and RuBisCO progressing with development of water stress. These compounds with cytokinin activity also accelerated restoration of the compounds studied to their initial concentrations during rehydration. The cartolin preparations caused a maximal protective effect. Water stress had a more pronounced negative effect on cultivar Lyutestsens 758. Dehydration resulted in a more extensive destruction of seedlings compared to leaves of adult plants.

Adenine↗

[On the determination of chlorpropham, metobromuron and chlorbromuron residues in drugs of the 2. AB-DDR (author's transl)].

A method for analyzing drugs of the 2. AB-DDR for residues of chlorpropham, metobromuron and chlorbromuron is proposed. It is based on the detection of aniline derivatives resulting from alkaline hydrolysis. Herbicide concentrations greater than 0.25 mg/kg drug may be detected and semiquantitatively estimated by thin-layer chromatography. Smaller amounts of herbicide residues are detected gas chromatographically (using an electron attachment detector) after bromination of the hydrolysis products. The limits of detection are: chlorpropham, 0.006 mg/kg drug; chlorbromuron, 0.008 mg/kg drug; and metobromuron, 0.04 mg/kg drug. For impregnated drugs, the recovery rates lie between 82 and 102%. The herbicide residues are released to infusions at a varying extent, depending on the kinds of drugs used.

Chlorpropham↗

Modeling of an annular photocatalytic reactor for water purification: oxidation of pesticides.

Photocatalytic oxidation (PCO) over titanium dioxide (TiO2) is a "green" sustainable process for the treatment and purification of water and wastewater. However, the application of PCO for wastewater treatment on an industrial scale is currently hindered by a lack of simple mathematical models that can be readily applied to reactor design. Current models are either too simplistic or too rigorous to be useful in photocatalytic reactor design, scale-up, and optimization. In this paper a simple mathematical model is presented for slurry, annular, photocatalytic reactors that still retains the essential elements of a rigorous approach while providing simple solutions. The model extends the applicability of the thin-film model of photocatalytic reactors previously presented to include the case of geometrically thick photoreactors (i.e., those reactors in which the thickness of the annular zone is significant as compared to the outer radius of the reactor). The model uses a novel six-flux absorption-scattering model to represent the radiation field in the reaction space, which assumes that scattered photons follow the route of the six directions of the Cartesian coordinates. The model was successfully validated with experimental results from the photocatalytic oxidation of the pesticide isoproturon in an experimental reactor. The mathematical model presented may be used as a tool for the design, scale-up, and optimization of annular photocatalytic reactors for water treatment and purification.

Catalysis↗