Ab initio benchmark study for the oxidative addition of CH4 to Pd: importance of basis-set flexibility and polarization

To obtain a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the methane C-H bond to the palladium atom, we have explored this PES using a hierarchical series of ab initio methods (Hartree-Fock, second-order M?ller-Plesset perturbation theory, fourth-order M?ller-Plesset perturbation theory with single, double and quadruple excitations, coupled cluster theory with single and double excitations (CCSD), and with triple excitations treated perturbatively [CCSD(T)]) and hybrid density functional theory using the B3LYP functional, in combination with a hierarchical series of ten Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Counterpoise corrected relative energies of stationary points are converged to within 0.1-0.2 kcal/mol as a function of the basis-set size. Our best estimate of kinetic and thermodynamic parameters is -8.1 (-8.3) kcal/mol for the formation of the reactant complex, 5.8 (3.1) kcal/mol for the activation energy relative to the separate reactants, and 0.8 (-1.2) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). This agrees well with available experimental data. Our work highlights the importance of sufficient higher angular momentum polarization functions, f and g, for correctly describing metal-d-electron correlation and, thus, for obtaining reliable relative energies. We show that standard basis sets, such as LANL2DZ+1f for palladium, are not sufficiently polarized for this purpose and lead to erroneous CCSD(T) results. B3LYP is associated with smaller basis set superposition errors and shows faster convergence with basis-set size but yields relative energies (in particular, a reaction barrier) that are ca. 3.5 kcal/mol higher than the corresponding CCSD(T) values.     

Titania-Doped Silica Fibers Prepared by Electrospinning and Sol-Gel Process

Titania-doped silica fibers were prepared by electrospinning of the sol of silica containing titania. The electrospun fibers had ribbon type morphology. The fibers had significant quantities of hydroxyl groups of Si—OH and Ti—OH. The fibers did not have crystalline structure. Diameters of the fibers were reduced by solvent evaporation and calcination. The hydroxyl groups on the fibers disappeared by calcination. The hydroxyl groups, M—OH (MSi, Ti) were changed to M—O—M by intermolecular and intramolecular condensation reactions.     

Estimation on the optic loss for acrylic polymers by theoretical modification

Various fluorinated/chlorinated polymers were synthesized and characterized by FT-IR and NMR. Also, theoretical optic loss of the POF were investigated and proposed for the purpose of finding a definite rule of the optic loss.From the computation of the results, the modified equation was theoretically deduced, and the optic loss of each prepared polymer was measured and compared with the calculated optical loss of polymers. Also, it was found that the optic loss from the modified equation fitted well with the experimental data.     

Monolithic catalysts for the fixed-bed hydrogenation of polymers

Monolithic catalysts were successfully applied in a true fixed-bed hydrogenation of polymers such as SBS rubbers and polystyrene.     

Analysis of hydroxyurea in human plasma by high performance liquid chromatography with electrochemical detection

An improved HPLC-electrochemical detection (ED) method is described for the analysis of hydroxyurea (HU) in human plasma. After extraction process, HU was determined on a C18 column ( mm) by the mobile phase (25 mM sodium acetate-acetonitrile, 97.5:2.5; pH 6.5). The regression equations were linear (r>0.9990). The precision and accuracy of intra- and inter-batches were all below 5% for relative standard deviation (R.S.D.) and relative error (R.E.). Based on 20 μl of plasma, the limit of detection was 0.3 μM for HU (S/N=3, injection 10 μl). This method was applied for the HU drug monitoring of patients with myelofibrosis or polycythemia vera.     

New oxidative tools for the functionalization of the cephalostatin north 1 hemisphere

Dimethyldioxirane (DMDO) C-H oxidation of ketone 17 to hemiketal 18 (82%), bis-dehydration to vinyl ether 21 (77%), and DMDO again provides C-23 axial alcohol 23 (99%). Routine processing, including a double-stereoselective Sharpless AD reaction (de >98%), gives alcohols 7 and 32. C-23 deoxy substrate 7 undergoes Suarez hypoiodite oxidative cyclization to (natural) beta spiroketal 34, but compound 32, bearing a C-23 silyl ether, generates unnatural spiroketal 33. [reaction: see text]     

Complex Forming Ability of a Family of Isolated Cyclosophoraoses with Ergosterol and Its Monte Carlo Docking Computational Analysis

Neutral cyclosophoraoses (unbranched cyclic -1,2-d-glucans) produced by the Rhizo-bium meliloti 2011 were prepared by size exclusion and anion-exchange chromatographic techniques. The degree of polymerization (DP) of isolated cyclosophoraoses was determined by matrix associated laser desorption/ionization mass spectrometry (MALDI/MS) techniques. A family of purified neutral cyclosophoraoses (DP 17–27) was used as a host for the inclusion complexation with hardly soluble ergosterol. High performance liquid chromatographic (HPLC) analysis showed that it induced much enhanced solubility of ergosterol compared to -cyclodextrin. In order to understand the molecular basis of the complex forming ability of cyclosophoraoses, a Monte Carlo (MC) docking-minimization method was used for host-guest complex formation of cyclosophoraoses or -cyclodextrin with ergosterol. From the MC simulation we propose the `hand-shake' mechanism for complexation of cyclosophoraoses with ergosterol.     

Exchange coupled magnetic nanocomposites of Sm(Co1−xFex)5 / Fe3O4 with core/shell structure

Magnetic nanocomposites of Sm(Co_1−xFe_x)₅/Fe₃O₄ (x≈0.1) with the core/shell type structure were successfully fabricated using a two-step polyol process, where as-prepared SmCo_5(1−x) nanoparticles were used as seeds for the ferrite coating. The core/shell composites are quite stable in air and show a typical hysteric behavior of single component, yielding an enhanced coercivity of 2.2 kOe with a saturated magnetization of 130 emu/g at 5 T. The magnetization data clearly reveal the presence of effective exchange coupling between the hard-magnetic Sm(Co_1−xFe_x)₅ core and soft-magnetic Fe₃O₄ shell, suggestive of a single-phase structure rather than a distinctive two-phase one.     

Growth of InN films and nanorods by H-MOVPE

InN films and nanorods were grown by hydride metalorganic vapor phase epitaxy (H-MOVPE) and the effects of growth temperature, and NH₃/TMIn and HCl/TMIn ratios on morphological dependences were studied. The growth habit of InN varied from thin film to microrod to nanorod to no deposition as the growth conditions were changed about transition from growth to etching conditions. The growth and etch regimes were also predicted by chemical equilibrium calculations of In–C–H–Cl–N-inert system. The optical properties of InN nanorods and columnar structured films were measured by room temperature PL and a maximum intensity was observed at 1.08 eV for both structures.     

Photoluminescence of ZnO nanowires grown on sapphire (1 1 2¯ 0) substrates

ZnO nanowires were fabricated on c-plane (0 0 0 1), a-plane (1 1 2¯ 0) sapphire, and boron doped p-type (1 0 0) Si substrates in vacuum furnace by simple physical vapor deposition. Room temperature photoluminescence spectra of the nanowires show the near band-edge emission and the deep-level green light emission. The ZnO nanowires formed on sapphire (1 1 2¯ 0) substrates exhibited enhancement on optical properties and better crystalline structures than those of nanowires grown on other substrates. The formation mechanism and the effect of substrate direction on structural and optical properties of the nanowires are discussed.