Aircraft T-tail flutter predictions using computational fluid dynamics

The paper presents the application of computational aeroelasticity (CA) methods to the analysis of a T-tail stability in transonic regime. For this flow condition unsteady aerodynamics show a significant dependency from the aircraft equilibrium flight configuration, which rules both the position of shock waves in the flow field and the load distribution on the horizontal tail plane. Both these elements have an influence on the aerodynamic forces, and so on the aeroelastic stability of the system. The numerical procedure proposed allows to investigate flutter stability for a free-flying aircraft, iterating until convergence the following sequence of sub-problems: search for the trimmed condition for the deformable aircraft; linearize the system about the stated equilibrium point; predict the aeroelastic stability boundaries using the inferred linear model. An innovative approach based on sliding meshes allows to represent the changes of the computational fluid domain due to the motion of control surfaces used to trim the aircraft. To highlight the importance of keeping the linear model always aligned to the trim condition, and at the same time the capabilities of the computational fluid dynamics approach, the method is applied to a real aircraft with a T-tail configuration: the P180.     

Investigation of Jet-Flame Blowout with Lean-Limit Considerations

The current study utilizes digital image sequences of flames to better understand the blowout phenomenon. Methane flames are studied near blowout conditions to determine if the disappearance of the diffusion flame prior to extinguishment signifies the leading edge of the reaction zone reaching the lean-limit. Various concentrations of nitrogen are used to dilute methane flames. The axial position of the flames is compared with the calculated position of the lean flammability limit to determine the role of the diffusion flame. The blowout limits of these flames are established and a blowout parameter is empirically determined from the data. Results from flames in co-flow show agreement with the blowout parameter previously published; however, the analysis shows that, the disappearance of the bulk diffusive reaction zone occurs at the lean flammability limit and is an accurate predictor of blowout for diluted and non-diluted methane flames.     

Headspace sampling with in situ carbodiimide-mediated derivatization for the determination of ibuprofen in water samples

A method using headspace generation and in situ derivatization with water soluble EDC (1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide) and TFEA (2,2,2-trifluoroethylamine) has been optimized for the determination of ibuprofen (2-(p-isobutylphenyl)propionic acid), one of the most common non-steroid anti-inflammatory drug (NSAIDs) residues in surface and wastewater samples. Derivatization was carried out in the vial of the headspace sampler (HS) in only 15 min, after which instrumental measurements were made with gas chromatography-mass spectrometry (GC-MS). As the injection system, a programmed temperature vaporizer (PTV) in the solvent-vent injection mode is proposed in order to increase the sensitivity of the measurements. The effects of the variables affecting HS generation, the derivatization reaction, and the instrumental PTV conditions were studied. A limit of quantification as low as 32 ng/L was achieved, and repeatability values were below 10%. Accuracy of the method was evaluated using spiked ultrapure water at three concentration levels, obtaining apparent recoveries between 96% and 104%. The proposed method was applied to the quantification of ibuprofen in sea water and urban wastewater samples.     

Enantioselective synthesis of tetrahydroprotoberberines and bisbenzylisoquinoline alkaloids from a deprotonated α-aminonitrile

Under controlled conditions, 6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline-1-carbonitrile can be quantitatively deprotonated in the α-position. Its alkylation directly furnishes 3,4-dihydroisoquinolines which can serve as starting materials for the preparation of various alkaloids. Here, the preparation of the benzylisoquinolines (+)-laudanidine, (+)-armepavine, and (+)-laudanosine as well as the tetrahydroprotoberberines (-)-corytenchine and (-)-tetrahydropseudoepiberberine using Noyori's asymmetric transfer hydrogenation are described. The dimeric alkaloids (+)-O-methylthalibrine and (+)-tetramethylmagnolamine were obtained from nonracemic precursors in Ullmann diaryl ether syntheses.     

Reduction of benzylidene dibenzo[a,d]cycloheptenes: over-reduction of antiaromatic dianions to aromatic tetraanions

The antiaromaticity of a series of dianions of p-substituted benzylidene dibenzo[a,d]cycloheptenes was examined through calculated measures of antiaromaticity. The nucleus-independent chemical shifts (NICS) and magnetic susceptibility exaltation both showed substantial antiaromatic character in the benzannulated tropylium anion. When the antiaromaticity was normalized for the area of the ring, these tropylium anions were shown to be among the most antiaromatic anions in the chemical literature. Attempts to make the dianion through reduction with lithium or potassium gave the tetraanion as the only species observable in the (1)H NMR spectrum. Quench of the reaction mixture with trimethylsilyl chloride or D(2)O confirmed the presence of the tetraanion, but only as a small portion of the reaction mixture, with the major product being unreacted starting material. The failure to observe starting material was attributed to similarities in the structures of the starting material and anion radical (first reduction), allowing rapid electron transfer between them. The inability to see the dianion (second reduction) could be the result of the very small HOMO-LUMO gap anticipated for highly antiaromatic species, which would allow access to diradical species. The magnitude of the HOMO-LUMO gap was determined by the difference between the HOMO and LUMO energies from geometry optimization and the lowest energy transition from TD-DFT calculations. The HOMO-LUMO gap for the benzylidene dibenzocycloheptatriene dianions was shown to be much smaller than the HOMO-LUMO gap of species for which (1)H NMR spectra had been observed.     

Lithiation of diynyl-ruthenium complexes: Routes to novel metallated functional diynes

Conditions for the efficient lithiation of the diynyl group in complexes Ru(CCCCH)(PP)Cp′ [(PP)Cp′ = (dppe)Cp* 1, (PPh₃)₂Cp 2] have been investigated. Addition of two equiv. LiBu to the diynyl complexes in thf solution at −78°C effects rapid conversion to putative Ru(CCCCLi)(PP)Cp′. Assays using subsequent reactions with either SiClMe₃ or AuCl(PPh₃) indicate that up to 80% conversion can be achieved. Reactions of the lithiated species with organic electrophiles [MeI, MeC(O)Cl, PhC(O)Cl, ClC(O)OMe, PhCHO, Ph₂CO] and metal-containing substrates [MClPh₃ (M = Ge, Sn), trans-RhCl(CO)(PPh₃)₂, cis-PtCl₂(PPh₃)₂, CuCl(PPh₃), (AuCl)₂(μ-dppm)] proceed to give functionalised diynyl complexes or bimetallic derivatives which are accessible only with difficulty or not at all from the parent diynes. Single-crystal X-ray diffraction molecular structures of Ru(CCCCR)(dppe)Cp* (R = Me, GePh₃) are reported: there is significantly greater delocalisation along the Ru-C₄-R chain in the GePh₃ derivative.     

Arbitrary Lagrangian Eulerian formulation for two-dimensional flows using dynamic meshes with edge swapping

The dynamic modification of the computational grid due to element displacement, deformation and edge swapping is described here in terms of suitably-defined continuous (in time) alterations of the geometry of the elements of the dual mesh. This new interpretation allows one to describe all mesh modifications within the arbitrary Lagrangian Eulerian framework, thus removing the need to interpolate the solution across computational meshes with different connectivity. The resulting scheme is by construction conservative and it is applied here to the solution of the Euler equations for compressible flows in two spatial dimensions. Preliminary two dimensional numerical simulations are presented to demonstrate the soundness of the approach. Numerical experiments show that this method allows for large time steps without causing element invalidation or tangling and at the same time guarantees high quality of the mesh elements without resorting to global re-meshing techniques, resulting in a very efficient solver for the analysis of e.g. fluid-structure interaction problems, even for those cases that require large mesh deformations or changes in the domain topology.     

Linking Preservice Teachers' Mathematics Self‐Efficacy and Mathematics Teaching Efficacy to Their Mathematical Performance

This study examined preservice teachers' mathematics self‐efficacy and mathematics teaching efficacy and compared them to their mathematical performance. Participants included 89 early childhood preservice teachers at a Midwestern university. Instruments included the Mathematics Self‐Efficacy Scale (MSES), Mathematics Teaching Efficacy Beliefs Instrument (MTEBI), and the Illinois Certification Testing System (ICTS) Basic Skills Test. The results indicate that preservice teachers' mathematics self‐efficacy is positively correlated to their personal mathematics teaching efficacy. In addition, their mathematical performance is related to their mathematics self‐efficacy and mathematics teaching efficacy. In regard to affecting student outcomes, only those preservice teachers who are very confident in their ability to teach believe they can have an effect on their students. Implications on teacher education programs are discussed.     

On the Union of Cylinders in Three Dimensions

We show that the combinatorial complexity of the union of n infinite cylinders in ℝ³, having arbitrary radii, is O(n ^2+ε ), for any ε>0; the bound is almost tight in the worst case, thus settling a conjecture of Agarwal and Sharir (Discrete Comput. Geom. 24:645–685, 2000), who established a nearly-quadratic bound for the restricted case of nearly congruent cylinders. Our result extends, in a significant way, the result of Agarwal and Sharir (Discrete Comput. Geom. 24:645–685, 2000), in particular, a simple specialization of our analysis to the case of nearly congruent cylinders yields a nearly-quadratic bound on the complexity of the union in that case, thus significantly simplifying the analysis in Agarwal and Sharir (Discrete Comput. Geom. 24:645–685, 2000). Finally, we extend our technique to the case of “cigars” of arbitrary radii (that is, Minkowski sums of line-segments and balls) and show that the combinatorial complexity of the union in this case is nearly-quadratic as well. This problem has been studied in Agarwal and Sharir (Discrete Comput. Geom. 24:645–685, 2000) for the restricted case where all cigars have (nearly) equal radii. Based on our new approach, the proof follows almost verbatim from the analysis for infinite cylinders and is significantly simpler than the proof presented in Agarwal and Sharir (Discrete Comput. Geom. 24:645–685, 2000).     

Efficient photovoltaic current generation at ferroelectric domain walls

We elucidate the mechanism of a newly observed photovoltaic effect which occurs in ferroelectrics with periodic domain structures. Under sufficiently strong illumination, domain walls function as nanoscale generators of the photovoltaic current. The steps in the electrostatic potential function to accumulate electrons and holes on opposite sides of the walls while locally reducing the concentration of the oppositely charged carriers. As a result, the recombination rate adjacent to the walls is reduced, leading to a net diffusion current. In open circuit, photovoltages for periodically ordered domain walls are additive and voltages much larger than the band gap can be generated. The internal quantum efficiency for individual domain walls can be surprisingly high, approaching 10% for above band-gap photons. Although we have found the effect in BiFeO(3) films, it should occur in any system with a similar periodic potential.