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421.
Tatiana A. Stromnova Oleg N. Shishilov Kirill Yu. Monakhov Ludmila G. Kuz’mina 《Journal of organometallic chemistry》2006,691(18):3730-3736
The interaction of palladium(+1) cluster Pd4(μ-CO)4(μ-OAc)4 with saturated and unsaturated carboxylic acids was studied. It was found, that the substitution of acetates groups on others carboxylates leads to the clusters with different nuclearity. Palladium(+1) carbonyl carboxylate complexes of composition [Pd(μ-CO)(μ-OCOR)]n, where R = CF3, CCl3, CH2Cl, MeCH = CMe, Me, Pri, Bu, Bui, Butert, n-C5H11 and n = 4 or 6 were synthesized. According to X-ray data all clusters possess cyclic planar metal cores with alternate pairs of μ-carbonyl and μ-carboxylate ligands. The presence of bulky alkyl fragments in the carboxylate ligand increases the nuclearity of the cluster compared to that of the starting palladium(+1) carbonyl acetate of composition Pd4(μ-CO)4(μ-OAc)4 due, apparently, to steric hindrance. 相似文献
422.
Accurate determination of pK(a) values is important for proper characterization of newly synthesized molecules. In this work we have used CZE for determination of pK(a) values of new compounds prepared from intermediates, 2, 3 and 4-(2-chloro-acetylamino)-phenoxyacetic acids, by substituting chloride for 2-oxo-pyrrolidine, 2-oxo-piperidine or 2-oxo-azepane. These substances are expected to have a cognition enhancing activity and free radicals scavenging effect. Measurements were performed in a polyacrylamide-coated fused-silica capillary of 0.075 mm ID using direct UV detection at 254 nm. Three electrolyte systems were used for measurements to eliminate effects of potential interactions between tested compounds and components of the BGE. In the pH range 2.7-5.4, chloride, formate, acetate and phosphate were used as BGE co-ions, and sodium, beta-alanine and epsilon-aminocaproate as counterions. Mobility standards were measured simultaneously with the tested compounds for calculations of correct electrophoretic mobilities. Several approaches for the calculation of the pK(a) values were used. The values of pK(a) were determined by standard point-to-point calculation using Henderson-Hasselbach equation. Mobility and pH data were also evaluated by using nonlinear regression. Three parameter sigmoidal function fitted the experimental data with correlation coefficients higher than 0.99. Results from CZE measurements were compared with spectrophotometric measurements performed in sodium formate buffer solutions and evaluated at wavelength where the highest absorbance difference for varying pH was recorded. The experimental pK(a) values were compared with corresponding values calculated by the SPARC online calculator. Results of all three used methods were in good correlation. 相似文献
423.
For the determination of iodide in urine, where 80-90% of consumed iodine is excreted, a fast, simple, and sensitive method of capillary zone electrophoresis was elaborated and tested also for additional complex matrices such as human serum, cooking salt, and seawater. Several approaches were examined for the separation of iodide from other macro- and microcomponents in the tested matrices, and the best results were obtained when host-guest interaction with alpha-cyclodextrin or ion-pairing with polyethylenimine was employed. In both cases comparable resolution and sensitivity were reached. Due to the relatively high price of cyclodextrin only the method with polyethylenimine was further optimized and a simple procedure enabling the determination of iodide in untreated human urine, serum, cooking salt, and seawater was elaborated. The samples were injected for 20 s at 0.5 psi (3.45 kPa) into a fused-silica capillary (0.18 mm ID, 50 cm effective length) coated with polyacrylamide (electroosmotic flow < 2 x 10(-9) m(2)V(-1)s(-1)) and filled with the optimized background electrolyte composed of 20 mM KH(2)PO(4) and 0.7% m/v polyethylenimine. For detection, UV absorption at 200 and 230 nm was measured. Concentration limits of detection reached at 230 nm were for human urine 0.14 microM, for human serum 0.17 microM, for seawater 0.17 microM, and for cooking salt 89 nM. Relative standard deviations of iodide peak area and height in all matrices ranged within 0.93 to 4.19%. 相似文献
424.
Tatiana S. Glazneva Vera P. Shmachkova Ludmila G. Simonova Evgeny A. Paukshtis 《Reaction Kinetics and Catalysis Letters》2007,92(2):303-309
Acidic properties of fiberglass materials were investigated using the adsorption of NH3 and the rate of isopropanol dehydration. It is shown that the specific catalytic activity of such materials and amount of
the Br?nsted acid sites per their surface unit (100 ?2) exceed considerably those in zeolite HZSM-5. 相似文献
425.
Novák P Man P Tucková L Tlaskalová-Hogenová H Bezouska K Havlícek V 《Journal of mass spectrometry : JMS》2002,37(5):507-511
Celiac disease, a chronic disorder of the small intestine, is caused by dietary gluten and is characterized by villous atrophy and local inflammation associated with infiltration of B and T lymphocytes and/or macrophages into the intestinal wall. In genetically predisposed individuals, the infiltrating cells are activated by gluten, gliadin and their proteolytic fragments and produce chemokines, cytokines and reactive radicals. The sequence of one of the macrophage-stimulatory gliadin peptic fragment was determined by mass spectrometry (MS) as VSFQQPQQQYPSSQ. The role of tissue transglutaminase (tTG) in innate immunity stimulation was studied by mass spectrometric monitoring of sequence changes in this active peptide. Two sites of glutamine deamidation in this peptide were localized by high-resolution scanning in MS/MS mode in an ion trap. A single deamidation in the parent peptide led to the complete loss of its stimulatory effect on macrophages. 相似文献
426.
Emmanuel Richaud Bruno Fayolle Ludmila Audouin 《Polymer Degradation and Stability》2007,92(1):118-124
The thermal oxidation of unstabilised polypropylene (PP) was studied at 80 °C under various oxygen pressures: 0.02, 0.5 and 5.0 MPa, and, under 5.0 MPa oxygen pressure at various temperatures: 60, 80, 100 and 120 °C. Hydroperoxides were titrated using a chemical titration method and modulated DSC (taking an enthalpy of −325 kJ mol−1). Starting from a previous kinetic analysis of carbonyl growth in same exposure conditions, we have tried to simulate experimental results by a model based on the classical mechanistic scheme in which initiation results from POOH (mainly bimolecular) decomposition. The model, which takes into account substrate consumption and does not rely on usual simplifying assumptions (steady state for radicals, long kinetic chains, interrelations between termination rate constants), generates kinetic curves with the same shape as experimental ones and predicts well the effect of O2 pressure and temperature on hydroperoxide and carbonyl concentrations. 相似文献
427.
From analysis of numerous experimental data on grain boundary (GB) statistics in polycrystals it has been established that certain groups of materials with cubic structure reveal similar GB character distributions (GBCD) (distribution of GBs by reciprocal density of coincidence sites ). It has been shown that GBCD can be described with an empirical low with different parameters for various groups. Several criteria for classification of materials by these groups (the stacking fault energy value, hierarchy of GB energies and mechanism of replacement of high-energy GBs with low-energy ones) have been considered. It has been found that peculiarities of electronic structure of materials are correlated with the classification proposed. 相似文献
428.
Zusammenfassung Die Grundlagen der direkt-potentiometrischen Konzentrationsbestimmung von Anionen und Kationen werden beschrieben, für die keine ionensensitiven Elektroden bekannt sind. Es wird die Konzentrationsabnahme eines Hilfsions gemessen, das mit dem analytisch zu bestimmenden Ion einen stabilen Komplex bildet.Ausführliche Angaben werden zur Bestimmung von Al3+ mit F– als Hilfsion und von Ni2+ mit CN– als Hilfsion gemacht. Auf die prinzipiellen Möglichkeiten einer Bestimmung von Fe2+, Fe3+, Au+, Hg2+, Th4+, Zr4+, UO2
2+, SCN– und S2O3
2– wird eingegangen.
Direct-potentiometric determinations with ion-sensitive electrodes using complexing auxiliary reactions
The basic principles of the direct-potentiometric determination of several cations and anions are discussed, for which no ion-sensitive electrode is available. The decrease in concentration of an auxiliary ion is measured which forms stable complexes with the ion to be determined. Detailed information is given on the determination of Al3+ with F– as auxiliary ion and of Ni2+ with CN– as auxiliary ion. An outlook is presented on the possible determinations of Fe2+, Fe3+, Au+, Hg2+, Th4+, Zr4+, UO2 2+, SCN– and S2O3 2–.相似文献
429.
Alexander Z. Voskoboynikov Anton Yu. Agarkov Evgeni A. Chemyshev Irina P. Beletskaya Andrei V. Churakov Ludmila G. Kuz''mina 《Journal of organometallic chemistry》1997,530(1-2):75-82
An improved synthesis of 2,2′-bis(1-indenyl)propane and the corresponding ansa-complexes of zirconium are reported. Synthesis of a mixture of rac- and meso-2,2′-propylidene-bis(1-indenyl)zirconium dichlorides involves a treatment of ZrCl4 with bis[3-(trialkyltin)inden-1-yl]propane, where alkyl = ethyl, butyl, in toluene. This reaction gives the products in 92% yield and might be a convenient synthetic pathway to a number of straightforward ansa-metallocenes. Both rac- and meso-2,2′-propylidene-bis(1-indenyl)zirconium dichlorides were separated and isolated using simple work-up processes, and characterized by X-ray crystal structure analysis (rac:C2/c; a = 15.903(3) Å, b = 11.105(2) Å and c = 11.520(2) Å; β = 121.61(3)°; Z = 4; V = 1732.6(5) Å3; R = 0.0350; meso-: P1¯; a = 9.739(2) Å, b = 12.798(4) Å and c = 15.322(4) Å; = 101.18(2)°; β = 121.61(2)°; γ = 90.54(2)°, Z = 4; V = 1795.4(8) Å3; R = 0.0417). 相似文献
430.
Alexander S. Lyakhov Pavel N. Gaponik Yuri V. Grigoriev Ludmila S. Ivashkevich 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(7):o381-o383
In the title compound, alternatively named 5,5′‐diphenyl‐2,2′‐methyleneditetrazole, C15H12N8, the dihedral angles between the tetrazole and benzene rings in the two 5‐phenyltetrazole fragments are 2.45 (6) and 10.01 (9)°. There is weak intermolecular C—H?N hydrogen bonding involving the H atoms of the methylene groups, which is responsible for the formation of two‐membered aggregates. C—H?π interactions in the crystal structure are discussed. 相似文献