Numerical analysis of pressure oscillations over axisymmetric spiked blunt bodies at Mach 6.80

The pressure oscillations over a forward facing spike attached to an axisymmetric blunt body are simulated by solving time-dependent compressible Navier–Stokes equations. The governing fluid flow equations are discretized in spatial coordinates employing a finite volume approach which reduces the equations to semidiscretized ordinary differential equations. Temporal integration is performed using the two-stage Runge–Kutta time stepping scheme. A global time step is used to obtain a time-accurate numerical solution. The numerical computation is carried out for a freestream Mach number of 6.80 and for spike length to hemispherical diameter ratios of 0.5, 1.0 and 2.0. The flow features around the spiked blunt body are characterized by a conical shock wave emanating from the spike tip, a region of separated flow in front of the hemispherical cap, and the resulting reattachment shock wave. Comparisons of the numerical results are made with the available experimental results, such as schlieren pictures and the surface pressure distribution along the spiked blunt body. They are found to be in good agreement. Spectral analysis of the computed pressure oscillations are performed employing fast Fourier transforms. The surface pressure oscillations over the spike and phase plots exhibit a behaviour analogous to that of the Van der Pol equation for a self-sustained oscillatory flow. Received 28 February 2001 / Accepted 17 January 2002     

Pd-catalyzed amination as an alternative to nucleophilic aromatic substitution for the synthesis of N-alkyltacrines and analogues

A reliable Pd-catalyzed amination protocol is described for the synthesis of N-alkyltacrines and analogs. The Josiphos ligand CyPFtBu was found to provide optimum yields: 16 examples are given. Compared to the typical high-temperature nucleophilic aromatic substitution (NAS) routes, Pd-catalyzed aminations proceed at significantly lower reaction temperatures, and enable the synthesis of otherwise inaccessible products.     

Kinetics of copper(II)‐catalyzed oxidation of S(IV) by atmospheric oxygen in ammonia buffered solutions

To understand the chemistry of Cu(II)–NH₃–S(IV)–O₂ system, the kinetics of the oxidation of sulfur(IV) catalyzed by amminecopper(II) complexes has been studied in the ammonia‐buffered solutions. Sulfur(IV) is oxidized to sulfate. The complexes, Cu(NH₃)²⁺, Cu(NH₃)₂²⁺, and Cu(NH₃)²⁺₃ appear to be equally reactive and Cu(NH₃)₄²⁺ appears to be unreactive. The kinetics obey the rate law: where α₁ and γ₁ are the rate constants for O₂‐dependent and O₂‐independent pathways, respectively, for Cu(NH₃)²⁺, Cu(NH₃)²⁺₂, and Cu(N H₃)₃²⁺ complexes, which appear to be equally reactive. The values of α₁ and γ₁ were found to be (1.32 ± 0.21) × 10⁶ L² mol^?2 s^?1 (1.74 ± 0.40) × 10⁹ L³ mol^?3 s^?1respectively at 30°C. The reaction rate is not influenced by the presence of ethanol—a free radical scavenger, so a nonradical mechanism has been proposed. The results of this study are useful in understanding the atmospheric chemistry of aqueous phase autoxidation of dissolved sulfur dioxide in copper(II)–ammonia–sulfur(IV)–oxygen system at high pH. © 2011 Wiley Peiodicals, Inc. Int J Chem Kinet 43: 379–392, 2011     

Medium-ring aminocyclitols: a concise synthesis of nine-membered aminocarbasugar analogs and the solid-state supramolecular architectures of two key precursors

A stereocontrolled synthesis of nine-membered aminocarbasugar analogs (amino-cyclononanoses) from a rigid bicyclo[4.3.1]deca-2,4-dien-10-one platform, harboring a latent functionalized cyclononane ring, is described.     

Highly sensitive hydrazine chemical sensor based on mono-dispersed rapidly synthesized PEG-coated ZnS nanoparticles

Monodispersed PEG-coated ZnS (P-ZnS) nanoparticles (NPs) were synthesized by facile microwave process and utilized as efficient electron mediators for the fabrication of highly sensitive hydrazine chemical sensor. The detailed morphological and structural properties revealed the monodispersity and good crystallinity for synthesized P-ZnS NPs. A high-sensitivity of ∼89.3 μA cm⁻² μM and low limit of detection of 1.07 μM, based on S/N ratio, were obtained for the fabrication of hydrazine chemical sensor based on P-ZnS NPs. To the best of our knowledge, this is the first report which demonstrates the utilization of P-ZnS NPs for the fabrication of efficient hydrazine chemical sensor. By this work, it could be concluded that simply synthesized ZnS NPs can be used as efficient electron mediators for the fabrication of effective hydrazine chemical sensors.     

N-heterocyclic carbene catalyzed aroylation of 3,5-dichloro-2(1H)-pyrazinones

The N-heterocyclic carbene catalyzed chemoselective C3-aroylation of 3,5-dichloro-2(1H)-pyrazinones with various aldehydes is reported. We herein describe results of this remarkable mild and efficient procedure.     

Short,Convenient Preparative Procedures for 7-Isopropylidenenorbornane, 7-Isopropylidenenorbornene,and 7-Isopropylidenenorbornadiene

Short synthetic routes to the title compounds 1,–3, from readily available Diels-Alder adduct 5 of 6,6-dimethylfulvene and acrylonitrile are described.