Mass spectrometry of onium compounds-XVIII: Evaporation of N-arylpyridinium-3-oxides

Comparision of the fragmentation patterns and ionisation potentials for 3-hydroxy-2-phenylpyridine and N-arylpyridinium-3-oxides shows that the latter are evaporated as mesoins. The 2,4-dinitrophenyl derivative constitutes an exception in that transarylation to the corresponding ether takes place before evaporation.     

Free and total para-aminobenzoic acid analysis in plants with high-performance liquid chromatography/tandem mass spectrometry

para-Aminobenzoic acid (PABA), a precursor in the synthesis of folates in plants, is determined by liquid chromatography/tandem mass spectrometry (LC/MS/MS). In plants PABA can be converted into its beta-D-glucopyranosyl ester (PABA-Glc) and can also exist in its free form. In this work, we developed and validated a quantitative method to study free and total PABA in plants. The total PABA (free PABA plus PABA-Glc) can be evaluated after acid hydrolysis at 80 degrees C for 2 hours. The plant material is homogenized and the PABA content is quantified using the standard addition procedure. The validated method is selective, sensitive, simple, accurate, has a recovery between 99.6 to 102.5%, is reproducible (RSD between 1.4 and 4.4%), and is linear between 2.5 and 1538 ng/mL. Free and total PABA determinations in five vegetables showed that different plant species had different amounts of free and total PABA, and that the ratios of total versus free PABA were also variable. This new method could be valuable for studies of folate synthesis in plants.     

Activation of crystalline cellulose surfaces through the chemoenzymatic modification of xyloglucan

Cellulose constitutes an important raw material for many industries. However, the superb load-bearing properties of cellulose are accompanied by poor chemical reactivity. The hydroxyl groups on cellulose surfaces can be reacted but usually not without loss of fiber integrity and strength. Here, we describe a novel chemoenzymatic approach for the efficient incorporation of chemical functionality onto cellulose surfaces. The modification is brought about by using a transglycosylating enzyme, xyloglucan endotranglycosylase, to join chemically modified xyloglucan oligosaccharides to xyloglucan, which has a naturally high affinity to cellulose. Binding of the chemically modified hemicellulose molecules can thus be used to attach a wide variety of chemical moieties without disruption of the individual fiber or fiber matrix.     

Development of a high-performance liquid chromatography carbon column based method for the fractionation of dioxin-like polychlorinated biphenyls

A method to separate polychlorinated biphenyls (PCBs) by using high-performance liquid chromatography (HPLC) was developed. The HPLC column was packed with Amoco PX-21 activated carbon dispersed on octadecylsilane (ODS). The separation was carried out by gradient elution with n-hexane-dichloromethane and toluene in the forward direction followed by reversed elution with toluene. The results show that this HPLC method is useful for the separation of PCBs according to the number of substituted ortho chlorine atoms attached to the biphenyl structure. Average recoveries for a number of individual di-ortho PCBs, mono-ortho PCBs, and non-ortho PCBs in three selected elution windows were 97, 92, and 96%, respectively. Clophen A50, a herring sample, and a cod liver oil sample were fractionated on the column and the analytical results are compared with data from the literature. The method presented here is useful for quantitative separations of mono-ortho PCBs as well as non-ortho PCBs which have been assigned toxic equivalency factors by the World Health Organisation.     

Isotropie focusing of light rays in cosmology

It is shown that if the past light cone of an observer is isotropic and has a caustic (i.e., contains points which are conjugate to the observer along a null geodesic) then the spacetime admits a compact (S³) spacelike hypersurface. The result is valid for space-times with dimension 4.     

Determination of paramethoxyamphetamine and other amphetamine-related designer drugs by liquid chromatography/sonic spray ionization mass spectrometry

Paramethoxyamphetamine (PMA) is an amphetamine-like designer drug that has emerged recently on the European illicit drug market. This drug has a wicked reputation, as a number of lethal intoxications have occurred. A method using high-performance liquid chromatography coupled to ion trap based mass spectrometry (LC/MS) is described for the determination of this compound together with 3,4-methylenedioxymethamphetamine (XTC or MDMA), amphetamine and 3,4-methylenedioxyamphetamine (MDA) in human matrices. A liquid/liquid extraction (LLE) was applied to whole blood, urine and postmortem tissues. Reversed-phase liquid chromatography was performed on a narrow-bore phenyl-type column at a flow rate of 0.3 mL/min. A switch box allowed disposal of early-eluting irrelevant material to waste, protecting the mass spectrometer from contamination. The column effluent was directed into an ion trap mass spectrometer by a sonic spray ionization (SSI) interface. The method was validated for all three matrices, proving the applicability of SSI even when dealing with complex biological matrices. The within-and between-day precisions were less than 17.5% and accuracy was below 16.2%. Weighted (1/x) quadratic calibration curves were generated ranging from 10 to 1000 ng/mL (blood and urine) or 20 to 2000 ng/g (tissue) and correlation coefficients (r(2)) always exceeded 0.995. In addition, the mass spectrum of PMA is given together with a proposed fragmentation pattern for the obtained LC/MS spectrum. This information can be useful for future identification of PMA with LC/MS in biological matrices as well as in confiscated powders or tablets.     

An open-framework silicogermanate with 26-ring channels built from seven-coordinated (Ge,Si)10(O,OH)28 clusters

We report a new open-framework silicogermanate SU-61 containing 26-ring channels with a low framework density. It can be seen as a crystalline analogue to the mesoporous silica MCM-41. The structure is built from the assembly of (Ge,Si)10(O,OH)28 clusters. It is the first time that silicon has been successfully introduced in the Ge10 cluster in significant amounts ( approximately 21% of the tetrahedral sites). Five- and six-coordinated Ge10 clusters have previously been observed in other germanate compounds leading to either dense or open structures. In SU-61, the seven-coordinated clusters fall onto yet another underlying net, the osf net. SU-61, along with other Ge10 based frameworks, shows the versatility of the germanate system to adopt defined topologies playing on the connectivity of the clusters following the principles of net decoration and scale chemistry.     

Numerical Simulation with an Extinction Database for Use with the Eddy Dissipation Concept for Turbulent Combustion

A Local Extinction approach for treating chemical reaction kinetics within the Eddy Dissipation Concept (EDC) has been examined. It applies a database of pre-calculated chemical time scales, which contains the influence of chemical kinetics that is otherwise time-consuming to calculate. The approach was evaluated against experimental data for two piloted diffusion flames (Sandia/TNF Flame D and Flame E) and a piloted lean-premixed jet burner (PPJB). Results were also compared to the EDC with Fast Chemistry and with full Detailed Chemistry (GRI-Mech 3.0). All validation simulations were carried out using a standard k???ε turbulence model and the open-source CFD-toolbox OpenFOAM. The Local Extinction approach showed significantly better results than the Fast Chemistry approach while having a comparably small computational cost. For Flame D and the PPJB, the reactions along centerline and in the mixing layer near the nozzle, the reactions were reduced. For Flame E, the Local Extinciton model predicted some lift off of the flame. The Detailed Chemistry approach gave the best predictions compared to the experimental data, however the calculation effort was orders of magnitude higher.