Thermal properties of volatile ruthenium(III) complexes

Complexes of ruthenium(III) with the following beta-diketone derivatives: 2,4-pentanedione (Ru(acac)₃), 1,1,1,6,6,6-hexafluoro-2,4-pentanedione (Ru(hfac)₃), and 2-methoxy-2,6-dimethyl-3,5-heptanedione (Ru(mdhd)₃) were synthesized, purified, and identified by chemical analysis and melting points. By difference-scanning calorimetry (DSC) in vacuum the thermodynamic characteristics of melting processes were defined. Using the static method with quartz membrane zero-manometer, the temperature dependencies of saturated and unsaturated vapor pressure were obtained for Ru(hfac)₃. The standard thermodynamic characteristics of vaporization processes enthalpy ?H _T* and entropy ?S° _T* were determined.     

Wilson's theorem for consensus functions on hierarchies

Wilson in 1972 gave a generalization of Arrow's theorem without the Pareto axiom. We prove a version of Wilson's theorem for consensus functions on hierarchies.     

Reactions of 2-phenylpyrrole with bromobenzoylacetylene on metal oxides active surfaces

The solvent-free interaction of 2-phenylpyrrole with bromobenzoylacetylene (room temperature) upon their grinding with solid metal oxides (MgO, CaO, ZnO, BaO, Al₂O₃, TiO₂, ZrO₂) and salts (CaCO₃, ZrSiO₄) leads to either the cross-coupling product or the adduct of pyrrole addition to the riple bond of acetylene. The ethynylation is accompanied by the formation of intermediate and side products: E-2-(1-bromo-2-benzoylethenyl)-5-phenylpyrrole and 1,1-di(5-phenylpyrrol-2-yl)-2-benzoylethene. The activity of the metal oxides in the ethynylation reaction falls in the order (in the brackets, the content of 2-benzoylethynyl-5-phenylpyrrole in the reaction mixture is given): ZnO (81%), BaO (73%), Al₂O₃ (71%), MgO (69%), CaO (50%). The oxides, SiO₂, TiO₂, ZrO₂, and the salts, CaCO₃ and ZrSiO₄, are inactive in the ethynylation reaction affording only the intermediate adduct, with ZrO₂ the isolated yield of the bromoethenylpyrrole reaching 60%. ESR monitoring shows the reaction to start from one electron transfer from pyrrole to acetylene mediated by the oxide surface. The adduct is readily converted on Al₂O₃ to 2-(benzoylethynyl)-5-phenylpyrrole crystallized mostly as cis-rotamer (X-ray data).     

Amination of octafluoronaphthalene in liquid ammonia: 2,6- and 2,7-Diaminohexafluoronaphthalenes selective preparation

Monoamination of octafluoronaphthalene by liquid ammonia affords 2-aminoheptafluoronaphthalene mainly (isolated yield 85-90%). Diamination of octafluoronaphthalene or amination of 2-aminoheptafluoronaphthalene affords a mixture of isomeric 1,6-, 1,7-, 2,6-, and 2,7-diaminohexafluoronaphthalenes with considerable prevalence of the 2,7-isomer (∼70%), thus being the first example of the predominant substitution at position 7 in 2-substituted polyfluoronaphthalenes. The 2,7/2,6 ratio of 2-X-heptafluoronaphthalene (X = ⁻NH, NH₂ and NHAc) amination diminishes with the decrease of electron-donating effect of the substituent; 2,7-diaminohexafluoronaphthalene forms in the reactions of 2-aminoheptafluoronaphthalene or octafluoronaphthalene with excess of NaNH₂ in liquid ammonia and 2,6-diaminohexafluoronaphthalene—in the reaction of 2-acetylamidoheptafluoronaphthalene with liquid ammonia followed by acetylamido group hydrolysis. The method of the selective preparation of these diamines based on the reversible transformation of amino group and a convenient technique of their high purity isolation by complexation with crown ether have been elaborated.     

Comparison of direct sampling and emulsion analysis using a filter furnace for the determination of lead in crude oil by graphite furnace atomic absorption spectrometry

The determination of trace elements in crude oil is difficult due to the complex nature of the sample and the various different chemical forms in which the metals can occur. The advantage of graphite furnace atomic absorption spectrometry is that only a minimum of sample pretreatment is required. In this work two techniques have been compared to establish a fast and reliable method for lead determination in crude oil. In the first one the crude oil samples were weighed directly onto solid sampling (SS) platforms and introduced into the graphite tube for analysis. In the second one the samples were prepared as oil-in-water emulsions and analyzed in a filter furnace (FF). Twenty μL of a mixture of 0.5 mg L^− 1 Pd + 0.3 mg L^− 1 Mg + Triton X-100 has been used as the modifier, and calibration against aqueous solutions has been used for both methods. The sensitivity obtained with the FF was more than a factor of two better than that with SS; however, as a larger sample mass could be introduced in the latter case, so that the limits of detection for both techniques were 0.004 mg kg^− 1. Seven crude oil samples were analyzed using the two procedures, and all results were in agreement at a 95% confidence level using a paired Student's t-test. For validation purposes, three crude oil samples have been mineralized using an open-vessel acid digestion, and the results were in agreement with those found with direct sampling and with emulsion sampling using FF according to ANOVA test. Both methods are simple, fast and reliable, being appropriated for routine analysis; however, the direct method using SS technology should be preferred because of its simplicity, speed and commercial availability.     

Limiting distributions of the number of pure strategy Nash equilibria in n-person games

We study the number of pure strategy Nash equilibria in a “random” n-person non-cooperative game in which all players have a countable number of strategies. We consider both the cases where all players have strictly and weakly ordinal preferences over their outcomes. For both cases, we show that the distribution of the number of pure strategy Nash equilibria approaches the Poisson distribution with mean 1 as the numbers of strategies of two or more players go to infinity. We also find, for each case, the distribution of the number of pure strategy Nash equilibria when the number of strategies of one player goes to infinity, while those of the other players remain finite.     

Context-dependent effects of asparagine glycosylation on Pin WW folding kinetics and thermodynamics

Asparagine glycosylation is one of the most common and important post-translational modifications of proteins in eukaryotic cells. N-glycosylation occurs when a triantennary glycan precursor is transferred en bloc to a nascent polypeptide (harboring the N-X-T/S sequon) as the peptide is cotranslationally translocated into the endoplasmic reticulum (ER). In addition to facilitating binding interactions with components of the ER proteostasis network, N-glycans can also have intrinsic effects on protein folding by directly altering the folding energy landscape. Previous work from our laboratories (Hanson et al. Proc. Natl. Acad. Sci. U.S.A. 2009, 109, 3131-3136; Shental-Bechor, D.; Levy, Y. Proc. Natl. Acad. Sci. U.S.A. 2008, 105, 8256-8261) suggested that the three sugar residues closest to the protein are sufficient for accelerating protein folding and stabilizing the resulting structure in vitro; even a monosaccharide can have a dramatic effect. The highly conserved nature of these three proximal sugars in N-glycans led us to speculate that introducing an N-glycosylation site into a protein that is not normally glycosylated would stabilize the protein and increase its folding rate in a manner that does not depend on the presence of specific stabilizing protein-saccharide interactions. Here, we test this hypothesis experimentally and computationally by incorporating an N-linked GlcNAc residue at various positions within the Pin WW domain, a small β-sheet-rich protein. The results show that an increased folding rate and enhanced thermodynamic stability are not general, context-independent consequences of N-glycosylation. Comparison between computational predictions and experimental observations suggests that generic glycan-based excluded volume effects are responsible for the destabilizing effect of glycosylation at highly structured positions. However, this reasoning does not adequately explain the observed destabilizing effect of glycosylation within flexible loops. Our data are consistent with the hypothesis that specific, evolved protein-glycan contacts must also play an important role in mediating the beneficial energetic effects on protein folding that glycosylation can confer.     

Fundamentals of melt infiltration for the preparation of supported metal catalysts. The case of Co/SiO2 for Fischer-Tropsch synthesis

We explored melt infiltration of mesoporous silica supports to prepare supported metal catalysts with high loadings and controllable particle sizes. Melting of Co(NO(3))(2)·6H(2)O in the presence of silica supports was studied in situ with differential scanning calorimetry. The melting point depression of the intraporous phase was used to quantify the degree of pore loading after infiltration. Maximum pore-fillings corresponded to 70-80% of filled pore volume, if the intraporous phase was considered to be crystalline Co(NO(3))(2)·6H(2)O. However, diffraction was absent in XRD both from the ordered mesopores at low scattering angles and from crystalline cobalt nitrate phases at high angles. Hence, an amorphous, lower density, intraporous Co(NO(3))(2)·6H(2)O phase was proposed to fill the pores completely. Equilibration at 60 °C in a closed vessel was essential for successful melt infiltration. In an open crucible, dehydration of the precursor prior to infiltration inhibited homogeneous filling of support particles. The dispersion and distribution of Co(3)O(4) after calcination could be controlled using the same toolbox as for preparation via solution impregnation: confinement and the calcination gas atmosphere. Using ordered mesoporous silica supports as well as an industrial silica gel support, catalysts with Co metal loadings in the range of 10-22 wt % were prepared. The Co(3)O(4) crystallite sizes ranged from 4 to 10 nm and scaled with the support pore diameters. By calcination in N(2), pluglike nanoparticles were obtained that formed aggregates over several pore widths, while calcination in 1% NO/N(2) led to the formation of smaller individual nanoparticles. After reduction, the Co/SiO(2) catalysts showed high activity for the Fischer-Tropsch synthesis, illustrating the applicability of melt infiltration for supported catalyst preparation.     

Optimization and validation of an LC-fLD method for biotin in infant formula, infant cereals, cocoa-malt beverages, and clinical nutrition products

A fast and simple chromatographic method to determine biotin in foods is presented. Biotin is extracted using papain (60 degrees C, 1 h). After pH adjustment and filtration, biotin is determined by LC with fluorescence detection using postcolumn reagent avidin-FITC (avidin labeled with fluorescein isothiocyanate). The method has been validated in a large range of products: milk- and soy-based infant formulas, cereals, cocoa-malt beverages, and clinical nutrition products. The method showed recovery rates of 98.1 +/- 5.7% (average +/- SD) in a large range of concentrations. Biotin concentrations determined in infant formula standard reference materials 1846 and 1849 were in agreement with reference values. RSD of repeatability (RSDr) varied from 2.0 to 4.5%, and intermediate reproducibility (RSD(iR)) from 5.8 to 9.4%. LOD and LOQ were 3.0 and 5.0 microg/100 g, respectively. The proposed method is suitable for routine analysis of biotin in fortified foods (infant formulas, infant cereals, cocoa-malt beverages, and clinical nutrition products). It can be used as a faster, more selective, and precise alternative to the classical microbiological determination, and is easily transferable among laboratories.