Structural studies on ruthenium(II) complexes used in interphase catalysis for the hydrogenation of ketones

Structural studies were performed on catalytically active ruthenium(II) complexes used in interphases, by means of XAFS spectroscopy. The EXAFS investigations indicate that the complexes retain their structural integrity when they are embedded on polysiloxane matrices to form stationary phase materials. The AXAFS studies reveal that the variations in the catalytic activity of the complexes with different ligands can be correlated to the differences in the electronic structure around the active ruthenium center. The EXAFS investigations show that, in asymmetric transfer hydrogenation reactions catalysed by ruthenium(II) complexes, the co‐catalyst plays a crucial role not only in enhancing the catalytic activity, but also in determining the structure of the intermediate species. Copyright © 2007 John Wiley & Sons, Ltd.     

Structures of two ketals derived from a pentacyclic cage diketone

The structure of a compound derived from a symmetrical cage diketone in which one of the ketone C=O groups has been converted into a ketal is reported. An investigation into reasons for the selective functionalization resulted in the isolation of acis, cisoid, cis linear triquinane derivative in which both ketones are converted to ketals that share a transannular oxygen atom. Crystal data:2, monoclinic,P2₁/c,a=7.6298(9),b=7.673(3),c=22.125(3)Å,=97.59(1)°,V=1283.9(5)ų, andR=0.048 (1001 reflections);4, triclinic,P¯1,a=7.3864(9),b=9.6362(9),c=10.3889(9)Å,=75.749(6),=76.300(8), =83.100(8)°,V=694.8(4)ų, andR=0.088 (1284 reflections).     

A variational coupled cluster theory for closed shells using a propagator modification procedure

A general partial summation method for including arbitrary classes of diagrams to all orders in the coupled cluster based size consistent energy functional for closed shell states is developed. Since the various reduced density matrices which appear in the energy functional are essentially the time-independent analogues of the corresponding many body Green functions, it is possible to derive Dyson-like equations for these quantities. By expanding the associated proper self energy parts in terms of the T-amplitudes, one can carry out partial summations in the reduced density matrices and thus in energy. At a higher level, higher order terms in a proper self energy can also be generated by renormalizing the internal propagators in it, and considering only the irreducible self-energy terms.     

Spectrophotometric determination of copper(II) and its application to a plant sample containing zinc,iron, and manganese

Salicylaldehyde thiosemicarbazone instantaneously forms a green complex with copper(II) in the optimum pH range 5–7. A fivefold molar excess of the reagent is sufficient for the full development of the color. Beer's law is obeyed in the range 0.5–6.0 ppm of copper. The optimum concentration range as evaluated by Ringbom's method is 1.4–5.8 ppm. At 375 nm the sensitivity of the reaction and the molar absorptivity are 0.006 μg cm^?2 and 9.2 × 10³ liters mol^?1 cm^?1, respectively. The effects of pH, reagent concentration, time, order of addition of the solutions, and the interference of various ions were investigated. Copper in plant samples, containing zinc, iron, and manganese, was determined.     

The transition from bulk to nano as a phase transition

It is demonstrated that the chemical potential of bosons trapped in a harmonic potential shows a discontinuity as a function of the number of particles in the system. In the model used, it is shown that if the number of particles is of the order of 10⁶ or greater, bulk-like behaviour is exhibited by the system. This translates to a ratio of V/V_c>10⁶ for bulk behaviour, where V is the crystallite volume of the experimental sample and V_c is the volume of the unit cell. Several experimental results covering a wide range of physical phenomena that corroborate the fact that such a number-induced phase transition indeed exists are presented.     

Method of Generating N-dimensional Isochronous Nonsingular Hamiltonian Systems

In this paper we develop a straightforward procedure to construct higher dimensional isochronous Hamiltonian systems. We first show that a class of singular Hamiltonian systems obtained through the Ω-modified procedure is equivalent to constrained Newtonian systems. Even though such systems admit isochronous oscillations, they are effectively one degree of freedom systems due to the constraints. Then we generalize the procedure in terms of Ω _i -modified Hamiltonians and identify suitable canonically conjugate coordinates such that the constructed Ω _i -modified Hamiltonian is nonsingular and the corresponding Newton's equation of motion is constraint free. The procedure is first illustrated for two dimensional systems and subsequently extended to N-dimensional systems. The general solution of these systems are obtained by integrating the underlying equations and is shown to admit isochronous as well as amplitude independent quasiperiodic solutions depending on the choice of parameters.     

Measurement of K β K /α values using proton beamvalues using proton beam

The Measurement of K _β K _/α intensity ratios are measured in some 3d shell elements by using a 2 MeV proton beam along with a high resolution Si(Li) detector. The present Measurement of K _β K _/α intensity ratios are in good agreement with Scofield modified theoretical values, thus supporting the basic assumptions in that theory. From the present Measurement of K _β K _/α intensity ratios, it is evident that due to chemical effects, the experimental Measurement of K _β K _/α intensity ratios will be increased while they will be decreased due to the presence of simultaneous M-shell vacancies which are produced due to proton excitation.     

Orientational order parameter studies on 3.Om and 3O.Om liquid crystals

Orientational order parameter S is evaluated in the nematic phase of six liquid crystal compounds, N-(p-n-propyl benzylidene)-p-n-alkoxy anilines, 3.Om and N-(p-n-propyloxy benzylidene)-p-n-alkoxy anilines, 3O.Om compounds with m = 6, 7 and 8, using different methods. The techniques employed are S from birefringence δn, Haller's approximation from (1?T/T_c) ^β, effective geometry parameter α_g and Vuks’ scaling factor S_C. The values of S obtained using the above methods are compared with one another and with the results on a number of liquid crystals; the liquid crystals favor isotropic Vuks’ method.     

Transient Response of Particle Distribution in a Chamber to Transient Particle Injection

We inject a large number of newly created nano‐particle aggregates into a chamber for the purpose of removing harmful contents in an indoor environment. This study is to experimentally and numerically investigate transient response of particle distributions to particle injections. A room‐sized chamber of 4 m × 2.1 m × 2.4 m is connected to a specially designed particle‐injection system, with two Optical Particle Counters used to simultaneously measure particle‐number densities with the size range from 0.3 μm to 10 μm at the inlet and in the chamber. A velocity probe measures the flow that is up to 1 m/s. An Euler‐type particulate‐phase‐transport model is developed and validated by comparing with experimental data. The study shows that the transient behavior of particle distributions is determined by many factors, including particle size, particle settling speed, sampling location, and velocity distribution. Particle number densities decrease in time more quickly for large particles than for small particles, and locations farther downstream in the chamber correlate more weakly with the inlet injection.