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Enantiomerically pure alpha-amino esters were applied in palladium catalysed allylic substitution reactions with moderate diastereoselectivity (up to 70% d.e.) using achiral ligands on symmetrical allylic acetates. Nucleophilic substitution of amino esters with enantiomerically pure ligands enabled diastereoselective ratios of 95:5 to be obtained.
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We describe a method to coat fused silica, quartz, or glass electrophoresis tubes with hydrophilic polymers, such as methyl cellulose or dextran, in order to eliminate electroendosmosis and adsorption of solutes onto the tube wall. The coating was not split off upon exposure to a 5% solution of sodium dodecyl sulfate (SDS) at pH around 12 during a period of sixteen days or to 0.5 M HCl (pH 0.3) during 10 days. The high stability of the coating, which is attached to the silica surface via Si-O-Si-C bonds, permits electrophoresis experiments at extreme (besides neutral) pH values and allows short washes of the electrophoresis tubes between the runs with 0.05 M sodium hydroxide (pH 12.7) containing 5% SDS, and with 1 M HCl. These washing solutions release efficiently those solutes which have a tendency to adsorb onto the coating, which is a prerequisite for reproducible runs. The quality of the coating was strongly affected by the surface structure of the commercial fused silica tubing, which may vary from batch to batch. Attempts to standardize the surface structure of any tubing by treatments with NaOH and HCl to obtain a coating, the quality of which is independent of the original surface structure, were not successful. Therefore, it may be necessary to modify certain details of the coating procedure for each new batch of tubing to obtain optimum stability. Alternative coating procedures are therefore described, one of which is of general applicability (see last paragraph in Section 4).
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We have previously shown that the treatment with diallyl sulfide (DAS) and phenylethyl isothiocyanate (PIC) of rats receiving ethanol in the alcohol tube-feeding model effectively suppressed the induction of cytochrome P4502E1 (CYP2E1) by ethanol. Here we report that rat treatment with DAS and PIC significantly decreased the trapping of hydroxyethyl free radicals in liver microsomes incubated in vitro with ethanol. Furthermore, these inhibitors also greatly reduced the production of hydroxyethyl radical-derived epitopes detectable in vivo in the liver of ethanol-fed rats. The action of DAS and PIC on the formation of hydroxyethyl radicals paralleled their inhibitory effect on lipid peroxidation as monitored using, respectively, liver malonildialdehyde (MDA) and plasma lipid hydroperoxide levels as well as by the titers of antibodies versus MDA adducts to proteins. Thus, these results indicated a link between the induction of CYP2E1 by ethanol, the formation of hydroxyethyl radicals and the stimulation of lipid peroxidation. The pathological scores in the livers of rats fed with ethanol plus or minus DAS and PIC also correlated with levels of hydroxyethyl radical-derived epitopes. Rats fed intragastrically with ethanol developed antibodies and the formation of these antibodies was greatly reduced by DAS and PIC. Taken together these results suggest that CYP2E1 plays an important role in the generation of hydroxyethyl radicals during chronic alcohol feeding and that ethanol-derived free radicals might play a role in the onset of liver injury in this model of alcohol administration.
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Intraperitoneal administration of allylglycine resulted in a hypothermic response in rats. At a dosage of 90 mg/kg, a significant decrease in temperature was noted at 4 and 8 hr after administration, but no significant difference was noted at 12 hr. The same dose administered intraperitoneally to decapitated rats did not result in a hypothermic response, and intraventricular administration resulted in a rapid onset of hypothermia after 1 hr. These findings are indicative of a central site of action for the allylglycine-induced hypothermia. Quantitative assay of hypothalamic monoamines (norepinephrine, serotonin, and dopamine) did not show any significant changes at 4, 8, and 12 hr postadministration when compared to controls. A significant decrease in hypothalamic gamma-aminobutyric acid was noted at each of these time points when compared to controls. These data suggest an important role for gamma-aminobutyric acid in mammalian thermoregulatory control.
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THF solutions of the cationic chiral 1,3-diphenylallyl bidentate phosphine complexes [Pd(eta(3)-PhCHCHCHPh)(Duphos)](CF(3)SO(3)), Duphos = 1,2-Bis-((2R,5R)-2,5-dimethylphospholano)benzene), 2, and [Pd(eta(3)-PhCHCHCHPh)(P,S)]BF(4), 4, P,S = [8-((o-(diphenylphosphino)benzyl) thiomethyl]-(7,7'-dimethyl)-exo-norborneol, have been studied via pulsed gradient spin-echo (PGSE) diffusion, (1)H, (19)F HOESY and a variety of other multi-dimensional NMR methods. On the basis of the (1)H, (19)F HOESY data, the anions show a preference for a specific structural position with respect to the eta(3)-PhCHCHCHPh allyl ligand, i.e. the anion does not move evenly around the periphery of the cation. THF is shown to promote significant ion pairing, although neither 2 nor 4 shows 100% ion pairing.
Production and use of methyl bromide, a soil fumigant, are being restricted because of this chemical's deleterious effects on stratospheric ozone concentrations. Several products, some of which are currently used as soil fumigants, are being considered as possible replacements for methyl bromide, alone and in various combinations. Among these, 1,3-dichloropropene, methyl isothiocyanate generators such as metam-sodium, and chloropicrin are currently registered, while others such as methyl iodide and sodium azide are at different stages of the registration process. This review examines physicochemical properties, environmental fate, and metabolism of the various potential methyl bromide replacement products.
1,3-Dichloropropene (1,3-D), which consists of two isomers, (Z)- and (E)-1,3-D, is considered to be a viable alternative to methyl bromide, but atmospheric emission of 1,3-D is often associated with deterioration of air quality. To minimize environmental impacts of 1,3-D, emission control strategies are in need of investigation. One approach to reduce 1,3-D emissions is to accelerate its degradation by incorporating organic amendments into the soil surface. In this study, we investigated the ability of four organic amendments to enhance the rate of degradation of (Z)- and (E)-1,3-D in a sandy loam soil. Degradation of (Z)- and (E)-1,3-D was well described by first-order kinetics, and rates of degradation for the two isomers were similar. Composted steer manure (SM) was the most reactive of the organic amendments tested. The half-life of both the (Z)- and (E)-isomers in unamended soil at 20 degrees C was 6.3 days; those in 5% SM-amended soil were 1.8 and 1.9 days, respectively. At 40 degrees C, the half-life of both isomers in 5% SM-amended soil was 0.5 day. Activation energy values for amended soil at 2, 5 and 10% SM were 56.5, 53.4 and 64.5 kJ mol-1, respectively. At 20 degrees C, the contribution of degradation from biological mechanisms was largest in soil amended with SM, but chemical mechanisms still accounted for more than 58% of the (Z)- and (E)-1,3-D degradation. The effect of temperature and amendment rate upon degradation should be considered when describing the fate and transport of 1,3-D isomers in soil. Use of organic soil amendments appears to be a promising method to enhance fumigant degradation and reduce volatile emissions.
The complete phase-out of methyl bromide from use in developed countries by 1 January 2005 will cause many problems in agricultural industries that are now heavily reliant on its use. Three field experiments were established to compare management tactics on tomato and cucumber in commercial greenhouses naturally infested with root-knot nematodes (Meloidogyne spp). Reduction of nematode juveniles in soil and roots to nil detection levels was observed in all plots following soil fumigation with methyl bromide. A significant reduction of nematode juveniles and root-galling index was observed in plots treated with metham-sodium, dazomet and 1,3-dichloropropene compared with the control and plots treated with non-fumigant nematicides. Reduction of the nematode population led to an increase in fruit yield. However, data collected from the second cultivation season indicated that single control methods such as fumigant or contact nematicides alone cannot drastically decrease initial nematode population and those nematodes which escape control lead to population increase by the end of the cropping season.
The phase-out of methyl bromide as a soil fumigant has stimulated research into the use of other soil fumigants for weed control. Methyl bromide, methyl iodide, propargyl bromide, 1,3-dichloropropene (1,3-D) and metam-sodium were tested alone and in combination with chloropicrin in laboratory experiments to determine their efficacy against Cyperus esculentus L (yellow nutsedge) tubers. Propargyl bromide and metam-sodium were the most efficacious fumigants tested, with EC50 values of 3.7 and 6.5 microM, respectively. The relative potencies of methyl iodide and chloropicrin were not significantly different but were 2.6 and 2.9 times more potent than methyl bromide, respectively. The EC50 values for all fumigants other than 1,3-D were significantly lower than that of methyl bromide. Combining each fumigant with 17% chloropicrin resulted in a synergistic interaction. The greatest increase in potency between the expected result and the actual result was a relative potency of 3.8 with the methyl bromide/chloropicrin combination. The smallest increase in efficacy was with propargyl bromide and chloropicrin, with a relative potency of 1.5. There was no significant difference between the EC50 values of methyl bromide/chloropicrin and methyl iodide/chloropicrin combinations. Combining 1,3-D with 17% chloropicrin resulted in an EC50 value for C. esculentus control similar to that of methyl iodide applied alone.
Insecticidal fumigation toxicity of natural and synthetic cyanohydrins was evaluated with four stored-product pests: the lesser grain borer, Rhyzopertha dominica (F), the red flour beetle, Tribolium castaneum Herbst, the saw-toothed grain beetle Oryzaephilus surinamensis L, the maize weevil, Sitophilus zeamais (Motsch) and the house fly, Musca domestica L. The fumigation LC50 values were calculated by probit analysis. For house flies, all but one of the cyanohydrins tested were more potent than 1,3-dichloropropene (Telone). Three were as efficacious as chloropicrin. For the lesser grain borer, all cyanohydrins tested were more insecticidal than dichloropropene, and all but one were more potent than chloropicrin. Four were as insecticidal as dichlorvos. The acetate of 1-cyano-1-hydroxy-2-propene (CHP-ace) was also tested in soil for antifungal and antibacterial activity, and inhibition of weed seed germination. CHP-ace reduced the total soil bacterial and fungal counts significantly, and was effective in inhibiting the germination of weed seeds in soil, indicating a broad spectrum of activity as a soil fumigant.
The main objective of this study was to determine the influence of soil moisture, organic matter amendment and plastic cover (a virtually impermeable film, VIF) on diffusion and emissions of (Z)- and (E)-1,3-dichloropropene (1,3-D) in microplots of Florida sandy soil (Arredondo fine sand). Upward diffusion of the two isomers in the Arredondo soil without a plastic cover was greatly influenced by soil-water content and (Z)-1,3-D diffused faster than (E)-1,3-D. In less than 5 h after 1,3-D injection to 30 cm depth, (Z)- and (E)-1,3-D in air dry soil had diffused to a 10 cm depth, whereas diffusion for the two isomers was negligible in near-water-saturated soil, even 101 h after injection. The diffusion rate of (Z)- and (E)-1,3-D in near-field-capacity soil was between the rates in the two water regimes. Yard waste compost (YWC) amendment greatly reduced diffusion of (Z)- and (E)-1,3-D, even in air-dry soil. Although upward diffusion of (Z)- and (E)-1,3-D in soil with VIF cover was slightly less than in the corresponding bare soil; the cover promoted retention of vapors of the two isomers in soil pore air in the shallow subsurface. More (Z)-1,3-D vapor was found initially in soil pore air than (E)-1,3-D although the difference declined thereafter. As a result of rapid upward movement in air-dry bare soil, (Z)- and (E)-1,3-D were rapidly volatilized into the atmosphere, but emissions from the near-water-saturated soil were minimal. Virtually impermeable film and YWC amendment retarded emissions. This study indicated that adequate soil water in this sandy soil is needed to prevent rapid emissions, but excess soil water slows diffusion of (Z)- and (E)-1,3-D. Thus, management for optimum water in soil is critical for pesticidal efficacy and the environment.
Movement and biological activity of 1,3-dichloropropene (1,3-D) and chloropicrin applied through drip irrigation in raised beds was investigated at three locations in the southeastern USA. Tests were conducted in fields with dense populations of nutsedge (Cyperus spp), with one location also having a high level of soil nematodes, both of which served as biological indicators of the distribution of effective concentrations of 1,3-D and chloropicrin. Objectives were (1) to gain a better understanding of 1,3-D and chloropicrin movement and the extent of biological activity outside of the wetted bed area, and (2) to examine the effect of application rate, application concentration and subsequent irrigation events on movement and activity of 1,3-D and chloropicrin. InLine, an emulsifiable concentrate containing 60.8% w/w 1,3-D and 33.3% w/w chloropicrin, was injected into polyethylene mulched beds through the drip tubes and water movement in the beds was visualized by adding a blue dye to the injection system. Gas concentrations of 1,3-D and chloropicrin in soil were measured using Gastec detection tubes at different positions relative to the drip tube at 1-4 days after InLine application. After one week, mulch was removed and nutsedge survival evaluated at different positions in the bed. High concentrations of 1,3-D and chloropicrin were measured at the bed center and midway between the bed center and the shoulder, but concentrations were low at the bed shoulder. Width of nutsedge control was significantly greater than width of water movement. Plant-parasitic nematodes were controlled over the entire bed width, but nutsedge re-emerged at the bed shoulders regardless of treatment. Higher application rates and concentrations of 1,3-D + chloropicrin resulted in higher fumigant concentrations in soil air. Irrigations subsequent to application reduced soil air concentrations of 1,3-D and chloropicrin and increased water movement, as did the use of two drip tubes instead of one. The data show that the pesticidal activity of 1,3-D + chloropicrin extends beyond the waterfront and indicate a significant degree of fumigant activity of emulsifiable 1,3-D + chloropicrin. However, unlike plant-parasitic nematodes, nutsedge could not be controlled over the entire bed width, regardless of rate, concentration and volume of water applied.
Metam sodium (metam) is a widely used soil fumigant. Combined application of metam and other available fumigants is intended to produce synergic pesticidal effects for a broad spectrum of pest control in soil fumigation. This study aimed to test the compatibility of metam with the halogenated fumigants 1,3-dichloropropene (1,3-D), chloropicrin, methyl bromide, methyl iodide and propargyl bromide. Halogenated fumigants and metam were spiked simultaneously into organic solvents, water and moist soils, and metam-induced degradation of these halogenated chemicals was evaluated. In all three media, the halogenated fumigants were incompatible with metam and degraded via rapid chemical reactions. The degradation rate varied with halogenated fumigant species and increased as the amount of metam present was increased. In moist soil, 15-95% of the halogenated fumigants were decomposed within 72 h by metam at a 1:1 molar ratio. Combined application of Telone C-35 (62.5% 1,3-D + 35% chloropicrin) at 265 mg kg(-1) and Vapam (42% metam) at 567 mg kg(-1) in soil resulted in complete disappearance of the applied chloropicrin and 20-38% of the 1,3-D within 8 h. The results suggest that simultaneous application of halogenated fumigants and metam at the same soil depth will not maximize pest control. In practice, sequential treatment of soil or application at different soil depths is recommended when these two types of fumigants are used in combination.