Palladium-catalysed three component synthesis of α,β-unsaturated amidines and imidates

Palladium-catalysed three component coupling of an alkenylbromide, isonitrile and an amine or alkoxide/phenoxide affords α,β-unsaturated-amidines and -imidates.     

Non-isothermal short-range-order kinetics of binary alloys as influenced by solute-vacancy complexes

A model describing the roles of bound and unbound vacancies is proposed in order to predict defect decay and short-range-order kinetics of quenched binary alloys during linear heating experiments. This is an alternative treatment of a previous approach. The model has been applied to the differential scanning calorimetry (DSC) curves of Cu-5 at.% Zn quenched from different temperatures. An expression to calculate the activation energy for migration of solute-vacancy complexes was also developed which make use of DSC trace data. A value of 89.12±0.32 kJ mol^-1 was obtained for the above alloy. The relative contribution of bound and unbound vacancies to partition of effective activation energy corresponding to the ordering process as influenced by quenching temperature was also assessed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal conductivity of crystalline chrysotile asbestos

The thermal conductivity of crystalline chrysotile asbestos made up of hollow tubular Mg₃Si₂O₅(OH)₄ filaments is measured in the range 5–300 K. The paper discusses the possibility of using this material in studies of the thermal conductivity of thin filaments of metals and semiconductors incorporated into the channels of crystalline chrysotile asbestos tubes.     

On Bayes and unbiased estimators of loss

We consider estimation of loss for generalized Bayes or pseudo-Bayes estimators of a multivariate normal mean vector, θ. In 3 and higher dimensions, the MLEX is UMVUE and minimax but is inadmissible. It is dominated by the James-Stein estimator and by many others. Johnstone (1988, On inadmissibility of some unbiased estimates of loss,Statistical Decision Theory and Related Topics, IV (eds. S. S. Gupta and J. O. Berger), Vol. 1, 361–379, Springer, New York) considered the estimation of loss for the usual estimatorX and the James-Stein estimator. He found improvements over the Stein unbiased estimator of risk. In this paper, for a generalized Bayes point estimator of θ, we compare generalized Bayes estimators to unbiased estimators of loss. We find, somewhat surprisingly, that the unbiased estimator often dominates the corresponding generalized Bayes estimator of loss for priors which give minimax estimators in the original point estimation problem. In particular, we give a class of priors for which the generalized Bayes estimator of θ is admissible and minimax but for which the unbiased estimator of loss dominates the generalized Bayes estimator of loss. We also give a general inadmissibility result for a generalized Bayes estimator of loss. Research supported by NSF Grant DMS-97-04524.     

Necessary stationary condition for polarized radiation in scattering media

The stationary condition is derived taking into account the polarization of radiation in the general case of a scattering inhomogeneous medium in an arbitrary-shape emitter. The necessary stationary condition for an emitter in which radiation is emitted and extinguished simultaneously is complete extinction of the entire emitted radiation. Radiation extinction as a result of absorption by the medium and the emergence of radiation from the emitter is analyzed. The stationary condition is an analytical form of writing that extinction of radiation is a sure event whose probability is equal to unity. The passage of radiation through the medium is described on the basis of the linear transport theory with the help of the matrices of the Green functions. The stationary condition includes the characteristics of polarized radiation extinction of which is analyzed, the absorption coefficients of the medium, and the elements of the matrices of the Green functions, which are determined by optical and geometrical parameters of the emitter. The stationary condition obtained is used for deriving the relations between the components of scalar intensity observed in an arbitrary region of the emitter. These relations include, in addition to the absorption coefficients and the matrix elements of the Green functions, the powers of the primary radiation. Possible applications of the stationary condition and the relations between intensity components in computations and experimental studies are considered.     

Ionic liquids as reagents and solvents in conjunction with microwave heating: rapid synthesis of alkyl halides from alcohols and nitriles from aryl halides

We show that using ionic liquids as reagents in conjunction with microwave heating it is possible to prepare primary alkyl halides from the corresponding alcohols rapidly. Using ionic liquids as solvents in conjunction with microwave heating it is possible to prepare aryl nitriles from the corresponding aryl bromides or iodides. The scope and limitations of using microwave-promotion as a tool in these reactions is discussed.     

Grain-boundary diffusion in nanocrystals with a time-dependent diffusion coefficient

A solution to the equation of grain-boundary diffusion is obtained under conditions where migration of the diffusant from the boundaries into the grains is absent and the diffusion coefficient decreases with time from an increased value to a value characteristic of equilibrium grain boundaries. The specific features of the grain-boundary diffusion in nanocrystals are qualitatively analyzed in terms of this solution.