(Eta3-phenylallyl)(phosphanyloxazoline)palladium complexes: X-ray crystallographic studies,NMR investigations,and Ab initio/DFT calculations

All possible (eta(3)-allyl)palladium complexes (1-4) of the ligand (4S)-[2-(2'-diphenylphosphanyl)phenyl]-4,5-dihydro-4-(2-propyl)-oxazole (L 1) and eta(3)-allyl ligands with one to three phenyl substituents at the terminal allylic centers were synthesized and characterized by X-ray crystal structure analysis and, with respect to allylic isomers, by NMR investigations. Equilibrium geometries, electronic structures, and relative energies of isomeric complexes were computed by restricted Hartree-Fock (RHF) and density functional theory (DFT) calculations; experimentally determined isomer ratios could be reproduced. The results allowed important conclusions to be drawn regarding the mechanism of Pd-catalyzed asymmetric allylic substitutions.     

Selective flow injection analysis of ultra-trace amounts of Cr(VI), preconcentration of it by solvent extraction, and determination by electrothermal atomic absorption spectrometry (ETAAS)

A rapid, robust, sensitive and selective time-based flow injection (FI) on-line solvent extraction system interfaced with electrothermal atomic absorption spectrometry (ETAAS) is described for analyzing ultra-trace amounts of Cr(VI). The sample is initially mixed on-line with isobutyl methyl ketone (IBMK). The Cr(VI) is complexed by reaction with ammonium pyrrolidine dithiocarbamate (APDC), and the non-charged Cr(VI)–PDC chelate formed is extracted into IBMK in a knotted reactor made from PTFE tubing. The organic extractant is separated from the aqueous phase by a gravity phase separator with a small conical cavity and delivered into a collector tube, from which 55 μl organic concentrate is subsequently introduced via an air flow into the graphite tube of the ETAAS instrument. The operations of the FI-system and the ETAAS detector are synchronously coupled. A significant advantage of the approach is that matrix constituents, such as high salt contents, effectively are eliminated. The extraction procedure was optimized by a simplex approach. A central composite design was subsequently employed to verify the estimated operational optimum. An 18-fold enhancement in sensitivity of Cr(VI) was achieved after preconcentration for 99 s at a sample flow rate of 5.5 ml min⁻¹, as compared to direct introduction of 55 μl of sample, yielding a detection limit (3σ) of 3.3 ng l⁻¹. The sampling frequency was 24.2 samples h⁻¹. The proposed method was successfully evaluated by analyzing a NIST Cr(VI)-reference material, synthetic seawater and waste waters, and waste water samples from an incineration plant and a desulphurization plant, respectively.     

Monophthalates with Oxidized C5-Carbon in the Ester Chain: A Simple Synthetic Access to Two Major Metabolites of Bis-(2-ethylhexyl)-phthalate

Summary.  The synthesis of two oxidized metabolites of bis-(2-ethylhexyl)-phthalate is described. The target structures were obtained by esterification of the appropriate alcohol carrying a protected hydroxy group with phthalic anhydride, followed by deprotection and further oxidation. Received February 26, 2002. Accepted March 6, 2002     

Acylderivate cyclischer Verbindungen, 7. Mitt.: o-Diacetyl-cyclopentadien

Bei der Umsetzung von Acetylchlorid mit Cylopentadien entstehen zwei leicht isolierbare Isomere C₉H₁₀O₂. Das tiefer schmelzende Isomere ist o-Diacetyl-cyclopentadien, das als Monoenol (I) vorliegt.

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6. Mitt., Mh. Chem.90, 571 (1959).—Über o-Diacetyl-benzol vgl. 9. Mitt., Mh. Chem.90, 579 (1959). Frühere Literatur ebenda.

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Gleichzeitig 4. Mitt. der Reihe Substitutionsprodukte des Cyclopentadiens; 3. Mitt., Mh. Chem.90, 568 (1959).     

Multiresidue determination of pesticides in drinking and related waters by gas chromatography/mass spectrometry after solid-phase extraction: interlaboratory study

As part of a project funded by the European Commission (EC) for the development and evaluation of multiresidue methods for analysis of drinking and related waters, 15 European laboratories evaluated a method using styrene-divinylbenzene co-polymer solid-phase extraction followed by gas chromatography/mass spectrometry. The main aim of the study was to evaluate whether the method meets the requirements of EC Directive 98/83 in terms of accuracy, precision, and detection limit for 22 pesticides according to the following requirements: limit of detection, < or = 0.025 microg/L; accuracy, expressed as recovery between 75 and 125%; and precision, expressed as repeatability relative standard deviation of the method of < 12.5% and as reproducibility relative standard deviation of the method of < 25%. Analyses for unknown concentrations were performed with fortified commercial bottled and tap waters. All laboratories were able to achieve detection limits of 0.01 microg/L for all pesticides except dimethoate and desisopropylatrazine (0.02 microg/L). The criteria for repeatability were met for all compounds except trifluralin, dimethoate, and lindane in bottled water and chlorpyrifos, dimethoate, and lindane in tap water. The criteria for reproducibility were met for all compounds except trifluralin, dimethoate, and lindane in bottled water and pendimethalin, chlorpyrifos, dimethoate, terbutryn, and lindane in tap water. In terms of accuracy, the method meets the requirements for all pesticides in both matrixes, except for lindane in bottled water and lindane and chlorpyrifos in tap water.     

Determination of water traces in various organic solvents using Karl Fischer method under FIA conditions

Flow injection methods utilising the Karl Fischer (KF) reaction with spectrophotometric and potentiometric detection are described for the determination of the trace water content in various organic solvents. Optimisation of the methods resulted in an accessible (linear) working range of 0.01-0.2% water for many solvents studied with a typical precision of 1-2% R.S.D. Only 50 mul of organic solvent was injected and the sampling frequency was about 120 samples per h. Since the slopes of the calibration curves were different for different solvents appropriate calibration was required. Problems associated with spectrophotometric detection and caused by refractive index changes were pointed out and a nested-loop configuration was proposed to overcome this kind of interference. The potentiometric method with a novel flow-through detector cell was shown to surpass the performance of spectrophotometric detection in any respect. The characteristics of the procedures developed made them well applicable for on-line monitoring of technical solvent distillations in an industrial plant.     

Photocatalytic oxidation of phenol in aqueous solutions with oxygen catalyzed by supported metallophthalocyanine catalyst

In this paper, zinc tetraaminophthalocyanine (Zn-APc) was immobilized on cellulosic fiber by covalent bond to obtain a novel cellulosic fiber supported metallophthalocyanine, named Zn-TDTAPc-F. At pH 11, upon visible light irradiation for 6 h in the presence of O2, Zn-TDTAPc-F was found to be highly effective for the degradation of phenol in aqueous solution, and the degradation rate of phenol was more than 95%. HPLC was used to confirm formic acid, fumaric acid and maleic acid as its main degradation products.     

Analysis of aerosols at the bosporus bridge of Istanbul

Air samples collected at the second Bosporus bridge of Istanbul which carries a heavy traffic load between Asia and Europe, were analyzed for 22 elements by the INAA method. Pb, Cd and Fe concentrations in the samples were determined by AAS. Iron concentrations were used as a cross check between the two methods. In order to define the enrichment factors for the elements in the bridge area, a sample collected from our university campus which can be considered as a rural site, was also analyzed. Differences were observed especially for Br, Al, Mg, Ti, Cu and Na between the two sites. Based on the results of the samples from the bridge, we got a value of 0.58(16) for the Br/Pb-ratio.     

Röntgenographische,thermoelektrische, und IR-spektroskopische Untersuchung des Spinellsystems LixMn1−xV2O4

The spinels of the system Li_xMn_1?xV₂O₄ (0 ? x ? 1) have been prepared at 700–750°C from LiV₂O₄ and MnV₂O₄. The lattice constants decrease linearly with increasing x. In the region x>0.75, the d-electrons of V should be delocalized as the VV distances are lower than the critical VV separation of 2.94 Å. Experimentally, the samples with x>0.6 show no IR absorption bands and the Seebeck coefficient is near zero. The Seebeck coefficient can be described with a model of intermediate polarons and can be expressed by the equation $\text{Θ = 198}\text{log}\text{[1 +}\text{(1 ? x)}{}^5\text{x}\text{]}$.