Computational advances in organic chemistry: Molecular structure and reactivity. Edited by C. Ögretir and I. G. Csizmadia,NATO ASI Series C,Vol, 330.

We here report an AM 1 study for the reaction of different types of radicals with the acetone enolate ion 1 and other ambident nucleophiles. The theoretical reactivity order determined is phenyl > methyl > tert-butyl ? bicyclo-[2.2.1]hept-1-yl. The activation energy for the coupling of aliphatic radicals is ascribed mainly to nonbonded interactions. Considering possible solvent effects, we propose the same order of reactivity in solution. The coupling reaction of phenyl radical with 1 is an exothermic process with nonactivation energy in the gas phase. Any energy barrier in solution is here ascribed to desolvation of the anion. The regiochemistry of the coupling of radicals with ambident nucleophiles such as 1 , phenoxide, or phenylamide anions is also explained on a theoretical basis. © 1992 John Wiley & Sons, Inc.     

An extension of the Borel-Weil construction to the quantum groupU q (n)

The Borel-Weil (BW) construction for unitary irreps of a compact Lie group is extended to a construction of all unitary irreps of the quantum groupU _q(n). Thisq-BW construction uses a recursion procedure forU _q(n) in which the fiber of the bundle carries an irrep ofU _q(n–1)×U _q(1) with sections that are holomorphic functions in the homogeneous spaceU _q(n)/U _q(n–1)×U _q(1). Explicit results are obtained for theU _q(n) irreps and for the related isomorphism of quantum group algebras.Supported in part by the National Science Foundation, No. PHY-9008007     

19F NMR study of relative polarities and reactivities of N-H,N-Hg,and N-Au bonds in 2-(4-fluorophenyl)benzimidazole and its PhHg and Ph3PAu derivatives in intermolecular exchange

It has been shown by the¹⁹F NMR method that the relative polarities of nitrogenelement bonds in 2-(4-fluorophenyl)benzimidazole and its PhHg and PPh₃Au derivatives increase in the order N-H19F NMR. It has been found that these reactions occur by a bimolecular associative mechanism and that the N-H bond is substantially less reactive than the N-Hg and N-Au bonds, which have identical reactivities within the limits of sensitivity of the method used.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1574–1580, August, 1995.This work was carried out with financial support from the Russian Foundation for Basic Research (Project No. 93-03-5528).     

Comparison of steam pretreatment of eucalyptus,aspen, and spruce wood chips and their enzymatic hydrolysis

Applied Biochemistry and Biotechnology - Enzymatic hydrolysis of SO2-impregnated, steam-explodedEucalyptus viminalis was carried out at increasing substrate concentrations and enzyme loadings. When...     

On the localization of topological invariants

The approach of formal differential geometry to the topological invariants which can be localized is developed. The universal space and universal characteristic forms are constructed. They give rise to primary and secondary characteristic forms.     

The use of sulfide cluster-derived catalysts to understand the promotional effect in hydrotreatment catalysis

Sulfide cluster-derived ensembles are promising models of the active sites in commercial hydrotreatment catalysts. A series of sulfide clusters were adsorbed intact onto high-surface-area γ-alumina, magnesium oxide and activated carbon supports, then pretreated to produce highly dispersed catalytic ensembles with sizes similar to those of their precursor clusters. The activities of the bimetallic cluster-derived catalysts were significantly higher than those of the monometallic catalysts. We took this as evidence that direct interactions between molybdenum and the promoter element cause the promotional effect observed in commercial hydrotreatment catalysts. The hydrodesulfurization and hydrodenitrogenation activities correlated with the extent of molybdenum reduction. Our results suggested that the active sites in promoted hydrotreatment catalysts are centered on molecular-scale ensembles containing molybdenum, sulfur and the promoter element.     

An analysis of the radiation reaction in a charged dumbbell

We make a thorough non-covariant analysis of the derivation of the equation of motion for a charged particle, including radiation reaction, by means of a simple model for the charge: a dumbbell. This model and our method to expand retarded quantities, based on complex-variable theory, allow us to avoid some of the usual approximations, so we can show several features of the radiation reaction problem.     

Parabolic Harnack inequality for divergence form second order differential operators

Old and recent results concerning Harnack inequalities for divergence form operators are reviewed. In particular, the characterization of the parabolic Harnack principle by simple geometric properties -Poincaré inequality and doubling property- is discussed at length. It is shown that these two properties suffice to apply Moser's iterative technique.