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.     

Geochemical and physical analysis of the bedrock formations and lowest tills at the Wellsch Valley Site,Saskatchewan, Canada

Nine bedrock and two till samples were analyzed to determine whether their chemical and physical properties could be used to distinguish between bedrock units and to differentiate local bedrock from overlying tills. The bedrock samples came from The North Cliff subsite of the Wellsch Valley Site, and the till samples from Jaw Face subsite. Eight of the nine bedrock samples show great similarity. However, their geochemical differences from the overlying Quaternary tills establish that the tills contain much material entrained, during one or more early Quaternary glaciations, from older bedrock outcrops to the north and northeast. The glaciers that laid down the tills appear to have reworked and concentrated elements compatible with a dry climate, probably formed by weathering during long interglacial, and perhaps preglacial, intervals when the surface was undergoing slow degradation.     

RESTRICTION RESPECTUEUSE ET RECONSTRUCTION DES CHAINES ET DES RELATIONS INFINITES

We show a faithful restriction theorem among infinite chains which implies a reconstructibility conjecture of Halin. This incite us to study the reconstructibility in the sense of Fraïssé and to prove it for orders of cardinality infinite or ≥ 3 and for multirelations of cardinality infinite or ≥ 7, what improves the theory obtained by G. Lopez in the finite case. For this work we had to study the infinite classes of difference which have to be a linear order of type ω, ω* or ω* + ω; this complete the theory made by G. Lopez for the finite case ([13]). We show also Ulam-reconstructibility for linear orders which have a fixed point.     

The automatic conversion of spinor equations to dyad form in MAPLE

A new package in the symbolic algebra system MAPLE is presented for the conversion of complicated spinor equations to their expansions with respect to a normalized spinor dyad. By following a simple index convention, we obtain a powerful computational tool with a straightforward and easy to use syntax. A number of examples, including nontrivial applications of the package to recent research, are provided.     

Periodic solutions of second-order quasilinear hyperbolic equations

We study a periodic boundary-value problem for a quasilinear equation with the d'Alembert operator on the left-hand side and a nonlinear operator on the right-hand side and establish conditions under which the solution of the indicated problem is unique.Translated from Ukrainskii Matematicheskii Zhurnal, Vol. 47, No. 10, pp. 1370–1375, October, 1995.     

Single LED based dual wavelength referenced optical fibre sensor system using intensity modulation

An intensity-modulated optical fibre sensor system is described which employs a single LED source to provide the measurand and the reference signals with two separate wavelength bands. The allocated wavelength bands are selected to minimize any differential intensity effects that may arise from LED thermal variations. The sensor system, comprising a transceiver unit connected to an optical displacement sensor using a single optical fibre, provides an output fully referenced for all major common-mode variations that are likely to occur. Performance characteristics for the prototype system are reported which show a linear displacement range of over 20 mm.     

Smectic liquid-crystalline phases of F(CF2)7(CHOH)(CH2)8H and F(CF2)9(CHOH)(CH2)10H Comparison with other partially fluorinated molecules

Partially fluorinated alcohols F(CF₂)_m(CHOH)(CH₂)_nH (where m = 7, n = 8 and m = 9, n = 10) exhibit highly ordered smectic liquid-crystalline phases, as confirmed by optical microscopy and differential scanning calorimetry. Miscibility studies show that the smectic phases of the two alcohols are not of the same type. The related partially fluorinated ketones F(CF₂)_mCO(CH₂)_nH do not form a detectable mesophase. This is rather surprising since the (more polar) corresponding alcohols and the (less polar) analogous iodides and n-alkanes do. A brief discussion of the results and a comparison among partially fluorinated alkanes with various functional groups are presented.     

An efficient hydrodynamic cellular automata for simulating fluids with large viscosities

A hydrodynamic cellular automata (HDCA) for simulating two-dimensional fluids with large viscosities is proposed. The model is characterized by a mean free path which is of the same size as in the FHP-II model, but with a viscosity more than 10 times larger. This new model should make simulations of flows at low Reynolds number more efficient.     

Identification by high-performance liquid chromatography of tyrosine ammonia-lyase activity in purified fractions of Phaseolus vulgaris phenylalanine ammonia-lyase.

Activities of phenylalanine ammonia-lyase (PAL) and tyrosine ammonia-lyase (TAL) were assessed at each stage of a three-step purification of PAL. Assays were performed by high-performance liquid chromatographic (HPLC) separation and ultraviolet detection of reaction products. Use of HPLC permitted assay of low activities of PAL and TAL for periods up to approximately four and two days, respectively. HPLC also facilitated the accurate quantitation of the product of the TAL reaction, trans-p-coumaric acid, which was observed to isomerize readily under experimental conditions. PAL and TAL were associated throughout the purification procedure, with TAL activity at 0.6-1.3% of PAL activity. It was concluded that, contrary to previous reports, TAL and PAL activities are mediated by the same enzyme, or else by chromatographically very similar enzymes.