Laser performance of pyrromethene 567 dye in solid matrices of methyl methacrylate with different comonomers

Laser performance of pyrromethene 567 (PM567) dye dissolved in pure poly(methyl methacrylate) homopolymer and its copolymers with 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1-vinyl-2-pyrrolidone, 2-phenoxyethyl acrylate, and 2,2,2-trifluoromethyl methacrylate has been investigated. The chosen monomers were selected to mimic solvents used in a previous study on the photophysical and lasing properties of PM567 in liquid solution in order to establish correlations between the lasing properties of PM567 in liquid and solid solutions. The vol/vol proportion of the different comonomers in each copolymer formulation was systematically varied, and the effect of each composition on the lasing properties of PM567 was evaluated. The laser samples were transversely pumped at 534 nm with 5.5-mJ pulses from a frequency-doubled Q-switched Nd:KGW laser. Lasing efficiencies of up to 30% and good photostabilities, with a drop of the initial laser output of 20% after 10000 pump pulses in some of the solid samples, were demonstrated. Received: 2 June 1999 / Revised version: 18 July 1999 / Published online: 3 November 1999     

Experimental Study of a Ka-Band Cylindrical Open Resonator

A study of the electrodynamical properties of a Ka-band gyrotron open resonator was experimentally conducted. Experiments were accomplished to measure resonant frequencies and their respective loaded quality factors for TE modes in the frequency range from 26 to 40 GHz. In particular, a perturbation technique was used to determine the axial, radial and azimuthal electric field profiles, as an identification method of the TE₀₂₁ mode operating around 35 GHz. In any experimental event, good agreement with the values predicted by theory was found.     

Vibrational overtone spectroscopy, energy levels, and intensities of (CH3)3C-C≡C-H

The vibrational overtone spectra of the acetylenic (Δυ = 4, 5) and methyl (Δυ = 5, 6) C-H stretch transitions of tert-butyl acetylene [(CH(3))(3)C-C≡C-H] were obtained using the phase shift cavity ring down (PS-CRD) technique at 295 K. The C-H stretch fundamental and overtone absorptions of the acetylenic (Δυ = 2 and 3) and methyl (Δυ = 2-4) C-H bonds have been obtained using a Fourier transform infrared and near-infrared spectrophotometer. Harmonic frequency ω(ν(1)) and anharmonicities x(ν(1)) and x(ν(1), ν(24)) are reported for the acetylenic C-H bond. Molecular orbital calculations of geometry and vibrational frequencies were performed. A harmonically coupled anharmonic oscillator (HCAO) model was used to determine the overtone energy levels and assign the absorption bands to vibrational transitions of methyl C-H bonds. Band strength values were obtained experimentally and compared with intensities calculated in terms of the HCAO model where only the C-H modes are considered. No adjustable parameters were used to get order of magnitude agreement with experimental intensities for all pure local mode C-H transitions.     

Optimization of a New Extraction Technique for Analysis of Verbenone and cis-Verbenol in Pine Seeds

Results from a systematic study of the factors affecting extraction of cis-verbenol and verbenone from pine seeds are presented. Five extraction conditions were investigated: extraction solvent, method of extraction, extraction temperature, volume of solvent, and the ratio of the mass of sample to the amount of extraction solvent. The resulting optimized method uses magnetic-stirring-assisted extraction of pine seeds (5 g) with ethyl acetate (75 mL) for 20 min, at room temperature. RSDs were less than 5% for both compounds. GC–FID was used for quantification of cis-verbenol and verbenone in the extracts.     

In-line pressurized-fluid extraction-solid-phase extraction for determining phenolic compounds in grapes

A procedure to determine 3-alkyl-2-methoxypyrazines in wines is described. It is based on the headspace solid-phase microextraction (HS-SPME) technique after a clean-up of the sample by distillation (previously acidified to pH 0.5) to remove ethanol and other volatile compounds that can interfere in the SPME. Determination is performed by means of capillary gas chromatography using a nitrogen-phosphorus detector. The method allows quantification of 3-isobutyl-2-methoxypyrazine, 3-sec-butyl-2-methoxypyrazine and 3-isopropyl-2-methoxypyrazine at their natural concentration levels and below their sensory thresholds in Cabernet Sauvignon and Merlot wines. The method was successfully applied to experimental red wines and the evolution of their pyrazine contents during the winemaking process was monitored. Pyrazine content increased during the first maceration day but did not change significantly during alcoholic and malolactic fermentation. Final contents in wines were 12-27 ng/l of 3-isobutyl-2-methoxypyrazine and 5-10 ng/l of 3-sec-butyl-2-methoxypyrazine.     

The vacuum of supersymmetric SU(3) × SU(2) × U(1)

We show that in supersymmetric SU(3) × SU(2) × U(1) it is possible to break SU(2) with an Higgs singlet and at the same time to avoid vacuum expectation values for s-fermions. With rather simple constraints we obtain important restrictions on the values of the model parameters.     

Validation of two analytical methods for the determination of ochratoxin A by reversed-phased high-performance liquid chromatography coupled to fluorescence detection in musts and sweet wines from Andalusia

Some Spanish sweet wines are made from raisins, grapes dried by direct exposure to the sun after picking. This drying process can encourage ochratoxin A (OTA) formation. OTA is a mycotoxin formed by several fungi. It has been linked to nephropathy in humans, and may have a long half-life in humans. The aim of this study is to develop and to apply two procedures for the analysis of OTA in grape musts (during the raisining process) and sweet wines, respectively. Reversed-phase high-performance liquid chromatography (RP-HPLC) coupled to fluorescence detection (FLD) was employed in both analytical methods. In grape must, the method involves the direct injection of the sample in a HPLC-FLD system without any kind of prior clean-up procedure. The complexity of the sweet wine samples requires a solid-phase extraction (SPE) clean-up on a C18 column which enables the OTA to be isolated from the matrix. The methods used were statistically validated. The validation also included the comparison of the slopes of the curve obtained with standards and the regression curves obtained by the addition of a standard. Two different studies of standard additions were conducted. One method was validated without sample preparation and it was applied to must samples. The other method was validated with SPE extraction and it was applied to sweet wine samples. Recovery was always better than 89.69%. The limit of detection (S/N = 3) and limit of quantification (S/N = 10) were established at 0.22 and 0.77 μg l⁻¹, respectively. In general, the analytical data obtained provided good results at the sub-μg l⁻¹ concentration level.     

Exploiting Synergistic Effects in Organozinc Chemistry for Direct Stereoselective C‐Glycosylation Reactions at Room Temperature

Pairing a range of bis(aryl) zinc reagents ZnAr₂ with the stronger Lewis acidic [(ZnAr^F₂)] (Ar^F=C₆F₅), enables highly stereoselective cross‐coupling between glycosyl bromides and ZnAr₂ without the use of a transition metal. Reactions occur at room temperature with excellent levels of stereoselectivity, where ZnAr^F₂ acts as a non‐coupling partner although its presence is crucial for the execution of the C(sp²)–C(sp³) bond formation process. Mechanistic studies have uncovered a unique synergistic partnership between the two zinc reagents, which circumvents the need for transition‐metal catalysis or forcing reaction conditions. Key to the success of the coupling is the avoidance of solvents that act as Lewis bases versus diarylzinc compounds (e.g. THF).     

Structure and Bonding in CE5− (E=Al–Tl) Clusters: Planar Tetracoordinate Carbon versus Pentacoordinate Carbon

The structure, bonding, and stability of clusters with the empirical formula CE₅^? (E=Al–Tl) have been analyzed by means of high‐level computations. The results indicate that, whereas aluminum and gallium clusters have C_2v structures with a planar tetracoordinate carbon (ptC), their heavier homologues prefer three‐dimensional C_4v forms with a pentacoordinate carbon center over the ptC one. The reason for such a preference is a delicate balance between the interaction energy of the fifth E atom with CE₄ and the distortion energy. Moreover, bonding analysis shows that the ptC systems can be better described as CE₄^?, with 17‐valence electrons interacting with E. The ptC core in these systems exhibits double aromatic (both σ and π) behavior, but the σ contribution is dominating.