Determination of copper, lead, cadmium, zinc, and iron in calcium fluoride and other fluoride-containing samples by means of direct solid sampling GF-AAS

Direct solid sampling graphite furnace AAS (SS-GF-AAS) provides an advantageous alternative to the conventional AAS which requires wet digestion of the samples. This method is suitable for trace element determination in calcium fluoride and other fluoride-containing samples. Matrix effects were studied by using calibration standards, certified reference materials with different matrices and by means of three-dimensional calibration. 3D calibration is suitable for selection of calibration samples for more reliable analyses. Cu, Pb, Cd, Zn, and Fe were determined by means of calibration with variation of sample weight using certified reference materials and suitable fluoride-containing calibration samples. Received: 25 July 1997 / Revised: 15 December 1997 / Accepted: 20 December 1997     

Copper(II), nickel(II), cobalt(II) and zinc(II) complexes of 2-[2-(6-methylbenzothiazolyl)azo]-5-dimethylaminobenzoic acid: synthesis,spectral, thermal and molecular modelling studies

Complexes of copper(II), nickel(II), cobalt(II), and zinc(II) with 2-[2-(6-methylbenzothiazolyl)azo]-5-dimethylaminobenzoic acid have been prepared and characterized by elemental analysis, vibrational spectra, magnetic susceptibility measurements, conductance measurements and e.p.r. spectra. Stability constants have been evaluated potentiometrically. Electronic spectra, magnetic susceptibility measurements and molecular modeling studies support a distorted square planar geometry around the metal ions. Vibrational spectra indicate the coordination of the azo group, nitrogen of benzothiazole, the carboxylate anion and the acetate ion on complexation with the metal ion. All complexes are found to be monomers. The stability of the complexes follow the order: copper(II) > nickel(II) > cobalt(II) > zinc(II).     

Capillary electrophoresis with field-enhanced stacking for rapid and sensitive determination of strychnine and brucine

A new capillary electrophoresis procedure with field-enhanced stacking concentration for the analysis of strychnine and brucine is established. After optimization of the separation and concentration conditions, the two alkaloids can be separated within 5 min and quantified with high sensitivity (The detection limits were 1.0 ng mL(-1) for strychnine and 1.4 ng mL(-1) for brucine). The method was useful for qualitative and quantitative analysis of strychnine and brucine in Strychnos nux-vomica L with recovery of 105.1% for strychnine and 98.4% for brucine.     

Synthesis and new rearrangements of 4-isoxazolin-4,5-dicarboxylic acid derivatives

Acyclic nitrones react with dimethyl acetylenedicarboxylate (DMAD) to give stable isoxazolines, from which the ones that contain electron-donating aromatic rings at the C3 position (R¹) were shown to undergo unprecedented fragmentation at room temperature, giving the R¹-aldehyde and inseparable product mixtures, probably due to the formation of highly reactive species such as iminocarbenes. Attempts to convert the isoxazolines to the corresponding stable azomethine ylides, by refluxing in toluene, again led to the same product mixtures as above (e.g., the room temperature decomposition). Isoxazolines when reacted with methoxide at room temperature afforded highly functionalised diastereomeric mixtures. Also, isoxazolines, when reacted with propylamine, gave the corresponding amides regioselectively, all of which were more stable than the parent isoxazolines.     

Determination of thiol by high-performance liquid chromatography and fluorescence detection with 5-methyl-(2-(<Emphasis Type="Italic">m</Emphasis>-iodoacetylaminophenyl)benzoxazole

A new high-performance liquid chromatographic (HPLC) method for measuring low molecular weight (LMW) thiol-containing compounds, including cysteine (CysH), glutathione (GSH), N-acetylcysteine (Nac), penicillamine (PA), and 2-mercaptoethanol (2-ME), has been developed by using 5-methyl-(2-(m-iodoacetylaminophenyl)benzoxazole (MIPBO) as fluorescence-labeling reagent. The derivatization and separation conditions have been investigated in detail. Detection limits ranging from 3.5 to 15.0 fmol were achieved for the thiols investigated in a 16 min separation with detection wavelengths 310 and 375 nm for the excitation and emission, respectively. The utility of the proposed method has been validated by measuring CysH in human urine samples.     

An Efficient Route to Phenylselenoethers in the Presence of Ag2O

An efficient protocol for the preparation of phenylselenoethers from unsaturated alcohols using phenylselenenyl halides at room temperature was developed. The procedure employs phenylselenenyl chloride and bromide, some Δ ⁴- and Δ ⁵-alkenols and Ag₂O, as an additive, to generate the tetrahydropyrans or tetrahydrofurans. This method permits the preparation of cyclic phenylselenoethers in high yields and under extremely mild conditions.     

Use of biosensors for rapid drug residue analysis without sample deconjugation or clean-up: a possible way forward.

The drug salbutamol (SBL) is a beta-agonist that may be used illegally as an animal growth promoter. SBL is also a good example of a drug which is excreted in the form of glucuronides and sulfates. Such metabolites cause complexities in analysing for the presence of drug residues. In the majority of cases a process of deconjugation and sample clean-up is required prior to analysis. This is both time consuming and causes some loss of accuracy. In this study, the urine of calves treated with SBL orally for 3 d was collected during and after medication. Samples were assayed before and after hydrolysis by two different methods, radioimmunoassay (RIA) and a newly developed biosensor immunoassay (BIA). Some samples were also analysed by GC-MS. The results clearly showed that both screening assays (RIA and BIA) found high concentrations of SBL residues throughout the study. This was especially true in the BIA method. It was also demonstrated that urine sample analysis without the need for deconjugation or clean-up could be achieved. Results obtained by GC-MS tended to be an order of magnitude lower than the corresponding screening test results. This work showed that biosensor based veterinary drug residue testing procedures can be developed which can generate results in real time without the need for time consuming sample preparation.     

Separation of positional isomers by the use of coupled shape-selective stationary phase columns

The successful separation of 2- and 3-methyl-substituted positional isomers of butanol, butyl acetate, and butanoic acid and its ethyl ester, is reported. These compounds are of interest in the study of wine flavour, however the separation of the 2- and 3-methyl isomers may present problems, and more so in the presence of the wine matrix components, when single capillary column gas chromatography (GC) is used. The strategy to achieve separation was based on the use of shape-selective cyclodextrin derivative (CDD) capillary columns (commonly referred to as chiral columns). These columns provide simultaneous resolution of the enantiomeric pairs of the 2-methyl isomers, and at the same time the ability to separate the 3-methyl isomer from the 2-methyl is achieved in all but the case of the ( S)-2- and 3-methylbutanol. The advantages of using shape-selective columns to perform this study is demonstrated, with coupling of two CDD columns giving improved separations of these compounds. Although these compounds are relatively volatile, cryogenic modulated comprehensive two-dimensional GC was shown to provide good pulsed peak profiles with chiral separation in the first dimension when a thicker film trapping column segment was employed. The components of interest were well separated from other wine matrix components.     

Radionuclides in a sediment trap and bottom sediment samples from the eastern Turkish coast of the Black Sea

Summary Radionuclide (¹³⁷Cs, ²³⁸U, ²³²Th and ⁴⁰K) concentrations were determined in a sediment trap and bottom sediment samples collected from a station at the eastern Turkish coast of the Black Sea. The specific activity of the ¹³⁷Cs radionuclide in the settling particles ranged from 0.04±0.01 to 0.10±0.02 Bq^. g^-1dry weight. The calculated flux rate of the ¹³⁷Cs was between 0.37 and 2.59 Bq^. m^-2. d^-1in the sampling periods of 2002 and 2003. The ¹³⁷Cs concentration in the bottom sediment profile were between 0.039±0.013-9.083±0.017 Bq^. g^-1dry weight in the same station. The vertical profile of the radionuclides suggests that they have little mobility during the 17 years after the Chernobyl accident.     

Bienzymatic analytical microreactors for glucose, lactate, ethanol, galactose and l-amino acid monitoring in cell culture media

A new alternative method for bioprocess monitoring based on bienzymatic analytical microreactors integrated in a flow injection analysis (FIA) system is described. Glucose-, alcohol-, lactate-, galactose- and l-amino acid oxidases (GO, AO, LacO, GalO and LAAO) and horseradish peroxidase (HRP) are immobilized on controlled pore glass (CPG) and used for the development of glucose, ethanol, lactate, galactose and amino acid sensors. The analytical methodology is based on HRP catalysed reaction of hydrogen peroxide produced by oxidases with phenol-4-sulfonic acid and 4-aminoantipyrine. The immobilized enzymes are characterized and used for preparation of the packed bed analytical microreactors. Shelf life and operational stability of the microeactors are determined. GO/HRP, AO/HRP and LAAO/HRP microreactors showed excellent shelf life, they could be stored and reused for more than 6 months with no or very little activity loss, while GalO/HRP and LacO/HRP could be stored for shorter periods of time (10-20 days). Operational stability of GO and LacO microreactors was very good: an equivalent to 16,900 FIA injections of 25 μl to a LacO microreactor resulted in loss of half of its activity, immobilized GO was so stable that it was impossible to evaluate enzyme halflife. Immobilized GalO and LAAO lose their operational activity much faster: approximately 1400 and 8000 FIA injections of the respective substrate solution in a FIA set-up resulted in 50% activity loss. The methods with all the described microreactors were successfully validated using off-line samples from S. cerevisiae, E. coli and mesenchymal stem cell cultures with HPLC as the reference method.