On the molecular structure of uranium dicarbide: T-shape versus linear isomers

A theoretical study of the molecular structure of uranium dicarbide has been carried out employing DFT, coupled cluster, and multiconfigurational methods. A triangular species, corresponding to a (5)A(2) electronic state, has been found to be the most stable UC(2) species. A triplet linear CUC species, which has been observed in recent infrared spectroscopy experiments, lies much higher in energy. A topological analysis of the electronic density has also been carried out. The triangular species is shown to be in fact a T-shape structure with a U-C interaction which can be considered to be a closed-shell interaction.     

Kinetics and mechanism of oxidation of cyclopentanone by N-bromosuccinimide

N-bromosuccinimide oxidation of cyclopentanone in acidic media in presence of mercuric acetate has been made. A zero order dependance to N-bromosuccinimide and a first order dependence to cyclopentanone and hydrogen ion concentration has been observed. Ionic strength, mercuric acetate and succinimide has negligible effect while methanol addition has a positive effect. Various rate parameters have been computed and 1,2-cyclopentanedione identified as the end product. A suitable mechanism in confirmity with the above observations has been proposed.With 2 Figures     

Thermodynamics and mechanism of reduction of silicon with carbon in a crucible reaction

A thermodynamic analysis of a crucible reaction, which takes place in crucible induction furnaces, has been represented. A new diagram of a crucible reaction, with due account for partial pressures and activities of the participating components, has been suggested. For the first time ever, the electrochemical mechanism of a crucible reaction has been studied; the research has confirmed the correctness of the suggested diagram.     

Design of potential angiogenin inhibitors

Summary A model of angiogenin has been prepared by homology modelling, based upon the structure of ribonuclease A. This model has been used to postulate an inhibitor based upon the angiostatic agent TAN1120. The complex of ribonuclease A with a dinucleotide has been modelled and used as a guide to the binding orientation of daunomycin—the closest TAN1120 analogue for which the crystal structure and stereochemistry are available.     

Isolation of fusicoccin from a culture filtrate ofFusicoccum amygdali

Fusicoccin A has been isolated from a culture filtrate of the filtrate of the fungusFusicoccum amygdali Del., and it has been characterized as an α-glycoside of a tricyclic diterpenoid. The trimethylsilyl derivative of fusicoccin A has been investigated by combined GLC and mass spectrometry.     

A portable gas chromatograph with air carrier gas for the determination of explosive traces

A three-step scheme for a miniature air purification filter for a gas chromatograph has been proposed. A method for controlling the selectivity of a new ion gas chromatography detector has been considered using a simulating model. The possibility of determining explosive traces by a gas chromatograph with air as a carrier gas has been demonstrated.     

Synthesis and characterization of a bisadduct of La@C82

A bisadduct of La@C82 has been synthesized in a good yield by a Bingel-Hirsch reaction. Its structure has been well-defined by X-ray crystallographic analysis. A pair of enantiomers of the adduct form a dimer in the single crystal.     

Polysaccharides of the protein-lipoid-polysaccharide complex of the mycelium ofVerticillium dahliae. I. Isolation and fractionation

A phytotoxic PLPC has been isolated from the mycelium of the fungusVerticillium dahliae Kleb., strain 614. The polysaccharide component has been split out from the PLPC by mild acid hydrolysis. The polysaccharide has been fractionated and the monosaccharide compositions of the fractions have been determined. A phytotoxic polysaccharide homogeneous according to gel chromatography and chromatography on DEAE-cellulose has been isolated which consists of an α-glucan containing a minor amount of D-glucosamine.     

A reversed-phase thin-layer chromotographic method for the determination of relative partition coefficients of very lipophilic compounds.

A reversed-phase thin-layer chromatographic method has been developed for the determination of partition coefficients. A support phase has been chosen, following investigation of the lack of adsorptive properties, which has a minimal effect on the pH of the buffer system. A stationary phase has been chosen to give deltaRm values of the same magnitude as Hansch pi values for a series of phenothiazines. The method can be applied to molecules of a wide range of lipophilicity following preliminary investigations of suitable phase-volume ratios and of the pH and composition of the binary mobile phase, providing adsorption on the support phase is excluded.     

Synthesis and alkylation of 2-mercapto-4-quinazolone and the fungicidal activities of the compounds obtained

A convenient method of obtaining 2-mercapto-4-quinazolone has been developed and the alkylation of its ambidentate anions has been studied. It has been found that they exhibit a dual reactivity in alkylation reactions. It has been shown that alkylated 2-mercapto-4-quinazolones possess a moderate fungicidal activity.     

Change in the activity of the proteolytic enzymes of cotton seeds when the plants are affected by wilt

The change in the proteolytic activity of the seeds of the cotton plant varieties Tashkent-1- Tashkent-6, S-4727, and 108-F when the plants are affected by wilt has been studied. A relationship has been established between the decrease in activity for seeds of the Tashkent-1 and Tashkent-6 varieties and the degree of attack by wilt. A hypothesis has been put forward on the existence of variety differences in the response reaction of the cotton plant to the introduction of the pathogen. The appearance of distinctive electrophoretic protein components in the seeds of wilt-affected cotton plants of the Tashkent-1 and Tashkent-6 varieties has been shown. A hypothesis has been made of a possible increase in the amount of proteinase inhibitors in response to the infection of the plants by wilt, a consequence of which is a sharp decrease in proteolytic activity and the appearance of distinctive electrophoretic components.     

Synthesis of the JKLM-ring fragment of ciguatoxin

A stereoselective synthesis of the LM-ring fragment has been achieved starting from a sugar derivative. A stereoselective synthesis of the JKLM-ring fragment has been achieved through a coupling between two segments via heteroconjugate addition, seven-membered ether ring formation mediated by an acetylene cobalt complex, and spiroketalization reaction.     

Potentiometric titration of peptides and the starting materials and intermediates of their synthesis. I. Acidimetric determination of N-acetylamino acids

The potentiometric titration of N-acetylamino acids and their sodium salts in nitromethane-acetic anhydride (2:1) with a nitromethane solution of perchloric acid has been investigated. A procedure has been developed for the quantitative determination of N-acetylamino acids in the presence of acetic acid in aqueous solutions. A differentiation determination of N-acetylamino acids and their salts in the presence of sodium acetate has been carried out.     

Application of the photoionization detector for the determination of ethanol in aqueous solutions and human breath

A determination of ethanol is described, which is based on a purging system in conjunction with a photoionization detector. With that system a fast and reliable determination of ethanol in aqueous solutions is possible. The system has been used for the analysis of wine. The 3delta-detection limit has been 0.005% ethanol, the relative standard deviation 4.8 to 6.0% and the time constant of the entire analytical system 20 s. The photoionization detector has been also applied to the analysis of artificial and genuine human breath. A comparison with gas-chromatography and non-dispersive IR-detection has been proven the reliability of results.     

Immunological determination of triazine pesticides bound to soil humic acids (bound residues)

An immunological method for the determination of triazine herbicides covalently bound to soil humic acids has been developed. A sandwich-immunoassay has been performed, based on both polyclonal humic acid-antibodies and monoclonal triazineantibodies. A peroxidase-labelled third antibody has been used for the photometric detection. A triazine-humic acid conjugate served as calibration standard. The coupling density for this conjugate has been determined by measuring the difference of free amino groups both with ninhydrin and with the trinitrobenzene sulfonic acid method. In addition, the coupling density has been confirmed by scintillation counting using a ¹⁴C-atrazine derivative. Due to nonspecific interactions between antibody proteins and humic acids, different blocking steps had to be performed. Finally, the assay has been applied to a triazine contaminated soil sample. Humic acids (including bound residues) have been extracted by diluted sodium carbonate solution. Concentrations of bound atrazine residues have been found in the range of 2 mg/kg soil on fields where triazine herbicides has been applied over a period of 21 years. These results are comparable to both the applied amount and the nonextractable fraction.     

Immunological determination of triazine pesticides bound to soil humic acids (bound residues)

An immunological method for the determination of triazine herbicides covalently bound to soil humic acids has been developed. A sandwich-immunoassay has been performed, based on both polyclonal humic acid-antibodies and monoclonal triazineantibodies. A peroxidase-labelled third antibody has been used for the photometric detection. A triazine-humic acid conjugate served as calibration standard. The coupling density for this conjugate has been determined by measuring the difference of free amino groups both with ninhydrin and with the trinitrobenzene sulfonic acid method. In addition, the coupling density has been confirmed by scintillation counting using a (14)C-atrazine derivative. Due to nonspecific interactions between antibody proteins and humic acids, different blocking steps had to be performed. Finally, the assay has been applied to a triazine contaminated soil sample. Humic acids (including bound residues) have been extracted by diluted sodium carbonate solution. Concentrations of bound atrazine residues have been found in the range of 2 mg/kg soil on fields where triazine herbicides has been applied over a period of 21 years. These results are comparable to both the applied amount and the nonextractable fraction.     

Convenient preparation of a novel class of imidazo[1,5-a]pyridines: decisive role by ammonium acetate in chemoselectivity

A facile and one-pot straightforward methodology has been developed to prepare a novel class of imidazo[1,5-a]pyridines. A key role played by ammonium acetate in chemoselectivity has been examined.     

Adiabatic passage in a three-state system with non-Markovian relaxation: the role of excited-state absorption and two-exciton processes

The influence of excited-state absorption (ESA) and two-exciton processes on a coherent population transfer with intense ultrashort chirped pulses in molecular systems in solution has been studied. A unified treatment of adiabatic rapid passage (ARP) in such systems has been developed using a three-state electronic system with relaxation treated as a diffusion on electronic potential energy surfaces. We have shown that ESA has a profound effect on coherent population transfer in large molecules that necessitates a more accurate interpretation of experimental data. A simple and physically clear model for ARP in molecules with three electronic states in solution has been developed by extending the Landau-Zener calculations putting in a third level to random crossing of levels. A method for quantum control of two-exciton states in molecular complexes has been proposed.     

Fixed-bed adsorption of carbon dioxide/methane mixtures on silicalite pellets

The adsorption of carbon dioxide and methane on silicalite pellets packed on a fixed bed has been studied. Equilibrium and kinetic measurements of the adsorption of carbon dioxide and methane have been performed, and a binary adsorption isotherm for carbon dioxide/methane mixtures has been obtained. A model based on the LDF approximation for the mass transfer has been used to describe the breakthrough curves obtained experimentally. A PSA cycle has been proposed for obtaining methane with purity higher than 98% from carbon dioxide/methane mixtures containing 38% and 50% methane, and its performance has been simulated using the proposed model. The simulation results show that silicalite can be a suitable adsorbent for employment in a PSA separation process for carbon dioxide removal from coalseam and landfill gases.     

New efficient and totally stereoselective copper allylic benzoyloxylation of sterol derivatives

A new efficient and totally stereoselective copper allylic benzoyloxylation of sterol derivatives has been developed. This methodology has been successfully applied to the synthesis of 7α-hydroxy DHEA and 7α-hydroxy cholesterol in a two-step synthesis with high chemical yields (77% and 61% overall yield, respectively). A mechanistic rationale justifying the total stereoselectivity encountered has been proposed.