1H NMR study on the inclusion of bicyclo[3.3.1]nonanes in cyclodextrins

- and -cyclodextrins were found to form 1:1 inclusion complexes with 2,6- and 2,9-substituted bicyclo[3.3.1]nonanes. The binding constants and the structure of the complexes were estimated from titration studies and 2D ROESY experiments.     

Microwave sputtering of conductors and insulators for optical emission and mass spectrometry

A microwave-powered slab-line cavity was used to excite a discharge in low pressure argon or neon and to demonstrate the sputtering of conducting and non-conducting samples by a microwave excited discharge. Both optical emission spectroscopy and mass spectrometry were used as detection systems. The dependence of the signals on gas pressure and net microwave power was investigated.     

High resolution FTS studies of glow discharge spectra line profiles and line widths

High resolution studies using Fourier transform spectrometry of the spectra emitted in the visible and ultraviolet regions by a microwave boosted glow discharge source have shown that when the source is operated in the dc (unboosted) mode, two anomalous forms of line profile occur for some analyte elements. (1) Some Fe I lines appear to have a triangular base of half-width about five times greater than that of the line proper. (2) Some Fe II and Ti II lines exhibit satellites about 8 cm(-1) wide and an intensity of up to 2% of the peak value on either side of the main line. Both effects depend on the carrier gas and its pressure and are much less pronounced or even absent in the boosted mode. They could both affect the accuracy of analytical results, particularly for depth-profiling. Further studies are in progress.     

Synthesis and X-ray analysis of 1-((1S)-phenylethyl)-azetidine-(2R)-piperidinamide

The crystal and molecular structure of a new azetidine-2-carboxylic amide derivative is described. The structure was solved by direct methods and refined by least squares methods toR1=0.0393 for 4264 reflections (withI>2(I)) The structure consists of two independent molecules which are chemically the same with slight differences in geometry. Crystal data: C₁₇H₂₄N₂O, monoclinic, space groupP2₁,a=8.3782(4),b=20.0342(13),c=9.7769(8) Å, =109.687(6)°,V=1545.1(2)ų,Z=4.     

A Product Formed from Glycylglycine in the Presence of Vanadate and Hydrogen Peroxide: The (Glycylde-N-hydroglycinato-kappa(3)N(2),N(N)(),O(1))oxoperoxovanadate(V) Anion

A crystalline glycylglycine complex of monoperoxovanadate has been obtained and its X-ray structure determined. The coordination is pentagonal bipyramidal with the peroxo group and a tridentate glycylglycine occupying the equatorial positions. The axial positions of the anion are occupied by the oxo ligand and by one oxygen of the peroxo group of the adjacent anion. The latter interaction establishes the seventh bond and produces a dimeric structure in the crystalline material. NMR studies of its dissolution in water combined with previously reported results from equilibrium measurements show that the dimer dissociates in water to the monomeric precursor. It is proposed that this monomer corresponds to the complex responsible for the inhibition of the vanadium-catalyzed decomposition of hydrogen peroxide by glycylglycine. Crystal structure of [NEt(4)][VO(O(2))(GlyGly)].1.58H(2)O: monoclinic, space group P2(1); Z = 4; a = 10.618(2) ?; b = 14.803(2) ?; c = 11.809(2) ?; beta = 101.37(2) degrees; V = 1819.7 ?(3); T = 198 K; R(F)() = 0.029 for 2664 data (I(o) >/= 2.5sigma(I(o))) and 431 variables.     

Formation of the pyrroline-N-oxide ring by the reaction of isonitrosoketones with enamines and some conversions of the pyrroline-N-oxides obtained

Compounds containing the pyrroline-N-oxide ring are obtained when isonitrosoketones — 2,6-dihydroxyiminocyclohexanone and -isonitrosoacetophenone — react with enamines. The compounds obtained behave as synthetic equivalents of 1,4-dicarbonyl compounds when undergoing reaction with amines, hydrazine, and hydroxylatnine.Novosibirsk Institute of Organic Chemistry, Siberian Section of the Russian Academy of Sciences (SO RAN) Novosibirsk, 630090. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1055–1061, August, 1996. Original article submitted February 28, 1996.     

Some aspects of the interactions of orthopositronium with perfect and defect surfaces of insulating materials

ETLA (Elastic Thermalisation Lifetime Analysis) is a new model function for the fitting of lifetime spectra of slowly thermalising orthopositronium in the free space between the grains of insulating oxide powders. From this model one can obtain three fundamental parameters; the mass of the cluster of atoms which scatters the o-Ps, the probability that the o-Ps is forced into two-quantum decay at each collision and the emission energyE(0) of the o-Ps from the powder surface. As a consequence of full thermalisation of the Ps it is shown that the o-Ps quenching constant _q () follows atT ^1/2 dependency for MgO, Al₂O₃ and SiO₂ and for temperatures between 77 and 500 K. In MgO powder at low temperatures the irradiation by the positrons induces surface paramagnetic defects which are identified as Mg⁺ sites. These surface defects do not affect the thermalisation, but they induce paramagnetic o-p conversion i.e., an increase in , and they are also responsible for an increase in the emission energyE(0) of the o-Ps.     

Heavy metals as indirect causative factors of capillaropathy

By applying systemic analysis to a set of random variables, representing blood or urine concentrations of certain enzymes, lipids and metals, three direct causative factors of capillaropathy, in its early stage, i.e. leucine amino peptidase, free erythrocyte protoporphyrin and C(3)-complement, have been found. The interactions between the early stage of capillaropathy and these factors have been quantitatively described and a formula for prognosing the capillaropathy occurrence has been proposed. It has also been shown that the following heavy metals Pb, Cd, Cr, Cu, Mg, Fe and Ca, through their direct or indirect interactions with C(3)-complement, exert an influence on the occurrence and intensity of capillaropathy. Since direct causative factors of a given pathology can serve as its markers, the completeness of the set of the capillaropathy markers, formed from the causative factors, and their contributions to this pathology have been evaluated. The results were obtained by examining a population of male residents chronically exposed to heavy metals (Pb, Cu) in the environment.     

Marginal separation in three-dimensional flows

The boundary layer in the vicinity of the zero skin-friction point on the leeward symmetry line of a prolate spheroid placed at an angle of attack is considered. The existence of this flow was established by Cebeci et al. (1980) for an angle of attack =40°. The current study is based on the results of Brown (1985) who described the marginal separation in the symmetry plane for a zero skin-friction point and on the results of Zametaev (1989) who included the spatial extension of Brown's solution but without interaction between the boundary layer and the outer flow. It is found that the three-dimensional boundary-layer equations in the vicinity of the zero skin-friction point are reduced to a single nonlinear partial differential equation of hyperbolic type which governs the longitudinal skin-friction component. Smooth solutions of this equation may be found which contain separation lines as well as double-valued regions. It is likely that the latter regions are related to the tip of the separation line obtained as a result of calculations of the full boundary-layer equations. The influence of interaction is also considered, in which case the flow is governed by a partial integro-differential equation. Numerical solutions are given for each of these problems.This study was supported by the United Technologies Research Center