Comparison of different fibers for the solid-phase microextraction of phthalate esters from water

Solid-phase microextraction (SPME) coupled to gas chromatography-mass spectrometry (GC-MS) has been applied to determine six phthalate esters and one adipate ester in water. The SPME parameters were optimized for several commercially available fibers. A 65-microm polydimethylsiloxane-divinylbenzene (PDMS-DVB) was the fiber selected and was applied to analysis of water from the Ebro river and the industrial port of Tarragona. The studied compounds were found at concentrations ranging from 0.4 microg l(-1) for di-n-butyl phthalate ester (DnBP) to 3.2 microg l(-1) for bis(2-ethylhexyl) phthalate ester (DEHP). The linear range for real samples was from 0.1 to 10 microg l(-1) for most phthalates, and the limits of detection of the method were between 3 and 30 ng l(-1). Repeatability and reproducibility between days (n = 5) for 1 microg l(-1) samples were below 13 and 18%, respectively.     

Concentration and clean-up of trace hydrocarbons from atmospheric particulate matter

Summary The aim of this work is to establish the best conditions for concentration and purification steps in the trace analysis of aliphatic and polycyclic aromatic hydrocarbons (PAH) from atmospheric particulate matter by gas chromatography-flame ionisation detection (GC-FID) and high performance liquid chromatography with ultraviolet and fluorescence detection (HPLC-UV-FL). The best results for the more volatile compound were obtained with a combination of rotary evaporation and a stream of nitrogen (near to 100% for aliphatic hydrocarbons and from 70 to 105% for PAH). Two types of solid phase extraction (SPE)cartridges (Supelclean ^tm LC-Silica SPE tubes and Sep-Pak^? Plus silica cartridges) and glass column were examined for the purification and fractionation step. Blank chromatograms of both types of cartridges analysed by GC-FID made this study difficult, because a PSS (programmed split-splitless) injector was employed thereby increasing the sensitivity. This problem was not observed in the HPLC-UV-FL blank chromatograms of these cartridges. Glass columns filled with silica and alumina were chosen because no interference was found in the GC-FID blank chromatograms and the best recoveries in the fractionation of both aliphatic hydrocarbons and PAH were achieved. This is especially important when aliphatic hydrocarbons concentrations are lower than 1 μg mL⁻¹. Finally, the selected conditions were applied to the analysis of hydrocarbons in real atmospheric particulate samples.     

A comparative study of several HPLC methods for determining free amino acid profiles in honey

A study of the viability of three derivatizing reagents for obtaining amino acid profiles in honey through high performance liquid chromatography (HPLC) is presented. A method using diode array detection based on a reaction with diethyl ethoxymethylene malonate (DEMM) and two other methods using fluorescence detection based on derivatization with fluorenylmethyl chloroformate (FMOC-Cl) and 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) have been developed. The three methods yield detection limits close to the ppb level, but vary in relation to other analytical characteristics. The use of methyl chloroformate derivatives allows the profile to be obtained with the greatest sensitivity within a short time frame. On applying such methods to honey samples of diverse botanical origin, we observe that the proline values obtained are always lower than those found using the official spectrophotometric method, thereby underlining the advisability of using HPLC methods to reduce uncertainty in these results.     

From cyclopentadiene to isoxazoline-carbocyclic nucleosides: a rapid access to biological molecules through nitrosocarbonyl chemistry

A rapid access to carbocyclic nucleosides containing a fused isoxazoline ring is proposed starting from cyclopentadiene. The route involves an hetero Diels-Alder cycloaddition reaction of nitrosocarbonylbenzene followed by a 1,3-dipolar cycloaddition of nitrile oxides, cleavage of the N-O tether and elaboration of the heterocyclic aminols into nucleosides via linear construction of purine and pyrimidine heterocycles.     

Reactions of organomercury fulminates with acetylene derivatives

Organomercury fulminates react with acetylene derivatives to give unstable 3-(organomercurio)isoxazoles, which isomerize to 2-cyanoenolates. These are hydrolyzed with hydrochloric acid to the corresponding enols and are cleaved by water at the double bond. With monosubstituted acetylenes, substitution at the free position by the organomercury residue is predominant.     

Structural study of copper-nickel aluminate (CuxNi1−xAl2O4) spinels

CuAl₂O₄, NiAl₂O₄, and three ternary spinels Cu_xNi_1?xAl₂O₃ have been prepared, in polycrystalline form, by solid-state reaction of mixtures of CuO, NiO, and Al₂O₃ at 1223 K. X-Ray powder diffractometry, coupled with adequate computational methods, allowed determination of the unit-cell length, oxygen positional parameter, and cation distribution for each compound. Interdependence of these structural parameters is closely analyzed on the ternary oxide spinels. The one-electron difference between the Cu²⁺ and Ni²⁺ ions was found to be enough to render them distinguishable by X-ray powder diffraction.     

Application of a mercuric iodide detector for the exploration and exploitation of niobium deposits in remote areas

The comparison of an ambient temperature mercuric iodide spectrometer (HgI₂) with a conventional cooled Si(Li) spectrometer is presented for the determination of niobium in Venezuelan laterites in the laboratory. The energy resolution of the HgI₂ spectrometer was only about 590 eV (FWHM) at 5.9 keV compared to about 150 eV for the conventional Si(Li) spectrometer. The efficiency was about 5 times lower in the region of the Nb_K peak as compared to the Si(Li) detector. Even though its energy resolution and efficiency is much poorer than the conventional Si(Li), the results it produced for the determination of niobium were acceptable for use in the exploration and exploitation of a niobium-rich deposit such as Cerro Impacto, Estado Bolívar, Venezuela.     

Development and Validation of a High-Performance Thin-Layer Chromatographic Method,with Densitometry,for Quantitative Analysis of Tizoxanide (a Metabolite of Nitazoxanide) in Human Plasma

JPC – Journal of Planar Chromatography – Modern TLC - A new simple, rapid, and selective high-performance thin-layer chromatographic (HPTLC) method with metronidazole as the internal...