A convenient and high-yield synthesis for pyridinium and metal hexafluorocomplexes of vanadium, chromium, iron and cobalt

Pyridinium poly(hydrogen fluoride) reacts with the oxide of vanadium(V) and chlorides of chromium(III), iron (III) and Co(II) at room temperature forming the pyridinium salts of hexafluoro vanadate(V), hexafluorochromate(III), hexafluoroferrate(III) and hexafluorocobaltate(II) in near quantitative yields (80%). These pyridinium salts are the precursors for the preparation of the alkali metal hexafluorometallates by metathetic reactions in acetonitrile medium with the corresponding metal chlorides. The prepared salts have been identified by their infrared spectral data and elemental analysis.

The Relay Selection and Transmission Trade-off in Cooperative Communication Systems

A common and practical paradigm in cooperative communication systems is the use of a dynamically selected `best' relay to decode and forward information from a source to a destination. Such systems use two phases - a relay selection phase, in which the system uses transmission time and energy to select the best relay, and a data transmission phase, in which it uses the spatial diversity benefits of selection to transmit data. In this paper, we derive closed-form expressions for the overall throughput and energy consumption, and study the time and energy trade-off between the selection and data transmission phases. To this end, we analyze a baseline non-adaptive system and several adaptive systems that adapt the selection phase, relay transmission power, or transmission time. Our results show that while selection yields significant benefits, the selection phase's time and energy overhead can be significant. In fact, at the optimal point, the selection can be far from perfect, and depends on the number of relays and the mode of adaptation. The results also provide guidelines about the optimal system operating point for different modes of adaptation. The analysis also sheds new insights on the fast splitting-based algorithm considered in this paper for relay selection.

Diastereoisomeric (η6-arene)ruthenium(II) chiral Schiff base complexes: crystal structure of a triphenylphosphine adduct

Reaction of [(eta-6-p-cymene)RuCl(L star)] with AgClO4 in Me2CO gives a perchlorate complex which on subsequent treatment with PPh3, gamma-picoline or Cl- yields adducts showing that there can be retention as well as inversion of configuration at the metal centre. The (R)Ru,(S)C absolute configurations of the chiral centres in the triphenylphosphine adduct have been established by an X-ray diffraction study [HL star, (S)-alpha-methylbenzylsalicylaldimine]. The CD spectral study reveals that there is an inversion of configuration during formation of the PPh3 adduct.

Thermoanalytical studies of hydrazidocarbonic acid derivatives

Preparation, thermal analysis and IR spectra of a number of transition metal hydrazidocarbonates have been described. Metal hydrazido carbonates decompose exothermically through oxalate and carbonate intermediates to the respective metal oxides. Reaction of ammonium carbonate with hydrazine hydrate yields hydrazinium derivative of hydrazidocarbonic acid; N2H3COON2H5

Synthesis of graphene oxide-intercalated alpha-hydroxides by metathesis and their decomposition to graphene/metal oxide composites

Graphene oxide-intercalated alpha-metal hydroxides were prepared using layers from the delaminated colloidal dispersions of cetyltrimethylammonium-intercalated graphene oxide and dodecylsulfate-intercalated alpha-hydroxide of nickel/cobalt as precursors. The reaction of the two dispersions leads to de-intercalation of the interlayer ions from both the layered solids and the intercalation of the negatively charged graphene oxide sheets between the positively charged layers of the alpha-hydroxide. Thermal decomposition of the intercalated solids yields graphene/nanocrystalline metal oxide composites. Electron microscopy analysis of the composites indicates that the nanoparticles are intercalated between graphene layers. (C) 2010 Elsevier Ltd. All rights reserved.

Lubricated Tribology of a Eutectic Aluminium-Silicon Alloy in the Ultra-Mild Wear and Mild Wear Regimes for Long Sliding Times

Aluminium-silicon alloy, an important material used for the construction of internal combustion engines, exhibit pressure induced distinct regimes of wear and friction; ultra-mild and mild. In this work the alloy is slid lubricated against a spherical steel pin at contact pressures characteristic of the two test regimes, at a very low sliding velocity. In both cases, the friction is controlled at the initial stages of sliding by the abrasion of the steel pin by the protruding silicon particles of the disc. The generation of nascent steel chips helps to breakdown the additive in the oil by a cationic exchange that yields chemical products of benefits to the tribology. The friction is initially controlled by abrasion, but the chemical products gain increasing importance in controlling friction with sliding time. After long times, depending on contact pressure, the chemical products determine sliding friction exclusively. In this paper, a host of mechanical and spectroscopic techniques are used to identify and characterize mechanical damage and chemical changes. Although the basic dissipation mechanisms are the same in the two regimes, the matrix remains practically unworn in the low-pressure ultra-mild wear regime. In the higher pressure regime at long sliding times a small but finite wear rate prevails. Incipient plasticity in the subsurface controls the mechanism of wear.

C-H…O hydrogen bond mediated chain reversal in a peptide containing g-amino acid residue, determined directly from powder X-ray diffraction data

The finding that peptides containing -amino acid residues give rise to folding patterns hitherto unobserved in -amino acid peptides[1] has stimulated considerable interest in the conformational properties of peptides built from , and residues,[2] as the introduction of additional methylene (CH2) units into peptide chains provides further degrees of conformational freedom.

Interaction of nitrogen with fullerenes: nitrogen derivatives of C60 and C70

On the basis of N(1s) core-level spectroscopic studies, it is found that nitrogen interacts with multimolecular films of C60. More interestingly, mass spectrometric studies show that contact-arc vaporization of graphite in a partial atmosphere of N2 or NH3 yields nitrogenous products tentatively assigned to species such as C70N2, C59N6, C59N4, and C59N2 involving addition of or substitution by nitrogen along with the species due to C2 and C4 losses.

Low-Temperature Fluorination Of Some Nonmetals And Nonmetal Compounds With Fluorine

Low temperature fluorination with elemental fluorine of elemental phosphorus, sulphur, silicon, amorphous carbon and phosphorus trichloride, phosphorus pentoxide, triphenylphosphine, hexafluorodisilane, hexachlorodisilane, hexabromodisilane, tetrasulphur tetranitride, sulphur dioxide, thionyl chloride and sulphuryl chloride has been carried out in freon-11 medium. The corresponding fluoro compounds have been isolated in near quantitative yields, purified by low temperature fractional condensation and characterised by IR spectroscopy and elemental analysis.

Steady incompressible flow of cohesionless granular materials through a wedge-shaped hopper: Frictional 14kinetic solution to the smooth wall, radial gravity problem

Hybrid frictional-kinetic equations are used to predict the velocity, grain temperature, and stress fields in hoppers. A suitable choice of dimensionless variables permits the pseudo-thermal energy balance to be decoupled from the momentum balance. These balances contain a small parameter, which is analogous to a reciprocal Reynolds number. Hence an approximate semi-analytical solution is constructed using perturbation methods. The energy balance is solved using the method of matched asymptotic expansions. The effect of heat conduction is confined to a very thin boundary layer near the exit, where it causes a marginal change in the temperature. Outside this layer, the temperature T increases rapidly as the radial coordinate r decreases. In particular, the conduction-free energy balance yields an asymptotic solution, valid for small values of r, of the form T proportional r-4. There is a corresponding increase in the kinetic stresses, which attain their maximum values at the hopper exit. The momentum balance is solved by a regular perturbation method. The contribution of the kinetic stresses is important only in a small region near the exit, where the frictional stresses tend to zero. Therefore, the discharge rate is only about 2.3% lower than the frictional value, for typical parameter values. As in the frictional case, the discharge rate for deep hoppers is found to be independent of the head of material.

Studies on nonlinear optical materials: structure of diphenylmethyl (Z)-1-(1-methylthio-2-nitrovinyl)tetrahydropyrrole-2-carboxylate

C21H22N2045, M r = 398.5, orthorhombic, P212~21, a = 9.799 (1), b = 11.853 (1), c = 17.316(2)/~, V=2011.4A 3, Z=4, Dm=l.320, Dx=1.314Mgm -3, CuKa, A=1.5418A, Iz= 1.63 ram-1, F(000) = 840.0, T = 293 K, R = 0.055 for 1735 significant reflections. In the 1-methylthio-2- nitrovinyl moiety the C--C bond, 1.368 (7)A, is significantly longer than in ethylene, 1.336 (2)/~. The second harmonic generation (SHG) efficiency of this compound is only 0.25 of the urea standard. The correlation between the molecular packing and SHG is discussed.

Radiative interactions in boundary layers

A detailed description of radiative interactions in laminar compressible boundary layers for moderate Mach numbers is presented by way of asymptotic analysis and supporting solutions. The radiation field is described by the differential approximation. While the asymptotic analysis is valid for large N (the ratio of photon mean free path to molecular mean free path) and arbitrary Boltzmann number, Bo (the ratio of convective heat flux to radiation heat flux), the solutions are obtained for Bo [double less-than sign] 1, the case of strong radiative interactions. The asymptotic analysis shows the existence of an optically thin boundary layer for large N and all Bo. For Bo [double less-than sign] 1, two outer regions are observed — one optically thin (at short distances from the leading edge) and the other optically thick (at large distances from the leading edge). An interesting feature not pointed out in the previous literature is the existence of a wall layer at large distances from the leading edge where convective heat flux can be ignored to the leading order of approximation. The radiation field in all cases can be very well approximated by a one-dimensional description. The solutions have been constructed using the ideas of matched asymptotic expansions by approximate analytical procedures and numerical methods. It is shown that, to the leading order of approximation, the radiation slip method yields exactly the same result as the more complicated matching procedure. Both the cases of linear and nonlinear radiation have been considered, the former being of interest in developing approximate methods which are subsequently generalized to handle the nonlinear problem. Detailed results are presented for both cases.

Synthesis Of (+/-)-2-Isopropyl-5,6-Dimethylbicyclo[3.2.1]Oct-6-En-8-One

Methanolic hydrogen chloride cyclization of the triketone 8, prepared from the Mannich base 7 and 2-methylcyclopentane-1,3-dione, gives ketones 9 and 10. NaBH4 reduction of 9 followed by Grignard reaction with CH3MgI affords the diol 12. Catalytic hydrogenation of 12 followed by PCC oxidation yields the ketoalcohol 13. Dehydration of 13 with SOCl2/pyridine results in a 1:1 mixture of the endo-14 and exo-15 olefins, separated by chromatography.

A new general method for the introduction of the aldehyde function in aromatic compounds

Side chain bromination of aromatic amidomethylated compounds yields aldehydes.

The velocity dispersion of giant molecular clouds. II - Mathematical and numerical refinements

The energy input to giant molecular clouds is recalculated, using the proper linearized equations of motion, including the Coriolis force and allowing for changes in the guiding center. Perturbation theory yields a result in the limit of distant encounters and small initial epicyclic amplitudes. Direct integration of the motion equations allows the strong encounter regime to be studied. The present perturbation theory result differs by a factor of order unity from that of Jog and Ostriker (1988). The result of present numerical integrations for the 2D (planar) velocity dispersion is presented. The accretion rate for a molecular cloud in the Galactic disk is calculated.