The structure of pyrazoles in the solid state: a combined CPMAS, NMR, and crystallographic study

The structures of six N-unsubstituted pyrazoles, three already known and three newly synthesized, have been studied by a combination of X-ray crystallography, multinuclear NMR (solution and solid state), and density functional theory (DFT) calculations. In those cases where crystal structure and CPMAS NMR were available, the agreement was almost perfect, allowing a prediction of the tautomer (with certitude) and the tetrameric structure (with high probability) in the case of 5-isopropyl-3-phenyl-1H-pyrazole without knowing the X-ray structure. In the case of the 5-(2-benzylphenyl)-3-trifluoromethyl-1H-pyrazole above represented, the DFT calculations at the B3LYP/6-31G level justify the great stability of this tautomer by the presence of an intramolecular N-H...pi interaction, present in solution.     

Reaction of N-vinylic phosphazenes with alpha,beta-unsaturated aldehydes. Azatriene-mediated synthesis of dihydropyridines and pyridines derived from beta-amino acids

Aza-Wittig reaction of N-vinylic phosphazenes (1,2 addition), derived from diphenylmethylphosphine or derived from trimethylphosphine with alpha,beta-unsaturated aldehydes, leads to the formation of 3-azatrienes through a [2 + 2]-cycloaddition-cycloreversion sequence. The presence of an alkyl substituent in position 3 of N-vinylic phosphazenes increases the steric interactions, and [4 + 2] periselectivity (1,4 addition) is observed. Reaction of azatrienes with alpha,beta-unsaturated aldehydes yields pyridines.     

An approach for optimization of robot-generated rigid-body interpolation using dynamic criteria

The present paper describes an approach for generating spatial trajectories in multibody systems including rigid–body rotations such that dynamic criteria such as forces, accelerations, velocities, etc. as well as limiting restrictions for the motion–generating mechanical device, e.g., a robot, can be considered. The task is to find a rigid–body interpolation that fulfills optimality criteria at the target trajectory as well as in the mechanical system. Application of general optimization methods fails due to the difficulty of finding feasible initial guesses that will converge. The present approach proposes to decouple the general problem into two stages, a first stage in which a pure trajectory optimization is carried out without regard of the mechanical system, and a second stage in which the carrying mechanical system is incorporated. The trajectory planning involves the use of splines of 5–th order as well as an SQP optimization for determining the spline support points as design variables. The approach is illustrated for the example of the generalized waiter problem. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Comparison between computational fluid dynamics,fluid–structure interaction and computational structural dynamics predictions of flow-induced wall mechanics in an anatomically realistic cerebral aneurysm model

Haemodynamically induced stress plays an important role in the progression and rupture of cerebral aneurysms. The current work describes computational fluid dynamics (CFD), fluid–structure interaction (FSI) and computational structural dynamics (CSD) simulations in an anatomically realistic model of a carotid artery with two saccular cerebral aneurysms in the ophthalmic region. The model was obtained from three-dimensional (3D) rotational angiographic imaging data. CFD and FSI were studied under a physiologically representative waveform of inflow. The arterial wall was assumed elastic or hyperelastic, as a 3D solid or as a shell depending on the type of modelling used. The flow was assumed to be laminar, non-Newtonian and incompressible. The CFD, FSI and CSD models were solved with the finite elements package ADINA. Predictions of velocity field and wall shear stress (WSS) on the aneurysms made using CFD and FSI were compared. The CSD model of the aneurysms using complete geometry was compared with isolated aneurysm models. Additionally, the effects of hypertensive pressure on CSD aneurysm models are also reported. The vortex structure, WSS, effective stress, strain and displacement of the aneurysm walls showed differences, depending on the type of modelling used.     

Deterministic solution of the kinetic theory model of colloidal suspensions of structureless particles

A direct modeling of colloidal suspensions consists of calculating trajectories of all suspended objects. Due to the large time computing and the large cost involved in such calculations, we consider in this paper another route. Colloidal suspensions are described on a mesoscopic level by a distribution function whose time evolution is governed by a Fokker–Planck-like equation. The difficulty encountered on this route is the high dimensionality of the space in which the distribution function is defined. A novel strategy is used to solve numerically the Fokker–Planck equation circumventing the curse of dimensionality issue. Rheological and morphological predictions of the model that includes both direct and hydrodynamic interactions are presented in different flows.     

Folding of fiber composites with a hyperelastic matrix

This paper presents an experimental and numerical study of the folding behavior of thin composite materials consisting of carbon fibers embedded in a silicone matrix. The soft matrix allows the fibers to microbuckle without breaking and this acts as a stress relief mechanism during folding, which allows the material to reach very high curvatures. The experiments show a highly non-linear moment vs. curvature relationship, as well as strain softening under cyclic loading. A finite element model has been created to study the micromechanics of the problem. The fibers are modeled as linear-elastic solid elements distributed in a hyperelastic matrix according to a random arrangement based on experimental observations. The simulations obtained from this model capture the detailed micromechanics of the problem and the experimentally observed non-linear response. The proposed model is in good quantitative agreement with the experimental results for the case of lower fiber volume fractions but in the case of higher volume fractions the predicted response is overly stiff.     

Weakly (and not so weakly) bound states of a relativistic particle in one dimension

We present the first exact calculation of the energy of the bound state of a one dimensional Dirac massive particle in weak short-range arbitrary potentials, using perturbation theory to fourth order (the analogous result for two dimensional systems with confinement along one direction and arbitrary mass is also calculated to second order). We show that the non-perturbative extension obtained using Padé approximants can provide remarkably good approximations even for deep wells, in certain range of physical parameters. As an example, we discuss the case of two gaussian wells, comparing numerical and analytical results, predicted by our formulas.     

The tetrahexahedric Calogero model

We consider the spherical reduction of the rational Calogero model (of type A _n-1, without the center of mass) as a maximally superintegrable quantum system. It describes a particle on the (n = 2)-sphere in a very special potential. A detailed analysis is provided of the simplest non-separable case, n = 4, whose potential blows up at the edges of a spherical tetrahexahedron, tesselating the two-sphere into 24 identical right isosceles spherical triangles in which the particle is trapped. We construct a complete set of independent conserved charges and of Hamiltonian intertwiners and elucidate their algebra. The key structure is the ring of polynomials in Dunkl-deformed angular momenta, in particular the subspaces invariant and antiinvariant under all Weyl reflections, respectively.     

Use of molecular beams for kinetic measurements of chemical reactions on solid surfaces

In this review we survey the contributions that molecular beam experiments have provided to our understanding of the dynamics and kinetics of chemical interactions of gas molecules with solid surfaces. First, we describe the experimental details of the different instrumental setups and approaches available for the study of these systems under the ultrahigh vacuum conditions and with the model planar surfaces often used in modern surface-science experiments. Next, a discussion is provided of the most important fundamental aspects of the dynamics of chemical adsorption that have been elucidated with the help of molecular beam experiments, which include the development of potential energy surfaces, the determination of the different channels for energy exchange between the incoming molecules and the surface, the identification of adsorption precursor states, the understanding of dissociative chemisorption, the determination of the contributions of corrugation, steps, and other structural details of the surface to the adsorption process, the effect to molecular steering, the identification of avenues for assisting adsorption, and the molecular details associated with the kinetics of the uptake of adsorbates as a function of coverage. We follow with a summary of the work directed at the determination of kinetic parameters and mechanistic details of surface reactions associated with catalysis, mostly those promoted by late transition metals. This discussion we initiate with an overview of what has been learned about simple bimolecular reactions such as the oxidation of CO and H₂ with O₂ and the reaction of CO with NO, and continue with the review of the studies of more complex systems such as the oxidation of alcohols, the conversion of organic acids, the hydrogenation and isomerization of olefins, and the oxidative activation of alkanes under conditions of short contact times. 6 Reactions on supported nanoparticles: Materials gap, 7 Low-probability reactions: Pressure gap of this review deal with the advances made in the use of molecular beams with more realistic models for catalysis, using surfaces comprised of metal nanoparticles dispersed on the oxide surfaces used as catalyst support and high-flux beams to approach the pressures used in catalysis. The next section deals with the study of systems associated with fields other than catalysis, mainly with the etching and oxidation of semiconductor surfaces and with the chemistry used to grow thin solid films by chemical means (chemical vapor deposition, CVD, or atomic layer deposition, ALD). We end with a personal assessment of the past accomplishments, present state, and future promise of the use of molecular beams for the study of the kinetics of surface reactions relevant to practical applications.     

Photocatalytic properties of Ta-doped TiO2

Ionics - This work reports the effect of tantalum (0.1–1 at.% Ta) on the photocatalytic performance of TiO2 annealed at 1373 and 1673 K in air. It was shown that addition of...