The application of differential pulse polarography to the determination of a pharmacologically active benzhydrylpiperazine derivative and its major electroactive metabolites in the plasma and urine of animals.

A method for the determination of 1–500 p.p.m. of acid-soluble aluminium and 2–500 p.p.m. of acid-insoluble aluminium in low-alloy and stainless steels by flameless atomic absorption with a HGA 74 graphite furnace is described. A typical value of the relative standard deviation for acid-soluble aluminium at concentrations larger than 10 p.p.m. was 5 %. The steel sample was dissolved in hydrochloric and nitric acid and filtered. Ammonium sulphate was added to the filtered sample in order to overcome interferences caused by hydrochloric acid. No concentration steps were used. Acid-soluble aluminium was determined within 20 min. The influence of iron, chromium, nickel, molybdenum, hydrochloric acid, nitric acid and ammonium sulphate respectively was investigated.     

Atomic absorption spectrometric determination of aluminium in whole blood

Two methods are described for atomic absorption spectrometric determinations of aluminium m heparinized and haemolyzed samples of undiluted whole human blood. In the direct method 2μl of blood are pipetted into a graphite cup atomizer; after a drying and two ashing steps aluminium is determined by atomization at 2500°C. In the second method, 15μl of blood are decomposed by nitric acid in polytetrafluoroethylene tubes; 2-μl portions of the solution are then analyzed with the graphite tube atomizer. The direct method was applied to the determination of aluminium in whole blood from 48 Norwegian workers occupationally unexposed to the element; the concentrations of aluminium ranged from 0.05—0.59 p.p.m. (mean value, 0.20 p.p.m.). For 0.35 p.p.m. aluminium, the relative standard deviation of both methods was 8%. The detection limit of the direct method is 0.05 p.p.m. aluminium.     

Spectrophotometric determination of aluminium with stilbazo

The use of stilbazo as a spectrophotometric reagent for aluminium has been investigated. The reagent forms a stable coloured complex with aluminium showing an absorption maximum at 500 mμ. The system obeys Beer's law from 0.1–0.8 p.p.m. aluminium. The molar extinction coefficient and the stoichiometric composition of the coloured complex have been determined.     

Séparation de traces de fluorure des sels d'aluminium(III) par échangeurs d'ions

A method is proposed for the separation of aluminium(III) fluoride by chromatographie by means of an anion exchanger in alkaline medium, The methode is applicable to a minimum of 100 p.p.m. of fluoride in the aluminium.     

Dosage colorimetrique de traces de zinc dans la bauxite,l'alumine et l'aluminium raffine

A method for the colorimetric determination of traces of zinc in bauxite, alumina, and refined aluminium by means of dithizone is proposed. Ga, Fe, Si, Ti, Ni, Pb, Ca, Mg, Na, etc. do not interfere; Co interferes but can be masked with cyanide. The limit of sensitivity of the method is 2 p.p.m. for bauxite and alumina and 0.4 p.p.m. for aluminium.     

Vacuum-fusion determination of oxygen in aluminium and aluminium-aluminium oxide composites

A copper bath-vacuum fusion method for the determination of oxygen in aluminium was modified because the extensive evaporation of copper at the operating temperature gave trouble in a commercial instrument with unlidded crucibles. The evaporation can be decreased by making use of graphite capsules, where the samples and the copper are sealed before being dropped into the hot crucible. The procedure gives good results for specimens of aluminium and of aluminium-aluminium oxide composites, the oxygen content of which ranged from some tens of p.p.m. to some weight percent. The sensitivity of the method is of the order of 20 p.p.m. for sample weights of 100 mg, if copper of very low oxygen content is used.     

Correlation between hydroxyl fraction and O/Al atomic ratio as determined from XPS spectra of aluminium oxide layers

A set of five different aluminium oxide layers has been investigated using XPS. The oxide layers were made by oxidizing aluminium in a vacuum, with an alkaline and acidic pretreatment and in boiling water. Hydroxyl fractions of the aluminium oxide layers ranging from 0.0 to 0.5 were determined by constrained curve-fitting of the O 1s peak. The O/Al atomic ratios of the aluminium oxide layers, ranging from 1.5 to 2.0, were determined from the O 1s and Al 2p photoelectron intensities. A method is presented to account for the attenuation of the photoelectron intensities by the contamination overlayer. For the studied oxide layers, a linear relation is observed between the hydroxyl fraction and the O/Al atomic ratio of the aluminium oxide layers. It is concluded that the results obtained by the curve-fitting procedure are reliable. Furthermore, a linear relation is observed between the hydroxyl fraction and the O 1s peak width. The O 1s binding energies of the O²⁻ and OH⁻ components of the oxide layers correspond to 531.0 ± 0.1 eV and 532.4 ± 0.1 eV, respectively. Only pseudoboehmite showed 0.5 eV lower binding energies for these components. Angle-resolved XPS analysis showed that most of the studied oxides are enriched in hydroxyl groups at their outermost surface. Copyright © 2004 John Wiley & Sons, Ltd.     

Chemistry of aluminium(I)

In this article, we discuss the synthesis of tetrameric and monomeric aluminium(I) compounds. These compounds are prepared by reduction of the respective Al-X (X = halide) bond containing precursor. The tetrameric aluminium(I) compounds are synthesized by using sterically bulky ligands whereas a stable monomeric aluminium(I) compound is obtained using a monovalent chelating ligand. Theoretical studies are carried out on the monomer to understand the Lewis basicity. The presence of a lone pair of electrons plays an important role in the preparation of aluminium containing heterocyclic compounds, main group-main group and transition metal-main group compounds having donor-acceptor bonds by carrying out reactions with unsaturated compounds and Lewis acids.     

The determination of sulphur in copper,nickel and aluminium alloys by proton activation analysis

The ³⁴S(p, n)^34mCl reaction induced by 13-MeV protons is used for the determination of sulphur in copper, nickel and aluminium alloys. The ^34mCl is separated by repeated precipitation as silver chloride. The results obtained were 3.08 ± 0.47, 1.47 ± 0.17 and <1μg g^-1 for copper, nickel and aluminium alloys, respectively.     

Catalytic alkylation of phenol with methanol over zinc aluminate

Two samples (A and B) of zinc aluminate spinel were prepared and used as catalysts of phenol methylation. Both catalysts were synthesised at hydrothermal conditions from zinc acetate and from various aluminium precursors: aluminium isopropoxide (catalyst A) or basic aluminium nitrate (catalyst B). Catalyst A was pure ZnAl₂O₄ and B - besides ZnAl₂O4 contained traces of -Al₂O₃. Reactions of phenol alkylation with methanol were carried out in the gas phase under atmospheric pressure in a standard flow reactor with fixed bed. Catalysts indicated different properties in dependence on the aluminium precursor used during preparation. In the presence of catalyst A higher selectivity of ortho-methylation of phenol was obtained. Catalyst B was active both in O-alkylation and C-alkylation.     

Production of high-purity26Al

²⁶Al is a positron emitting radioisotope of aluminium and has a half-life of 7.16×10⁵y. In addition to annihilation -rays of 511 keV, there are three high energy -rays 1129 (2.4%), 1809 (99.73%) and 2938 (0.27%) keV.²⁶Al is the only radioisotope of aluminium available for radiochemical applications, the half-lives of the other aluminium isotopes are seconds and minutes. The usage of²⁶Al is very important in the investigations of the metabolism of Al in human body (for example in Alzheimer disease studies) or as a tracer in radiochemical studies. But²⁶Al is such a long-lived isotope that the task of producing it in tangible amounts is a very difficult one.     

The determination of beryllium in geological and industrial materials by atomic-absorption spectrometry after cation-exchange separation

A method is described for the determination of beryllium in geological and industrial samples. After dissolution of the sample in mineral acids, beryllium is separated from the matrix elements by chloroform extraction of its acetylacetonate from a solution of pH 7 containing ascorbic acid and EDTA. Beryllium is separated from the organic extract and from co-extracted aluminium by means of a column of the strongly acidic cation-exchanger Dowex 50; beryllium is adsorbed from a medium consisting of 60 % (v/v) tetrahydrofuran, 30 % (v/v) chloroform and 10 % (v/v) methanol containing hydrochloric acid, aluminium is removed with 0.4 M oxalic acid and after elution with 6 M hydrochloric acid, beryllium is determined by atomic-absorption spectrometry with a nitrous oxide-acetylene flame. The method was used to determine p.p.m. and sub-p.p.m. quantities of beryllium in geochemical reference materials, U₃O₃ and yellow cake samples, and manganese nodules.     

Influence of aluminium on the oxidation of titanium between 550 and 750 °C

In order to study the influence of aluminium on the oxidation resistance of titanium at high temperature, a range of binary alloys containing 1.65, 3, 5 and 10 wt.% of aluminium was prepared. Their oxidation kinetics were studied at temperatures between 500 and 750 °C using either continuous thermogravimetry or daily weighing for periods of up to several thousand hours. The results obtained for oxidation in air confirm the beneficial role of aluminium which has been observed previously for oxidation in oxygen. With regard to morphology and structure, aluminium modifies the internal structure of the oxide layers and their growth laws. A general dispersion of aluminium in rutile is observed, although a concentration of this phase is noted near the external interface; there is also a reduction in the amount of oxygen dissolved in the metal substrate which is related to the aluminium content in the alloy. Moreover, the presence of aluminium also modifies the adhesion of the oxide layers to the substrate.     

Determination of magnesium in iron by atomic absorption spectrophotometry

An atomic absorption spectrophotometric method for the determination of 0.001–0.10% magnesium in irons has been proposed. After suitable dissolution of the sample, 1500 p.p.m. of strontium is added to suppress aluminium interference and the solution is atomised in an atomic absorption spectrophotometer. The method is rapid, has high sensitivity, is free from interference and no preliminary separations are required.     

Simultaneous determination of nickel and cobalt traces by neutron activation analysis

Nickel and cobalt traces may be determined by measuring the ⁵⁸Co and ⁶⁰Co activities produced in a nuclear reactor. Solvent extraction of cobalt, and γ-spectrometry on the extracted phase allow a rapid and simple analysis of both metals. The method is applied to the determination of nickel (100–0.2 p.p.m.) and cobalt (0.15–0.001 p.p.m.) in various materials (petroleum, polyphenyls, aluminium).     

Radical Cyclisation of α‐Halo Aluminium Acetals: A Mechanistic Study

α‐Bromo aluminium acetals are suitable substrates for Ueno–Stork‐like radical cyclisations affording γ‐lactols and acid‐sensitive methylene‐γ‐lactols in high yields. The mechanistic study herein sets the scope and limitation of this reaction. The influence of the halide (or chalcogenide) atom X (X=Cl, Br, I, SPh, SePh) in the precursors α‐haloesters, as well as influence of the solvent and temperature was studied. The structure of the aluminium acetal intermediates resulting from the reduction of the corresponding α‐haloesters has been investigated by low‐temperature ¹³C‐INEPT diffusion‐ordered NMR spectroscopy (DOSY) experiments and quantum calculations, providing new insights into the structures of these thermally labile intermediates. Oxygen‐bridged dimeric structures with a planar Al₂O₂ ring are proposed for the least hindered aluminium acetals, while monomeric structures seem to prevail for the most hindered species. A comparison against the radical cyclisation of aluminium acetals derived from allyl and propargyl alcohols with the parent Ueno–Stork has been made at the BHandHLYP/6‐311++G(d,p) level of theory, highlighting mechanistic similarities and differences.     

MCD spectroscopy and magnetization studies of matrix-isolated aluminium atoms

The electronic absorption spectra and magnetic circular dichroism (MCD) spectra of matrix-isolated aluminium atoms have been studied with particular reference to the 3p4s and 3p3d transitions. The g values of the isolated atoms also have been measured via the MCD magnetization technique. It is found that, in all matrices, the orbital angular momentum of the atom is heavily quenched giving g values very near 2.0. A consistent analysis of this phenomenon and of the spectra has been developed using a model in which the surrounding noble gas atoms exert an electrostatic field upon the aluminium atom and also enter into molecular orbital formation with it. This interpretation leads to the conclusion that the spin-orbit coupling of the optical electron is negative in both ground and excited states for Al/Kr and Al/Xe, but in the excited state only for Al/Ar. These results confirm and extend the findings of earlier EPR measurements.     

Analysis of aluminosilicate particles in biological matrices using histochemistry and X-ray microanalysis

Aluminosilicates are a group of ubiquitous environmental particles that, in some cases, have been implicated in human disease. Characterisation of aluminosilicates in tissue samples requires, first, their in situ identification and, secondly, analysis of their aluminium and silicon content or, at least, aluminium:silicon ratio. Here, histochemical staining, microscopy and X-ray microanalysis were investigated as potential methods for the detection of aluminosilicates in biological samples. In contrast to aluminium phosphate or hydroxide, aluminosilicates were refractory to histochemical staining for aluminium. However, using electron microscopy, back scattered electrons allowed identification of aluminosilicates in tissue-like (gelatine) sections. X-ray microanalysis, using conventional peak:background ratios, did not provide a sufficiently accurate assessment of the aluminium content of various standard aluminosilicates to allow their identification. However, the similar spectral energies of aluminium and silicon allowed spectral peak heights to be directly compared and, using simple standards, aluminium:silicon ratios were found for a range of reference particles. Application of this technique should allow the localisation and identification of aluminosilicates in biological samples.     

Phosphorescence detection in flowing systems: selective determination of aluminium by flow-injection liquid room-temperature phosphorimetry

The concept of the micelle stabilized liquid room-temperature phosphorescence (MS-LRTP) was applied to the determination of a metal (aluminium) in a flowing system. A three-line flow-injection manifold was developed and various parameters were optimized. A linear calibration graph was obtained for 0–4 μg ml^?1 aluminium. The limit of detection was 50 ng ml^?1 and the relative standard deviations for 0.1 and 1.0 μg ml^?1 aluminium were 2.7 and 1.3% respectively. The proposed procedure is fairly selective. More than 20 common ions studied did not interfere with the determination of aluminium or could be masked by appropriate reagents. The flow-injection method proposed was applied without any preliminary separation to the determination of aluminium in simulated synthetic samples in water and in clinical samples of particular importance in the control of aluminium toxicity in renal failure patients.     

Trace analysis of fluorine by the Coulomb excitation method

The reaction¹⁹F(p, p′ γ)¹⁹F was used for the determination of fluorine concentration in biological materials such as lichen tissues and human bones. By means of this method, fluorine air contamination in the vicinity of aluminium works and the level of fluorine intoxication of exposed persons were investigated.