Analysis of the method for studying the zenith-angle EAS distribution

The methodical problems related to analysis of the zenith-angle distribution of extensive air showers with N _e > 10⁷ particles are discussed. The effect of the array geometry on the angle measurement error is considered. Possible distortions of angular distribution due to errors have been calculated. The presence of excess showers detected at large zenith angles is shown.     

A Stable Single‐Site Palladium Catalyst for Hydrogenations

We report the preparation and hydrogenation performance of a single‐site palladium catalyst that was obtained by the anchoring of Pd atoms into the cavities of mesoporous polymeric graphitic carbon nitride. The characterization of the material confirmed the atomic dispersion of the palladium phase throughout the sample. The catalyst was applied for three‐phase hydrogenations of alkynes and nitroarenes in a continuous‐flow reactor, showing its high activity and product selectivity in comparison with benchmark catalysts based on nanoparticles. Density functional theory calculations provided fundamental insights into the material structure and attributed the high catalyst activity and selectivity to the facile hydrogen activation and hydrocarbon adsorption on atomically dispersed Pd sites.     

Mechanistic insights into ring-closing enyne metathesis with the second-generation Grubbs-Hoveyda catalyst: a DFT study

The full catalytic process (precatalyst activation, propagating cycle and active-species interconversion) of the ring-closing enyne metathesis (RCEYM) reaction of 1-allyloxy-2-propyne with the Grubbs-Hoveyda complex as catalyst was studied by B3LYP density functional theory. Both the ene-then-yne and yne-then-ene pathways are considered and, for the productive catalytic cycle, the feasibility of the endo-yne-then-ene route is also explored. Calculations predict that the ene-then-yne and yne-then-ene pathways proceed through equivalent steps, the only major difference being the order in which they take place. In this way, all alkene metathesis processes studied here involve four steps: olefin coordination, cycloaddition, cycloreversion and olefin decoordination. Among them, the two more energetically demanding ones are the olefin coordination and decoordination steps. The reaction of the alkyne fragment consists of two steps: alkyne coordination and alkyne skeletal reorganization, the latter of which has the highest Gibbs energy barrier. Comparison between the ene-then-yne and yne-then-ene pathways shows that there is no clear energetic preference for either of the two processes, and thus both should be operative when unsubstituted enynes are involved. In addition, although the endo orientation is computed to be slightly disfavored, it is not ruled out for 1-allyloxy-2-propyne, and thus calculations seem to indicate that the exo versus endo selectivity is strongly influenced by the presence of substituents in the reagent.     

Ceria in hydrogenation catalysis: high selectivity in the conversion of alkynes to olefins

Active and selective: Ceria shows a high activity and selectivity in the gas-phase hydrogenation of alkynes to olefins. This unprecedented behavior has direct impact on the purification of olefin streams and, more importantly, it opens new perspectives for exploring this fascinating oxide as a catalyst for the selective hydrogenation of other functional groups.     

Rotation of an elastic sphere about its mass center in the gravitational field of two attracting points

A planet model as a uniform elastic sphere in the gravitational field of two mass points whose mutual motion causes tidal deformations is considered. The sphere rotation about its mass center is studied with consideration of its deformations caused by the centrifugal force field and the gradient fields of gravitational forces. The sphere’s inertia tensor whose components are time dependent is found. The sphere’s angular velocity projections onto the axes associated with the sphere according to an integral law are determined. The results obtained are illustrated for the case of the Earth. For this case, the equivalent values of the elasticity modulus and Poisson’s ratio and the angular velocity disturbances are found.     

Influence of ionization on the conformational preferences of peptide models. Ramachandran surfaces of N‐formyl‐glycine amide and N‐formyl‐alanine amide radical cations

Ramachandran maps of neutral and ionized HCO–Gly–NH₂ and HCO–Ala–NH₂ peptide models have been built at the B3LYP/6‐31++G(d,p) level of calculation. Direct optimizations using B3LYP and the recently developed MPWB1K functional have also been carried out, as well as single‐point calculations at the CCSD(T) level of theory with the 6‐311++G(2df,2p) basis set. Results indicate that for both peptide models ionization can cause drastic changes in the shape of the PES in such a way that highly disallowed regions in neutral PES become low‐energy regions in the radical cation surface. The structures localized in such regions, and are highly stabilized due to the formation of 2‐centre‐3‐electron interactions between the two carbonyl oxygens. Inclusion of solvent effects by the conductor‐like polarizable continuum model (CPCM) shows that the solute‐solvent interaction energy plays an important role in determining the stability order. © 2008 Wiley Periodicals, Inc. J Comput Chem 2009     

The motion of a railway wheelset

The rolling of a railway wheelset along rails without slipping is investigated taking the creep hypothesis into account. The wheelset is represented by two cones that have a common base, and the rails are represented by two circular cylinders with parallel axes. The kinematic characteristics of the unperturbed rolling motion of the wheelset, which occurs when the centre of mass moves along a straight line, and of the perturbed motion, which occurs when the centre of mass of the wheelset describes a sinusoidal trajectory, are determined. The constraint reactions are found for the motions investigated up to small second-order values of the perturbed variables. When the elastic properties of the material in the contact area are taken into account, the creep hypothesis is used, averaging over the fast variables is employed, and the value of the critical speed, above which the rectilinear rolling of the wheelset becomes unstable, is found using averaged equations. In the latter case a periodic mode with two time intervals when the wheel flanges come into contact with the rails is investigated. The reaction force, the work of the dry friction force, and the moment of the active forces needed to maintain the periodic mode are found at the flange/rail contact point within the dry friction model. The boundaries of the stability regions, the parameters of the periodic mode and the moment of the resistance forces as functions of the problem parameters are determined from the formulae obtained by analytical methods.     

Motion of a wheel on snow

A model of a snow layer represented by a continuous set of columns whose deformations are described by the nonlinear model of an ideal elastoplastic continuous medium with viscous properties is proposed. Under the action of a rigid wheel on snow, the field of shear stresses is specified by the law of dry friction. Prom the equations of motion describing the plane-parallel motion of the wheel, there are determined a zone of contact of the wheel with snow, the steady motions of the wheel, and a mode of slipping the wheel. The numerical results are given in tables and figures. These results are obtained by solving the nonlinear equations of motion containing definite integrals with variable integration limits.     

Liquid chromatographic capacity factor as an indicator of lipophilicity in a series of betablocker drugs

Summary The reverse-phase, high-pressure liquid chromatographic capacity factors (k') of a series of 18 betablocking agents were determined in order to establish correlations with their distribution coefficient values (D), obtained from four bibliographic sources. Under the three pH conditions studied (3.5, 6.2 and 7.5) statistically significant linear correlations (p< 0.002) between log k' and log D values were obtained for the four series studied. In this series it is concluded that the k' factor is a useful and reliable relative lipophilicity parameter.