Determination of gold and palladium in rocks and ores by atomic absorption spectrometry using two-stage probe atomization

The efficiency of two-stage probe atomization for the determination of gold and palladium in geological samples by electrothermal atomic absorption spectrometry is studied. The effects of temperature–time program and the position of the probe in an atomizer on the fractionation of sample components and the magnitude of the analytical signal are studied. It is demonstrated that gold and palladium can be quantitatively determined by atomic absorption spectrometry in rocks and ores, using a two-stage probe atomization with the limits of detection for gold and palladium 0.01 and 0.04 g/t, respectively.     

Determination of the surface area of loose metal deposits by impedance spectroscopy

The surface area and fractal dimensions of the surface of loose copper and zinc deposits obtained within 30 and 300 s at direct current sixfold exceeding limiting diffusion current on a smooth electrode were in situ determined by impedance spectroscopy. Impedance measurements were performed in 0.5 M Na₂SO₄ solution. A constant phase element taking into account the distribution of double-layer capacitance over the fractal surface of the electrode was used in the equivalent impedance scheme. Specific surface calculated with regard to the weight of the released metal slightly varied within 300 s (from 6.16 to 6.55 and from 7.12 to 5.89 m²/g for copper and zinc deposits, respectively). Fractal dimensions estimated by chronopotentiometry were given for comparison. Fractal dimensions found by two methods for loose copper and zinc deposits agree with each other; their values (2.19–2.75) testify that the surface of the deposits densely fills the space.     

Mechanism of reaction of selenium elimination in diacetophenonyl selenide under the action of reduced glutathione

Products of reaction between the organoselenium xenobiotic, diacetophenonyl selenide (1,5-diphenyl-3-selenapenta-1,5-dione), and reduced glutathione at different molar ratios and pH values were studied by HPLC and TLC. Reaction intermediates, S-(acetophenylselenyl)glutathione and glutathione selenodisulfide, and reaction products, acetophenone and hydroselenide anion, were detected. The reaction scheme proposed earlier was confirmed.     

Use of PLS Discriminant Analysis for Revealing the Absence of a Compound in an Electron Ionization Mass Spectral Database

A mathematical model is proposed for revealing the absence of a compound to be identified in an electron impact mass spectral library. The mathematical model (developed based on PLS Discriminant Analysis) can be represented as a “black box” which provides an answer whether a compound to be sought is absent or present in a database. The match factors of top ten candidates among the possible ones were used as input data. More than 5000 objects (mass spectra) were used at the steps of training, validation, and testing. The developed classification model provides correct prediction (of whether a compound is absent from the library) in 28.4% cases, while only 1.2% of compounds present in the database were incorrectly classified as the absent ones.     

Primary photophysical and photochemical processes for Pt(SCN)<Subscript>6</Subscript><Superscript>2–</Superscript> complex

Photosolvation of a Pt^IV hexathiocyanate complex Pt(SCN)₆ ^2– in water and ethanol was studied by steady-state photolysis, nanosecond laser flash photolysis, and ultrafast kinetic spectroscopy. Complexes Pt(SCN)₅(H₂O)^– and Pt(SCN)₅(C₂H₅OH)^– were found to be the only reaction products. The quantum yields of photosolvation are independent of the excitation wavelength, being equal to 0.25 and 0.5 for the solutions of the complex in water and ethanol, respectively. Photosolvation proceeds by the mechanism of heterolytic metal—ligand bond dissociation without involvement of redox processes. The characteristic time of formation of the end products for both solvents is about 10 ps. Three successive intermediates detected on the picosecond time scale were interpreted as Pt^IV complexes. The nature of the intermediates and possible mechanisms of photosolvation are discussed.     

Alkylation of phenol with olefins in the presence of catalysts based on mesoporous aromatic frameworks

Mesoporous polyaromatic frameworks (PAFs) based on tetraphenylmethane were obtained and modified with sulfonic acid groups. The compounds were characterized by solid-state ¹³C NMR and IR spectroscopy, low-temperature nitrogen adsorption-desorption, and transmission electron microscopy. The acidities of the PAF-1-SO₃H and PAF-2-SO₃H samples determined by titration were 3.99 mmol g^–1 and 0.91 mmol g^–1, respectively. The catalytic activity of PAF-SO₃H for alkylation of phenol with linear terminal olefins was investigated. The reaction products were isomeric monoalkylphenols (C-alkylates), and alkyl phenyl ethers (O-alkylates).     

A comparative study of the reactions of fluorinated oxi- and thiiranes with acyl chlorides

The CoCl₂-catalyzed reactions of fluorinated 1,2-oxi- and thiiranes with acyl chlorides were studied. It was found that a regioselective heterocycle opening reaction resulted in two isomers having normal and abnormal structure in a ratio predetermined by the substituents in both the starting heterocycles and acyl chlorides.     

Synthesis of substituted 3-acyl-1-hydroxyindoles and azoles on their basis

A general approach to the synthesis of new 3-acetyl-substituted pyrrolo[3,4-f]indole-5,7-diones, 3-[3-(dimethylamino)acryloyl]-1-methoxypyrrolo[3,4-f]indole-5,7-diones and similar indole-5,6-dicarbonitriles has been developed. Dimethylaminoacryloyl derivatives synthesized on their basis regioselectively reacted with hydrazine hydrochlorides and hydroxylamine with the formation of the corresponding 5-substituted azoles.     

Conjugation of indole derivatives by copper-catalyzed alkyne-azide cycloaddition

An efficient synthetic procedure to combine biologically active indole derivatives by the triazole-containing spacer in a molecule has been proposed. The procedure was based on a copper-catalyzed alkyne-azide cycloaddition of azide-containing carbazoles and N-propargyl-containing carbazoles, tetrahydrocarbazoles, and tetrahydro-γ-carbolines.     

The importance of glyceraldehyde radiolysis in chemical evolution

Studies in chemical evolution are intended to demonstrate how compounds of biological importance are generated from substances that could have been found in abiotic conditions on the primitive Earth or in extraterrestrial environments. In this context, the aim of the present work was to examine the behavior of dl-glyceraldehyde in both aqueous solution and solid samples under gamma irradiation. We irradiated dl-glyceraldehyde at different doses and temperatures with a gamma source; even at low doses and temperature (77 K), free radicals were detected. Among the products formed were ethylene glycol and glycolaldehyde. Some sugar-like compounds were also detected.