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101.
Electrochemical detection without derivatization was used to detect thiol-containing degradation products of V-type nerve
agents. Electropolymerization of pyrrole was used for entrapment of the biocatalyst PQQ to produce a sensor. Various parameters
which affect the detection processes such as the type of the supporting electrolyte used during electrodeposition and the
thickness of the polypyrrole film were examined and optimized. Electocatalytic oxidation of thiols by the PPy/PQQ electrode
was strongly affected by the presence of Ca2+ cations during electrodeposition of the PPy/PQQ. Cyclic voltammetry, linear sweep voltammetry and amperometry have been used
for electrode characterization. Amperometric detection of the V-type nerve agent thiol degradation products 2-(dimethylamino)ethanethiol
(DMAET) and 2-(diethylamino)ethanethiol (DEAET) was performed at 0.38 V. Linear calibration plots were observed for these
compounds. The detection limits of 4.5 and 3 μM were obtained for DMAET and DEAET respectively, with sensitivities of 1.18
and 1.37 nA μM−1 cm−2. 相似文献
102.
103.
Andrej?Voronov Sergej?Minko Alexander?Shulga Emile?PefferkornEmail author 《Colloid and polymer science》2004,282(9):1000-1007
The poly(2-vinylpyridine) layer was established at the Pyrex glass/water interface with periodic phases of adsorption/desorption runs observed over several days. This was evidenced by determining the concentration of radio-labelled molecules in the solution equilibrating the glass beads as a function of time (the effluent) while the same radio-labelled polymer was slowly supplied by injecting the polymer solution into the reactor containing the adsorbent at a controlled extremely slow rate. Although the adsorption (or the desorption) steps seemed to present some periodic character, they were better correlated with the successive bulk concentration thresholds that were established with time when the initial surface was free of polymer at time zero. Even when the adsorbent was coated at different degrees, desorption steps were correlated to the overstepping of decreasing concentration thresholds. Adsorption and desorption runs were attributed to the existence of different typical interfacial conformations of the adsorbed macromolecules that only can be stabilised in the adsorbed state when the layer was equilibrated with the polymer solution of a certain concentration. Macromolecule were definitely adsorbed when the reconformation process led to a flat conformation (trains). Macromolecules adsorbed with a conformation close to their solution conformation may be desorbed as a result of the reconformation process affecting previously adsorbed neighbour molecules (in the case of partially coated surfaces at time zero of injection). Macromolecules with loops and tails were retained on the surface when the polymer concentration in the bulk was progressively increased (for uncoated surfaces at time zero of injection). All these effect were attributed to the combined influence of topological effects on adsorption and reconformation of adsorbed macromolecules that characterise the non-equilibrium adsorption processes. 相似文献
104.
D. V. Konarev R. N. Lyubovskaga O. S. Roshchupkina B. P. Tarasov Yu. M. Shulga 《Russian Chemical Bulletin》1997,46(1):32-35
Compounds C60(S4N4)2−x
(C6H6)
x
(1a-d) withx=0.67 (a), 1.0 (b), 1.1 (c), and 1.2 (d), in which isomorphous replacement of S4N4 with benzene takes place, were obtained by the reaction of fullerence C60 with tetrasulfur tetranitride in benzene. Complexes C60·S4N4 (2) and C60(S4N4)2 (3) containing no solvent were isolated from toluene. The compositions of the compounds were established by elemental and thermogravimetric
analyses. The data of IR and X-ray photoelectron (XP) spectroscopies show that in the complexes studied the transfer of electron
density occurs mainly from the nitrogen atoms of S4N4.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 37–40. January 1977. 相似文献
105.
Talyzin AV Tsybin YO Schaub TM Mauron P Shulga YM Züttel A Sundqvist B Marshall AG 《The journal of physical chemistry. B》2005,109(26):12742-12747
Complex solid hydrofulleride mixtures were synthesized by prolonged hydrogenation of C(60) at 120 bar hydrogen pressure, 673 K temperature, and different reaction periods. The high degree of hydrogenation was confirmed by infrared spectroscopy and X-ray diffraction. The identity of hydrogenation products was determined by high-resolution field desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry. Despite partial gas-phase fragmentation of hydrofullerene ions during mass analysis, the data suggest that the synthesized mixtures consist of mostly C(58-60)H(x) hydrofullerenes. Increasing the duration of hydrogenation results in synthesis of C(59)H(x) and C(58)H(x) as major products. Possible hydrofullerene fragmentation pathways during both material synthesis and mass spectrometric analysis are discussed. Gas-phase fragmentation in the mass spectrometer arises from hydrofullerene ions C(60)H(x)(+) with x > 40 and C(59)H(44)(+) with drastically decreased molecular stability relative to the known C(60)H(36). 相似文献
106.
Turov V. V. Gorbik P. P. Ogenko V. M. Shulga O. V. Chuiko A. A. 《Journal of Thermal Analysis and Calorimetry》2000,62(2):473-478
A study has been made on samples of dispersed vanadium dioxide (VO2) in a matrix of polyethylene glycol (PEG) doped with a quaternary ammonium salt (QAS), namely tetraethylammonium bromide.
It has been established that under the influence of the dopant the heating of a sample up to the temperature of the metal-semiconductor
phase transition (MSPT) results in a phase in homogeneity of the sample. On the basis of the results of this study it is possible
to conclude that small concentrations of QAS in a PEG matrix can exert a strong effect on the electronic structure of dispersed
VO2 particles. This is accompanied by the appearance of phase heterogeneity of VO2 which manifests itself in the fact that - with the onset of MSPT with increasing temperature - one portion of the substance
passes into the metallic state, and the other remains in the semiconductive state.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
107.
D.A. Shulga A.A. Oliferenko S.A. Pisarev V.A. Palyulin 《SAR and QSAR in environmental research》2013,24(1-2):153-165
Two novel approaches to construct empirical schemes for partial atomic charge calculation were proposed. The charge schemes possess important benefits. First, they produce both topologically symmetrical and environment dependent charges. Second, they can be parameterised to reasonably reproduce ab initio molecular electrostatic potential (MEP), which guarantees their successful use in molecular modelling. To validate the approaches, the parameters of the proposed charge schemes were fitted to best reproduce MEP simultaneously on grids around a set of 227 diverse organic compounds. The residual errors in MEP reproduction due to calculated atomic charges were compared to those due to charges from known charge schemes. 相似文献
108.
Shulga Yu. M. Martynenko V. M. Berestenko V. I. Domashnev I. A. Kurkin E. N. Torbov V. I. 《Technical Physics》2011,56(10):1531-1534
Nonpyrophoric tungsten powders with an average particle size of about 30 nm were obtained by pyrolysis of tungsten hexacarbonyl
in a flow of microwave discharge nitrogen plasma. It is found that these powders are stable in air up to 300°C. The reason
for such stability is that the structure of powder particles is of the core-double shell type, in which the metal core is
covered with an oxide film approximately 1 nm in thickness, coated in turn with roentgenoamorphous layer consisting of carbon,
oxygen, and nitrogen atoms. It is also established that the powders under investigation mainly release carbon oxides (CO and
CO2) and water into the gas phase upon heating in vacuum. Among the molecules present in the gas phase in small concentrations,
nitrogen monoxide (NO) and formaldehyde (H2CO) are worth mentioning apart from C1–C3 hydrocarbons. 相似文献