Niobium (V) peroxocomplexes as a catalyst of oxidation of methylphenylsulphide by hydroperoxide

The electrospray ionization-mass spectrometry (ESI-MS) method has been used for determination of the structure of niobium peroxocomplexes. The formation of mono- and bisperoxocomplexes has been established. These complexes contain Schiff bases and 8-quinolinol as ligands. Trisperoxocomplexes are formed when pyridine and 1,10-phenanthroline are used. Peroxocomplexes with Schiff bases as ligands has shown a high activity as catalysts in the methylphenylsulphide oxidation.     

The thermodynamic characteristics of formation of copper(II) ion complexes with carboxylic acids in aqueous solutions

The heat effects of complex formation between copper(II) ions and malonic, maleic, and succinic acids were measured in an isothermic-shell calorimeter at 298.15 K and several ionic strength values against the background of NaNO₃. The standard thermodynamic characteristics of complex formation in aqueous solutions were calculated.     

Identification of sildenafil,tadalafil and vardenafil by gas chromatography–mass spectrometry on short capillary column

Sildenafil and its analogues (tadalafil and vardenafil) are phosphodiesterase type 5 inhibitors used in the treatment of male erectile dysfunction. Some dietary supplements, herbal preparations and food products which claim to enhance male sexual function have been found to be adulterated with these drugs. In this study, a gas chromatograph–mass spectrometer (GC–MS) assay was developed for identification of the drugs. In addition to good and short chromatographic separation that can be achieved within 6 min by using a short 10 m capillary column, no prior sample clean-up before GC–MS analysis was required, thus making this assay a cost saving and rapid method. Furthermore, the assay is specific as the identification of sildenafil, tadalafil and vardenafil were done by detection of molecular ions; m/z 474, 389 and 448, respectively, and several other characteristic ions resulted from the mass fragmentation of individual molecules. Using our currently developed assay, sildenafil and its analogues were successfully identified in food and herbal matrices.     

The influence of the nature of background anions on the buffer capacity of glycine-containing electrolytes for nickel electroplating

The buffer properties of acetate, sulfate, and chloride glycine-containing electrolytes for nickel electroplating were studied. Various forms of the amino acid and background anions were shown to act in solution as two buffer systems related by competitive complex formation. The buffer capacity of a solution was then the result of the joint action of these systems. The contribution of each of them was determined by its absolute concentration in solution on the one hand and changes in this concentration caused by the addition of H⁺ or OH^? ions on the other.     

Photolysis of pure solid O3 and O2 films at 193 nm

We studied quantitatively the photochemistry of solid O(3) and O(2) films at 193 nm and 22 K with infrared spectroscopy and microgravimetry. Photolysis of pure ozone destroyed O(3), but a small amount of ozone remained in the film at high fluence. Photolysis of pure O(2) produced O(3) in an amount that increased with photon fluence to a stationary level. For both O(2) and O(3) films, the O(3):O(2) ratio at large fluences is ～0.07, about two orders of magnitude larger than those obtained in gas phase photolysis. This enhancement is attributed to the increased photodissociation of O(2) due to photoabsorption by O(2) dimers, a process significant at solid-state densities. We obtain initial quantum yield for ozone synthesis from solid oxygen, Φ(O(3)) = 0.24 ± 0.06, and quantum yields for destruction of O(3) and O(2) in their parent solids, Φ(-O(3)) = 1.0 ± 0.2 and Φ(-O(2)) = 0.36 ± 0.1. Combined with known photoabsorption cross sections, we estimate probabilities for geminate recombination of 0.5 ± 0.1 for O(3) fragments and 0.88 ± 0.03 for oxygen atoms from O(2) dissociation. Using a single parameter kinetic model, we deduce the ratio of reaction cross sections for an O atom with O(2) vs. O(3) to be 0.1-0.2. The general good agreement of the model with the data suggests the validity of the central assumption of efficient energy and spin relaxation of photofragments in the solid prior to their reactions with other species.     

The influence of chemical activation of the M45K20 sorbent on the heat effects of sorption of ammonium ions

Calorimetric measurements were performed and the heat effects of sorption of ammonium ions from aqueous solutions by the M₄₅K₂₀ natural sorbent and its acid- and alkali-activated forms were calculated.     

Exact results for a model of a three-level atom

For a three-level atom interacting with two modes of the quantized radiation field the time dependence of transition operators, photon amplitudes, and of operators of level populations and photon numbers is examined rigorously. It is shown that the availability of a mode detuning leads to the splitting of the “soft branch” of frequencies of two-photon Rabi oscillations.