Resolution and identification of co‐eluting alkylphenols in comprehensive two‐dimensional gas chromatography–mass spectrometry by multivariate curve resolution‐alternating least squares

The interest in the analysis of alkylphenols (APs) has widely increased in the last decades because of the endocrine disrupting features of these phenol derivatives. However, the isolation and identification of many of the multiple chemical structures of all APs is a very challenging task because of their similar physicochemical properties. In this work, the co‐elution of the isomers present in technical mixtures and using comprehensive two‐dimensional gas chromatography coupled to quadrupole mass spectrometry was resolved using multivariate curve resolution‐alternating least squares algorithm. The mass spectrum of each resolved compound was compared with the theoretical mass spectrum obtained from the literature, in order to assign the appropriate identification of each isomer. Two commercial mixtures were studied; in one of them, 34 compounds were resolved, and in the second mixture, 40 compounds were resolved. The relative abundances of the compounds were also calculated in both mixtures. Copyright © 2015 John Wiley & Sons, Ltd.     

Ion-beam irradiation of lanthanum compounds in the systems La2O3-Al2O3 and La2O3-TiO2

Thin crystals of La₂O₃, LaAlO₃, La_2/3TiO₃, La₂TiO₅, and La₂Ti₂O₇ have been irradiated in situ using 1 MeV Kr²⁺ ions at the Intermediate Voltage Electron Microscope-Tandem User Facility (IVEM-Tandem), Argonne National Laboratory (ANL). We observed that La₂O₃ remained crystalline to a fluence greater than 3.1×10¹⁶ ions cm⁻² at a temperature of 50 K. The four binary oxide compounds in the two systems were observed through the crystalline-amorphous transition as a function of ion fluence and temperature. Results from the ion irradiations give critical temperatures for amorphisation (T_c) of 647 K for LaAlO₃, 840 K for La₂Ti₂O₇, 865 K for La_2/3TiO₃, and 1027 K for La₂TiO₅. The T_c values observed in this study, together with previous data for Al₂O₃ and TiO₂, are discussed with reference to the melting points for the La₂O₃-Al₂O₃ and La₂O₃-TiO₂ systems and the different local environments within the four crystal structures. Results suggest that there is an observable inverse correlation between T_c and melting temperature (T_m) in the two systems. More complex relationships exist between T_c and crystal structure, with the stoichiometric perovskite LaAlO₃ being the most resistant to amorphisation.     

Preparation of a reference mussel tissue material for polycyclic aromatic hydrocarbons and trace metals determination

Due to high cost of certified reference materials (CRMs), reference materials (RMs) are preferred to check the method performance in environmental analysis. In this work, a laboratory reference material (LRM) was prepared and characterised to carry out the quality control in monitoring analysis of eight polycyclic aromatic hydrocarbons (PAHs) and nine trace metals in mussel tissue. Mussels were collected in a naturally polluted area. Before the reference material was bottled, the mussel tissue was stabilised by freeze-drying, ground and sieved. For the material characterisation, several statistical tests were applied to check the homogeneity of the analytes in the tissue, and a stability test was performed to study the effect of the storage temperature in the analyte concentration. Other characteristics such as specific density, moisture and lipid contents as well as particle size distribution of the material were determined. Although the LRM had a homogeneous distribution for all PAHs and almost all metals, the stability study showed different results at both storage temperatures studied. For both PAHs and trace metals, the material was suitable to assure the quality control of the analysis.     

Thermogravimetric analysis of polyester/cotton blends treated with Thpc-urea-poly(vinyl bromide)

Polyester/cotton fabric swith blend ratios of 0/100, 11/89, 20/80, 30/70, 50/50, and 65/35 were investigated via thermogravimetric analysis in both nitrogen and air atmospheres. The samples were heated from ambient to 750°C at a heating rate of 5°C min^?1. The same fabrics were analyzed after treatment with tetrakis (hydroxymethyl) phosphonium chloride-urea-poly(vinyl bromide) (Thpc-urea-PVBr) flame retardant.Weight losses observed during pyrolysis were assigned to the cotton and polyester portions of the blends. Both cotton and polyester thermally decompose to yield gases and solid char byproducts. In nitrogen the 100% cotton fabric undergoes one major weight loss between 270 and 370°C, with the maximum rate of weight loss, 0.15 mg/min-mg occurring at 346°C. Thermal decomposition of the 100% polyester occurs over a range of 335–470°C, with the peak rate of weight loss, 0.11 mg/min-mg, measured at 416°C. In an air atmosphere, both volatile gases and solid char by- products of pyrolysis undergo combustion. The combustion reactions are associated with measured weight losses. The maximum rate of weight loss for the cotton portion increases to 0.25 mg/min-mg and occurs at 317°C. The maximum rate of polyester decomposition remains the same in both air and nitrogen, but the temperature decreases to 405°C.     

Synthesis and mass spectra of some 1-aroylamino-5-arylaminomethyl-1,2,3-triazoles

The title compounds 2 are prepared from the reaction of 1-(N, N-diaroyl)amino-5-bromomethyl-1,2,3-triazoles with aromatic amines. The fragmentation pattern upon electron impact at 70 eV of compounds 2 is studied. The molecular ion peak is present in all the spectra examined. Besides the [M-28]⁺⁺, there is also a more abundant [M-29]⁺ peak, corresponding to a N₂H loss of the molecular ion. The ion Ar²NH = CH₂ is the base or the most prominent peak.     

Improvement of the chromatographic separation of several 1,4-dihydropyridines calcium channel antagonist drugs by experimental design

A high-performance liquid chromatographic method with diode array detection has been developed and optimized for the separation of five calcium channel blockers belonging to the 1,4-dihydropyridine subgroup (nifedipine and related drugs). The possibility of the simultaneous drug analysis allows a decrease of time during the assay as well as a saving of reagents and solvents. In this work, the effect of four experimental parameters (organic modifier percentage, pH value, concentration of the buffer in the mobile phase, and column temperature) on the chromatographic resolution are investigated by experimental design in order to optimize the chromatographic separation of five 1,4-dihydropyridines (amlodipine, nitrendipine, felodipine, lacidipine, and lercanidipine). Fractional factorial design, central composite design, and finally the Multisimplex program are used to establish the optimal conditions in terms of resolution and minimum analysis time. Optimal separation of the five compounds under study is achieved in less than 12 min using a Sulpecosil LC-ABZ+Plus C18 column, a composition of mobile phase of acetonitrile-10mM acetic acid acetate buffer pH 5 (72:28, v/v) at a flow rate of 1 mL/min, a column temperature of 30 degrees C +/- 0.1 degrees C, and a detection wavelength of 238 nm.     

Synthesis and spectroscopic characterization of 1-[1,2,3-triazol-1-yl]-4-aroylazetidin-2-ones

1-(N-Phenacylidene)amino-1,2,3-triazoles 3 react with propionylchloride and phenoxyacetylchloride in the presence of triethylamine to give trans- ( 5 ) and cis- ( 6 ) 1-(1,2,3-triazol-1-yl)-4-aroylaztidin-2-ones in a 1:1 ratio, on the contrary to the 1-(N-arylidene)amino-1,2,3-triazoles, which do not give any reaction product with the same acid chlorides. The spectroscopic characteristics of these new N-triazolyl-β-lactams are also discussed.     

Potentiometric determination of the protonation constants of some phenols in 1.0 mol/L NaCl at 25°C

The potentiometric determination of the protonation constants of phenol, 2-chlorophenol, 2-nitrophenol, 2,4-dichlorophenol and 2-methylphenol in 1.0 mol/L NaCl at 25°C is presented. An automated system has been used in the experiments. The determination of the constants has been carried out using both graphical and numerical methods.     

Gas phase thermolysis of sulfur compounds. II. Ditertiary butyl sulfide

The pyrolysis of di-tert-butyl sulfide has been investigated in static and stirred-flow systems at subambient pressures. The rate of consumption of the sulfide was measured in some experiments, and the rate of pressure increase was followed in others. The results suggest that the reaction is essentially homogeneous in a seasoned reactor and proceeds through a free radical mechanism. In the initial stages, the decomposition rate follows first-order kinetics, and the rate coefficient in the absence of an inhibitor is given by between 360 and 413°C. The stoichiometry of the uninhibited reaction at 380°C and 50% decomposition is approximately between 360 and 413°C. The stoichiometry of the uninhibited reaction at 380°C and 50% decomposition is approximately.