Observation of photochemical C-N bond cleavage in CH3N3: a new photochemical route to cyclic N3

We report VUV-photoionization based photofragmentation-translational spectroscopy data, providing a comprehensive study of the collision free photochemistry of methyl azide (CH3N3) at 193 nm. We report the first observation of the production of methyl and the N3 radical and derive the translational energy release distribution of this reaction. The most probable translation energy is only 8%, and the maximum translational energy is only 60% of the available energy, taking CH3 + linear N3 as the zero of energy. However, the maximum translational energy release is quantitatively consistent with production of the higher energy isomer cyclic N3. Threshold photoionization of the N3 fragment using tunable synchrotron radiation shows results consistent with theoretical predictions of the cyclic N3 ionization potential. The secondary dissociation of N3 --> N(2D) + N2 is also observed and its translational energy release is derived. This distribution peaks at approximately 6 and extends to 11 kcal/mol as would be expected from the size of the exit channel barrier for spin-allowed dissociation of cyclic N3 (7 kcal/mol) and, furthermore, inconsistent with the barrier height of the spin-allowed dissociation of linear N3 (3 kcal/mol). A large fraction (approximately 45%) of the N3 does not dissociate on the microsecond time scale of the experiment suggesting methyl azide may be the most attractive photochemical precursor of cyclic N3 yet found.     

Cryo-fracture TEM: direct imaging of a random mesh phase

A novel and a simple method that allows direct imaging of viscous samples by cryo-TEM (cryo-transmission electron microscopy) is presented. A fracture on the vitrified sample is created in a controlled way. In the fracture, some edges are thin enough to allow direct imaging in transmission mode. The method was used to directly image a nonionic surfactant lamellar phase where a random mesh structure is formed at lower temperatures (<10 degrees C). A so-called random mesh phase, characterized by the presence of perforated surfactant bilayers, is imaged here for the first time. Images from the mesh structure are compared with images from the classical lamellar structure formed at room temperature.     

A convenient method for the preparation of fluorous tin derivatives for the fluorous labeling strategy

A convenient method for the preparation of fluorous aryl stannanes was developed as a means of expanding the general utility of the fluorous labeling strategy (FLS). Following the synthesis of a novel fluorous distannane, a palladium-catalyzed cross-coupling reaction was used to prepare the target compounds from aryl halides. The scope of the reaction was investigated by preparing a small library of model compounds where the reaction yields were similar to those reported for the analogous procedures employing hexamethyl- or hexabutyldistannanes. The utility of the reported methodology was demonstrated through the successful synthesis of fluorous precursors to two established molecular imaging and therapy agents (FIAU, IUdR). These were radiolabeled with iodine-125 and the desired products isolated in high yield and effective specific activity.     

Conformational domino effect in saccharides. 2. Anomeric configuration control

A series of alkyl beta-D-glucopyranosyl-(1-->6)-alpha-D-glucopyranosides were synthesized and analyzed by NMR and CD techniques. As in their beta-anomer series, the rotational populations of the hydroxymethyl group involved in the interglycosidic linkage (torsion angle omega) are shown to depend on the aglycon and the solvent. However, for this alpha-anomer series the rotational dependence arises directly from steric effects. Correlations between rotational populations and molar refractivity (MR) steric parameters, but not Taft's steric parameters (beta-anomers), of the alkyl substituents were observed. The conformational domino effect previously predicted from alkyl beta-(1-->6)-diglucopyranosides is now supported by the conformational properties of their alpha-anomers, the anomeric configuration controlling the domino effect. In addition, the rotational populations around the C5'-C6' bond (torsion angle omega') depend weakly on the structure of the aglycon and the anomeric configuration.     

Defect energy levels in density functional calculations: alignment and band gap problem

For materials of varying band gap, we compare energy levels of atomically localized defects calculated within a semilocal and a hybrid density-functional scheme. Since the latter scheme partially relieves the band gap problem, our study describes how calculated defect levels shift when the band gap approaches the experimental value. When suitably aligned, defect levels obtained from total-energy differences correspond closely, showing average shifts of at most 0.2 eV irrespective of band gap. Systematic deviations from ideal alignment increase with the extent of the defect wave function. A guideline for comparing calculated and experimental defect levels is provided.     

Effect of metal elements in catalytic growth of carbon nanotubes

Using first-principles calculations, we model the chemical vapor deposition (CVD) growth of carbon nanotubes (CNT) on nanoparticles of late-transition (Ni, Pd, Pt) and coinage (Cu, Ag, Au) metals. The process is analyzed in terms of the binding of mono- and diatomic carbon species, their diffusion pathways, and the stability of the growing CNT. We find that the diffusion pathways can be controlled by the choice of the catalyst and the carbon precursor. Binding of the CNT through armchair edges is more favorable than through zigzag ones, but the relative stability varies significantly among the metals. Coinage metals, in particular Cu, are found to favor CVD growth of CNTs at low temperatures and with narrow chirality distributions.     

Coupled Processes Modeling in Rock Salt and Crushed Salt Including Halite Solubility Constraints: Application to Disposal of Heat-Generating Nuclear Waste

This paper presents numerical modeling of coupled thermal, hydraulic and mechanical processes in rock salt and crushed salt considering halite solubility constraints. The TOUGH-FLAC simulator is used, with a recently enhanced Equation-Of-State module that includes the thermodynamic properties of aqueous fluids of variable salinity. Laboratory and field scale tests performed on rock salt and crushed salt under temperature gradients are modeled first to evaluate the capabilities of the simulator to reproduce important features, such as porosity changes induced by halite dissolution/precipitation, and brine and heat migration. Since the results are quite satisfactory, the simulator is used to predict the long-term response of a generic salt repository for heat-generating nuclear waste. To evaluate the impacts of halite solubility on the predictions, two simulations that respectively consider or neglect solubility constraints are performed. In the scenario studied, the results are not significantly affected by dissolution/precipitation, and only some differences are observed due to changes in porosity, but the dominating processes remain the same. With the new provisions, TOUGH-FLAC is more complete in terms of processes occurring around a heat-releasing nuclear waste package and can therefore provide more accurate predictions of the long-term performance of a nuclear waste repository in salt formations.     

Numerical Simulation of a Passive Control of the Flow Around an Aerofoil Using a Flexible,Self Adaptive Flaplet

Self-activated feathers are used by almost all birds to adapt their wing characteristics to delay stall or to moderate its adverse effects (e.g., during landing or sudden increase in angle of attack due to gusts). Some of the feathers are believed to pop up as a consequence of flow separation and to interact with the flow and produce beneficial modifications of the unsteady vorticity field. The use of self adaptive flaplets in aircrafts, inspired by birds feathers, requires the understanding of the physical mechanisms leading to the mentioned aerodynamic benefits and the determination of the characteristics of optimal flaps including their size, positioning and ideal fabrication material. In this framework, this numerical study is divided in two parts. Firstly, in a simplified scenario, we determine the main characteristics that render a flap mounted on an aerofoil at high angle of attack able to deliver increased lift and improved aerodynamic efficiency, by varying its length, position and its natural frequency. Later on, a detailed direct numerical simulation analysis is used to understand the origin of the aerodynamic benefits introduced by the flaplet movement induced by the interaction with the flow field. The parametric study that has been carried out, reveals that an optimal flap can deliver a mean lift increase of about 20% on a NACA0020 aerofoil at an incidence of 20 ^o degrees. The results obtained from the direct numerical simulation of the flow field around the aerofoil equipped with the optimal flap at a chord Reynolds number of 2 × 10⁴ shows that the flaplet movement is mainly induced by a cyclic passage of a large recirculation bubble on the aerofoil suction side. In turns, when the flap is pushed downward, the induced plane jet displaces the trailing edge vortices further downstream, away from the wing, moderating the downforce generated by those vortices and regularising the shedding cycle that appears to be much more organised when the optimal flaplet configuration is selected.     

The PELskin project: part IV—control of bluff body wakes using hairy filaments

The passive control of bluff body wakes using a sparse layer of elastic hairy filaments has been investigated via a series of numerical simulations and compared to selected experiments under well-controlled boundary conditions. It has been found that a distribution of filaments spaced half of the dominant three dimensional instability and resonating with the main shedding frequency can drastically delay the three dimensional transition of the wake behind a circular cylinder. It will also be shown that when using a pair of rows of filaments symmetrically spaced by an azimuthal angle, the wake topology can be deeply affected as well as the value of the integral force coefficients of the cylinder. In the most favourable case, a coupled three dimensional transition delay and strongly reduced values of the drag and of the lift fluctuation can be simultaneously achieved. These results hold also for higher Reynolds-number flows as shown in experiments on a cylinder with hairy flaps attached to the aft part. The lock-in effect of structural vibration of the flaps with the vortex shedding is assumed to be the reason for a sudden change in the shedding cycle as soon as the motion amplitude is high enough to modify the wake. In line with this hypothesis, it has been demonstrated that a long elastic filament pinned on the centerline of a forced spatially developing mixing layer can interact with the vortex dynamics delaying the pairing process-leading to a reduced thickness of the layer. These findings show that a properly designed fluid structure interaction can indeed lead to technological benefits in terms of wake control: drag reduction, vibration control and possibly palliation of aeroacoustic emissions.     

New Mixed Ligand Organotellurium(IV) Compounds Containing Dithiocarbamates and the More Flexible Imidotetraphenyldithiodiphosphinates. The Crystal Structures of C8H8Te(S2CNEt2)[(SPPh2)2N] · H2O,C8H8Te(S2CNC5H10)[(SPPh2)2N], and C8H8Te(S2CNC4H8S)[(SPPh2)2N]

The synthesis of the following mixed ligand organotellurium(IV) compounds C₈H₈Te(S₂CNEt₂)[(SPPh₂)₂N] · H₂O ( 1 ), C₈H₈Te(S₂CNC₅H₁₀)[(SPPh₂)₂N] ( 2 ), C₈H₈Te(S₂CNC₄H₈O)[(SPPh₂)₂N] ( 3 ) and C₈H₈Te(S₂CNC₄H₈S)[(SPPh₂)₂N] ( 4 ) was achieved. They were characterized by IR, ¹H, ¹³C, ³¹P and ¹²⁵Te NMR, mass spectroscopy, and elemental analyses. The X‐ray crystal structures of 1 , 2 and 4 were determined. The both types of ligands display an asymmetrical chelating coordination mode on interaction with the tellurium atom. When these aniso‐bonded donor atoms are included in the coordination sphere, the tellurium atom exhibit an effective co‐ordination number of seven. The arrangement may be described as 1 : 2 : 2 : 2 coordination with a presumably stereoactive lone‐pair of electrons.