Extraction of Pb2+ with sodium dicarbollylcobaltate in the presence of 15-crown-5

From extraction experiments with ²² Na as a tracer, the exchange extraction constant corresponding to the equilibrium Pb²⁺ (aq)+2 NaL⁺ (nb)PbL₂ ²⁺ (nb)+2 Na⁺ (aq) in the two-phase water-nitrobenzene system (L = 15-crown-5; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K_ex (Pb²⁺ , 2NaL⁺ ) = 4.7±0.1. Moreover, the stability constant of the complex PbL₂ ²⁺ in nitrobenzene saturated with water was calculated for a temperature of 25 °C as log _nb (PbL₂ ²⁺ ) = 17.9±0.1.     

Homogeneous sample preparation for automated high throughput analysis with matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry

This work presents a simple method for obtaining homogeneous sample surfaces in matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS) for the automated analysis of peptides and proteins. The sample preparation method is based on applying the sample/matrix mixture onto a pre-deposited highly diluted matrix spot. The pre-deposited crystals act as seeds for the new sample containing crystals which become much smaller in size and more evenly distributed than with conventional methods. This 'seed-layer' method was developed, optimised and compared with the dried-droplet method using peptides and proteins in the 1000-20,000 Da range. The seed-layer method increases the surface homogeneity, spot to spot reproducibility and sample washability as compared with the commonly used dried-droplet method. This methodology is applicable to alpha-cyanohydroxycinnamic acid, sinapinic acid and ferulic acid, which all form homogeneous crystal surfaces. Within-spot variation and between-spot variation was investigated using statistics at a 95% confidence level (n = 36). The statistical values were generated from more than 5000 data points collected from 500 spectra. More than 90% of the sample locations results in high intensity spectra with relatively low standard deviations (RSDs). Typically obtained data showed an RSD of 19-35% within a sample spot as well as in-between spots for proteins, and an RSD of < or = 50% for peptides. Linear calibration curves were obtained within one order of magnitude using internal calibration with a point-RSD of 3% (n = 10). The sample homogeneity allows mass spectra (average of 16 laser shots) to be obtained on each individual sample within 15 sec, whereby a 100 spot target plate can be run in 25 min. High density target plates using the seed-layer method were prepared by spotting approximately 100 picoliter droplets onto the target, resulting in sample spots < or = 500 microns in diameter using a flow-through piezo-electric micro-dispenser. By using this automated sample preparation step lower standard deviations are obtained in comparison to manually prepared samples.     

Rare earth metal complexes with 1,3-bis-(2-hydroxyphenyl)-1,3-propanedione. An example of anhydrous rare earth β-diketonates

Summary The interaction of non-anhydrous solutions of the ligand 1,3-bis-(2-hydroxyphenyl)-1,3-propanedione (bhppH₃) with hydrated rare earth chlorides resulted in the formation of anhydrous, non-solvated, complexes M(bhppH₂)₃ (M=Y, La, Nd, Pr, Sm or Yb). The complexes have been characterized by elemental analysis, t.g., i.r. and¹H n.m.r. spectroscopy. The evidence suggests that the coordination is through the -diketone site.     

Determination of aflatoxins in peanuts by matrix solid-phase dispersion and liquid chromatography

A new method based on matrix solid-phase dispersion (MSPD) extraction was studied to determine aflatoxin B1, B2, G1 and G2 from peanuts. Optimization of different parameters, such as type of solid supports for matrix dispersion and elution solvents were carried out. The method used 2 g of peanut sample, 2 g of C18 bonded silica as MSPD sorbent and acetonitrile as eluting solvent. Recoveries of each aflatoxin spiked to peanut samples at 2.5 ng/g (5 ng/g for aflatoxin G2) level were between 78 and 86% with relative standard deviations ranging from 4 to 7%. The limits of quantification ranged from 0.125 to 2.5 ng/g for the four studied aflatoxins using liquid chromatography (LC) with fluorescence detection. In addition, LC coupled to mass spectrometry with an electrospray interface was used for confirmation of aflatoxins present in real samples. Eleven peanut samples from different countries were analyzed by the proposed method and by using an enzyme-linked immunosorbent assay (ELISA). ELISA test is a good screening method for investigation of these mycotoxins in peanut samples.     

Determination of cadmium,aluminium, and copper in beer and products used in its manufacture by electrothermal atomic absorption spectrometry

Procedures were developed for determining cadmium, aluminium, and copper in beer and the products used in its manufacture by electrothermal atomic absorption spectrometry. Beer samples were injected into the furnace and solid samples were introduced as suspensions after preparation in a medium containing hydrogen peroxide, nitric acid, and ammonium dihydrogen phosphate for cadmium atomization. Calibration was performed with aqueous standards, and characteristic masses and detection limits were, respectively, 1 and 0.3 pg for cadmium, 18 and 5.4 pg for aluminium, and 5.6 and 6.8 pg for copper. Different samples of beer, wort, brewer's yeast, malt, raw grain, and hops were analyzed by the proposed procedures. Cadmium was found in low concentrations (0.001-0.08 microg/g and 0-1.3 ng/mL); copper (3-13 microg/g and 25-137 ng/mL) and aluminium (0.6-9 microg/g and 0.1-2 microg/mL) were found at higher levels. The reliability of the procedure was confirmed by comparing the results obtained with others based on microwave oven sample digestion, and by analyzing several certified reference materials.     

Dilatational rheology of beta-casein adsorbed layers at liquid-fluid interfaces

The rheological behavior of beta-casein adsorption layers formed at the air-water and tetradecane-water interfaces is studied in detail by means of pendant drop tensiometry. First, its adsorption behavior is briefly summarized at both interfaces, experimentally and also theoretically. Subsequently, the experimental dilatational results obtained for a wide range of frequencies are presented for both interfaces. An interesting dependence with the oscillation frequency is observed via the comparative analysis of the interfacial elasticity (storage part) and the interfacial viscosity (loss part) for the two interfaces. The analysis of the interfacial elasticities provides information on the conformational transitions undergone by the protein upon adsorption at both interfaces. The air-water interface shows a complex behavior in which two maxima merge into one as the frequency increases, whereas only a single maximum is found at the tetradecane interface within the range of frequencies studied. This is interpreted in terms of a decisive interaction between the oil and the protein molecules. Furthermore, the analysis of the interfacial viscosities provides information on the relaxation processes occurring at both interfaces. Similarly, substantial differences arise between the gaseous and liquid interfaces and various possible relaxation mechanisms are discussed. Finally, the experimental elasticities obtained for frequencies higher than 0.1 Hz are further analyzed on the basis of a thermodynamic model. Accordingly, the nature of the conformational transition given by the maximum at these frequencies is discussed in terms of different theoretical considerations. The formation of a protein bilayer at the interface or the limited compressibility of the protein in the adsorbed state are regarded as possible explanations of the maximum.     

Rapid determination of lead, cadmium and thallium in cements using electrothermal atomic absorption spectrometry with slurry sample introduction

 A method is proposed for the determination of Pb, Cd and Tl in cements by ETAAS. The samples are suspended in a medium containing 10% v/v ethanol and 1% v/v both conc. nitric and hydrofluoric acids and are directly introduced into the electrothermal atomizer. The drying stage is performed by programming a 400 °C temperature, a ramp time of 5 s and a hold time of 30 s on the power supply to the atomizer. No ashing step is used. Atomization is carried out at 2100, 1800 and 1700 °C for Pb, Cd and Tl, respectively. For Cd determination, ammonium dihydrogen phosphate is added to the suspension medium. No modifier other than hydrofluoric acid is required for the Pb and Tl determination. It is shown that the results obtained by using direct calibration with aqueous standards for five commercial samples agree with those found by means of the standard additions method. Received: 29 March 1996/Revised: 24 May 1996/Accepted: 30 May 1996     

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%.