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Illudalane sesquiterpenoids from the soft coral Alcyonium paessleri: the first natural nitrate esters.

Fifteen illudalane sesquiterpenoids, alcyopterosins A-O (1-15) have been isolated from the subAntarctic soft coral Alcyonium paessleri which was collected at a depth of 200 m near the South Georgia Islands, and their structures were elucidated by spectroscopic techniques. Eight of these compounds (2, 3, 5-8, 10, and 13) are the first natural nitrate esters, while the other four (1, 4, 11, and 12) are chlorinated. These compounds are as well the first illudalane sesquiterpenoids to be isolated from the marine environment. Compounds 1, 3, 5, and 8 showed mild cytotoxicity toward human tumor cell lines.

Animals↗

Ansa versus spiro substitution of cyclophosphazenes: is fluorination essential for ansa to spiro transformation of cyclophosphazenes?

Fluorinated ansa substituted cyclophosphazenes endo-FcCH(2)P(S)(CH(2)O)(2)[P(F)N](2)(F(2)PN) [Fc = ferrocenyl] (1) and exo-FcCH(2)P(S)(CH(2)O)(2)[P(F)N](2)(F(2)PN) (2) readily transform to the spirocyclic compound [FcCH(2)P(S)(CH(2)O)(2)PN](F(2)PN)(2) (3) not only in the presence of CsF but also with non-fluorinated bases such as Cs(2)CO(3), K(2)CO(3), KOBu(t), Et(3)N, DABCO, DBN, and DBU. The analogous tetrachloro ansa compound exo-FcCH(2)P(S)(CH(2)O)(2)[P(Cl)N](2)(Cl(2)PN) (5), however, did not transform to the chlorinated spiro compound (6) in the presence of these bases. With excess of CsF, P-Cl bonds of 5 were found to undergo fluorination leading to the formation of 2, which transformed to spirocyclic compound 3. Time dependent (31)P NMR spectroscopy was used to monitor this transformation. Crystal structure studies on the ansa substituted compounds 4 and 5 have shown weak bonding interactions involving C-H...Cl, C-H...O, and C-H...S interactions.

Journal Article↗

Organic halogen removal from chlorinated humic ground water and lake water by nitrifying fluidized-bed biomass characterised by electron microscopy and molecular methods.

The dechlorinating and genotoxicity-removing activities of nitrifying fluidized-bed reactor biomass towards chlorinated organic compounds in water were shown at level below 1 ppm. The removal rates of adsorbable organic halogens were 200 micrograms Cl (g VS day)-1 for chlorinated humic ground water and 50 micrograms Cl (g VS day)-1 for chlorinated lake water when studied in batch mode. In a sequenced batch mode the removal rates [micrograms Cl (g VS day)-1] were 2000 from chlorohumus, 1400-1800 from chlorophenols in chlorinated ground water, and 430-720 from chlorohumus in chlorinated lake water. Genotoxicity was removed to a large extent (60%-80%) from the chlorinated waters upon incubation with nitrifying reactor biomass. 2,6-Di-, 2,4,6-tri and 2,3,4,6-tetrachlorophenols competed with chlorinated water organohalogens for dechlorination. The dechlorination of chlorophenols and chlorohumus required no ammonia and was not prevented by inhibitors of ammonia oxidation, nitrapyrin, parathion, sodium diethyldithiocarbamate, or allylthiourea. Electron microscopical inspection of the biomass showed the dominance of clusters of bacteria resembling known nitrifying species, Nitrosomonas, Nitrobacter, and Nitrosospira. This was supported by polymerase chain reaction amplification of the biomass DNA with four different primers, revealing the presence of 16S rDNA sequences assignable to the same species. The most intensive band obtained with the Nitroso4E primer was shown to be closely related to Nitrosomonas europaea by restriction analysis.

Ammonia↗

Xenobiotic organic compounds in leachates from ten Danish MSW landfills--chemical analysis and toxicity tests.

A monitoring program comprising chemical analysis and biological toxicity testing of leachate samples from 10 Danish landfills (six engineered and four uncontrolled) revealed the presence of 55 different xenobiotic organic compounds (XOCs) and 10 degradation products of XOCs. The compounds belong to the following groups: BTEX, C3-benzenes, bicyclo compounds, napthalenes, chlorinated aliphatics, phenols (chloro-, methyl-, dimethyl, nonyl-), pesticides, and phthalates. Concentrations of single XOCs ranged from <0.1 to 2220 microg/L. A pesticide screening including 101 different compounds resulted in detection of 18 pesticides and three degradation products. The findings of degradation products of toluene, phenols, phthalates, pesticides, and nonylphenol ethoxylates show that degradation occurred inside the landfills. In biotests with bacteria and algae it was found that the non-volatile organic compounds were toxic as the samples only needed to be pre-concentrated from 1.3 to 9.4 times to give 50% inhibition of the test organisms. One of the ten samples proved to be genotoxic in the umuC test after 141 times pre-concentration. A major part of the organic chemicals causing toxicity remains unknown and it is recommended to combine chemical analyses and biotests in future monitoring programs.

Bacteria↗

Identification and structural analysis of synthetic oligosaccharides of Shigella sonnei using MALDI-TOF MS.

MALDI-TOF mass spectroscopy was used for the molecular weight determination of protected synthetic oligosaccharides related to a cell surface bacterial polysaccharide. By-products containing chlorinated protecting groups caused isotopic patterns characteristic of the natural isotopic distribution of chlorine, were identified on the basis of isotopic distribution. 2,4,6-Trihydroxyacetophenone (THAP) as a matrix was better than 2,5-dihydroxybenzoic acid (DHB) for compounds containing chlorine, since monoisotopic resolution and no fragmentation were observed. In the post source decay (PSD) mode the identification of the oligosaccharide sequence through cleavage of the interglycosidic linkages was also possible, thus providing a sensitive and accurate tool for the structural verification of synthetic oligosaccharide intermediates.

Carbohydrate Conformation↗

Carbon isotope effects resulting from equilibrium sorption of dissolved VOCs.

To accurately interpret isotopic data obtained for volatile organic compounds (VOCs) dissolved in groundwater systems, the isotopic effects of subsurface processes must be understood. Previous work has demonstrated that volatilization and dissolution of BTEX and chlorinated ethene compounds are not significantly isotopically fractionating. This study characterized the carbon isotopic effects of equilibrium sorption of perchloroethylene, trichloroethylene, benzene, and toluene to both graphite and activated carbon directly in batch experiments over a range of 10-90% sorption. Results demonstrate that, over this range, equilibrium sorption of these VOCs to graphite and activated carbon does not result in significant carbon isotopic fractionation within the +/-0.5% accuracy and reproducibility associated with compound-specific isotope analysis. This implies that the isotopic values of dissolved VOCs will not be significantly affected by equilibrium sorption in the subsurface. Therefore, isotopic analysis has potential to be used in the field to differentiate between mass losses due to isotopically fractionating processes such as biodegradation versus mass loss due to nondegradative processes.

Journal Article↗

[Heterocyclic compounds containing the residue of a 4-aminophenylalkanoic acid with potential anti-inflammatory activity. IV. Derivatives of 2-phenyl-2H-indazole].

Numerous derivatives of 2-phenyl-2H-indazole were prepared. The compounds were of general formula I: where R is an acid, neutral or basic radical and R1, R2, R3 represent various functional groups, hydrogen atom or chlorine. The compounds were examined for analgesic-antiinflammatory properties and in some cases as inhibitors of platelets aggregation. Among the compounds where R is an alkanoic acid residue, the only compound showing interesting activity was M.G. 18755 [R = CH(CH3) COOH; R1, R2, R3 = H] and its lysine salt (M.G. 18334), which in various tests showed activity greater than that of ibuprofen. The homologous butyric derivative (M.G. 18860) showed a good anti-aggregatin activity.

Animals↗

Capillary zone electrophoresis with indirect UV detection of haloacetic acids in water.

A capillary zone electrophoresis (CZE) system for determining haloacetic acids in water was optimized with indirect photometric detection. Two different carrier electrolytes, potassium hydrogenphthalate and sodium 2,6-naphthalenedicarboxylate, were evaluated in terms of sensitivity and two different electroosmotic flow modifiers, tetradecyltrimethylammonium bromide and hexadecyltrimethylammonium bromide, were tested. Parameters such as electrolyte concentration and pH, and the concentration of the electroosmotic flow modifiers, which affect the CZE separations, were investigated. The method was used to determine haloacetic acids in chlorine tap water using the liquid-liquid extraction process.

Acetates↗

Halogenated compounds in a dated sediment core of the Teltow Canal, Berlin: time related sediment contamination.

To study the recent contamination history of DDT (1,1,1-trichloro-2,2-bis(chlorophenyl)ethane) and its metabolites, as well as methoxychlor (1,1,1-trichloro-2,2-bis(p-methoxyphenyl)ethane), chlorfenson (4-chlorophenyl-p-chlorobenzenesulfonate), and further halogenated aromatics, a sediment core was collected from the Teltow Canal in Berlin (Germany). The sampling site is located nearby a former industrial point source, where recently analyses on pre-samples have indicated high concentrations of halogenated organic compounds. The deposition time of the investigated sediments was determined by gamma-spectrometrical dating. Pollution trends of selected contaminants were attributed to a time period between 5 and 10 years. Concentration profiles reflect not only the recent pollution history of these compounds, but also the time-depending effects of the ban, restriction and termination of DDT-production in the German Democratic Republic (GDR). DDT and other chlorinated aromatic compounds were produced onsite until the late 1980s. Maximum values of 133 mg kg(-1) (dry weight) for p,p'-DDD (1,1-dichloro-2,2-bis(chlorophenyl)ethane) and approximately 100 mg kg(-1) (dry weight) for p,p'-DDMS (1-chloro-2,2-bis(chlorophenyl)ethane), main metabolites of the anaerobic degradation of DDT, were determined. The occurrence of all selected contaminants, most of which have been banned more than 10 years ago, demonstrate recent contamination pathways, and the necessity of a continuous long-term monitoring of the affected environment.

Berlin↗

Atmospheric organochlorine pesticide concentrations near the Great Lakes: temporal and spatial trends.

As a part of the Integrated Atmospheric Deposition Network, atmospheric organochlorine pesticide concentrations were measured in both the gas and particle phases at seven sites near the Great Lakes. Much higher organochlorine pesticide concentrations were found in the gas phase compared to that in the particle phase. Long-term decreasing trends were observed for most pesticides in both phases. Two different seasonal trends were observed in the particle phase: (a) in-use pesticides, such as endosulfan, showed higher concentrations in the summer, a time corresponding to their agriculture use, and (b) restricted organochlorine pesticides, such as lindane, showed higher particle-phase concentrations in the winter, presumably due to their enhanced partitioning from the gas phase to particles. Generally, Chicago had the highest concentrations of chlordanes, dieldrin, and sigmaDDT, suggesting that urban areas could be sources of these compounds to atmosphere. Point Petre had the highest concentrations of endosulfan, likely due to its agricultural application in Southern Ontario.

Air Pollutants↗

Reduction of AOX in the bleach plant of a pulp mill.

The reconfiguration of an existing five-stage bleaching D0E1D1E2D2 sequence is proposed to ensure the minimal formation of organochlorine compounds, expressed as AOX, in the bleach plant of a kraft pulp mill processing Eucalyptus globulus wood. This reduction of the load of AOX in the effluents can be achieved without introducing new and expensive technologies in the bleaching process. In practice, this goal can be achieved by eliminating the washing step between the D0 and the E1 stages. With this strategy, the total AOX in the liquid effluent of the bleach plant can be reduced by almost 65% while maintaining a level of 90% ISO brightness of the pulp and even diminishing the degradation of its polysaccharides. With this process redesign, the total AOX discharge from the bleach plant can be decreased from 1.2 to 0.42 kg/t prior to any biological treatment. Furthermore, the proposed modified (D0E1)D1E2D2 sequence enables the reduction of the total flow rate of effluent to be treated and also the total consumption of water, which is quite critical in these types of plants. Moreover, with this strategy, one is able to move the first drum washer of a conventional bleaching sequence to the entrance of the bleach plant. This gives rise to a cleaner pulp and therefore to lower requirements of chlorine dioxide, which in turn will enable further reductions in the global AOX generation.

Adsorption↗

2,6-dichlorophenol, sex pheromone of the lone star tick.

The compound 2,6-dichlorophenol was identified from female lone star ticks, Amblyomma americanum, and is believed to be a sex pheromone of this arthropod. The natural occurrence of a chlorinated organic compound in a land animal is new. The presence of similar compounds of exogenous origin is common in animals, but efforts to implicate an outside source for the halogenated phenol have failed.

Animals↗

Enhanced electro-catalytic degradation of chloroorganic compounds in the presence of ultrasound.

The application of finely divided (black) Pd and Pd-Fe powder in the sono-electro-catalytic reduction of chlorophenoxy herbicides (2,4-D) and chlorophenols (2,4-DCP) in aqueous solutions allows for effective destruction of toxic chlorinated aromatic compounds. At 20 degrees C complete conversion of these compounds is observed within 10 min. On bimetallic Pd/Fe catalyst, intermediates due to the oxidation reaction are detected in addition to the products of dechlorination. The bimetallic catalyst appears to be energetically and economically superior to the Pd. In both cases, the reaction times were considerably shortened in comparison with traditional electro-catalytic processes.

Catalysis↗