Highly selective solid-phase extraction and large volume injection for the robust gas chromatography-mass spectrometric analysis of TCA and TBA in wines

A reliable solid-phase extraction (SPE) method for the simultaneous determination of 2,4,6-trichloroanisole (TCA) and 2,4,6-tribromoanisole (TBA) in wines has been developed. In the proposed procedure 50 mL of wine are extracted in a 1 mL cartridge filled with 50 mg of LiChrolut EN resins. Most wine volatiles are washed up with 12.5 mL of a water:methanol solution (70%, v/v) containing 1% of NaHCO3. Analytes are further eluted with 0.6 mL of dichloromethane. A 40 microL aliquot of this extract is directly injected into a PTV injector operated in the solvent split mode, and analysed by gas chromatography (GC)-ion trap mass spectrometry using the selected ion storage mode. The solid-phase extraction, including sample volume and rinsing and elution solvents, and the large volume GC injection have been carefully evaluated and optimized. The resulting method is precise (RSD (%) < 6% at 100 ng L(-1)), sensitive (LOD were 0.2 and 0.4 ng/L for TCA and TBA, respectively), robust (the absolute recoveries of both analytes are higher than 80% and consistent wine to wine) and friendly to the GC-MS system (the extract is clean, simple and free from non-volatiles).     

Effects of O ions beam irradiation on crystal structure of rare earth sesquioxides

We report the results of ion irradiation influence on rare earth sesquioxides structure, which are materials of practical importance as a radiation resistant ceramics in nuclear applications. Y₂O₃, Gd₂O₃ and Er₂O₃ sesquioxides in the pellet form were irradiated by oxygen ions (O²⁺) beam with the energy of 30 keV and implantation fluence of 5 × 10²⁰ m⁻². Samples are characterized by Grazing Incidence X-ray Diffraction (GIXRD), Raman spectroscopy and atomic force microscopy (AFM). By GIXRD it was found partial transformation from cubic (C) to monoclinic (B) phase only in Gd₂O₃, induced by O²⁺ irradiation. This was confirmed by Raman spectroscopy. Although full phase transition from C to B phase in Y₂O₃ was not observed, the splitting and broadening of the main intensity Raman band for C phase could be explained by the stress and the disorder induced by the quenching. Analysis done by AFM showed changes in surface topology, i.e. values of average roughness (Ra) and root mean squared roughness (RMS) were significantly changed after irradiation for all samples. RMSs in Y₂O₃ before and after irradiation were 35 nm and 26 nm, respectively.     

Odour-causing organic compounds in wastewater treatment plants: evaluation of headspace solid-phase microextraction as a concentration technique

Odorous emissions from wastewater collection systems and treatment facilities affecting quality of life have given local populations reasons to complain for decades. In order to characterise the composition of such malodorous emissions, a method based on headspace solid-phase microextraction (HS-SPME) and gas chromatography coupled to mass spectrometry (GC-MS) has been developed to determine a list of compounds belonging to different chemical families, which have been previously described as potentially responsible for odour complaints, in wastewater matrices. Some parameters affecting the chromatographic behaviour of the target compounds were studied (e.g. splitless time). Experimental conditions affecting the extraction process (temperature, time and salt content) were evaluated by applying a factorial design at two levels. Using a DVB/CAR/PDMS fibre and the optimised HS-SPME conditions, calibration curves were constructed with detection limits in the range of 0.003-0.6 μg L(-1). Recovery values higher than 70% and relative standard deviation values between 5 and 16% (n=5) were obtained for all compounds and found to be satisfactory. In wastewater samples, a decrease in the concentration of the analysed compounds through the different treatments was observed. Most of the target analytes were found in influent samples while only octanal and carvone were detected in samples from the plant effluent.     

Development of solid-phase extraction and solid-phase microextraction methods for the determination of chlorophenols in cork macerate and wine samples

Tri-, tetra- and pentachlorophenol (TCP, TeCP and PCP) can be considered the precursors in the formation of corresponding chloroanisoles, known to be powerful odorants in corks and wine. Determining the presence of these chlorophenolic compounds in cork soaking solutions (ethanol/water mixtures, 12% (v/v) ethanol used for cork quality control testing), or in wine can be achieved by acetylation/gas chromatography electron-capture detection. In order to reach the required sensitivity, a previous preconcentration step is necessary. Solid-phase extraction (SPE) and headspace solid-phase microextraction (HS-SPME) have given good results for the preconcentration of TCP, TeCP and PCP in such matrices. The use of Oasis HLB cartridges gives acceptable recoveries for the three compounds when different volumes (50-250 mL) of cork macerate with concentrations ranging from 20 to 150 ng/L are processed. Preconcentration based on HS-SPME has also been optimised with a 100 microm polydimethylsiloxane fibre and in situ derivatization. The HS-SPME method allows chlorophenols in a cork soaking solution and in wine to be determined with a limit of detection of 1 ng/L for each compound (in cork macerate) and a repeatability of around 0.5%-5% (n=8) for a concentration level of 30 ng/L.     

Tetra­aqua(3,4,7,8‐tetra­methyl‐1,10‐phenanthroline‐κ2N,N′)­zinc(II) thio­sulfate

In the title complex of zinc(II) with 3,4,7,8‐tetra­methyl‐1,10‐phenanthroline (tmph), viz. [Zn(C₁₆H₁₆N₂)(H₂O)₄](S₂O₃), the metal atom has a monomeric octahedral ZnN₂O₄ complex environment comprising two N‐atom donors from the tmph group and four aqua O‐atom donors. The complex cation is connected to four thio­sulfate anions through a compact hydrogen‐bonding network involving all coordinated aqua H‐atom donors and all the outer acceptors (O and S) of the anion.     

The Bott-Borel-Weil Theorem for direct limit groups

We show how highest weight representations of certain infinite dimensional Lie groups can be realized on cohomology spaces of holomorphic vector bundles. This extends the classical Bott-Borel-Weil Theorem for finite-dimensional compact and complex Lie groups. Our approach is geometric in nature, in the spirit of Bott's original generalization of the Borel-Weil Theorem. The groups for which we prove this theorem are strict direct limits of compact Lie groups, or their complexifications. We previously proved that such groups have an analytic structure. Our result applies to most of the familiar examples of direct limits of classical groups. We also introduce new examples involving iterated embeddings of the classical groups and see exactly how our results hold in those cases. One of the technical problems here is that, in general, the limit Lie algebras will have root systems but need not have root spaces, so we need to develop machinery to handle this somewhat delicate situation.

     

A Power Interruption Technique for Investigation of Temperature Difference in Stabilized Low Direct-Current Arc Burning in Pure Argon on Atmospheric Pressure

Plasma of argon stabilized arc column, in a current range 3-11 A, is investigated using emission spectrometric diagnostic techniques. Temperatures are evaluated using several methods： argon line to adjacent recombinational continuum intensity ratio, absolute emissivity of argon line, measurement of electron number density, and power interruption. Electron number density is evaluated from absolute emissivity of recombinational continuum. The difference between electron Te and heavy particle Th temperature ranged from 4500 K for 3 A to 2300 K for 11A arc current. By comparing the present with the previously obtained results, using the same arc device but with the introduction of water aerosol, it is concluded that water aerosol reduces the difference Te - Th and brings plasma closer to the partial thermodynamic equilibrium state.     

An anisaldehyde sodium bisulfite derivative: poly[[μ4‐(hydroxy)(4‐methoxyphenyl)methanesulfonato]sodium]

The title complex, [Na(C₈H₉O₅S)]_n, is polymeric and consists of broad layers parallel to (100) made up of an inner hydrophilic core of Na⁺ cations and polar SO₃C(OH)– groups, padded on both sides by two hydrophobic layers of pendant methoxyphenyl groups. The Na⁺ cations in the inner core are six‐coordinated into highly distorted NaO₆ octahedra by four symmetry‐related (hydroxy)(4‐methoxyphenyl)methanesulfonate anions, leading to a tightly woven two‐dimensional structure. While there are some hydrogen bonds providing interplanar cohesion, interactions between adjacent layers are weak hydrophobic ones. The present compound appears to be the first reported structure containing the (hydroxy)(4‐methoxyphenyl)methanesulfonate ligand.     

Selective linkage detection of O‐sialoglycan isomers by negative electrospray ionization ion trap tandem mass spectrometry

Sialylated O‐linked oligosaccharides are involved in many biological processes, such as cell‐cell interactions, cell‐substance adhesion, and virus‐host interactions. These activities depend on their structure, which is frequently determined by tandem mass spectrometry. However, these spectra are frequently analyzer‐dependent, which makes it difficult to develop widely applicable analytical methods. In order to deepen the origin of this behavior, two couples of isomers of sialylated O‐linked oligosaccharides, NeuAcα2‐3Galβ1‐3GalNAc‐ol/Galβ1‐3(NeuAcα2‐6)GalNAc‐ol and NeuGcα2‐3Galβ1‐3GalNAc‐ol/Galβ1‐3(NeuGcα2‐6)GalNAc‐ol, were analyzed by liquid chromatography/negative electrospray ionization ion trap tandem mass spectrometry (LC/ESI(?)‐MSⁿ) using both an ion trap and a triple quadrupole mass spectrometer. Results clearly showed that while ions obtained in the triple quadrupole instrument fitted very well with the standard fragmentation routes, in the ion trap several intense ions could not be explained by these rules, specially a fragment at m/z 597. Furthermore, this ion was observed in the mass spectrum of those isomers that sialic acid binds to GalNAc by an α2‐6 linkage. From the MS³ spectrum of this ion an unexpected structure was deduced, and it led to propose alternative fragmentation pathways. Molecular mechanics calculations suggested that the found atypical route could be promoted by a hydrogen bond located only in α2‐6‐linked oligosaccharides. It has also been demonstrated that this process follows a slow kinetic, explaining why it cannot be observed using an ion beam‐type mass analyzer. In conclusion, ion traps seem to be more appropriate than triple quadrupoles to develop a reliable analytical method to distinguish between isomeric O‐linked glycans. Copyright © 2010 John Wiley & Sons, Ltd.