pi conjugation across the tetrathiafulvalene core: synthesis of extended tetrathiafulvalene derivatives and theoretical analysis of their unusual electrochemical properties

A series of extended tetrathiafulvalene (TTF) derivatives bearing one or two 1,4-dithiafulven-6-yl substitutents has been prepared. The new compounds present remarkable electrochemical singularities compared with other TTF derivatives, which are strongly affected by the nature of the substitution on the lateral heterocycle(s). This unusual electrochemical behaviour follows a square-scheme sequence and is attributed to structural changes upon oxidation of the pi-donating molecules. Digital simulations of the electrochemical data have been used to reach the values of the kinetic and thermodynamic constants involved in the square scheme. Theoretical calculations establish an important contribution of a highly delocalised resonant form involving a tetravalent sulphur in oxidised species, which could justify the occurrence of an electrochemical behaviour distinct from that of TTF. Finally, third-order susceptibilities chi 3 of two of these systems, for which electron-donating and electron-withdrawing substituents coexist and are conjugated through the TTF pi system, are given.     

Density functional theory (DFT) investigation of the adsorption of the CH3OH/Au(100) system

The adsorption of methanol on flat Au (100) surface with different coverages (θ = 1.0, 0.5 and 0.25 monolayer (ML)) is studied using density functional theory. Among the three sites (top, bridge and hollow) and coverages investigated in the present work, no adsorption is stable for θ = 1.0 ML. The most energetically preferred site of adsorption for CH₃OH is found to be the hollow site for coverages of 0.25 ML and 0.50 ML. We also find that for all adsorption sites, an increase in CH₃OH coverage triggers a decrease in the adsorption energy. The geometric parameters, local density of states and work function changes are analysed in detail. The coadsorption of methoxy and hydrogen has also investigated. In addition, the dissociation of methanol on Au(100) has been studied, and an activation energy was found to be 1.72 eV. This result compare with existing data in the literature for Au(111) surface. Copyright © 2013 John Wiley & Sons, Ltd.     

Single crystals of mesoporous tungstenosilicate W-MCM-48 molecular sieves for the conversion of methylcyclopentane (MCP)

Highly ordered W-MCM-48 mesoporous materials containing isolated W atoms in tetrahedral framework positions were successfully synthesized following the S⁺I⁻ pathway, up to a Si/W of 40. When tungsten content was increased up to a Si/W of 20, the ordered cubic structure was only partially maintained, and for a Si/W of 10 an amorphous phase was obtained. Highly isolated tetrahedral framework tungsten atoms in the W-MCM-48 with a Si/W of 40, have been identified by UV-vis band at 225 nm, IR-TF band at 970 cm⁻¹ and XRD. The W 4f XPS results suggest that the tungsten atoms exist in two oxidation states, W⁴⁺ and W⁵⁺. The morphology of the samples varies as a function of tungsten content. The W-MCM-48 samples with a Si/W ratio of 40 existed as crystals with a unique crystalline morphology consisting of cubes truncated rhombic dodecahedrons belonging to the cubic Ia3d space group, while the samples with a Si/W ratio of 20 exhibited a different morphology consisting of spheres and cubes truncated by rhombic dodecahedrons. A comparison of samples with Si/W of ∞, Si/W of 40 and Si/W of 20 was performed using the conversion of MCP carried out at 450 °C under H₂.     

Stability of mycophenolate mofetil in polypropylene 5% dextrose infusion bags and chemical compatibility associated with the use of the Equashield® closed‐system transfer device

Stability studies are necessary in healthcare settings as they facilitate fast, cost‐effective and efficient work related to batch manufacturing and availability of supplies. We studied the stability of 1–10 mg/mL mycophenolate mofetil (MMF) in polypropylene 5% dextrose infusion bags prepared from Cellcept^® and with a generic brand name (Micofenolato de Mofetilo Accord) at different storage temperatures. To ensure chemical compatibility during preparation, we also tested MMF sorption to the Equashield^® closed‐system drug transfer device used in this step. For this, a validated stability‐indicating high‐performance liquid chromatography method was developed for the quantification and identification of MMF in the infusion bags. The analytical selectivity of the assay was determined by subjecting an MMF sample to extreme values of pH, oxidative stress and heat conditions to force degradation. Protected from light, 1–10 mg/mL MMF in infusion polypropylene bags prepared from reconstituted Cellcept^® 500 mg or Accord 500 mg in 5% dextrose was stable for at least 35 days when stored at 2–8°C or between ?15 and ?25°C, and for 14 days when stored at 25°C. MMF loss owing to chemical sorption to the Equashield^® closed‐system drug transfer device set was negligible.     

Use of Average Mutual Information and Derived Measures to Find Coding Regions

One of the important steps in the annotation of genomes is the identification of regions in the genome which code for proteins. One of the tools used by most annotation approaches is the use of signals extracted from genomic regions that can be used to identify whether the region is a protein coding region. Motivated by the fact that these regions are information bearing structures we propose signals based on measures motivated by the average mutual information for use in this task. We show that these signals can be used to identify coding and noncoding sequences with high accuracy. We also show that these signals are robust across species, phyla, and kingdom and can, therefore, be used in species agnostic genome annotation algorithms for identifying protein coding regions. These in turn could be used for gene identification.     

Dielectric losses in CVD diamonds in the millimeter-wave range at temperatures 300–900 K

We study losses in different CVD diamonds in the frequency range 50–210 GHz at temperatures 300– 900 K by using a high-Q open Fabry-Perot cavity. It is found that the effective activation energies determining a sharp increase in losses at high temperatures are distributed in the range 0.4–0.8 eV. We propose a formula which relates the frequency and temperature dependences of losses for different CVD-diamond specimens in the first approximation. Suggestions on the nature of these losses are put forward.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 47, No. 12, pp. 1087–1095, December, 2004.     

On the structure of admissible nonstationary Hamiltonians in quantum mechanics

The quantum mechanical motion of a parabolic potential well is considered. It is shown that the motion results in a drag of a quantum particle are located in such a well and that the characteristics of the drag depend on the frequency spectrum of the motion.Russian Peoples' Friendship University, Moscow. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 46–49, November–December, 1994.     

Some solid state properties of enantiomers and their racemates

Heats of sublimation and fusion for l and dl-menthol, d and dl-carvoxime and d and dl-dimethyl tartrate were measured. Values of 22.9, 18.8, 21.7, 24.3, 18.5 and 26.9 $\text{kcal}\text{mole}$ and 18.2, 15.7, 24.3, 30.9, 23.3 and 36.2 $\text{cal}\text{g}$ were obtained for heats of sublimation and fusion respectively. Heats of sublimation are believed known to ±5% while heats of fusion are believed qualitatively correct. Generally good agreement was observed with literature values when available. Higher heats of fusion and sublimation are observed for the enantiomer or racemate with the higher fusion temperature. Correlation of these physical properties with the phase diagram for fusion and solubility suggest that differences in the temperature dependence of vapor pressure and solubility might be useful diagnostic tests for discontinuities in molecular packing and phase behavior in the solid state. Prediction of the temperature where racemic mixture to conglomerate transitions occur would be extremely useful for resolving racemates.     

Evaluated benchmark experiments at critical assemblies simulating features of an HTHR at the ASTRA facility

The design of the ASTRA facility and critical assemblies that simulate physics features of modular high-temperature reactors (HTHR-Ms) with a graphite moderator and reflectors loaded with fuel particles having multilayer ceramic coatings is described in detail. Geometrical dimensions of the main elements and regions of the critical assemblies, composition of the materials used, and experimental results for various configurations of the critical assemblies are presented. A detailed computational benchmark model allowing for the structural and compositional features of the critical assembly configurations in question is developed on the basis of all the above data. The results are to be used for verification of the neutronics codes used for calculations of high-temperature helium-cooled reactors.     

One-pot synthesis to engineer a Co-KIT-6 catalyst for the ring opening of methylcyclopentane

Co-KIT-6 mesoporous materials with Ia3d symmetry and Si/Co ratios of 50, 25, and 10 were prepared using hydrothermal one-pot synthesis. The Co-KIT-6 mesoporous materials were characterized by X-ray diffraction, N₂ adsorption–desorption isotherms, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared, and X-ray photoelectron spectroscopy. The physicochemical characterization results show that all of the samples have well-ordered cubic mesostructures and that the structural integrity is preserved for n_Si/n_Co ratios as high as 10. It was found that most of the cobalt ions exist as isolated framework species, but for Co-KIT-6 with an n_Si/n_Co ratio of 10, the presence of extra-framework species/small cobalt oxide clusters cannot be excluded. The ability of these catalysts was tested by examining the conversion of the reaction of methylcyclopentane with hydrogen at atmospheric pressure and temperatures between 200 and 450 °C. The catalytic results show that their catalytic activity increases significantly with increasing cobalt content. The active sites, tetrahedrally coordinated Co and isolated atomic Co sites, were responsible for the endocyclic CC bond rupture between substituted secondary–tertiary carbon atoms, whereas the small clusters serve as active sites for the successive CC bond rupture. The ring-opening selectivity can be improved by increasing the density of isolated cobalt atom sites at low reaction temperatures.