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1.
Hydrogenation of the ketone group in di-O-benzylderivative ( 8 ) of the known macrocyclic lactone zeralenone ( 7 ) using a novel chiral borane complex 3 . BH3, prepared in situ, proceeded at lower temperatures with moderate diastereoselectivity (~40%, d. e. at ?60°). Unsaturated diastereomers 9 and 10 were separated, and 9 converted into zeranol ( 11 ), a known anabolic agent. Restricted conformational mobility at lower temperatures is assumed for the intermediate 8 on the basis of the temperature-dependent CD spectra of its acetyl congeners 18 and 19 . X-Ray structure analysis of 7-O-acetylderivative ( 13 ) of 11 revealed the (R)-configuration at C(7). Two crystallographically independent H2O molecules are involved in the H-bonds, one of them (O(21)) rises the helices of the molecules of 13 along b. Small positive torsional angle [C(16)-]C(161)-C(1) [=O] (+19.3°), transoid(E) conformation of the lactone group, and nearly achiral arrangement of the C(11)-C(12) bond (torsional angle [C(11)-]C(12)-C(121)[C(161)] is ?93°) are the main conformational features that differentiate the macrocylic RAL (resorcinic-acid lactone) derivatives from the 6-membered lactone derivative 20 , studied earlier by CD. Consequently, the rules developed for the CD effects within conjugation band (around 270 nm), and n→π* band (around 255 nm) of the latter compound, cannot be applied the macrocyclic lactones.  相似文献   
2.
Let $G$ be a locally finite group which contains a non-cyclic subgroup $V$ of order four such that $C_{G}\left( V\right) $ is finite and $C_{G}\left( \phi \right)$ has finite exponent for some $\phi \in V$ . We show that $[G,\phi ]^{\prime }$ has finite exponent. This enables us to deduce that $G$ has a normal series $1\le G_1\le G_2\le G_3\le G$ such that $G_1$ and $G/G_2$ have finite exponents while $G_2/G_1$ is abelian. Moreover $G_3$ is hyperabelian and has finite index in $G$ .  相似文献   
3.
Electronic sputtering of lithium fluoride by swift heavy ions was studied as a function of electronic energy loss (dE/dx) e . The single crystal targets were irradiated with swift heavy ion beams (166Z P 692; 46E P /M P (MeV/u) 611). This allowed varying the deposited energy by a factor of 20 (1.86dE/dx (keV/nm) 632). The sputtered secondary ions were measured from well controlled LiF targets without surface contaminations, by means of the time-of-flight technique (TOF-SIMS). The mass spectrum reveals an important contribution of clusters (over single ions), which increases with (dE/dx) e . Another observation for the strongest perturbation at high dE/dx (>8 keV/nm) is that the secondary ion yields saturate: Y(dE/dx) = constant. In contrast, at lower dE/dx (<8 keV/nm) for weaker perturbation, the yield Y scales with (dE/dx)2. This quadratic increase would rather point towards a thermal evaporation-like mechanism leading to electronic sputtering, however, the origin of the yield saturation remains an open finding.  相似文献   
4.
An experimental study of convective boiling of refrigerants R-22, R-134a and R-404A in a 12.7 mm internal diameter, 2 m long, horizontal copper tube has been performed. Experiments involved a relatively wide range of operational conditions. Experiments were performed at the evaporating temperatures of 8°C and 15°C. Quality, mass velocity and heat flux varied in the following ranges: 5% to saturated vapor, 50–500 kg/(s m2); and 5–20 kW/m2. Effects of these physical parameters over the heat transfer coefficient have been investigated. High quality experiments were also performed up to the point of the tube surface dryout, a mechanism which was investigated from the qualitative point of view. Two heat transfer coefficient correlations from the literature have been evaluated through comparisons with experimental data. Deviations varied in the range from −25% to 42%.  相似文献   
5.

This work reports the first results of atmospheric radon measurements performed at the Italian Antarctic station located at Terra Nova Bay (74.69°S; 164.12°E) during summer campaigns of 1995-96, 1996-97 and 1997-98. Mean222Rn concentrations was 0.51 - 0.43 Bq mm3 (median = 0.37 Bq mm3), and ranged from 0.01 to 2.74 Bq mm3 . On the average, these values were considered high, in comparison to results reported for other sites in Antarctica at equivalent latitudes. This could be explained by two causes: radon data for Terra Nova Bay were only for the summer period, when the ice-free area is at its maximum and thus the radon emission to the atmosphere; and by the larger ice-free area at Terra Nova Bay compared, for example, to measurements taken at another Antarctic site by the same technique (Ferraz station - 62°05'S; 058°23.5'W). The mean 222Rn to 220Rn activity ratio was 4.4 - 4.2, ranging between 0.1 and 45.3. The highest ratios indicated that some of observed surges of concentration of 222Rn could be attributed to not local sources. Lower radon concentrations were observed during katabatic wind events. The diurnal radon variation followed the general trend observed for continental areas located at lower latitudes.  相似文献   
6.
Calculations are performed to model several phenomena observed when a photosensitive oscillating chemical reaction, the Briggs–Rauscher (BR) reaction, is subject to irradiation in a continuous-flow stirred-tank reactor. The BR mechanism proposed earlier by De Kepper and Epstein is supplemented by additional steps involving the photogeneration and subsequent reaction of iodine atoms. The calculations show qualitative agreement with the following experimentally observed phenomena: (a) change in the period and amplitude of oscillation as a function of the intensity of constant illumination, (b) synchronization between periodically varying illumination and the period of chemical oscillation, (c) phase shifts induced by single light pulses, and (d) dark steady states which are excitable by single light pulses and become oscillatory at appropriate levels of constant illumination.  相似文献   
7.
Resolution of racemic cis-3-(2-aminophenylthio)-2-hydroxy-3-(4-methoxyphenyl) propionic acid ( 2 ) via the cinchonidine salt 3 , and brucine salt 4 , isolation of the calcium salts (+)- and (?)- 5 , as well as their cyclization to enantiomeric 1,5-benzothiazepines (+)- and (?)- 1 , are described. X-Ray single-crystal analysis reveals (2S, 3S) absolute configuration of (+)- 1 on the basis of tentative comparison of CD data with those for the 1,4-benzodiazepine derivative (+)- 8 of known absolute configuration.  相似文献   
8.
Absolute conformation of 7-chloro-5-phenyl-1-[(S)-α-phenylethyl]-1, 3-dihydro-2H-1, 4-benzodiazepin-2-one ( 1c ) in crystal, and its inversion rate in solution were determined, enabling prognosis of direction of asymmetric induction during C(3)-alkylation.  相似文献   
9.
Journal of Thermal Analysis and Calorimetry - In the current research, viscosity and thermal conductivity of hybrid Cu/CNTs water-based nanofluids were investigated at various concentrations of...  相似文献   
10.
A high purity Fe50Ni50 nanometric alloy was synthesized by ultra rapid autocatalytic chemical reduction of the corresponding transition metal ions in an aqueous solution. The ratio of metal concentration in solution is preserved in the precipitated powder alloy and no metal segregation has been detected. The alloy was characterized as a nanostructured chemically disordered taenite phase by X-ray diffraction (XRD) and Mössbauer spectroscopy (MS). Transmission electron microscopy (TEM) showed that the as prepared alloy contained spherical particles with 96 nm mean diameter size. The particles are composed of crystallites (of ∼15 nm size) and a predominant disordered interfacial region. A thermal treatment of 673 K/2 h produced a structural relaxation with a significant narrowing in the XRD and Mössbauer lines with a exothermic flow in the DSC signal and an increase in the crystallite size to 30 nm.  相似文献   
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