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Amino acid changes in abiogenic mixtures containing p-nitroaniline and p-phenylene diamine.

Mixtures containing diammonium hydrogen phosphate, ammonium molybdate, and minerals in presence of p-nitroaniline resulted in formation of glycine, methionine, phenylalanine, tryptophan, and tyrosine. Proline and valine were observed in a few tubes. When p-phenylene diamine was present in the mixture, glycine was absent, while isoleucine and leucine were observed in the tubes. Predominance of proline was observed in all the studies executed.

Amino Acids↗

Study of the effect of amines on structure of coacervates formed by photochemical effect on metal ions in presence of formaldehyde.

If an aqueous mixture of ammonium molybdate, diammonium hydrogen phosphate, biological minerals, and formaldehyde is exposed to sunlight, typical "Jeewanu", mixtures are observed. However, if a little solution of p-phenylene diamine, p-nitroaniline, alpha-naphthylamine or beta-naphthyl amine is added to it, a dense white precipitate is obtained. This precipitate, under a microscope at X1200 magnification, appears as large clusters of very tiny cream-coloured spherules. But if the mixture is first exposed to sunlight for four hours, when the formation of typical microstructures appears, and then the amine solution is added, the formation of the precipitate is retarded as the exposure time of amine-free mixture is enhanced, till finally the formation of spherules as precipitate is stopped. Microscopic study in twenty days of exposure of the amine-containing mixture tube shows that the number of typical microstructures decreases; they get larger in size and gradually disintegrate, while the formation of tiny sdpherules is accelerated.

1-Naphthylamine↗

Reactions of indoles with nitrogen monoxide: unexpected formation of azo-bis-indoles from 1,2-disubstituted indoles.

1-Methyl-, 1-ethyl-2-phenylindoles react with nitrogen monoxide, forming mainly 3,3(')-azo-bis-indoles, nitrosoindoles together with traces of nitroindoles. 2-Phenylindole, under the same experimental conditions, forms isonitrosoindole in good yields. The formation mechanism of azo-bis-indoles has been demonstrated to occur through 1,2-disubstituted nitrosoindoles by the intermediate formation of a diazonium salt.

Azo Compounds↗

Subcritical water extraction to evaluate desorption behavior of organic pesticides in soil.

We evaluated the feasibility of extracting organic pesticides in soil using a hot-water percolation apparatus at 105 degrees C and 120 kPa pressure. Efficiency of the method was assessed by extracting six selected pesticides (acetochlor, atrazine, diazinon, carbendazim, imidacloprid, and isoproturon) from previously equilibrated soil at 13.6-65.8 mg/kg concentration range. Studies were performed on brown forest soil with clay alluviation (Luvisol). The method developed was compared to the traditional batch equilibrium method in terms of desorbed amount of pesticides from soil and extraction time. Pesticides in the liquid phase from the batch sorption experiment and in the effluent from the hot-water percolation were quantified by high-performance liquid chromatography with UV detection. The results of the percolation experiment are in close correlation with those of the conventional soil testing method. Desorbed quantities by hot-water percolation were 85% acetochlor, 62% atrazine, 65% carbendazim, 44% diazinon, 95% imidacloprid, and 84% isoproturon, whereas using batch equilibrium method 101, 66, 64, 37, 81, and 90% were desorbed, expressed as the percentage of the adsorbed amount of pesticide on soil following equilibration. The average time for hot-water extraction was 3.45 min, in contrast to the 16 h time consumption of the traditional batch method. The effect of temperature on stability of selected compounds was also evaluated using pesticide-spiked sand without soil. Recoveries of analytes ranged between 84.6 and 91.1% with reproducibility of 7.9-10.2%, except for diazinon, for which recovery was 59.4% with 14.4% relative standard deviation since decomposition occurred at elevated temperature. The percolation process has been described by a first-order kinetic equation. The parameters calculated from the equation provide an opportunity to estimate the amount of compound available for desorption, the rate of desorption processes in the studied soil-pesticide-water system, and modeling the leaching process to obtain additional information on the environmental behavior of the examined pesticide.

Atrazine↗

Modeling of single-step and multistep adsorption isotherms of organic pesticides on soil.

The aim of this study was to investigate the sorption behavior and mechanisms of the organic pesticides on soil. To establish the sorption isotherms of six commonly used pesticides (acetochlor, atrazine, diazinon, carbendazim, imidacloprid, and isoproturon), laboratory equilibrium studies were performed at extended concentration ranges on brown forest soil using the batch equilibrium technique. The pesticide concentrations in the equilibrated liquid phase were quantified with high-performance liquid chromatograph by ultraviolet detection. The adsorption processes could be described by a single-step (Langmuir) isotherm for acetochlor and carbendazim, by a two-step curve for diazinon, isoproturon, and atrazine, and by a three-step curve for imidacloprid. A nonlinear mathematical model-derived from the Langmuir equation-has been developed that represents well the detected single-step and multistep shaped adsorption isotherms. The interpreted model was found to fit the experimental data well and allows the description of the adsorption profile with great precision. The altered adsorption activity, which was indicated by the step arising on the plot, may represent the existence/occurrence of a different specific type of adsorption mechanism. This binding force starts to operate simultaneously at a critical concentration of solute in the studied soil-pesticide system. The parameters calculated from the equation provide an opportunity to estimate the extent of absorption constant, adsorption capacity, and concentration limit characteristic to the measured stepwise isotherms.

Adsorption↗

Tandem double intramolecular [4+2]/[3+2] cycloadditions of nitroalkenes. The fused/bridged mode.

A new class of tandem [4+2]/[3+2] cycloadditions of nitroalkenes is described in which both pericyclic processes are intramolecular. Two subclasses of intra [4+2]/intra [3+2] cycloadditions have been explored in which the dipolarophile is tethered at either C(5) or C(6) of the nitronate. For both families of precursors, the cycloadditions occur in good yield and are found to be highly regio- and stereoselective. This method converts linear polyenes to functionalized polycyclic systems bearing up to six stereogenic centers.

Alkenes↗

Structural specificity of aromatic compounds with special reference to mutagenic activity in Salmonella typhimurium--a series of chloro- or fluoro-nitrobenzene derivatives.

The mutagenicity of 21 chloro- or fluoronitrobenzene compounds and 9 chloro- or fluorobenzene compounds in Salmonella typhimurium (strains TA98, TA1538, TA1537, TA100 and TA1535) was examined. The tests were carried out under the conditions of absence and presence of liver microsomal activation. 15 nitro-group compounds had mutagenic activity; above all, compounds of fluoronitrobenzene were mutagenic for both types of strain. On the other hand, chloronitrobenzene compounds were mutagenic for base-pair substitution strains only. Mutagenic activity was exhibited by all compounds having a chloro or fluoro substituent at the para and ortho position in the nitrobenzene nucleus. All compounds without a nitro substituent showed no mutagenic activity.

Animals↗

Measurements of secondary organic aerosol from oxidation of cycloalkenes, terpenes, and m-xylene using an Aerodyne aerosol mass spectrometer.

The Aerodyne aerosol mass spectrometer (AMS) was used to characterize physical and chemical properties of secondary organic aerosol (SOA) formed during ozonolysis of cycloalkenes and biogenic hydrocarbons and photo-oxidation of m-xylene. Comparison of mass and volume distributions from the AMS and differential mobility analyzers yielded estimates of "effective" density of the SOA in the range of 0.64-1.45 g/cm3, depending on the particular system. Increased contribution of the fragment at m/z 44, C02+ ion fragment of oxygenated organics, and higher "delta" values, based on ion series analysis of the mass spectra, in nucleation experiments of cycloalkenes suggest greater contribution of more oxygenated molecules to the SOA as compared to those formed under seeded experiments. Dominant negative "delta" values of SOA formed during ozonolysis of biogenics indicates the presence of terpene derivative structures or cyclic or unsaturated oxygenated compounds in the SOA. Evidence of acid-catalyzed heterogeneous chemistry, characterized by greater contribution of higher molecular weight fragments to the SOA and corresponding changes in "delta" patterns, is observed in the ozonolysis of alpha-pinene. Mass spectra of SOA formed during photooxidation of m-xylene exhibit features consistent with the presence of furandione compounds and nitro organics. This study demonstrates that mixtures of SOA compounds produced from similar precursors result in broadly similar AMS mass spectra. Thus, fragmentation patterns observed for biogenic versus anthropogenic SOA may be useful in determining the sources of ambient SOA.

Aerosols↗