Sample stacking with matrix removal for the determination of paraquat, diquat and difenzoquat in water by capillary electrophoresis

Conditions for the simultaneous determination of paraquat, diquat and difenzoquat by capillary zone electrophoresis using a stacking technique in a chemically modified capillary have been established. To apply the stacking method with sample matrix removal for the analysis of cations, an anodic electroosmotic flow is mandatory. For quats, 50 mM acetic acid-ammonium acetate (pH 4.0) with 5% (v/v) methanol as electrophoretic buffer and the addition of 0.8 mM cetyltrimethylammonium bromide as wall capillary organic modifier was proposed. Field polarity reversal time was optimised for several sample matrices. Detection was carried out at 220 and 255 nm. Detection limits, based on a signal-to-noise ratio of 3:1, were lower than 15 microg l(-1) for standards in Milli-Q water and two to ten times higher for drinking water samples. Run-to-run and day-to-day reproducibility have been established. The method was successfully applied to the determination of the three herbicides in spiked drinking water.     

Multistep mass spectrometry of heterocyclic amines in a quadrupole ion trap mass analyser

The fragmentation of heterocyclic amines (HAs) in an ion trap was studied by means of the infusion of methanolic solutions containing the compounds under assay, and using an atmospheric pressure chemical ionization (APCI) as ion source. The MS(n) spectra obtained for compounds included in the same family, either aminoimidazoazaarenes (AIAs) or carbolines, were compared in order to propose fragmentation pathways for each HA. Moreover, labelled AIAs were used to establish the mechanisms. The protonated molecule was always obtained, but subsequent fragmentation was different for both families. In the case of AIAs, major product ions came from the fragmentation of the aminoimidazole moiety, thus the base peak in MS(2) corresponded to the loss of the methyl group, and losses of C(2)NH(3) and CN(2)H(2) were also observed. Further fragmentation occurred in the heterocyclic rings, mainly with losses of HCN and CH(3)CN. For carbolines, the most important product ions came from the loss of ammonia, except for harman and norharman, the loss of a methyl group for methylated carbolines or the loss of diverse fragments from the heterocyclic rings. In some cases, ion-molecule reactions into the ion trap were observed. For instance, for AalphaC or MeAalphaC one ion originating from these reactions corresponded to the base peak.     

Optimization of a clean-up procedure for the determination of heterocyclic aromatic amines in urine by field-amplified sample injection-capillary electrophoresis-mass spectrometry

Heterocyclic amines (HAs), generated when proteinaceous food is cooked, are of special interest since they can be carcinogenic for humans. In this paper, the optimization of a clean-up procedure for the isolation and preconcentration of 15 heterocyclic amines in urine samples is described. The method proposed combines liquid extraction on a solid support of diatomaceous earth with solid-phase extraction in cartridges. Tests were performed on several cartridges containing graphitic carbon or mixed phases, i.e., combining reversed-phase and cation-exchange mechanism, and the best results were obtained with Oasis MCX. The optimized purification method was applied to the quantification of heterocyclic amines in hydrolyzed spiked human urine. The method was carried out by capillary electrophoresis (CE) coupled to mass spectrometry (MS) and applying field-amplified sample injection (FASI) as in-line preconcentration procedure. We obtained detection limits down to 0.3 ng/ml of urine and errors lower than 17%.     

Determination of heterocyclic amines by pneumatically assisted electrospray liquid chromatography-mass spectrometry

Electrospray ionization mass spectrometry was applied to the study of the amines IQ, Trp-P-1, Trp-P-2, PhIP and AC and the co-mutagens harman and norharman. The results obtained on a triple quadrupole mass spectrometer equipped with a pneumatically assisted electrospray source are reported. The chromatographic conditions were optimized with a reversed-phase column (1 mm I.D.) using acetonitrile-5 mM ammonium acetate (pH 6.7) (50:50) as the mobile phase at a flow-rate of 50 μl min⁻¹. Different parameters influencing the mass spectra were investigated. For these compounds [M + H]⁺ in the positive-ion mode and also some fragments produced through collisionally activated decomposition in the interface were observed. Detection limits of 5.4–44 pg were obtained for standard solutions of these amines. Analysis of a meat extract was performed by HPLC-MS using single-ion monitoring after a solid-phase extraction clean-up.     

Thermal investigation of PEG 4000 — oxazepam binary system

A thermal study using DSC and Hot Stage Microscopy (HSM) was carried out to investigate the interaction in solid state of the binary system PEG 4000 — oxazepam, and to establish their phase diagram. The eutectic composition, which melting occurs at lower temperature as compared with the pure components, has been determined. The results obtained by DSC and HSM have indicated that PEG 4000 — oxazepam mixtures displays no obvious incompatibilities, and that the system shows a typical eutectic behaviour. However because of the closeness of the melting of PEG 4000 to the eutectic temperature, it was difficult to determine precisely the eutectic composition and temperature on the basis of DSC measurements alone. The use of heats of fusion corresponding to physical mixtures allowed an estimation of the eutectic composition at 6% w/w oxazepam. Additional information of temperature (57.6C) and composition (5–10% w/w oxazepam) of the eutectic was obtained by HSM using the contact method. This low melting temperature in this range of compositions offers advantages in terms of drug stability and easy manufacture.     

A Convenient Stereoselective Synthesis of (1R,2S,3R,4S)-3-(Neopentyloxy)isoborneol

A convenient preparation of (1R,2S,3R,4S)-3-(neopentyloxy)isoborneol (= (1R,2S,3R,4S)-3-(2,2-dimethyl-propoxy)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol; 1a ), a valuable chiral auxiliary, is described. The synthesis involves six steps starting from the readily available camphorquinone ( 5 ) and gives 1a in 48% overall yield. The key step is the chemoselective hydrolysis of the less hindered 1,3-dioxolane moiety in the camphorquinone di-acetal 4 .     

On-line preconcentration and determination of nickel in natural water samples by flow injection-inductively coupled plasma optical emission spectrometry (FI-ICP-OES)

An on-line nickel preconcentration and determination system implemented with inductively coupled plasma optical emission spectrometry (ICP-OES) associated to flow injection (FI) was studied. Trace amounts of nickel were preconcentrated by sorption on a conical minicolumn packed with activated carbon (AC) at pH 5.0. The nickel was removed from the minicolumn with 20% nitric acid. An enrichment factor of 80-fold for a sample volume of 50 ml was obtained. The detection limit (DL) value for the preconcentration method proposed was 82 ng l⁻¹. The precision for ten replicate determinations at the 0.5 μg l⁻¹ Ni level was 3.0% relative standard deviation (R.S.D.), calculated from the peak heights obtained. The calibration graph preconcentration method for nickel was linear with a correlation coefficient of 0.9997 at levels near the detection limits (DL) up to at least 100 μg l⁻¹. The method was successfully applied to the determination of nickel in natural water samples.     

Asymmetric organocatalytic anthrone additions to activated alkenes

Asymmetric organocatalytic additions of anthrones to activated alkenes are discussed. The reaction between anthrone or dithranol and α,β-unsaturated aldehydes is catalyzed by diphenylprolinol trimethylsilyl ether in toluene at −40 °C, giving the Michael adducts with good yields and enantioselectivities. Bifunctional amino-thioureas efficiently catalyze the additions of anthrones to both nitroalkenes and maleimides, and high enantioselectivities can be achieved in both instances at room temperature. In the case of nitroalkenes, a Michael addition takes exclusively place. Anthrone generally gives Diels-Alder cycloadducts in the reaction with maleimides, while dithranol affords the Michael adducts. Transition state working models in which the bifunctional catalyst binds simultaneously to the alkene and to the anthrone enolate account for the stereochemical outcome of these additions.     

Reversing the stereoselectivity of the intermolecular Pauson-Khand reaction: formation of endo-fused norbornadiene adducts

[reaction: see text] An unprecedented endo-selective and regioselective intermolecular Pauson-Khand reaction takes place when heterobimetallic (Mo-Co) complexes derived from N-(2-alkynoyl)oxazolidinones or sultams are heated in the presence of norbornadiene.     

Determination of ebrotidine and its metabolites by capillary electrophoresis with UV and mass spectrometry detection

This study describes the application of capillary electrophoresis (CE) to the analysis of ebrotidine and its metabolites as an alternative analytical technique to liquid chromatography. Comparison between UV-diode array spectroscopy and mass spectrometry (MS) using an ion-trap system with electrospray ionization as detection systems has been performed. The quality parameters of the UV detection method were established, obtaining linear calibration curves over the range studied (8-200 mg ml(-1)), limits of detection between 3.4 and 4.3 microg ml(-1), and run-to-run and day-to-day precision lower than 14%. For these compounds the protonated species [M+H]+ and, in some cases, sodium adducts were observed in the MS spectra. Using MS coupled to CE, limits of detection were between 0.5 and 2.6 microg ml(-1).