Measurement of PCDDs, PCDFs, and non-ortho-PCBs by comprehensive two-dimensional gas chromatography-isotope dilution time-of-flight mass spectrometry (GC x GC-IDTOFMS)

Comprehensive two-dimensional gas chromatography with isotope-dilution time-of-flight mass spectrometry (GC × GC-IDTOFMS) was used to measure polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF), and coplanar polychlorinated biphenyl (cPCB) concentrations in ash, sediment, vegetation, and fish samples. The GC × GC capability was achieved by using a quad jet, dual stage, thermal modulator. Zone compression of the GC peaks from modulation resulted in a significant increase of the signal intensity over classical GC-IDTOFMS. The GC × GC column set used an Rtx-Dioxin 2 phase as the first dimension (¹D) and an Rtx-500 as the second dimension (²D). The chromatographic separation of the 17 PCDD/Fs and the 4 cPCBs was attained in ¹D except for 2,3,7,8-TCDD and CB126 for which deconvoluted ion currents (DIC) were required to be reported separately. The Rtx-500 phase separated the bulk matrix interfering compounds from the target analytes in ²D. The instrumental limit of detection (iLODs) was 0.5 pg for 2,3,7,8-TCDD. The calibration curves showed good correlation coefficients for all the compounds investigated in the concentration range of 0.5–200 pg. GC × GC-IDTOFMS results compared favorably to those from conventional isotope-dilution one-dimensional gas chromatography-high resolution mass spectrometry (GC-IDHRMS). The comprehensive mass analysis of the TOFMS further permitted the identification of other contaminants of concern in the samples.     

Sensing and photocatalytic properties of nanosized Cu(I)CN organotin supramolecular coordination polymer based on pyrazine

Orange prismatic crystals of the supramolecular coordination polymer (SCP) _∞³[Cu(CN)₂(Me₃Sn)(Pyz)], SCP 1 , were synthesized using a self‐assembly method under ambient conditions. Nanosized 1 was obtained using the same molar ratio in water by ultrasonic irradiation. SCP 1 was characterized using single‐crystal X‐ray diffraction, elemental analysis, thermal analysis and Fourier transform infrared spectroscopy. SCP 1 and its nanosized 1 particles were also examined using powder X‐ay diffraction and scanning electron microscopy. The luminescence emission of SCP 1 was studied as well as its use as a sensor for the detection of common organic solvents and metal ions. Also, the catalytic activities of nanosized 1 towards various organic dyes were investigated under ambient conditions, UV irradiation and ultrasonic irradiation. Nanosized 1 as a heterogeneous nanoparticle catalyst exhibits high catalytic activity for the degradation of eosin‐Y and acid blue dyes. The mechanism of degradation investigated using various scavenger techniques is proposed and discussed. The catalytic oxidation process is mainly caused by ?OH radicals.     

A New Reaction Involving the Formation of Unsaturated Carbenes

Treatment of 5,5-dialkyl-N-nitrosooxazolidones (1) with Lithium ethoxide (and other bases) under certain conditions yields reaction products the formation of which seems best explained by assuming that unsaturated carbenes [A] are involved.^3–5     

The Effect of Added Salts and Organics on the Cloud Point of TX‐114

Herein we report the effect of additives (salts and organics) on the cloud point (CP) of nonionic surfactant Triton X‐114 (TX‐114) aqueous solutions. CP showed a concentration dependent variation in the absence of any added compound. Addition of quaternary ammonium (or phosphonium) bromides to 0.8 mM TX‐114 solutions increased the CP. It was found that long chain alcohols and amines decreased the CP of 0.8 mM TX‐114 +80 mM Bu₄AmB aqueous system, while it either remained constant or increased in the presence of short chain additives. The effect of first group additives (long chain) can be explained by considering that these additives solubilize in interfacial region and assist in micellar growth. Short chain additives remain in aqueous phase and affect the micelle hydration by affecting the solvent. Pentylamine behaved differently than pentanol: pentylamine increased the CP (like short chain additives) while pentanol decreased the CP. In pentylamine, the hydrophilicity of NH₂ group and its dissociation into NH₃ ⁺ dominates over the hydrophobicity of its alkyl chain. Aliphatic hydrocarbons first decreased and then increased the CP. The overall behavior depended upon the chain length of the hydrocarbon. With decane, the CP decreasing region disappeared completely.     

Kinetics of an exciton-trion system in shallow GaAs/AlGaAs quantum wells

The formation of three-particle charged exciton complexes (trions) in shallow GaAs/AlGaAs quantum wells in the temperature range 1.7–15 K has been investigated by luminescence spectroscopy and resonant light scattering. The effect of the photon energy and the intensity of additional above-barrier illumination on the trion formation kinetics has been analyzed. It is established that, upon intrawell excitation, illumination leads to the formation of trions when the light photon energy corresponds to the regions of effective formation of trions in the photoluminescence excitation spectra. It is shown that, with an increase in the illumination level, the trion concentration first increases and then reaches a plateau since the quantum well acquires an electric charge whose field equalizes the electron and hole capture rates.     

Role of cationic gemini surfactants toward enhanced ninhydrin–tryptophan reaction

In this paper we report the effect of dicationic ‘gemini’ surfactants (CH₃)₂C₁₆H₃₃N⁺? (CH₂)_m? N⁺C₁₆H₃₃(CH₃)₂, 2Br^? (where m = 4, 5, 6) on the reaction of ninhydrin with DL ‐tryptophan. The gemini surfactant micellar media are comparatively more effective than their conventional monomeric counterpart cetyltrimethylammonium bromide (CTAB) micelles. Also, whereas typical rate constant (k_ψ) increase and leveling‐off regions, just like CTAB, are observed with geminis, the latter produce a third region of increasing k_ψ at higher concentrations. These subsequent increases are ascribed to changes in micellar morphologies, consistent with changes in ¹H NMR line widths. Quantitative kinetic analysis of the rate constant–[surfactant] data has been performed on the basis of modified pseudophase model. Copyright © 2007 John Wiley & Sons, Ltd.     

Three‐dimensional organotin–hexacyanoferrate polymers as effective oxidizing reagents towards phenols

Three‐dimensional organotin–hexacyanoferrate polymers of the type _∞³[(R₃Sn)₃Fe^III(CN)₆] where R = Me (I), n‐butyl (II) and phenyl (III), represent members of the family of supramolecular coordination polymers (SCPs) which have zeolitic‐like structure containing micropores. The structures of I–III contain wide channels capable of encapsulating resorcinol, which undergoes in situ oxidation to 1,3,4‐trihydroxy benzene (THB) or p‐nitrophenol (PNP), which converts to 1,4‐benzoquinone (BQ) and 2‐hydroxybenzoquinone (2‐HBQ). The oxidation products were investigated by spectroscopic methods and by HPLC. The SCP III was found to be a more effective oxidizing reagent than I and II due to the presence of terminal Sn‐OH₂ groups hydrogen bonded to one‐sixth of the terminal CN groups, causing more wide expandable channels. In addition, mechanisms of the oxidation processes of resorcinol and PNP have been proposed. Copyright © 2010 John Wiley & Sons, Ltd.     

Evaluation of the morphology of particles produced by plasma-chemical synthesis of ceramic powders

A physicomathematical model of thermal and diffusion processes in a drop of a dilute metal salt solution during its heating in a plasma-chemical reactor for synthesizing metal oxide powders is presented. The results of numerical calculations are analyzed to assess the possible influence of the operation parameters of the reactor and the characteristics of the initial solution (precursor) on the morphology of the particles formed.     

Detecting and filtering a flow of different pulsed signals against the noise background

We consider the problem of separate detection and filtration of a flow of pulsed signals. We assume that statistically independent pulsed signals of different shape and random amplitude appear randomly against the background of noise. An algorithm for estimation of the detection probability of each signal is obtained. Recurrent expressions for thea posteriori probability density of each signal are found. The results of numerical simulation of the proposed algorithms of signal processing are presented. Lobachevsky State University of Nizhny Novgorod Russia. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 42, No. 1, pp. 92–100, January, 1999.     

Definability of Abelian groups by homomorphism groups and endomorphism semigroups

In the paper, the isomorphism problem for completely decomposable Abelian torsion-free groups of finite rank is treated under the assumption that the groups of homomorphisms of these groups into some Abelian group are isomorphic and, moreover, the endomorphism semigroups of the groups are isomorphic.