New insights into the biodegradation of chlorpyrifos by a novel bacterial consortium: Process optimization using general factorial experimental design.

Himalayan mountains are subjected to the intensive and unjudicial application of chlorpyrifos (CP) in agricultural practices; hence it has spurred concerns over food safety and environmental consequences. These low-temperature mountainous regions are foremost ecosystems, representing the large-scale distribution of cold trapped CP residues. A bacterial consortium ECO-M was formed by isolating the CP degrading bacterial strains viz Agrobacterium tumefaciens strain ECO1, Cellulosimicrobium funkei strain ECO2, Shinella zoogloeoides strain ECO3 and Bacillus aryabhattai strain ECO4. At an initial concentration of 50 mg L-1, consortium ECO-M degraded 100% of CP within 6 days. Emergence and subsequent degradation of the two metabolites, 3, 5, 6-trichloro-2-pyridinol (TCP) and 2-hydroxypyridine were confirmed by GC-MS analysis. A degradation pathway of CP by isolated strains has been proposed. A general factorial experimental design was effectuated to prognosticate the optimum biodegradation by manifesting the optimal biological and physicochemical factors. Fitness of the experimental design was affirmed experimentally by employing optimized factors i.e., temperature 30 °C, CP concentration 50 mg L-1 and an inoculum size of 10% (v/v). The model appropriacy and the rationality of the optimization procedure were appraised by installing an in-situ microcosms experiment using the real contaminated soil collected from the Himalayan mountain ecosystem. The augmentation culture seems to be effectively conspicuous in stimulating maximum degradation up to 94.3% in the CP contaminated soil.

Pyridines from azabicyclo[3.2.0]hept-2-en-4-ones through a proposed azacyclopentadienone.

Pyridines have been formed by heating azabicyclo[3.2.0]hept-2-en-4-ones in toluene. The generation of a 3-azacyclopentadienone intermediate via a [2 + 2]-cycloreversion is proposed as the key step. A Diels-Alder reaction of a styrene, extrusion of carbon monoxide, and loss of hydrogen then gives the pyridine. The process parallels the well-known synthesis of benzenes from cyclopentadienones. The azabicyclo[3.2.0]hept-2-en-4-ones were synthesized from the reaction between readily available cyclopropenones and 1-azetines, in which the cyclopropenones behave as all-carbon 1,3-dipolar equivalents.

Enantiomeric analysis of drugs of abuse in wastewater by chiral liquid chromatography coupled with tandem mass spectrometry.

The manuscript concerns the development and validation of a method for enantiomeric analysis of structurally related amphetamines (amphetamine, methamphetamine, 4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyamphetamine (MDA) and 3,4-methylenedioxy-N-ethylamphetamine (MDEA)), ephedrines (ephedrine, pseudoephedrine and norephedrine) and venlafaxine in wastewater by means of chiral chromatography coupled with tandem mass spectrometry. Solid-phase extraction on Oasis HLB sorbent used for sample clean-up and concentration of analytes resulted in very good recoveries accounting for >70%. Signal suppression during MS analysis was negligible for most studied analytes. Resolution of enantiomers of chiral drugs was found to be higher than 1. Preliminary assay validation was undertaken. The mean correlation coefficients of the calibration curves, which were on average higher than 0.997 for all studied analytes, showed good linearity of the method in the studied range. Intra- and inter-day repeatabilities were on average less than 5%. The method quantification limits in wastewater were at low ppt levels and varied from 2.25 to 11.75ng/L. The method was successfully applied for the analysis of raw and treated wastewater samples collected from four wastewater treatment plants. A common occurrence of 1R,2S (-)-ephedrine, 1S,2S (+)-pseudoephedrine and venlafaxine in both raw and treated wastewater samples was observed. Amphetamine, methamphetamine, MDMA and MDEA were also detected in several wastewater samples. The study of enantiomeric fractions of these chiral drugs proved their variable non-racemic composition. The influence of wastewater treatment processes on the enantiomeric composition of chiral drugs was also noted and might indicate enantioselective processes occurring during treatment, although more comprehensive research has to be undertaken to support this hypothesis.