Synthesis Of (+/-)-2-Isopropyl-5,6-Dimethylbicyclo[3.2.1]Oct-6-En-8-One

Methanolic hydrogen chloride cyclization of the triketone 8, prepared from the Mannich base 7 and 2-methylcyclopentane-1,3-dione, gives ketones 9 and 10. NaBH4 reduction of 9 followed by Grignard reaction with CH3MgI affords the diol 12. Catalytic hydrogenation of 12 followed by PCC oxidation yields the ketoalcohol 13. Dehydration of 13 with SOCl2/pyridine results in a 1:1 mixture of the endo-14 and exo-15 olefins, separated by chromatography.

A new general method for the introduction of the aldehyde function in aromatic compounds

Side chain bromination of aromatic amidomethylated compounds yields aldehydes.

The velocity dispersion of giant molecular clouds. II - Mathematical and numerical refinements

The energy input to giant molecular clouds is recalculated, using the proper linearized equations of motion, including the Coriolis force and allowing for changes in the guiding center. Perturbation theory yields a result in the limit of distant encounters and small initial epicyclic amplitudes. Direct integration of the motion equations allows the strong encounter regime to be studied. The present perturbation theory result differs by a factor of order unity from that of Jog and Ostriker (1988). The result of present numerical integrations for the 2D (planar) velocity dispersion is presented. The accretion rate for a molecular cloud in the Galactic disk is calculated.

Amplitude Frequency Response Measurement: A Simple Technique

A simple method is described to combine a modern function generator and a digital oscilloscope to configure a setup that can directly measure the amplitude frequency response of a system. This is achieved by synchronously triggering both instruments, with the function generator operated in the ``Linear-Sweep'' frequency mode, while the oscilloscope is operated in the ``Envelope'' acquisition mode. Under these conditions, the acquired envelopes directly correspond to the (input and output signal) spectra, whose ratio yields the amplitude frequency response. The method is easy to configure, automatic, time-efficient, and does not require any external control or interface or programming. This method is ideally suited to impart hands-on experience in sweep frequency response measurements, demonstrate resonance phenomenon in transformer windings, explain the working principle of an impedance analyzer, practically exhibit properties of network functions, and so on. The proposed method is an inexpensive alternative to existing commercial equipment meant for this job and is also an effective teaching aid. Details of its implementation, along with some practical measurements on an actual transformer, are presented.

Thermal decomposition of zirconyl oxalates I. Barium zirconyl oxalate

Conditions for the preparation of stoichiometric barium zirconyl oxalate heptahydrate (BZO) have been standardized. The thermal decomposition of BZO has been investigated employing TG, DTG and DTA techniques and chemical and gas analysis. The decomposition proceeds through four steps and is not affected much by the surrounding gas atmosphere. Both dehydration and oxalate decomposition take place in two steps. The formation of a transient intermediate containing both oxalate and carbonate groups is inferred. The decomposition of oxalate groups results in a carbonate of composition Ba2Zr2OsCO3, which decomposes between 600 and 800 ~ and yields barium zirconate. Chemical analysis, IR spectra and X-ray powder diffraction data support the identity of the intermediate as a separate entity.

Thermal decomposition of zirconyl oxalates I. Barium zirconyl oxalate

Conditions for the preparation of stoichiometric barium zirconyl oxalate heptahydrate (BZO) have been standardized. The thermal decomposition of BZO has been investigated employing TG, DTG and DTA techniques and chemical and gas analysis. The decomposition proceeds through four steps and is not affected much by the surrounding gas atmosphere. Both dehydration and oxalate decomposition take place in two steps. The formation of a transient intermediate containing both oxalate and carbonate groups is inferred. The decomposition of oxalate groups results in a carbonate of composition Ba2Zr2O5CO3, which decomposes between 600 and 800° and yields barium zirconate. Chemical analysis, IR spectra and X-ray powder diffraction data support the identity of the intermediate as a separate entity.Die Bedingungen für die Herstellung von stöchiometrischem Barium-zirconyl-oxalat Heptahydrat (BZO) wurden standardisiert. Die thermische Zersetzung von BZO wurde unter Einsatz der TG-, DTG- und DTA, sowie der chemischen und Gasanalyse untersucht. Die Zersetzung verläuft über vier Stufen und wird von der umgebenden Gasathmosphäre nicht besonders beeinflusst. Sowohl die Dehydratisierung als auch die Oxalatzersetzung erfolgt in zwei Stufen. Die Bildung einer intermediären Übergangsverbindung mit sowohl Oxalat- als auch Carbonatgruppen wirken hierbei mit. Die Zersetzung der Oxalatgruppen ergibt ein Carbonat der Zusammensetzung Ba2Zr2O5CO3, das zwischen 600 und 800° zersetzt wird und Bariumzirconat ergibt. Die Angaben der chemischen Analyse, der IR-Spekren und der Röntgen-Pulver-Diffraktion unterstützen die Identität der Intermediärverbindung als eine separate Einheit.On a standardisé les conditions de préparation de l'oxalate heptahydraté de zirconyle et de baryum (BZO) stoechiométrique. On a étudié la décomposition thermique de BZO par TG, TGD et ATD ainsi que par analyses chimiques et analyses des gaz. La décomposition a lieu en quatre étapes et n'est pas trop influencée par l'atmosphère ambiante. La déshydratation et la décomposition de l'oxalate ont lieu en deux étapes. Il se forme un composé intermédiaire de transition contenant à la fois les groupes oxalate et carbonate. La décomposition des groupes oxalate fournit un carbonate de composition Ba2Zr2O5CO3 qui se décompose entre 600 et 800° pour fournir du zirconate de baryum. L'analyse chimique, les spectres IR et la diffraction des rayons X sur poudre, apportent les preuves de l'existence d'un composé intermédiaire comme entité séparée.

A geodesic constant method for computing high-frequency mutual coupling between antennas on general quadric cylinders

A Geodesic Constant Method (GCM) is outlined which provides a common approach to ray tracing on quadric cylinders in general, and yields all the surface ray-geometric parameters required in the UTD mutual coupling analysis of conformal antenna arrays in the closed form. The approach permits the incorporation of a shaping parameter which permits the modeling of quadric cylindrical surfaces of desired sharpness/flatness with a common set of equations. The mutual admittance between the slots on a general parabolic cylinder is obtained as an illustration of the applicability of the GCM.

Theory of the effects of destruction of localization by inelastic scattering in the resistivity of pure thin potassium wires

Measurements of the electrical resistivity of thin potassium wires at temperatures near 1 K have revealed a minimum in the resistivity as a function of temperature. By proposing that the electrons in these wires have undergone localization, albeit with large localization length, and that inelastic-scattering events destroy the coherence of that state, we can explain both the magnitude and shape of the temperature-dependent resistivity data. Localization of electrons in these wires is to be expected because, due to the high purity of the potassium, the elastic mean free path is comparable to the diameters of the thinnest samples, making the Thouless length lT (or inelastic diffusion length) much larger than the diameter, so that the wire is effectively one dimensional. The inelastic events effectively break the wire into a series of localized segments, whose resistances can be added to obtain the total resistance of the wire. The ensemble-averaged resistance for all possible segmented wires, weighted with a Poisson distribution of inelastic-scattering lengths along the wire, yields a length dependence for the resistance that is proportional to [L3/lin(T)], provided that lin(T)?L, where L is the sample length and lin(T) is some effective temperature-dependent one-dimensional inelastic-scattering length. A more sophisticated approach using a Poisson distribution in inelastic-scattering times, which takes into account the diffusive motion of the electrons along the wire through the Thouless length, yields a length- and temperature-dependent resistivity proportional to (L/lT)4 under appropriate conditions. Inelastic-scattering lifetimes are inferred from the temperature-dependent bulk resistivities (i.e., those of thicker, effectively three-dimensional samples), assuming that a minimum amount of energy must be exchanged for a collision to be effective in destroying the phase coherence of the localized state. If the dominant inelastic mechanism is electron-electron scattering, then our result, given the appropriate choice of the channel number parameter, is consistent with the data. If electron-phason scattering were of comparable importance, then our results would remain consistent. However, the inelastic-scattering lifetime inferred from bulk resistivity data is too short. This is because the electron-phason mechanism dominates in the inelastic-scattering rate, although the two mechanisms may be of comparable importance for the bulk resistivity. Possible reasons why the electron-phason mechanism might be less effective in thin wires than in bulk are discussed.

Purification and properties of xylanase from the thermophilic fungus, Humicola lanuginosa (Griffon and Maublanc) Bunce

An extracellular xylanase was purified to homogeneity from the culture filtrate of the thermophilic fungus, Humicola lanuginosa (Griffon and Maublanc) Bunce and its properties were studied. A fourfold purification and a yield of 8% were achieved. The molecular-weight of the protein was found to be 22,500 based on electrophoretic mobility and 29,000 by gel filtration behavior. The protein is rich in acidic amino acids, glycine and tyrosine, and poor in sulfur-containing amino acids. The kinetic properties of the enzyme are similar to those of other fungal xylanases. The enzyme shows high affinity toward larchwood xylan (Km = 0.91 mg/ml) and hydrolyzes only xylan. The enzyme becomes inactivated when stored for more than 2 months at −20 °C in the dry state. Such an inactivation has not been reported so far for any xylanase. Using chromatographic techniques, one species of protein differing from the native protein in charge but enzymatically active was isolated in low yields. However, a large molecular-weight species of the protein devoid of enzyme activity was isolated in substantial quantities and further characterized. Based on ultracentrifugation and gel electrophoretic studies, it was concluded that this species may be an aggregate of the native protein and that such an aggregation might be taking place on storage in the dry state at −20 °C, leading to loss in activity.

Chemical potential of oxygen for iron-rutile-ilmenite and iron-ilmenite-ulvospinel equilibria

The chemical potential of oxygen corresponding to the iron-rutile-ilmenite (IRI) and iron-ilmenite-ulvospinel (IIU) equilibria has been measured employing solid-state galvanic cells,$$Pt, Fe + TiO_2 + FeTiO_3 //(Y_2 O_3 ) ZrO_2 //Fe + FeO, Pt$$ and $${\text{Pt, Fe + FeTiO}}_{\text{3}} {\text{ + Fe}}_{\text{2}} {\text{TiO}}_{\text{4}} {\text{//(Y}}_{\text{2}} {\text{0}}_{\text{3}} {\text{) ZrO}}_{\text{2}} {\text{//Fe + FeO, Pt}}$$ in the temperature range of 875 to 1275 K and 900 to 1373 K, respectively. The cells are written such that the right-hand electrodes are positive. The electromotive force (emf) of both the cells was found to be reversible and to vary linearly with temperature over the entire range of measurement. The chemical potential of oxygen for IRI equilibrium is represented by Δμo2(IRI) = -550,724 - 29.445T + 20.374T InT(±210) J mol−1 (875 <-T<- 1184 K) = -620,260 + 369.593T - 27.716T lnT(±210) J mol−1 (1184 <-T<- 1275 K) and that for IIU equilibrium by Δμo2(IIU) = -501,800 - 49.035T + 20.374T lnT(±210) J mol−1 (900 <-T<- 1184 K) = -571,336 + 350.003T− 27.716T lnT(=−210) J mol-1 (1184 <-T<- 1373 K) The standard Gibbs energy changes for IRI and IIU equilibria have been deduced from the measured oxygen potentials. Since ilmenite contains small amounts of Ti³+ ions, a correction for the activity of FeTiO3 has been incorporated by assuming ideal mixing on each cation sublattice in the FeTiO3-Ti2O3 system. Similarly, the ulvospinel contains some Fe³+ ions and a correction for the activity of Fe2TiO4 has been included by modeling the Fe2TiO4-Fe3O4 system. The third-law analysis of the results obtained for IRI equilibrium gives ΔH 298 0 = -575 (±1.0) kJ mol-1 and for IIU equilibrium yields ΔH 298 0 = -523.7 (±0.7) kJ mol−1}. The present results suggest that Fe2+ and Ti4+ cations mix almost ideally on the octahedral site of spinel lattice in Fe2TiO4, giving rise to a configurational contribution of 2R In 2 (11.5256 J mol-1 K-1) to the entropy of Fe2TiO4.

Detection of edges from projections

In a number of applications of computerized tomography, the ultimate goal is to detect and characterize objects within a cross section. Detection of edges of different contrast regions yields the required information. The problem of detecting edges from projection data is addressed. It is shown that the class of linear edge detection operators used on images can be used for detection of edges directly from projection data. This not only reduces the computational burden but also avoids the difficulties of postprocessing a reconstructed image. This is accomplished by a convolution backprojection operation. For example, with the Marr-Hildreth edge detection operator, the filtering function that is to be used on the projection data is the Radon transform of the Laplacian of the 2-D Gaussian function which is combined with the reconstruction filter. Simulation results showing the efficacy of the proposed method and a comparison with edges detected from the reconstructed image are presented

Electroless nickel hydroxide: synthesis and characterization

An electroless method of nickel hydroxide synthesis through the complexation-precipitation route which yields a fine particle material having a specific surface area of 178 m2 g–1 has been described. The morphology of this material as revealed by electron microscopy is distinctly different from the turbostratic nature of electrosynthesized nickel hydroxide. While the long range structure as shown by the X-ray diffraction pattern is similar to that of beta-Ni(OH)2, the short range structure as revealed by infrared spectroscopy incorporates characteristics similar to that of agr-Ni(OH)2. Cyclic voltammetry studies show that the electroless nickel hydroxide has a higher coulombic efficiency (>90%), a more anodic reversible potential and a higher degree of reversibility compared to the electrosynthesized nickel hydroxide and conventionally prepared nickel hydroxide.

A Convenient High-Yield Room-Temerature Synthesis of Mixed Tri(Amino) Silanes by Transmination of Tris(Dicyclohexylamino) Silane And-Their Characterization

Tris(dicyclohexylamino)silane. (DCA)3SiH. is prepared by the reaction of trichlorosilane with dicyclohexylamine. This is found to undergo transamination reactions with other secondary amines (R2NH). such as pyrrolidine, piperidine, hexamethyleneimine. morpholine. N-methylpiperazine and diethylamine to yield mixed tri(amino)silanes of the formula (DCA)(R2N)2SiH in quantitative yields. These new derivatives are found to be moisture sensitive and hydrolyze to yield their respective amines, hydrogen and silica. They are found to be stable in an inert atmosphere. They have been characterized by IR, NMR (H-1, Si-29), mass spectroscopy and CHN analysis. N-15 NMR for one of the compounds has been done.

A model for static foam drainage

A model for static foam drainage, based on the pentagonal dodecahedral shape of bubbles, that takes into account the surface mobility of both films and Plateau border walls has been developed. The model divides the Plateau borders into nearly horizontal and nearly vertical categories and assigns different roles to them. The films are assumed to drain into all the adjacent Plateau borders equally. The horizontal Plateau borders are assumed to receive liquid from films and drain into vertical Plateau borders, which in turn form the main component for gravity drainage. The model yields the liquid holdup values for films, horizontal Plateau borders and vertical Plateau borders as functions of height and time. The model has been tested on static foams whose cumulative drainage was measured as a function of time. The experimental data on the effect of foam height, initial holdup, surface viscosity, etc. can be explained by the model quantitatively.

An unusual anti-markovnikov hydration of alkenes with titanium(III) tetrahydroborates

Titanium(III) tetrahydroborate formed by the reaction of titanium tetrachloride and benzyltriethylammonium borohydride (1:4) reacts with alkenes in dichloromethane (-20-degrees-C) very readily to yield directly the corresponding alcohols in excel lent yields after a simple aqueous work up.