N-Bromoamides as versatile catalysts for aziridination of olefins using chloramine-T

N-Bromoamides catalyze effectively the aziridination of electron-deficient as well as electron-rich olefins using chloramine-T (N-chloro-N-sodio-p-toluenesulfonamide) as a nitrogen source under ambient conditions to afford the corresponding aziridines in good to excellent yields.     

An experimental study on the kinetics of leaching for the preparation of a Raney-silver catalyst

A Raney-Ag catalyst was prepared by leaching out aluminium from a Raney Ag-Al alloy with NaOH solution. The kinetics of leaching has been investigated in a stirred-batch-reactor at various temperatures by using alloy particles of different sizes. The kinetic model best fitting the experimental results has been determined. This revised version was published online in June 2006 with corrections to the Cover Date.     

On the Physical Origin of Long-Ranged Fluctuations in Fluids in Thermal Nonequilibrium States

Thermodynamic fluctuations in systems that are in nonequilibrium steady states are always spatially long ranged, in contrast to fluctuations in thermodynamic equilibrium. In the present paper we consider a fluid subjected to a stationary temperature gradient. Two different physical mechanisms have been identified by which the temperature gradient causes long-ranged fluctuations. One cause is the presence of couplings between fluctuating fields. Secondly, spatial variation of the strength of random forces, resulting from the local version of the fluctuation-dissipation theorem, has also been shown to generate long-ranged fluctuations. We evaluate the contributions to the long-ranged temperature fluctuations due to both mechanisms. While the inhomogeneously correlated Langevin noise does lead to long-ranged fluctuations, in practice, they turn out to be negligible as compared to nonequilibrium temperature fluctuations resulting from the coupling between temperature and velocity fluctuations.     

Calculation of Normal Vibrations of Chlorin by the Method of Density Functionals

Using the DFT/B3LYP method with a 6-31G(d) basis set, the structure, normal vibration frequencies, and the absolute band intensities in the IR spectra of the chlorin molecule and its four symmetric isotopomers have been calculated. Scaling of the force field by the Pulay method in independent and natural coordinates has been carried out. A method for obtaining effective force fields without using experimental data on the fundamental vibration frequencies is proposed. By comparing the vibration modes and constructing special matrices, complete assignment of the fundamental frequencies of porphin and chlorin has been carried out. It has been shown that the majority of porphin macroring vibrations upon pyrrolenine ring hydrogenation are frequency-characteristic and only 12 vibrations change considerably. A frequency correlation with regard for the mode transition between chlorin and all its isotopomers under consideration has been established. Comparative analysis of the force fields of porphin and chlorin in dependent natural coordinates has revealed the unique nonlocal character of the change in force constants of the macroring upon hydrogenation of one pyrrolenine ring. Modeling of the IR spectra of chlorin and its isotopomers has been performed. Assignment and interpretation of the normal vibrations of the molecules under consideration have been carried out.     

Sound radiation from a joint of plates of different thickness

A method of solving the problem of sound radiation from a plate with elements of different thickness in its plane is proposed, and the results obtained with this method are presented. It is shown that the main sources of sound radiation are the inhomogeneous flexural fields formed in the elements on both sides of their joint.     

Separating Classical and Quantum Correlations

We examine to what extent the correlation between two quantum observables at a mixed state can be separated into a classical and a quantum term. The nonunique decomposition of quantum mixed states into pure states makes such a separation ambiguous. We outline this fact by a simple example, which also shows that classical and quantum correlations may cancel each other out.     

Role of Bulk Vaporization in the Dynamics of Laser-Induced Erosion Plumes of Metals

In different regimes of exposure of metals to pulsed laser radiation, we show the role played by the liquid-drop phase formed from the target material in a laser-induced erosion plume due to bulk vaporization, in the dynamics of this plume. For some metals, the ranges of power densities of the acting laser radiation, at which the condensed-phase particles influence the passage of laser radiation to the target surface, have been determined experimentally. The mechanism of realization of a low-threshold breakdown has been revealed.     

Modification of Paving Asphalts with Sulfur

Sulfur dissolved in oil components of asphalt is a binder, filler, and chemical co-reagent at once. The structure of sulfur-extended asphalt depends on its formula and heating temperature. Road pavement based on sulfur-extended asphalt demonstrates higher durability as compared to that with the conventional binders.     

Dynamics of two-mode radiation in optical waveguides with strong mode coupling

Amplitude equations, as well as the effective dispersion and nonlinearity parameters, which define the dynamics of a wave packet formed by two strongly coupled modes, are derived with allowance for the frequency dependence of the linear mode coupling coefficient. These equations are used to study the onset of the modulation instability of the two-mode wave packet, soliton-like pulses, and compression modes. Unlike single-mode systems, the last two effects in optical waveguides may arise for both a negative and positive disper-sion of the waveguide material.