Chiral comprehensive two-dimensional gas chromatography with electron-capture detection applied to the analysis of chiral polychlorinated biphenyls in food samples

The feasibility of comprehensive two-dimensional gas chromatography with electron-capture detection (GC x GC-ECD) for the enantioseparation of chiral PCBs from other possible interfering compounds has been evaluated. Three commercially available enantioselective beta-cyclodextrin-based capillary columns (Chirasil-Dex, BGB-172 and BGB-176SE) have been tested as first-dimension columns. Three non-enantioselective stationary phases (HT-8, BPX-50 and Supelcowax-10) were combined with the enantioselective columns to allow the unambiguous determination of the enantiomers of the target chiral PCBs. Each enantioselective first-dimension column tested was able to separate into enantiomers different PCB congeners, but in all cases, the use of Supelcowax-10 as second-dimension column provided the most satisfactory results. The Chirasil-Dex x Supelcowax-10 column combination allowed the determination of the enantiomeric fraction (EF) of PCBs 84, 91, 95, 132, 136, 149, 174 and 176 in the working standard solution, while that of congener 135 was hindered. The BGB-172 x Supelcowax-10 column set allowed a proper EF determination of congeners 45, 84, 131, 132, 135, 171, 174 and 183, while that of PCB 91 was interfered with co-elutants. The column combination BGB-176SE x Supelcowax-10 allowed the determination of all congeners that this enantioselective stationary phase was able to separate into enantiomers, i.e. PCBs 45, 91, 95, 136, 149 and 176. These column combinations have also been evaluated for the simultaneous determination of the 12 congeners with a toxic equivalency factor assigned by the WHO (PCBs 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, 169, 189) and the seven indicator congeners (PCBs 28, 52, 101, 118, 138, 153 and 180), and evaluated for the analysis of food samples.     

Investigating bidentate and tridentate carbamoylmethylphosphine oxide ligand interactions with rare-Earth elements using electrospray ionization quadrupole ion trap mass spectrometry

Electrospray ionization (ESI) quadrupole ion trap mass spectrometry (QIT-MS) and collisionally activated dissociation (CAD) were used to evaluate the rare-earth binding properties of two hydrophobic carbamoylmethylphosphine oxide (CMPO) ligands, the normal bidentate variety, (t-BuC6H4)2P(O)CH2C(O)N(i-Bu)2 (A), a new potentially tridentate extractant, (t-BuC6H4)2P(O)CH[CH2C(O)N(i-Bu)2]C(O)N(i-Bu)2 (B), and tributyl phosphate. The mass spectral results obtained from analysis of 1% HNO3/methanol solution containing the ligands and dissolved lanthanide salts reveal that the favorable stoichiometries of the ligand/metal/nitrate complexes are 2:1:2 for the bidentate ligand A, 1:1:2 for the tridentate ligand B, and 3:1:2 for the monodentate tributyl phosphate. These observed stoichiometries correlate with the number of available binding sites on each ligand as well as with potential steric effects. Energy-variable collisionally activated dissociation experiments showed that for the 2:1:2 complexes involving ligand A or B, as the ionic radius of the bound metal decreased, the removal of nitric acid required less energy and resulted in less extensive spontaneous solvent coordination. This experimental trend suggests that, as the ionic radius of the lanthanide ion decreases, a pair of the carbamoylmethylphosphine ligands is able to more completely solvate the bound metal ion thereby weakening the nitrate-metal interaction.     

Stereocontrolled synthesis of polysubstituted piperidines from vinylogous Mannich adducts and aldehydes

Condensation of readily available 5-(aminoalkyl)furan-2-ones, derived from the Mannich-type reaction between 2-silyloxyfurans and acyliminium ions, with an α-unsubstituted aliphatic aldehyde leads to substituted 1,2,3,4-tetrahydropyridines in a process involving an enamine conjugate addition. Reduction of the tetrahydropyridine double bond then affords 3,4,5-tri- or 3,4,5,6-tetra-substituted piperidines stereoselectively.     

Stereoselective Synthesis of Tetrahydrofuran Spiro‐β‐Lactams by Ru‐Catalyzed Metathesis of 7‐Oxabicyclo[2.2.1]heptenes

A new method for the synthesis of spiro‐β‐lactams tethered to tetrahydrofuran rings is described. The procedure is based on Ru‐catalyzed metathesis sequences with oxanorbornene precursors easily obtained by the Staudinger [2+2] cycloaddition of related imines.     

Evidence for quasi-intramolecular acid-base reactions in solutions of transition metal ammine complexes

We have investigated the effect of temperature on the postulated quasi-intramolecular acid-base reactions in aqueous solutions of Cu(NH₃)₄(MnO₄)₂ and Ag(NH₃)₂ClO₄. Pure ammonium permanganate and perchlorate were obtained above 5 C and at room temperature, respectively, due to quasi-intramolecular acid-base reactions.     

Mass distribution in a dynamic sample zone inside a flow injection manifold: modelling integrated conductimetric profiles

A mathematical model for fitting the experimental ICM (integrated conductimetric method) curves developed by the authors in a previous work, is presented for the first time in this study. The proposed model fits the experimental curves with great precision and allows to predict physical dispersion for single-line flow injection system. The correlation of the model’s parameters with typical reactionless FIA peak parameters is also assessed. The IDQ coefficient—a novel dispersion estimator previously reported by the authors—can also be predicted when operational FIA variables are changed. Experimental and modelled profiles are compared as a function of the system’s variables, showing an excellent agreement.     

Determination of sulfametoxazole, sulfadiazine and associated compounds in pharmaceutical preparations by capillary zone electrophoresis

A capillary zone electrophoresis method is presented to separate sulfadiazine, sulfamethoxazole, trimethoprim, bromhexine and guaiacol by using a fused-silica capillary (60.2 cm x 75 microm I.D.). The separation was carried out at 30 kV and 25 degrees C in a 15 mM phosphate buffer adjusted to pH 6.2 as electrolyte. Under these conditions, the run time was 6 min and the limits of quantification were about 1 mg/l for every component. The method was applied to pharmaceutical preparations and the results provided recoveries close to 100%.     

Structure analysis of intercalated layer silicates: combination of molecular simulations and experiment

Na(+)-montmorillonite type Wyoming, cloisite Na(+) from Southern Clay Products, Inc., was intercalated (i) with octadecylammonium cations and subsequently intercalated with octadecylamine molecules, (ii) with dodecylamine molecules, and (iii) with octylamine molecules to determine the applicability of these intercalates for nanocomposite materials on the base of polymer/clay. The structures were determined on the basis of a combination of results from X-ray diffraction and molecular simulations. The calculated values of basal spacings are in good agreement with experimental basal spacings when experimental samples were prepared. The interlayer space of intercalated montmorillonite shows a monolayer or bilayer arrangement of alkyl chains in dependence on the concentration of the intercalation solution. The values of the total sublimation energy, interaction energy, and exfoliation energy were calculated for all investigated samples. Low values of exfoliation energies lead to better exfoliation of intercalated silicate layers and this material appears suitable for use as a precursor for polymer/clay nanocomposites. The values of exfoliation energy for the investigated samples show that montmorillonite intercalated with dodecylamine or octadecylamine molecules is suitable for exfoliation of silicate layers.     

Solubility and first hidrolysis constants of europium at different ionic strength and 303 K

The solubility of europium at 0.02M, 0.1M and 0.7M NaClO₄ ionic strength solutions was determined by a radiometric method and pEu_s-pC_H diagrams were obtained. Hydrolysis constants were also determined at the same ionic strengths by pH titration and the values found were log *₁ = -7.68±0.11, -8.07±0.10 and -8.20±0.11. The log K _sp values were -23.5±0.2, -22.7±0.2 and -21.9±0.2 for 0.02M, 0.1M and 0.7M NaClO₄ ionic strengths, respectively, at 303 K under CO₂-free conditions and the extrapolated value at zero ionic strength was log K _sp ⁰ = -24.15. The working pC_H ranges for the calculation of the hydrolysis constants were selected from the pEu_s-pC_H diagrams in the region where precipitation of europium oxide or hydroxide was less than 20%. Europium removal from aqueous solutions with zeolites was explored.