Magnetic tight binding and the iron-chromium enthalpy anomaly

We describe a self-consistent magnetic tight-binding theory based in an expansion of the Hohenberg-Kohn density functional to second order, about a non-spin-polarized reference density. We show how a first order expansion about a density having a trial input magnetic moment leads to a fixed moment model. We employ a simple set of tight-binding parameters that accurately describes electronic structure and energetics, and show these to be transferable between first row transition metals and their alloys. We make a number of calculations of the electronic structure of dilute Cr impurities in Fe, which we compare with results using the local spin density approximation. The fixed moment model provides a powerful means for interpreting complex magnetic configurations in alloys; using this approach, we are able to advance a simple and readily understood explanation for the observed anomaly in the enthalpy of mixing.

Atomistic studies of interactions between the dominant lattice dislocations and γ/γ-lamellar boundaries in lamellar γ-TiAl

This paper reports on atomistic simulations of the interactions between the dominant lattice dislocations in ?-TiAl (<1 0 1] superdislocations) with all three kinds of ?/?-lamellar boundaries in polysynthetically twinned (PST) TiAl. The purpose of this study is to clarify the early stage of lamellar boundary controlled plastic deformation in PST TiAl. The interatomic interactions in our simulations are described by a bond order potential for L10-TiAl which provides a proper quantum mechanical description of the bonding. We are interested in the dislocation core geometries that the lattice produces in proximity to lamellar boundaries and the way in which these cores are affected by the elastic and atomistic effects of dislocation-lamellar boundary interaction. We study the way in which the interfaces affect the activation of ordinary dislocation and superdislocation slip inside the ?-lamellae and transfer of plastic deformation across lamellar boundaries. We find three new phenomena in the atomic-scale plasticity of PST TiAl, particularly due to elastic and atomic mismatch associated with the 60° and 120° ?/?-interfaces: (i) two new roles of the ?/?-interfaces, i.e. decomposition of superdislocations within 120° and 60° interfaces and subsequent detachment of a single ordinary dislocation and (ii) blocking of ordinary dislocations by 60° and 120° interfaces resulting in the emission of a twinning dislocation.

Chemoenzymatic synthesis of chiral 4,4 '-bipyridyls and their metal-organic frameworks

The first enantiopure 4,4'-bipyridyls, 6, 8, and 9 have been prepared in four or five steps via bacterial dioxygenase-catalysed cis-dihydroxylation of 4-chloroquinoline 1 and C-C coupling; ligands 6 and 9 are found to be effective building blocks for the preparation of chiral metal-organic frameworks as demonstrated with the rational synthesis of two pillared-grid structures [Zn-2(fumarate)(2)(L)], which exhibit interesting structural and dynamic aspects.

New families of enantiopure cyclohexenone cis-diol, o-quinol dimer and hydrate metabolites from dioxygenase-catalysed dihydroxylation of phenols

Toluene dioxygenase-catalysed cis-dihydroxylation of phenols has led to the discovery of new enantiopure cyclohexenone cis-diol, o-quinol dimer and phenol hydrate metabolites having synthetic potential.

Highly selective and efficient hydrogenation of carboxylic acids to alcohols using titania supported Pt catalysts

Selective hydrogenation of carboxylic acids to alcohols and alkanes has been achieved under remarkably mild reaction temperatures and H-2 pressures (333 K, 0.5 MPa) using Pt/TiO2 catalyst.

Total synthesis of (+)-A83586C, (+)-kettapeptin and (+)-azinothricin: powerful new inhibitors of beta-catenin/TCF4-and E2F-mediated gene transcription

Herein we describe our asymmetric total syntheses of (+)-A83586C, (+)-kettapeptin and (+)-azinothricin. We also demonstrate that molecules of this class powerfully inhibit beta-catenin/TCF4- and E2F-mediated gene transcription within malignant human colon cancer cells at low drug concentrations.

On the dissolution of non-metallic solid elements (sulfur, selenium, tellurium and phosphorus) in ionic liquids

Ionic liquids are shown to be good solvents for elemental sulfur, selenium, phosphorus and tellurium, and can be designed to maximise the solubility of these elements. The presence of the [S-3](center dot-) radical anion in diluted solutions of sulfur in some ionic liquids has been confirmed, and is the origin of their intense blue colour (cf. lapis lazuli).

Is the pinning of ordinary dislocations in γ-TiAl intrinsic or extrinsic in nature? A combined atomistic and kinetic Monte Carlo approach

We address the question of the observed pinning of 1/2

Thermodynamic properties and atomistic structure of the dry amorphous silica surface from a reactive force field model

A force field model of the Keating type supplemented by rules to break, form, and interchange bonds is applied to investigate thermodynamic and structural properties of the amorphous SiO2 surface. A simulated quench from the liquid phase has been carried out for a silica sample made of 3888 silicon and 7776 oxygen atoms arranged on a slab similar to 40 angstrom thick, periodically repeated along two directions. The quench results into an amorphous sample, exposing two parallel square surfaces of similar to 42 nm(2) area each. Thermal averages computed during the quench allow us to determine the surface thermodynamic properties as a function of temperature. The surface tension turns out to be gamma=310 +/- 20 erg/cm(2) at room temperature and gamma=270 +/- 30 at T=2000 K, in fair agreement with available experimental estimates. The entropy contribution Ts-s to the surface tension is relatively low at all temperatures, representing at most similar to 20% of the surface energy. Almost without exceptions, Si atoms are fourfold coordinated and oxygen atoms are twofold coordinated. Twofold and threefold rings appear only at low concentration and are preferentially found in proximity of the surface. Above the glass temperature T-g=1660 +/- 50 K, the mobility of surface atoms is, as expected, slightly higher than that of bulk atoms. The computation of the height-height correlation function shows that the silica surface is rough in the equilibrium and undercooled liquid phase, becoming smooth below the glass temperature T-g.

Overcoming hydrolytic sensitivity and low solubility of phosphitylation reagents by combining ionic liquids with mechanochemistry

Ionic liquids have been used in combination with ball milling on a range of chlorophosphoramidite reagents to phosphitylate nucleosides and 2-deoxynucleosides. The enhanced stability offered by the ionic liquid mediated processes combined with efficient mass transfer induced by ball milling has enabled excellent yields to be obtained even when using small dialkyl amino groups as well as the more commonly used diisopropylamino protection.

Detection of DNA base variation and cytosine methylation at a single nucleotide site using a highly sensitive fluorescent probe

A fluorescent DNA probe containing an anthracene group attached via an anucleosidic linker can identify all four DNA bases at a single site as well as the epigenetic modification C/5-MeC via a hybridisation sensing assay.

PtCl2/XPhos: A highly efficient and readily available catalyst for the hydrosilylation of propargylic alcohols

A highly regioselective hydrosilylation of propargylic alcohols has been developed using an in situ prepared PtCl2/XPhos catalyst system. The reaction is tolerant of many functional groups and exhibits excellent regio and geometric selectivity.

Effect of composition, solvent exchange liquid and drying method on the porous structure of phenol-formaldehyde gels

Organic gels have been synthesized by sol–gel polycondensation of phenol (P) and formaldehyde (F) catalyzed by sodium carbonate (C). The effect of synthesis parameters such as phenol/catalyst ratio (P/C), solvent exchange liquid and drying method, on the porous structure of the gels have been investigated. The total and mesopore volumes of the PF gels increased with increasing P/C ratio in the range of P/C B 8, after this both properties started to decrease with P/C ratio for P/C[8 and the gel with P/C = 8 showed the highest total and mesopore volumes of 1.281 and 1.279 cm3 g-1 respectively. The gels prepared by freeze drying possessed significantly higher porosities than the vacuum dried gels. The pore volume and average pore diameter of the freeze dried gels were significantly higher than those of the vacuum dried gels. T-butanol emerged as the preferred solvent for the removal of water from the PF hydrogel prior to drying, as significantly higher pore volumes and specific surface areas were obtained in the corresponding dried gels. The results showed that freeze drying with t-butanol and lower P/C ratios were favourable conditions for the synthesis of highly mesoporous phenol–formaldehyde gels.

Raman spectroelectrochemical studies and crystal structure of a binuclear copper(I) complex with a bridging diimine ligand

Raman spectroelectrochemical and X-ray crystallographic studies have been made for the binuclear copper(I) complex, [(Ph(3)P)(2)Cu(dpq)Cu(PPh(3))(2)][BF4](2), where dpq is the bridging ligand 2,3-di(2-pyridyl)quinoxaline. The X-ray data show that the pyridine rings are twisted out of plane with respect to the quinoxaline ring which is itself non-planar. The UV/VIS spectra of the metal-to-ligand charge-transfer excited state and those of the electrochemically reduced complex are similar. The resonance-Raman spectrum of the latter species exhibits little change in the frequency of the pyridinylquinoxaline inter-ring C-C bond stretching mode, compared to the ground electronic state. This suggests minimum change in the inter-ring C-C bond order in the electrochemically or charge-transfer generated radical anion. Semiempirical molecular-orbital calculations on both the neutral dpq and radical anion show two near-degenerate lowest unoccupied orbitals in the neutral species. One is strongly bonding across the inter-ring C-C bond while the other is almost nun-bonding. The Raman data suggest that it is this latter orbital which is populated in the transient and electrochemical experiments.