Recovery of some common solvents from protective clothing breakthrough indicator pads by microwave-solvent extraction and gas chromatography

The efficiency of solvent adsorption using Permea-Tec general solvent pads, used for the detection of chemical breakthrough of protective clothing, was determined for methanol, acetone, ethyl methyl ketone, trichloroethylene (TriCE), tetrachloroethylene (TetCE), toluene, m-xylene, and D-limonene. Known volumes of single or mixed solvents were added to pads in the range 0.2-5.0 microliters (0.16-8.13 micrograms). After microwave-solvent extraction (ME) into hexan-1-ol, the samples (0.5-3.0 microliters) of the filtered and extracted solutions were analyzed by gas chromatography. All solvents exhibited > 97% adsorption on the pads at spiking levels of 0.48-0.98 microgram for each solvent. The solvent recovery for the system was calculated for each solvent, with solvents with boiling points below 110 degrees C showing recoveries of > 90%, and with solvents with boiling points above 110 degrees C showing recoveries from 80 to 90%. The recovery precision was good (RSD < or = 4%) for all solvents over the range 1.0-2.5 microliters of applied solvents to pads for ME and 1.0 microliter of extracted solutions for GC analysis.     

Design of novel order mesostructured superacid catalyst from rice husk for the conversion of linseed oil to methyl esters

A novel ordered mesoporous catalyst was prepared from rice husk (MRH catalyst) through condensation–evaporation method in alkaline media. The process used cetyltrimethylammonium bromide (CTAB) as a structure-directing agent (template) and sulfonated biochar obtained from partial rice husk carbonization (SBRH) as precursor. Various parameters such as temperature and CTAB/SBRH mass ratios were investigated to improve the mesoporous structure. The chosen catalyst was based on its degree of order of the mesoporous channels, and its activity was also tested in the methanolysis of linseed oil to methyl esters which was considered as a valuable blending composition for commercial jet fuels. The results showed that the temperature and CTAB/SBRH mass ratio should be of 70 °C and 0.3/1, respectively. The catalyst samples were characterized by many techniques including X-ray diffraction (XRD), infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and ammonia-temperature programmed desorption (NH₃-TPD). The methyl ester composition of the as-synthesized biofuel was determined using gas chromatography supported by mass spectroscopy detector (GC–MS). The results of the characterizations showed that the catalyst possessed superacidic sites (NH₃-TPD) caused by –SO₃H groups (confirmed by FT-IR analysis) and ordered mesoporous structure (XRD). The mesoporous channel distribution was also observed by TEM images. The methanolysis yield reached 93.5% (calculated through GC–MS analysis) at mild conditions with high purity of methyl ester products strongly proving the catalyst activity and selectivity.     

Catalytic Synthesis of N-Aryladamantane-1-carboxamides Using Phosphorus Trichloride

Russian Journal of Organic Chemistry - N-Aryl(benzyl)adamantane-1-carboxamides were synthesized in 54–87% yields by reaction of adamantane-1-carboxylic acid with aromatic amines in the...     

Validated method for the determination of ethylglucuronide and ethylsulfate in human urine

Detection of the alcohol metabolites ethylglucuronide (EtG) and ethylsulfate (EtS) has become routine in many forensic laboratories over the last few years. Most previously published methods using liquid chromatography coupled with electrospray tandem mass spectrometry require a post-chromatographic addition of solvent and/or extensive sample preparation prior to analysis. The aim of the study was to develop a simplified method. To 20 μL urine, internal standard containing EtG-d5 and EtS-d ₅ was added and the mixture was treated with elution buffer internal standard. EtG and EtS were separated using a Shimadzu Prominence high performance liquid chromatography (HPLC) system with a C18 separation column (Restek Ultra Aqueous C18, 4.6 × 150 mm, 5 μm), using isocratic elution with a mobile phase consisting of 10 mM ammonium acetate buffer pH 7 (total run time, 6 min). The compounds were detected using an Applied Biosystems API 5000 liquid chromatography tandem mass spectrometry system (atmospheric pressure chemical ionization, multiple-reaction monitoring mode). The method was fully validated according to international guidelines. The assay was found to be selective for the compounds of interest. It was linear from 0.1 to 10 mg/L for all analytes (R ² > 0.99). Matrix effects studies showed the presence of a slight but consistent ion enhancement (n = 10 different urine samples) at low concentrations and no effects at higher concentrations. Accuracy data were between 0.75% and 8.1% bias for EtG and between −5.0% and −11.3% bias for EtS. Precision data were between 4.3% and 6.9% relative standard deviations (RSD) for EtG and between 6.0% and 7.5% RSD for EtS. No instability was observed after repeated freezing and thawing. This fast, reliable, and accurate method enables the detection and quantification of alcohol metabolites in urine. The method is easier to use and more sensitive than previously published methods.     

Self-assembled monolayers induced inter-conversion of crystal structure by vertical to lateral growth of aluminium doped zinc oxide thin films

In this communication, we demonstrate the inter-conversion of crystal structure of aluminium doped zinc oxide (AZO) thin films from highly (002) plane oriented vertical growth to (103) plane oriented lateral growth by adjusting the polarity of the self-assembled monolayers (SAMs) on glass substrates at room temperature.     

Analytical and numerical solutions of a two‐dimensional multi‐term time‐fractional Oldroyd‐B model

In this paper, we consider a two‐dimensional multi‐term time‐fractional Oldroyd‐B equation on a rectangular domain. Its analytical solution is obtained by the method of separation of variables. We employ the finite difference method with a discretization of the Caputo time‐fractional derivative to obtain an implicit difference approximation for the equation. Stability and convergence of the approximation scheme are established in the L_∞ ‐norm. Two examples are given to illustrate the theoretical analysis and analytical solution. The results indicate that the present numerical method is effective for this general two‐dimensional multi‐term time‐fractional Oldroyd‐B model.     

Facile Synthesis of 4-Oxo-4H-quinolizine-2-carboxamide Derivatives

A facile synthetic method for the construction of 2-substituted-4-oxo-4H-quinolizine-based core structure has been successfully developed. The synthesis made use of a one-pot Stobbe condensation followed by cyclization starting from the commercially available 2-pyridinecarbaldehyde. The structure of the formed 4-oxo-4H-quinolizine-2-carboxylate was fully confirmed by mass spectra, ¹H NMR and ¹³C NMR, correlation spectrography, heteronuclear multiple bond correlation, and heteronuclear single quantum coherence (HSQC) spectra. The ethyl carboxylate moiety was then further functionalized via direct aminolysis by a range of amines to afford the corresponding 4-oxo-4H-quinolizine-2-carboxamides 4a–i in moderate to good yields.     

Predicting the subcellular location of apoptosis proteins based on recurrence quantification analysis and the Hilbertben Huang transform

Apoptosis proteins play an important role in the development and homeostasis of an organism. The elucidation of the subcellular locations and functions of these proteins is helpful for understanding the mechanism of programmed cell death. In this paper, the recurrent quantification analysis, Hilbert-Huang transform methods, the maximum relevance and minimum redundancy method and support vector machine are used to predict the subcellular location of apoptosis proteins. The validation of the jackknife test suggests that the proposed method can improve the prediction accuracy of the subcellular location of apoptosis proteins and its application may be promising in other fields.     

The effect of silicon impurities on the phase diagram of iron and possible implications for the Earth's core structure

The hexagonal-close-packed (hcp) structure is the accepted stable form of pure iron (Fe) under Earth's core conditions. Recently, however, a body-centred-cubic (bcc) phase of iron alloyed with lighter elements has been proposed. At relatively modest conditions, experiments have shown that small amounts of silicon (Si) can stabilise the bcc phase with respect to the hcp phase. This result has motivated our present study examining the effect of silicon on the bcc-hcp phase transition. We have performed ab initio calculations on both phases at zero Kelvin; our results are in good agreement with experiment. Extending our results to core pressures and taking into account previous studies of pure iron at core temperatures, we conclude that the bcc phase of iron alloyed with silicon is likely to be the stable crystalline phase in the inner core.     

Idiosyncratic risk in the Dow Jones Eurostoxx50 Index

Recent evidence by Campbell et al. [J.Y. Campbell, M. Lettau B.G. Malkiel, Y. Xu, Have individual stocks become more volatile? An empirical exploration of idiosyncratic risk, The Journal of Finance (February) (2001)] shows an increase in firm-level volatility and a decline of the correlation among stock returns in the US. In relation to the Euro-Area stock markets, we find that both aggregate firm-level volatility and average stock market correlation have trended upwards.We estimate a linear model of the market risk–return relationship nested in an EGARCH(1, 1)-M model for conditional second moments. We then show that traditional estimates of the conditional risk–return relationship, that use ex-post excess-returns as the conditioning information set, lead to joint tests of the theoretical model (usually the ICAPM) and of the Efficient Market Hypothesis in its strong form.To overcome this problem we propose alternative measures of expected market risk based on implied volatility extracted from traded option prices and we discuss the conditions under which implied volatility depends solely on expected risk. We then regress market excess-returns on lagged market implied variance computed from implied market volatility to estimate the relationship between expected market excess-returns and expected market risk.We investigate whether, as predicted by the ICAPM, the expected market risk is the main factor in explaining the market risk premium and the latter is independent of aggregate idiosyncratic risk.