Atomization of Al in a tungsten coil electrothermal atomic absorption spectrophotometer

Electrothermal atomic absorption spectrophotometry of Al in a tungsten coil atomizer was evaluated and applied for its determination in hemodialysis fluid. The system was mounted on a Varian Spectra AA-40 spectrophotometer with continuum background correction and all measurements, in peak height absorbance, were done at 309.3 nm. The purge gas was a mixture of 90% Ar plus 10% H(2). Observation height, gas flow, drying, pyrolysis and atomization steps were optimized. The heating program was carried out by employing a heating cycle in four steps: dry, pyrolysis, atomization and clean. The determination of Al in hemodialysis solutions was performed by using a matrix-matching procedure. Al in hemodialysis solutions was determined by TCA and by electrothermal atomization with a graphite tube atomizer. There is no differences between results obtained by both methods at a confidence level of 95%. The characteristic mass of Al by using the TCA was 39 pg and the detection limit was 2.0 mug l(-1).     

Solvothermale Synthese und Bestimmung der Kristallstrukturen von AgBiI4 und Ag3BiI6

Solvothermal Synthesis and Crystal Structure Determination of AgBiI₄ and Ag₃BiI₆ AgBiI₄ and Ag₃BiI₆ were synthesized by solvothermal reaction from AgI and BiI₃ in diluted HI‐solution (20 %) at a temperature of 160 °C. The greyish‐black crystals grow as octahedra (AgBiI₄) or hexagonal/trigonal platelets (Ag₃BiI₆). AgBiI₄ crystallizes in space group Fd3¯m with a = 1222.3(1) pm (300 K) and Z = 8 whereas Ag₃BiI₆ shows the space group R3¯m with a = 435.37(6) pm, c = 2081.0(4) pm (300 K) and Z = 1. Both crystal structures show stacking sequence abcabc… of hexagonal layers containing Iodine. Bismuth and silver are sharing octahedral sites with different mass ratio in both structures. The part of silver which could be localized varies with temperature. This behaviour indicates mobility of silver within the crystal structure. The ionic conductivity of AgBiI₄ is explored. AgBiI₄ and Ag₃BiI₆ show close structural relationship, with AgBiI₄ as a variant with a higher degree of order.     

A rapid non-acidolytic method for deprotection and removal of peptides from solid phase resins - applications of ammonium formate catalytic transfer hydrogenation

Ammonium formate aided catalytic transfer hydrogenation has been employed in the cleavage, and concommitant deprotection, of the pentapeptide leucine enkephalin from the Merrifield peptide resin under ambient conditions of temperature and pressure in a neutral medium.     

Use of the internal standardization for difficult sampling by graphite furnace atomic absorption spectrometry

This work shows the potentiality of As as internal standard to compensate errors from sampling of sparkling drinking water samples in the determination of selenium by graphite furnace atomic absorption spectrometry. The mixture Pd(NO₃)₂/Mg(NO₃)₂ was used as chemical modifier. All samples and reference solutions were automatically spiked with 500 μg l⁻¹ As and 0.2% (v/v) HNO₃ by the autosampler, eliminating the need for manual dilutions. For 10 μl dispensed sample into the graphite tube, a good correlation (r=0.9996) was obtained between the ratio of analyte absorbance by the internal standard absorbance and the analyte concentrations. The relative standard deviations (R.S.D.) of measurements varied from 0.05 to 2% and from 1.9 to 5% (n=12) with and without internal standardization, respectively. The limit of detection (LD) based on integrated absorbance was 3.0 μg l⁻¹ Se. Recoveries in the 94-109% range for Se spiked samples were obtained. Internal standardization (IS) improved the repeatability of measurements and increased the lifetime of the graphite tube in ca. 15%.     

MSXα method and transition-state procedure

Theoretical aspects of the MS X_α method are analyzed. It is shown that real field self-consistency is not achieved in an MS X_α calculation and some consequences of this fact are discussed. The approximations involved in the use of the transition-state procedure to evaluate ionization and excitation energies from a MS X_α calculation are presented in some detail and commented.     

Immobilized enzyme electrode for the determination of salicylate in blood serum

This determination of salicylate in blood serum is based on application of an immobilized enzyme electrode. Salicylate hydroxylase (E.C.1.14.13.1) is chemically immobilized onto a pig intestine mounted on an oxygen electrode. The signals are monitored amperometrically and the resulting output voltage is read using a simple adapter. The experimental parameters and possible interferences are discussed. Samples containing 1.0 × 10^?5?1.87 × 10^?3 M (1.6–300 μg ml^?1) salicylate were assayed with relative standard deviations between 1.3% and 6% and recoveries between 98.7 and 103%. Results obtained by the proposed method and by the established clinical method for randomly spiked pooled serum samples correlated well (r = 0.99).     

The role of C-centered radicals on the mechanism of action of artemisinin

Artemisinin is a sesquiterpene lactone with an endoperoxide function that is essential for its antimalarial activity. Endoperoxides are supposed to act on heme leading to the reduction of the peroxide bond and production of radicals, which can be responsible for killing the parasite. The geometries of artemisinin, radical anions and neutral species generated by rearrangement after reduction of the peroxide bond were fully optimized with the AM1 and PM3 semi-empirical methods, in order to characterize the intermediates formed during the process. Among the radicals calculated along the pathway for reductive decomposition of artemisinin, the secondary radical centered on carbon C₄ has the highest stability when compared to other radicals that can be achieved either by hydrogen migration to the original O-centered radical or by homolytic break of C–C bond. This suggests that the C₄-centered radical may be the species responsible for killing the parasite, as has been indicated previously in experimental studies.     

Solvent extraction of phosphonium salts and their analytical applications : Separation and spectrophotometric determination of hexacyanoferrate(III)

The potentiometric determination of zinc in chloride solutions with a coated wire electrode is described. The electroactive membrane contains the chlorozincate(II) salt of Aliquat 336S in poly (vinyl chloride). The electrode shows a useful response over the range 10^-5 M–10^-1 M zinc(II) in 3 M total chloride solutions in the pH range 1.5–6. The electrode is more responsive to the divalent tetrachlorozincate(II) than to the monovalent trichlorozincate(II) species. Applications in compleximetric titrations, and to the analysis of zinc oxide and zinc concentrates are reported.     

Application of neutron activation analysis to bone samples

Summary Neutron activation analysis technique, using Au as flux monitor, was applied to determine element concentrations of Ca, K, Na, Mg, Mn and Sr in certified reference material (NIST 1400 Bone Ash). The results were compared with those using comparative INAA and they were compatible. The same results were obtained using the recommended k₀ factors, in order to obtain the activation cross section as input in concentration for the same reference material. Some applications in the health area aiming clinical evaluation in bone samples of medium and small-sized animals were performed and the viability of using this methodology was discussed.     

Lanthanide nitrate complexes with 2-azacyclononanone

Thermal behavior of rare earth nitrate complexes with 2-azacyclononanone (AZA) with Ln(NO₃)₃·3(AZA) composition (where Ln=Gd, Er and Ho) was analyzed in kinetic point of view. Kinetic parameters were calculated from thermogravimetric data. All obtained results were similar. The first decomposition step was representative to the loss of ligand and the residue was essentially Ln₂O₃. Furthermore, a reaction path was proposed for the thermal decomposition of the Ln(NO₃)₃·3(AZA).