Investigation of the addition of dialkyl(aryl)phosphine oxides to alkyl(aryl)vinyldialkoxysilanes

Conclusions Alkyl(aryl){2-[dialkyl(aryl)phosphoryl]ethyl}dialkoxysilanes were obtained as a result of addition of dialkyl(aryl)phosphine oxides to alkyl(aryl)vinyldialkoxysilanes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 183–186, January, 1985.     

Determination of enzyme kinetic parameters of cyclic CMP-specific phosphodiesterase by quantitative fast atom bombardment tandem mass spectrometry

The determination of cytidine 3′,5′-cyclic monophosphate-specific phosphodiesterase activity by means of fast-atom bombardment (FAB) mass Spectrometry with mass-analysed ion kinetic energy (MIKE) spectrum scanning is described. Initial efforts to determine the activity of the enzyme by this method were unsuccessful owing to the obfuscation of sample-related peaks by peaks emanating from the incubation buffer and cation adducts; dilution of buffer and a desalting procedure overcame these difficulties. In the resulting positive-ion FAB mass spectra, characteristic peaks of the enzyme substrate and product could be readily identified and the protonated molecular ions selected for MIKE scanning. By spiking enzyme incubates with known amounts of substrate and product, and measuring peak heights in the MIKE spectra of both spiked and unspiked samples, the substrate/product ratio at the end of a series of phosphodiesterase incubations was determined. From the data obtained, the K_m and V_max of the phosphodiesterase were calculated as 6.08 mM and 11 μmol min^?1 mg^?1, respectively, showing good agreement with the analogous values of 8.06 mM and 5.8 μmol^?1 min^?1 mg^?1 obtained by radioactive assay.     

Kinetics and electrochemical studies on superoxide

Rate constants for the reaction of superoxide O^- ₂ with various substrates were obtained through stationary electrode polarography theory and technique. In solvent acetonitrile, the substrate and the rate constants of the reaction O^- ₂ + AH^{- k2}Product, are, AH = isopropanol (k₂ < 0.01 M^-1 s^-1); ethanol (k₂ = 1.42 × 10² M^-1 s^-1); methanol (k₂ = 1.1 × 10⁷ M^-1 s^-1), H₂O (k₂ = 1.0 × 10⁵ M^-1 s^-1). In MeCN, O^-2 was found to be rather unreactive towards glucose and acetone but it reacts with fructose and sucrose catalytically. However, in DMF2, O^- ₂reacts with glucose and fructose with k2 order of 105 M-1 s-1. The mechanism of the reaction of O^- ₂ with the substrates (AH) is proposed as O^- ₃ + AH k₂O, AH^k2 _k-1 k [O₂H + AH]^-, _k-2O₂H + A^- with k₁ = 10⁹ M^-1 s^-1 and k^-1 = 10⁸ -10⁹ s^-1. With these values of k_-1 and k₁, k k₂(obs). The reversible E_1/2 for O₂ + e O^- ₂ in various solvents: MeCN, acetone, isopropanol, methanol, H₂O were obtained either directly from the reversible voltammogram or from experimental voltammograms and the rate constants obtained (as above) using stationary electrode polargraphy theory; E_1/2 being -0.82 (MeCN),-0.85 (acetone),-0.72 (isopropanol);-0.66 (MeOH),-0.56 (H2O) vs SCE.     

Three-stage sequential extraction procedure for metal partitioning in polluted soils and sediments

The sequential extraction procedure proposed by the Standard, Measurements and Testing program "SM&T" of the European Union has been applied to evaluate the amounts of Cr, Cu, Mn, Ni, Pb and Zn, extracted at each stage and indirectly their mobility and bioavailability in soil and sediment samples from a polluted area. Analysis of the extracts was carried out by flame atomic absorption spectrometry (FAAS). No significant matrix interferences were found except for Cr in the acetic acid and hydroxylammonium chloride extracts, which required determination by the standard additions method. Both of soils and sediments studied show similar partitioning of Mn, Ni, Cu and Cr. Mn and Ni can be considered to have significant component bound to the acido-soluble fraction, whereas, Cr and Cu occur largely in the organic and residual phases. The partitioning of Pb and Zn was different between soil and sediment. In terms of mobility and bioavailability, in soils, Ni and Mn can be regarded as moderately available followed by a lower availability of Pb while Cu, Zn and Cr have a very limited availability. In sediments, a higher availability (short-medium term) of Mn and Zn was presumed followed by a lower availability of Ni and Pb, whereas, Cu and Cr, occurring largely in the organic and residual phases, were of very limited availability.     

Hydroarylation of alkynes and alkenes through alumina-sulfuric acid catalyzed regioselective CC bond formation

A highly atom-efficient synthetic protocol for hydroarylation of terminal-aryl alkynes and styrene through the regioselective CC bond formation via the electrophilic addition of naphthols and substituted phenols has been developed using alumina-sulfuric acid as a heterogeneous supported solid acid catalyst. This methodology shows excellent regioselectivity and affords the desired product in good to excellent yield. The heterogeneous catalyst can also be recycled efficiently without much loss of activity.     

Structure and Stereochemistry of New Sesquiterpene Esters from Echinacea purpurea (L.) MOENCH. (Preliminary communication)

The structure elucidation of four new constituents from the roots of Echinacea purpurea is described. They are shown to be cinnamoyl esters of sesquiterpene alcohols with a germacrane or a guaiane skeleton. First pharmacological results indicate immunological activities.     

A new flavonol glycoside from the aerial parts of Astragalus vulneraria

A new flavonol glycoside, isorhamnetin 3-O-beta-D-apiofuranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->6)]-beta-D-galactopyranoside, and the known diglycoside, isorhamnetin 3-O-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-galactopyranoside were isolated from the aerial parts of Astragalus vulneraria. Characterization of the two compounds was done by spectroscopic methods (1D and 2D NMR, and FAB-MS).     

Electrochemically Induced Iron Release of Adsorbed Horse Spleen Ferritin: Quantitation of Iron Using Long Optical Path Length Thin‐Layer Spectroelectrochemistry

In this work, long optical path length thin‐layer electrochemical cell was constructed using indium‐tin oxide on glass as the electrode material. Iron release from ferritin adsorbed on the electrode was induced by applying a negative potential sweep in the presence of 1,10‐phenanthroline. The usefulness of spectroelectrochemistry as a means of determining the quantity of iron released from an adsorbed layer of ferritin is demonstrated.     

Theoretical elucidation of kinetic and thermodynamic control of radical addition regioselectivity

The cyclizations of two structurally similar 2-oxo-5-hexenyl-type radicals have been investigated by ab initio and density functional (UB3LYP/6-31+G**//UHF/6-31G* and UB3LYP/6-31G*//UB3LYP/6-31G*) calculations. The origin of apparently contradictory reports of 6-endo and 5-exo cyclizations is determined. Kinetic control favors 6-endo cyclization, while thermodynamic control gives 5-exo cyclization, and the observation of different products from different research groups arises from the difference in experimental conditions used by the two groups. The outcome of a new cyclization reaction was predicted by using these theoretical techniques. Kinetic control is predicted to yield exclusively the products of 6-endo cyclization, while thermodynamic control would lead to an approximately equal mixture of one 6-endo and one 5-exo cyclized product. Experimental studies revealed that the reaction yields only the products of 6-endo cyclization through kinetic control.     

Kinetic Analysis of Cobalt in Veterinary Products

A novel kinetic method for the determination of trace amounts of Co(II) has been developed. The proposed method based on the catalytic effect of Co(II) on the oxidation of xylenol orange tetra sodium salt by H₂O₂ in the presence of cationic surfactant (N‐dodecylpyridinium chloride). Co(II) at μg.mL^?1 was determined spectrophotometrically by measuring the decrease in the absorbance of xylenol orange at 577 nm by the differential method. The method is precise, selective, and sensitive. The detection limit of the procedure was 0.058 μg.mL^?1. The relative standard deviation for the replicate determination (n = 6) of 0.7 μg.mL^?1 was 1.285%. The results compared satisfactorily with those of atomic absorption spectrometry. The method was successful for the analysis of Co(II) in veterinary and synthetic samples.