Preparation and catalytic applications of partially fluorinated binaphthol ligands

New partially fluorinated binaphthols were obtained using a copper-catalyzed oxidative coupling. The corresponding enantiomerically pure compounds were prepared by fractional crystallization of the corresponding bis(menthyl)carbamates. Nucleophilic aromatic substitution using oxygen- and carbon-based nucleophiles resulted in functionalized derivatives without concomitant racemization. The titanium(IV) complexes of these ligands are catalytically active in the asymmetric oxidation of sulfides.     

Dynamics of molecular oxygen in micellar solutions

Fluorescence quenching by molecular oxygen has been employed to estimate dynamic parameters and solubility characteristics of molecular oxygen in micelle forming detergent solutions. A kinetic model which assumes that oxygen quenching occurs only in the micellar phase is employed to analyze the data.     

Non-isothermal pyrolysis of used lubricating oil and the catalytic effect of carbon-based nanomaterials on the process performance

Pyrolysis is a commonly used method for the recovery of used lubricating oil (ULO), which should be kinetically improved by a catalyst, due to its high level of energy consumption. In this research, the catalytic effects of carbon nanotube (CNT) and graphene nanoplatelets on the pyrolysis of ULO were studied through thermogravimetric analysis. First, the kinetic parameters of ULO pyrolysis including activation energy were calculated to be 170.12 and 167.01 kJ mol^?1 by FWO and KAS methods, respectively. Then, the catalytic effects of CNT and graphene nanoplatelets on pyrolysis kinetics were studied. While CNT had a negligible effect on the pyrolysis process, graphene nanoplatelets significantly reduced the temperature of maximum conversion during pyrolysis from 400 to 350 °C, due to high thermal conductivity and homogenous heat transfer in the pyrolysis process. On the other hand, graphene nanoplatelets maximized the rate of conversion of highly volatile components at lower temperatures (<?100 °C), which was mainly due to the high affinity of these components toward graphene nanoplatelets and also the effect of nanoplatelets’ edges which have free tails and can bond with other molecules. Moreover, graphene nanoplatelets decreased the activation energy of the conversion to 154.48 and 152.13 kJ mol^?1 by FWO and KAS methods, respectively.

     

Enantiopure Aminopyrans by a Lewis Acid Promoted Rearrangement of 1,2‐Oxazines: Versatile Building Blocks for Oligosaccharide and Sugar Amino Acid Mimetics

1,3‐Dioxolanyl‐substituted 1,2‐oxazines, such as syn‐ 1 and anti‐ 1 , rearrange under Lewis acidic conditions to provide bicyclic products 2 – 5 . Subsequent reductive transformations afforded enantiopure 3‐aminopyran derivatives such as 7 and 9 or their protected diastereomers 16 and 18 , which can be regarded as carbohydrate mimetics. An alternative sequence of transformations including selective oxidation of the primary hydroxyl groups in 21 and 24 led to two protected β‐amino acid derivatives with carbohydrate‐like backbone (sugar amino acids). Treatment of bicyclic ester 23 with samarium diiodide cleaved the N? O bond and furnished the unusual β‐lactam 27 in excellent yield. Alternatively, γ‐amino acid derivative 29 was efficiently prepared in a few steps. Fairly simple transformations gave azides 32 and 35 or alkyne 30 which are suitable substrates for the construction of oligosaccharide mimetics such as 34 by copper iodide catalyzed cycloadditions. With this report we demonstrate that enantiopure rearrangement products 2 – 5 are protected precursors of a variety of polyfunctionalized pyran derivatives with great potential for chemical biology.     

Steady laminar flow past a heated horizontal plate embedded in a saturated porous medium

In this paper we study the boundary layer equations for steady laminar flow past a heated horizontal plate embedded in a saturated porous medium by adopting the formulation of Chandrasekhara [3], Kolar and Sastri [7]. The velocity distribution and temperature distribution are determined by using the implicit Crank-Nicolson-Predictor-Corrector method of finite difference scheme [7] and [1]. With the help of a compute the distributions are estimated at both (i+1/2)th and (i+1)th levels and they are presented in tabular form. The curves for these distributions are plotted. We calculate the shear stress and skin friction at the wall and observe that the skin-friction directly depends upon the dimensions of the plate and inversely depends upon the Reynolds numberRe. The heat flux and the Nusselt number are evaluated. Further we observe that the Nusselt number depends upon the length of the porous plate.

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Stetige laminare Strömung über eine in einem gesättigten porösen Medium eingebettete horizontale Platte

Zusammenfassung Diese Untersuchung befaßt sich mit den Grenzschichtgleichungen für eine stetige laminare Strömung über eine beheizte Platte, die in ein gesättigtes poröses Medium eingebettet ist, mittels des Formalismus von Chandrasekhara [3], Kolar und Sastri [7]. Die Geschwindigkeits- und Temperaturverteilung wurden unter Benutzung der impliziten Crank-Nicolson-Korrekturmethode des Finiten-Elemente-Schemas bestimmt. Die (i+1/2). und die (i+1). Ebene der Verteilungen wurden mit Computer-Hilfe berechnet und in Tabellenform dargestellt. Die Graphen der Temperatur- und Geschwindigkeitsverteilung wurden ausgeplottet. Die Schubspannungen und die Oberflächenreibung an der Wand wurden berechnet und es konnte festgestellt werden, daß die Oberflächenreibung direkt von der Größe der Platte abhängt und umgekehrt proportional der Reynolds-ZahlRe ist. Der Wärmestrom und die Nusselt-Zahl wurden bestimmt. Weiterhin konnte festgestellt werden, daß die Nusselt-Zahl von der Länge der porösen Platte abhängt.

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Nomenclature C _p specific heat of the convective fluid - D skin friction - k permeability of the porous medium - k _f thermal conductivity of the fluid - k _m the coefficient of thermal conductivity of the porous medium - k _s the conductivity of the solid matrix - N(x) Nusselt number - q(x) specific heat flux - Re local Reynolds number - T temperature - T ₀ temperature of the free stream - T _w temperature of the plate - u velocity in thex-direction - u ₀ velocity of the free stream - V velocity iny-direction - x coordinate axis along the plate - y coordinate axis normal to the plate Greek symbols thermal diffusivity - thickness of the velocity boundary layers in thex direction - thickness of the velocity boundary layer in they-direction - the porosity of the medium - dimensionless variable - kinematic viscosity of the fluid - density of the fluid - shear stress     

Insight into Heterogeneity Effects in Methane Hydrate Dissociation via Pore-Scale Modeling

A large number (1253) of high-quality streaming potential coefficient (\(C_\mathrm{sp})\) measurements have been carried out on Berea, Boise, Fontainebleau, and Lochaline sandstones (the latter two including both detrital and authigenic overgrowth forms), as a function of pore fluid salinity (\(C_\mathrm{f})\) and rock microstructure. All samples were saturated with fully equilibrated aqueous solutions of NaCl (10\(^{-5}\) and 4.5 mol/dm\(^{3})\) upon which accurate measurements of their electrical conductivity and pH were taken. These \(C_\mathrm{sp}\) measurements represent about a fivefold increase in streaming potential data available in the literature, are consistent with the pre-existing 266 measurements, and have lower experimental uncertainties. The \(C_\mathrm{sp}\) measurements follow a pH-sensitive power law behaviour with respect to \(C_\mathrm{f}\) at medium salinities (\(C_\mathrm{sp} =-\,1.44\times 10^{-9} C_\mathrm{f}^{-\,1.127} \), units: V/Pa and mol/dm\(^{3})\) and show the effect of rock microstructure on the low salinity \(C_\mathrm{sp}\) clearly, producing a smaller decrease in \(C_\mathrm{sp}\) per decade reduction in \(C_\mathrm{f}\) for samples with (i) lower porosity, (ii) larger cementation exponents, (iii) smaller grain sizes (and hence pore and pore throat sizes), and (iv) larger surface conduction. The \(C_\mathrm{sp}\) measurements include 313 made at \(C_\mathrm{f} > 1\) mol/dm\(^{3}\), which confirm the limiting high salinity \(C_\mathrm{sp}\) behaviour noted by Vinogradov et al., which has been ascribed to the attainment of maximum charge density in the electrical double layer occurring when the Debye length approximates to the size of the hydrated metal ion. The zeta potential (\(\zeta \)) was calculated from each \(C_\mathrm{sp}\) measurement. It was found that \(\zeta \) is highly sensitive to pH but not sensitive to rock microstructure. It exhibits a pH-dependent logarithmic behaviour with respect to \(C_\mathrm{f}\) at low to medium salinities (\(\zeta =0.01133 \log _{10} \left( {C_\mathrm{f} } \right) +0.003505\), units: V and mol/dm\(^{3})\) and a limiting zeta potential (zeta potential offset) at high salinities of \({\zeta }_\mathrm{o} = -\,17.36\pm 5.11\) mV in the pH range 6–8, which is also pH dependent. The sensitivity of both \(C_\mathrm{sp}\) and \(\zeta \) to pH and of \(C_\mathrm{sp}\) to rock microstructure indicates that \(C_\mathrm{sp}\) and \(\zeta \) measurements can only be interpreted together with accurate and equilibrated measurements of pore fluid conductivity and pH and supporting microstructural and surface conduction measurements for each sample.     

One-pot synthesis of spiro-acridine/indoline and indoline derivatives using (MWCNTs)-COOH/La2O3 hybrid as an effective catalyst

Spiro-acridine/indoline and indoline derivatives were synthesized by the three-component reaction of isatin, dimedone, and amines or amino acids in the presence of acid-functionalized multiwalled carbon nanotubes/La₂O₃ (MWCNTs)-COOH/La₂O₃ hybrid (5 mol%) as a highly efficient catalyst in ethanol. The assigned structure was further established by CHN analysis, NMR, and FTIR spectra. (MWCNTs)-COOH/La₂O₃ was fabricated by the reaction of functionalized (MWCNTs)-COOH and La(NO₃)₃.6H₂O in acetic acid. Synthesis of La₂O₃ nanoparticles and their conjugation on the surface of MWCNT have been confirmed by FTIR, scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy.     

Velocity and temperature distributions on a semi-infinite flat plate embedded in a saturated porous medium

In this paper the velocity and temperature distributions on a semi-infinite flat plate embedded in a saturated porous medium are obtained for the governing equations (Kaviany [7]) following the technique adopted by Chandrashekara [2] which are concerned with the interesting situations of the existence of transverse, velocity and thermal boundary layers. Here the pressure gradient is just balanced by the first and second order solid matrix resistances for small permeability and observed that by increasing of the flow resistance the asymptotic value for the heat transfer rate increases. Further we concluded that the transverse boundary layers are thicker than that of axial boundary layers. Hence we evaluated the expressions for the boundary layer thickness, the shear stress at the semi-infinite plate and _T (the ratio of the thicknesses of the thermal boundary layer and momentum boundary layer). The variations of these quantities for different values of the porous parameterB and the flow resistanceF have been discussed in detail with the help of tables. The curves for velocity and temperature distributions have been plotted for different values ofB andF.Lastly we have evaluated the heat fluxq(x) and found that it depends entirely upon the Reynolds numberRe, Prandtl numberPr,B andF.