Transfer hydrogenation of aryl ketones with homogeneous ruthenium catalysts containing diazafluorene ligands

Novel cationic ruthenium(II) complexes bearing a 4,5‐diazafluorene unit and p‐cymene as ligands have been synthesised. The complexes were characterised based on elemental analysis and Fourier transform infrared and nuclear magnetic resonance spectroscopies. The synthesised Ru(II) complexes were employed as pre‐catalysts for the transfer hydrogenation of aromatic ketones using 2‐propanol as both hydrogen source and solvent in the presence of NaOH. All complexes showed high catalytic activity as catalysts in the reduction of substituted acetophenones to corresponding secondary alcohols. The products of catalysis were obtained with conversion rates of between 80 and 99%. Among the seven new complexes investigated, the most efficient catalyst showed turnover frequencies in the range 255–291 h^?1 corresponding to 85 to 97% conversion, respectively. Copyright © 2016 John Wiley & Sons, Ltd.     

Incorporation of an allene unit into 1,4-dihydronaphthalene: generation of 1,2-benzo-1,4,5-cycloheptatriene and its dimerization

1-Bromo-1-fluoro-[1a,2,7,7a]-tetrahydro-1H-cyclopropa[b]naphthalene (19) has been prepared by the addition of bromofluorocarbene to 1,4-dihydronaphthalene (18). Treatment of a solution of 19 in dry ether with MeLi afforded the tricyclic hydrocarbon 17, resulting from the intramolecular C-H insertion of carbene 16, and two dimerization products, the head-to-head 20 and head-to-tail 21 allene dimers, confirming the formation of title cycloallene 15 as a reactive intermediate. B3LYP/6-31G(d) calculation predicts the activation barriers for insertion product 17 and allene product 15 as 3.70 and 9.52 kcal/mol, respectively. This prediction was in good agreement with our experimental results.     

Double direct templating of periodically nanostructured ZnS hollow microspheres

We introduce a "double direct templating" method for obtaining hollow microspheres with periodically nanostructured walls. Silica or polystyrene colloids are dispersed in a self-assembled hexagonal lyotropic liquid crystal containing precursors for ZnS. The semiconductor ZnS mineralizes on the surface of the colloid, expressing a pore morphology that is a copy of the structure of the liquid crystal. After etching of the sacrificial colloids, hollow capsules with templated and uniform mesoporous shells are obtained.     

Synthesis,crystal structure and catalytic activity for H2O2 disproportionation of the manganese(II) coordination polymer {[Mn(O2C(CF2)8CO2)(phen)2]H2O}n (phen = 1,10-phenanthroline)

The title polymeric complex {[Mn(O₂C(CF₂)₈CO₂)(phen)₂]H₂O}_n was synthesized through the reaction of 1,10-phenanthroline, perfluorosebacic acid and MnCO₃ · H₂O. The molecular structure was characterized by X-ray diffraction, elemental analysis, thermal gravimetry, IR and UV–Vis spectroscopy and its catalytic activity has been studied. X-ray structure analysis shows that each Mn(II) ion is octahedrally coordinated by two bidentate phenanthroline ligands and the carboxylate oxygen atoms from two symmetry related perfluorosebacate ligands, which are coordinated in cisoid positions. The structure consists of polymeric chains, with the perfluorosebacato ligand bridging the Mn(II) ions in a monodentate fashion. Crystallographic characterization shows a supramolecular structure involving hydrogen bonds, π–π and π-ring interactions. The catalytic results indicated that the complex has reasonably good activity towards the disproportionation of hydrogen peroxide into water and dioxygen in methanol and it does not exhibit saturation kinetics with the substrate. The initial reaction rates and their temperature and base dependencies were investigated by monitoring the dioxygen evolution. Kinetic studies revealed a first-order dependence on the catalyst concentration. Activation parameters have been calculated at 301 K.     

Spectral amplitude and phase measurement of ultrafast pulses using all-optical differential tomography

We demonstrate a simple, all-optical, fiber-based method for characterizing the spectral amplitude and phase of ultrafast pulses using a differential tomographic measurement realized via four-wave mixing. The technique is applied to subpicosecond pulses in the C-band of the telecommunication spectrum. Characterization of amplified pulses and propagation through dispersive media is demonstrated and compared with autocorrelation measurements and calculated predictions. We show how our approach can be extended to larger bandwidths in similar systems, extending tomographic reconstruction of coherent fields to nearly an octave of bandwidth while maintaining a robust, waveguide-based geometry.     

Numerical simulation of the effects of plate separation and inclination on heat transfer in buoyancy driven open channels

 Effects of plate separation and inclination on free convection between asymmetrically heated vertical and inclined parallel plates have been simulated. The upper isothermally heated plate is facing downwards, the lower plate is passively heated by the upper one. The plate inclinations are chosen to be 0^∘, 30^∘, 45^∘ with respect to vertical position. Three-dimensional laminar numerical simulations are obtained by solving the full elliptic governing equations using a commercial finite volume based computational fluid dynamics (CFD) code. Comparisons of computational results with experiments and data from the literature are made in terms of relevant dimensionless numbers. It was observed that plate spacing and inclination influence the overall heat transfer rate. Received on 3 November 1998     

Transient heat conduction with uniform heat generation in a slab subjected to convection and radiation cooling

A finite difference scheme with fourth order Runge-Kutta method is employed to determine the unsteady state temperature distribution in a plane slab with uniform heat generation. The plane slab is insulated on one face and subjected to convective and radiative cooling at the other face. The plane slab has a uniform initial temperature and the ambient environment as well as the fluid temperatures are assumed to be constant. Heat conduction is considered to be one dimensional. Results are presented in dimensionless charts over a wide range of parameters.

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Instationäre Wärmeleitung mit gleichförmiger Wärmeerzeugung in einer Platte bei Kühlung durch Konvektion und Abstrahlung

Zusammenfassung Zur Ermittlung der instationären Temperaturverteilung in einer Platte mit gleichförmiger Wärmeerzeugung wird ein Differenzverfahren vierter Ordnung nach Runge-Kutta angewendet. Die ebene Platte ist einseitig isoliert und wird auf der anderen Seite durch Konvektion und Abstrahlung gekühlt. Zu Beginn befindet sich die Platte gleichförmig auf einer bestimmten Anfangstemperatur, die Temperaturen der umgebenden Objekte sowie des Fluids sind ebenfalls konstant. Der Wärmeleitungsvorgang sei eindimensional. Die Ergebnisse sind in dimensionsloser Form für einen weiten Parameterbereich in Diagrammform dargestellt.

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Nomenclature Bi Biot number - c specific heat - h heat transfer coefficient - k thermal conductivity - L half thickness of plate - Nr Radiation number - T absolute temperature - t time - F _o dimensionless time - T _e environment temperature - T _f fluid temperature - T _i initial plate temperature - u internal energy generation number - u internal energy generation - x space coordinate - x* dimensionless space coordinate Greek symbols thermal diffusivity - emissivity - dimensionless temperature - density - Stephan-Boltzman constant     

Cellular-level near-wall unsteadiness of high-hematocrit erythrocyte flow using confocal μPIV

In hemodynamics, the inherent intermittency of two-phase cellular-level flow has received little attention. Unsteadiness is reported and quantified for the first time in the literature using a combination of fluorescent dye labeling, time-resolved scanning confocal microscopy, and micro-particle image velocimetry (μPIV). The near-wall red blood cell (RBC) motion of physiologic high-hematocrit blood in a rectangular microchannel was investigated under pressure-driven flow. Intermittent flow was associated with (1) the stretching of RBCs as they passed through RBC clusters with twisting motions; (2) external flow through local obstacles; and (3) transitionary rouleaux formations. Velocity profiles are presented for these cases. Unsteady flow clustered in local regions. Extra-cellular fluid flow generated by individual RBCs was examined using submicron fluorescent microspheres. The capabilities of confocal μPIV post-processing were verified using synthetic raw PIV data for validation. Cellular interactions and oscillating velocity profiles are presented, and 3D data are made available for computational model validation.     

Experimental investigation of flow and heat transfer in rectangular cross-sectioned duct with baffles mounted on the bottom surface with different inclination angles

In this study, steady-state forced convection heat transfer and pressure drop characteristics in a horizontal rectangular cross-sectioned duct, baffles mounted on the bottom surface with different inclination angles were investigated experimentally in the Reynolds number range from 1 × 10³ to 1 × 10⁴. The study was performed under turbulent flow conditions. Effects of different baffle inclination angles on flow and heat transfer were studied. Results are also presented in terms of thermal enhancement factor. It is observed that increasing in baffle inclination angle enhances the heat transfer and causes an increase in pressure drop in the duct.