A study of a bluff-body combustor using laser sheet lighting

Laser sheet lighting is used to study reacting flows with and without heat release in an axisymmetric, unducted and vertically mounted bluff-body combustor. The fuel, which is seeded with titanium tetrachloride vapor, is ejected from a jet located in the center of the bluff-body. The TiCl₄ in the dry fuel reacts spontaneously with the water in the annulus air to form titanium dioxide particles. High speed movies and visual observations of vertically and horizontally located sheets of laser light provided remarkably detailed visualization (via Mie scattering) of the vortex dynamics in the near-wake region of the bluff-body.A version of this paper was presented at the ASME Winter Annual Meeting of 1984 and printed in AMD, Vol. 66     

Highly Stereoselective Synthesis of Natural‐Product‐Like Hybrids by an Organocatalytic/Multicomponent Reaction Sequence

In an endeavor to provide an efficient route to natural product hybrids, described herein is an efficient, highly stereoselective, one‐pot process comprising an organocatalytic conjugate addition of 1,3‐dicarbonyls to α,β‐unsaturated aldehydes followed by an intramolecular isocyanide‐based multicomponent reaction. This approach enables the rapid assembly of complex natural product hybrids including up to four different molecular fragments, such as hydroquinolinone, chromene, piperidine, peptide, lipid, and glycoside moieties. The strategy combines the stereocontrol of organocatalysis with the diversity‐generating character of multicomponent reactions, thus leading to structurally unique peptidomimetics integrating heterocyclic, lipidic, and sugar moieties.     

Concerted Ring Opening and Cycloaddition of Chiral Epoxy Enolsilanes with Dienes

Silyl‐triflate‐catalyzed (4+3) cycloadditions of epoxy enolsilanes with dienes provide a mild and chemoselective synthetic route to seven‐membered carbocycles. Epoxy enolsilanes containing a terminal enolsilane and a single stereocenter undergo cycloaddition with almost complete conservation of enantiomeric purity, a finding that argues against the involvement of oxyallyl cation intermediates which have been previously proposed for these types of reactions. Reported are theoretical and experimental investigations of the cycloaddition mechanism. The major enantiomers of the cycloadducts are derived from S_N2‐like reactions of the silylated epoxide with the diene, in which stereospecific ring opening and formation of the two new C? C bonds occur in a single step. Calculations predict, and experiments confirm, that the observed small losses of enantiomeric purity are traced to a triflate‐mediated double S_N2 cycloaddition pathway.     

Effect of magnesium and titanium on the cathodic behaviour of aluminium in nitric acid

Cathodic polarization of aluminium and Al–0.18 wt.% Mg and Al–0.08 wt.% Ti alloys in 0.24 mol dm^?3 nitric acid solution at 38 °C has been employed to assist understanding of the roles of alloying elements in electrograining. The findings indicate that additions of magnesium and titanium to aluminium accelerate the corrosion of the substrate under the alkalization caused by the cathodic reactions. The accelerated dissolution and the consequent formation of hydrated alumina result in a decreased net cathodic current density in potentiostatic and potentiodynamic polarization conditions relative to the behaviour of aluminium. Copyright © 2014 John Wiley & Sons, Ltd.     

Computer-aided photoelastic analysis of orthogonal 3D textile composites: Part 2. Combining least squares and finite-element methods for stress analysis

An approach combining least squares methods and finite element methods (FEM) is presented for subsequent photoelastic stress analysis of orthogonal 3D textile composites withR and α obtained in Part 1. Through this approach, these photoelastic stresses are obtained over a region of interest as if the composites were homogeneous materials. The least squares method is used for requiring the solution strain fields to best correlate with the distribution of the two photoelastic strain data of ɛ _x − ɛ _y and γ _xy calculated directly from the measuredR and α. The FEM uses the homogenized composite properties to construct the nodal force equilibrium equations as constraints in the least squares formulation. As a result of combining this least squares method and FEM with lagrange multipliers, a linear system of equations is formulated with the unknown nodal displacements. Once these nodal displacements are solved, the strains and stresses can be calculated through FEM formulations. This approach is tested with the two experimental results completed in Part 1 for the aluminum and composite plates. The stresses obtained for the aluminum plate show close agreement with those obtained with the plain FEM computation. In the case of the orthogonal 3D composite plate, the local variations as observed inR and α are already necessarily eliminated from these solved photoelastic stresses. Furthermore, these stresses also match well with those computed with the plain FEM from the homogenized composite properties.     

IR,Raman, and Surface‐enhanced Raman Spectroscopic Study on Triruthenium Dipyridylamide Diruthenium Nickel Dipyridylamide Family: Metal‐metal Bonding and Structures

We report the infrared, Raman, and surface‐enhanced Raman scattering (SERS) spectra of triruthenium dipyridylamido complexes and of diruthenium mixed nickel metal‐string complexes. From the results of analysis on the vibrational modes, we assigned their vibrational frequencies and structures. The infrared band at 323–326 cm^?1 is assigned to the Ru₃ asymmetric stretching mode for [Ru₃(dpa)₄Cl₂]^0–2+. In these complexes we observed no Raman band corresponding to the Ru₃ symmetric stretching mode although this mode is expected to have substantial Raman intensity. There is no frequency shift in the Ru₃ asymmetric stretching modes for the complexes with varied oxidational states. No splitting in Raman spectra for the pyridyl breathing line indicates similar bonding environment for both pyridyls in dpa^– , thus a delocalized structure in the [Ru₃]^6–8+ unit is proposed. For Ru₃(dpa)₄(CN)₂ complex series, we assign the infrared band at 302 cm^?1 to the Ru₃ asymmetric stretching mode and the weak Raman line at 285 cm^?1 to the Ru₃ symmetric stretching. Coordination to the strong axial ligand CN^– weakens the Ru‐Ru bonding. For the diruthenium nickel complex [Ru₂Ni(dpa)₄Cl₂]^0–1+, the diruthenium stretching mode ν_Ru‐Ru is assigned to the intense band at 327 and 333 cm^?1 in the Raman spectra for the neutral and oxidized forms, respectively. This implies a strong Ru‐Ru metal‐metal bonding.     

Non-cross-linked polystyrene-supported triphenylarsonium halides and their use in the arsa-Wittig reaction

Non-cross-linked polystyrene-supported (carbomethoxymethyl)triphenylarsonium bromide (1) and benzyltriphenylarsonium iodide (2) were synthesized. They showed similar reactivities compared with the free arsonium salts in the arsa-Wittig reaction. The use of the polymer-supported reagents facilitated product purification and rendered the organoarsenic reagents easily separable and recyclable.     

Quantitation of branched-chain amino acids in ascites by capillary electrophoresis with light-emitting diode-induced fluorescence detection

Branched-chain amino acids (BCAAs) are one of the important biomarkers for monitoring liver disease such as hepatitis or hepatoma. In this communication, we present the determination of the concentrations of BCAA in ascites by CE light-emitted diode-induced fluorescence (LEDIF) using 1.5% m/v poly(ethylene oxide) (average M(v) : ~8?000?000?g/mol) that was prepared in 10?mM sodium tetraborate solution (pH 9.3). Naphthalene-2,3-dicarboxaldehyde was used to derivatize 15 amino acids (AAs) to form naphthalene-2,3-dicarboxaldehyde (NDA)-AA derivatives prior to CE analysis. The separation of 15 NDA-AA derivatives was accomplished within 15?min, with RSD values of <5.8% (within-day) and 7.4% (between-days) with respect to their migration times. The limits of detection for the tested BCAAs ranged from 10.6 to 10.9?nM. We determined the concentrations of three BCAAs--leucine, isoleucine and valine--in ascites by applying a standard addition method, with recovery percentages ranging from 93.9 to 111%. The results obtained from this CE-LEDIF method is in good agreement with those by a gold standard method using an AA analyzer. We have found that the concentrations of the three BCAAs in ascites obtained from patients suffering from liver diseases were lower than those from healthy individuals. Our approach is highly efficient, sensitive, and cost-effective, which holds great potential for the diagnosis of liver diseases.     

Peptide-modified inverted colloidal crystal scaffolds with bone marrow stromal cells in the treatment for spinal cord injury

Carboxyl groups of surface-tethered poly(acrylic acid) (PAA) brushes should be able to serve as versatile moieties for a wide range of chemical modifications, including an attachment of bioactive species that can act as sensing probes for biosensors. In this research, poly(tert-butyl acrylate) (Pt-BA) brushes were prepared by surface-initiated atom transfer radical polymerization of tert-butyl acrylate. PAA brushes were then obtained after removal of the tert-butyl groups from the Pt-BA brushes by acid hydrolysis. The carboxyl group density of the PAA brushes can be varied as a function of chain length or molecular weight. The reactivity of the carboxyl groups of PAA brushes towards the immobilization of biotin, a frequently used model bioactive probe in biosensing applications, was evaluated. Qualitative determination of streptavidin (SA) binding to the biotin-attached PAA brushes was verified by fluorescence microscopy. The efficiency of the PAA brushes to act as a three dimensional (3D) precursor layer for biosensing applications was further demonstrated using surface plasmon resonance (SPR), where the biotin-attached PAA brushes showed an enhanced signal for the biospecific binding of SA in comparison with a self-assembled monolayer (SAM) of a carboxyl-terminated alkanethiol, used as a model two-dimensional (2D) conventional precursor layer. The PAA brushes showed very low non-specific interactions with two other tested proteins of a similar pI but different sizes. This desirable feature should be highly beneficial for the development of biosensors.