Simultaneous Determination of As,Bi, Sb,Se, Te,Hg, Pb and Sn by Small-Sized Electrothermal Vaporization Capacitively Coupled Plasma Microtorch Optical Emission Spectrometry Using Direct Liquid Microsampling

The simultaneous determination of chemical vapor-generating elements involving derivatization is difficult even by inductively coupled plasma optical emission spectrometry or mass spectrometry. This study proposes a new direct liquid microsampling method for the simultaneous determination of As, Bi, Se, Te, Hg, Pb, and Sn, using a fully miniaturized set-up based on electrothermal vaporization capacitively coupled plasma microtorch optical emission spectrometry. The method is cost-effective, free from non-spectral interference, and easy to run by avoiding derivatization. The method involves the vaporization of analytes from the 10 µL sample and recording of episodic spectra generated in low-power (15 W) and low-Ar consumption (150 mL min⁻¹) plasma microtorch interfaced with low-resolution microspectrometers. Selective vaporization at 1300 °C ensured the avoidance of non-spectral effects and allowed the use of external calibration. Several spectral lines for each element even in the range 180–210 nm could be selected. Generally, this spectral range is examined with large-scale instrumentation. Even in the absence of derivatization, the obtained detection limits were low (0.02–0.75 mg kg⁻¹) and allowed analysis of environmental samples, such as cave and river sediments. The recovery was in the range of 86–116%, and the accuracy was better than 10%. The method is of general interest and could be implemented on any miniaturized or classical laboratory spectrometric instrumentation.     

Semiclassical analysis of low and zero energy scattering for one-dimensional Schrödinger operators with inverse square potentials

This paper studies the scattering matrix S(E;?) of the problem

−?²ψ^″(x)+V(x)ψ(x)=Eψ(x)     

Slow dynamics in glassy methyl alpha-l-rhamnopyranoside studied by 1D NMR exchange experiments

It is widely known that the ability of sugar glasses to preserve anhydrobiotic systems in nature is important but the process is not yet fully understood. Molecular motions in the glassy state are likely to be important in the process but until now have remained largely uncharacterized. Here we describe the use of 1D 13C NMR exchange experiments using CODEX (centreband only detection of exchange) methods to study the dynamics of the well characterised model glassy monosaccharide, methyl alpha-l-rhamnopyranoside. The glass was prepared by fast cooling of a melt inside an NMR rotor. Molecular motions in the range of seconds to milliseconds were observed in the glass, whereas identical experiments using the crystalline material displayed no observable motions in the time-scales covered by the experiment. At 13 to 14 K above Tg the nature of the motion in the glass changed probably due to the onset of larger scale reorientation. A bimodal distribution of jump angles combined with a broad distribution of correlation times was found to best represent the observed motions.     

Giant proximity effect in a phase-fluctuating superconductor

When a tunneling barrier between two superconductors is formed by a normal material that would be a superconductor in the absence of phase fluctuations, the resulting Josephson effect can undergo an enormous enhancement. We establish this novel proximity effect by a general argument as well as a numerical simulation and argue that it may underlie recent experimental observations of the giant proximity effect between two cuprate superconductors separated by a barrier made of the same material rendered normal by severe underdoping.     

Superparamagnetic magnetite–divinylbenzene–maleic anhydride copolymer nanocomposites obtained by dispersion polymerization

Magnetite alternating copolymers divinylbenzene–maleic anhydride (DVB–MA) composites were prepared by dispersion polymerization. Because magnetite is used as a complex with oleic acid (Fe₃O₄OLA), the final hybrids show good dispersion of inorganic nanofillers in the polymer matrix. The obtained composites were analyzed by infrared absorption spectrometry, diffuse reflectance in visible light, thermogravimetry, X-ray fluorescence, X-ray diffraction, dynamic light scattering, scanning electron microscopy and vibrating sample magnetometry. The obtained results indicate the successful preparation of magnetite nanoparticles with an average size of about 23 nm dispersed in micrometer size copolymer spherical particles, which relative content can be controlled via the processing parameters. A relationship between the relative content of magnetite nanoparticles and the size of the polymer particles, with direct influence on the diffuse reflectance in the visible domain, was observed. A superparamagnetic behavior was evidenced at room temperature with a blocking temperature lower than as expected from the bulk anisotropy constant and the average size of the magnetite nanoparticles. Both the unexpected low blocking temperature and the observed low specific magnetizations were explained by a defected and poor crystalline structure of the magnetite nanoparticles, giving rise to spin disorder and diminished crystalline anisotropy constant.     

General Two‐Step Preparation of Chalcones Containing Thiazole

2‐Aryl‐4‐methyl‐5‐acetylthiazoles, which were prepared from arylthioamides and chloroacetylacetone, were treated with 6‐substituted‐3‐formylchromones or arylaldehydes to give a series of eighteen new thiazolylchalcones in good yields. The structures of all the synthesized compounds were characterized by ¹H NMR, ¹³C NMR, and ES‐MS spectrometry. Additionally, the crystal structures of two of these chalcones were determined by X‐ray diffraction analysis.     

Analysis of the flame retardant metabolites bis(1,3-dichloro-2-propyl) phosphate (BDCPP) and diphenyl phosphate (DPP) in urine using liquid chromatography–tandem mass spectrometry

Organophosphate triesters tris(1,3-dichloro-2-propyl) phosphate (TDCPP) and triphenyl phosphate are widely used flame retardants (FRs) present in many products common to human environments, yet understanding of human exposure and health effects of these compounds is limited. Monitoring urinary metabolites as biomarkers of exposure can be a valuable aid for improving this understanding; however, no previously published method exists for the analysis of the primary TDCPP metabolite, bis(1,3-dichloro-2-propyl) phosphate (BDCPP), in human urine. Here, we present a method to extract the metabolites BDCPP and diphenyl phosphate (DPP) in human urine using mixed-mode anion exchange solid phase extraction and mass-labeled internal standards with analysis by atmospheric pressure chemical ionization liquid chromatography tandem mass spectrometry. The method detection limit was 8 pg mL⁻¹ urine for BDCPP and 204 pg mL⁻¹ for DPP. Recoveries of analytes spiked into urine ranged from 82 ± 10% to 91 ± 4% for BDCPP and from 72 ± 12% to 76 ± 8% for DPP. Analysis of a small number of urine samples (n = 9) randomly collected from non-occupationally exposed adults revealed the presence of both BDCPP and DPP in all samples. Non-normalized urinary concentrations ranged from 46–1,662 pg BDCPP mL⁻¹ to 287–7,443 pg DPP mL⁻¹, with geometric means of 147 pg BDCPP mL⁻¹ and 1,074 pg DPP mL⁻¹. Levels of DPP were higher than those of BDCPP in 89% of samples. The presented method is simple and sufficiently sensitive to detect these FR metabolites in humans and may be applied to future studies to increase our understanding of exposure to and potential health effects from FRs.     

Recent developments in the analysis of brominated flame retardants and brominated natural compounds

This article reviews recent literature on the analysis of brominated flame retardants (BFRs) and brominated natural compounds (BNCs). The main literature sources are reviews from the last five years and research articles reporting new analytical developments published between 2003 and 2006. Sample pretreatment, extraction, clean-up and fractionation, injection techniques, chromatographic separation, detection methods, quality control and method validation are discussed. Only few new techniques, such as solid-phase microextraction (SPME) or pressurized liquid extraction (PLE), have been investigated for their ability of combining the extraction and clean-up steps. With respect to the separation of BFRs, the most important developments were the use of comprehensive two-dimensional gas chromatography for polybrominated diphenyl ethers (PBDEs) and the growing tendency for liquid-chromatographic techniques for hexabromocyclododecane (HBCD) stereoisomers and of tetrabromobisphenol-A (TBBP-A). At the detection stage, mass spectrometry (MS) has been developed as well-established and reliable technology in the identification and quantification of BFRs. A growing attention has been paid to quality assurance. Interlaboratory exercises directed towards BFRs have grown in popularity and have enabled laboratories to validate analytical methods and to guarantee the quality of their results. The analytical procedures used for the identification and characterization of several classes of BNCs, such as methoxylated polybrominated diphenyl ethers (MeO-PBDEs) (also metabolites of PBDEs), halogenated methyl or dimethyl bipyrroles (DBPs), are reviewed here for the first time. These compounds were generally identified during the routine analysis of BFRs and have received little attention until recently. For each topic, an overview is presented of its current status.     

1,1,1,1,4,4,4,4‐Octacarbonyl‐2,2,3,3,5,5,6,6‐octamethyl‐cyclo‐2,3,5,6‐tetraantimony‐1,4‐dichromium

The structure of the title compound, alternatively called bis(μ‐tetramethyldistibinediyl)bis(tetracarbonylchromium), [Cr₂Sb₄(CH₃)₈(CO)₈], consists of two Me₄Sb₂ bridging units between Cr(CO)₄ complex fragments. The centre of the molecule is located on a special position of 2/m symmetry. This is the first characterized Sb₄Cr₂ heterocycle.