The photochemistry of 3,4,5-trideuteriopyridine

Irradiation of 3,4,5-trideuteriopyridine at 254 nm in the vapor phase results in the formation of a mixture of 2,3,4-trideuteriopyridine and 2,3,6-trideuteriopyridine. The formation of these products is consistent with a photoisomerization mechanism involving equilibrating azaprefulvene intermediates. This is the first direct evidence that pyridine vapor undergoes photoisomerization resulting in transposition of the pyridine ring atoms.     

Temperature dependences of the low-frequency internal friction and shear modulus in a bulk amorphous alloy

The logarithmic decrement and shear modulus of a bulk amorphous Zr_52.5Ti₅Cu_17.9Ni_14.6Al₁₀ alloy were studied with an inverse torsion pendulum in the range from room temperature to the crystallization temperature and in the frequency range 5–40 Hz. The activation energy spectra of reversible and irreversible structural relaxation were estimated. The results obtained are discussed in the context of a two-energy-level model.     

A market-based computational approach to collaborative organizational learning

We draw upon the concepts of knowledge market, organizational tacit knowledge, credit assignment, and single-loop learning in proposing a market-based conceptual model for collaborative organizational learning. Our proposed model is characterized by the local competition among seller agents and the global collaboration among winner agents in forming a plan, through a chain of ‘upstream–downstream’ working relationship, for task accomplishment. This feature is achieved through three closely coupled processes: the expert selection process, the capital reallocation process, and the plan formation process. Our model is intended for multiple-step learning environment in which each task consists of a sequence of single-step learning tasks. Learning at the global level is the result of a sequence of nested single-loop learning at the local level.     

Generation of angular momentum of fission fragments in a cluster model

Based on the dinuclear system concept, the role of bending vibrations in creation of the angular momentum of primary fission fragments is investigated. For ²⁵²Cf spontaneous fission, the angular momenta of the fragments are calculated as a function of the neutron multiplicity and compared with available experimental data. Different cluster compositions of the ²⁵²Cf fission modes at the scission point are considered.     

Mild and efficient synthesis of propargylamines by copper-catalyzed Mannich reaction

Terminal alkynes undergo mild and efficient aminomethylation with aqueous formaldehyde and secondary amines under CuI catalysis. In most cases high to nearly quantitative yields of tertiary propargylamines are obtained in DMSO solution at room temperature. Aromatic, aliphatic and silylated acetylenes as well as alkynols can be used. Primary amines are less reactive and satisfactory yields of secondary propargylamines are obtained only with phenylacetylene.     

Preparation of colloidal solutions of noble metals stabilized by polyoxometalates and supported catalysts based on these solutions

Conditions for the preparation of stable aqueous monometallic and bimetallic colloidal solutions (sols) of noble metals (Ru, Rh, Pd, Pt, Ir, Ag, and Au) in the presence of polyoxometalates containing W, Mo, V, and Nb were found. The stability of sols against coagulation at room temperature was studied. The metal/C samples prepared by metal adsorption from sols were studied by powder X-ray diffraction analysis and transmission electron microscopy. The following factors of importance for the preparation of a stable sol are discussed: (1) the formation of a sol of a metal polyhydroxo complex stabilized by a polyoxometalate (preliminary stage) and (2) the formation of polyoxometalate-metal clusters in the course of reduction of polyhydroxo complexes.Translated from Kinetika i Kataliz, Vol. 45, No. 6, 2004, pp. 921–929.Original Russian Text Copyright © 2004 by Maksimova, Chuvilin, Moroz, Likholobov, Matveev.     

Scaling laws for the spatial distributions of the plasma parameters in the positive column of a dc oxygen discharge

Comprehensive self-consistent simulations of the positive column plasma of a dc oxygen discharge are performed with the help of commercial CFDRC software (), which enables one to carry out computations in an arbitrary 3D geometry using fluid equations for heavy components and a kinetic equation for electrons. The main scaling laws for the spatial distributions of charged particles are determined. These scaling laws are found to be quite different in the parameter ranges that are dominated by different physical processes. At low pressures, both the electrons and negative ions in the inner discharge region obey a Boltzmann distribution; as a result, a flat profile of the electron density and a parabolic profile of the ion density are established there. In the ion balance, transport processes prevail, so that ion heating in an electric field dramatically affects the spatial distribution of the charged particles. At elevated pressures, the volume processes prevail in the balance of negative ions and the profiles of the charged particle densities in the inner region turn out to be similar to each other.