Buffeting in transonic flow prediction using time‐dependent turbulence model

In transonic flow conditions, the shock wave/turbulent boundary layer interaction and flow separations on wing upper surface induce flow instabilities, ‘buffet’, and then the buffeting (structure vibrations). This phenomenon can greatly influence the aerodynamic performance. These flow excitations are self‐sustained and lead to a surface effort due to pressure fluctuations. They can produce enough energy to excite the structure. The objective of the present work is to predict this unsteady phenomenon correctly by using unsteady Navier–Stokes‐averaged equations with a time‐dependent turbulence model based on the suitable (k–ε) turbulent eddy viscosity model. The model used is based on the turbulent viscosity concept where the turbulent viscosity coefficient (Cμ) is related to local deformation and rotation rates. To validate this model, flow over a flat plate at Mach number of 0.6 is first computed, then the flow around a NACA0012 airfoil. The comparison with the analytical and experimental results shows a good agreement. The ONERA OAT15A transonic airfoil was chosen to describe buffeting phenomena. Numerical simulations are done by using a Navier–Stokes SUPG (streamline upwind Petrov–Galerkin) finite‐element solver. Computational results show the ability of the present model to predict physical phenomena of the flow oscillations. The unsteady shock wave/boundary layer interaction is described. Copyright © 2005 John Wiley & Sons, Ltd.     

Interference of transverse rings in multifilamentation of powerful femtosecond laser pulses in air

We observe multiple filaments and interference of their ring structures in the propagation of 14 mJ, 45 fs infrared laser pulse in air. We suggest a simple physical model describing the formation and the interference of rings as the result of superposition of the background field of the whole beam and the fields that diverge from the filaments due to the defocusing in the laser-produced plasma. The size and the number of maxima in the interference pattern depend on the position of the filament formation along the direction of propagation. The simulated picture of the ring structure interference is in qualitative agreement with the one obtained from the experiment.     

Density functional study of methyl chemisorption on polycyclic aromatic hydrocarbons.

The reactions of methyl radicals with large (up to C(96)H(24)) polycyclic aromatic hydrocarbons (PAHs) are studied by density functional calculations to shed light on the experimentally observed deposition of carbon on highly oriented pyrolytic graphite (HOPG), which occurs when hot HOPG (decorated by nanometre-sized defects) is exposed to methyl radicals. The equilibrium structures of the reaction products, together with transition structures for PAHs up to the size of phenanthroperylene, are determined using the density functionals B3LYP, TPSSh, BP86 and TPSS. The structures are analysed by computing the pi orbital axis vector (POAV) and the altitude of the reactive carbon above the molecular plane of the PAH. The strongest C-CH(3) bonds are found at the edges of the PAHs, where the s character of the C orbital involved in the bond is roughly 25 % (sp(3) hybrid orbital). Carbon atoms inside the PAH form bonds with the methyl radical through atomic orbitals with about 16 % s character in the POAV analysis. These bonds are much weaker than those at the edges of the PAH, while the reactive carbon has moved about 40 pm above the molecular plane. At the edges, the PAH carbon atoms do not leave the molecular plane to this extent. The computed barrier heights and geometrical parameters of the transition structures are in agreement with Hammond's postulate, and the relative energies of all of the equilibrium structures can be rationalized by Hückel molecular orbital (HMO) theory.     

Continuous-wave and femtosecond laser operation of Yb:CaGdAlO4 under high-power diode pumping

We demonstrate the generation of 68 fs secant hyperbolic pulses at a 105 MHz repetition rate with an average power of 520 mW from a diode-pumped Yb(3+):CaGdAlO(4) mode-locked laser. A semiconductor saturable absorber allows passive mode locking, and a 15 W diode laser is used to pump directly the crystal. To our knowledge this represents the highest average power ever obtained for a sub-100 fs diode-pumped Yb-bulk laser.     

A Highly Effective Ruthenium System for the Catalyzed Dehydrogenative Cyclization of Amine–Boranes to Cyclic Boranes under Mild Conditions

We recently disclosed a new ruthenium‐catalyzed dehydrogenative cyclization process (CDC) of diamine–monoboranes leading to cyclic diaminoboranes. In the present study, the CDC reaction has been successfully extended to a larger number of diamine–monoboranes ( 4 – 7 ) and to one amine–borane alcohol precursor ( 8 ). The corresponding NB(H)N‐ and NB(H)O‐containing cyclic diaminoboranes ( 12 – 15 ) and oxazaborolidine ( 16 ) were obtained in good to high yields. Multiple substitution patterns on the starting amine–borane substrates were evaluated and the reaction was also performed with chiral substrates. Efforts have been spent to understand the mechanism of the ruthenium CDC process. In addition to a computational approach, a strategy enabling the kinetic discrimination on successive events of the catalytic process leading to the formation of the NB(H)N linkage was performed on the six‐carbon chain diamine–monoborane 21 and completed with a ¹⁵N NMR study. The long‐life bis‐σ‐borane ruthenium intermediate 23 possessing a reactive NHMe ending was characterized in situ and proved to catalyze the dehydrogenative cyclization of 1 , ascertaining that bis σ‐borane ruthenium complexes are key intermediates in the CDC process.     

From the N‐Heterocyclic Carbene‐Catalyzed Conjugate Addition of Alcohols to the Controlled Polymerization of (Meth)acrylates

Among various N‐heterocyclic carbenes (NHCs) tested, only 1,3‐bis(tert‐butyl)imidazol‐2‐ylidene (NHC^tBu) proved to selectively promote the catalytic conjugate addition of alcohols onto (meth)acrylate substrates. This rather rare example of NHC‐catalyzed 1,4‐addition of alcohols was investigated as a simple means to trigger the polymerization of both methyl methacrylate and methyl acrylate (MMA and MA, respectively). Well‐defined α‐alkoxy poly(methyl (meth)acrylate) (PM(M)A) chains, the molar masses of which could be controlled by the initial [(meth)acrylate]₀/[ROH]₀ molar ratio, were ultimately obtained in N,N‐dimethylformamide at 25 °C. A hydroxyl‐terminated poly(ethylene oxide) (PEO‐OH) macro‐initiator was also employed to directly access PEO‐b‐PMMA amphiphilic block copolymers. Investigations into the reaction mechanism by DFT calculations revealed the occurrence of two competitive concerted pathways, involving either the activation of the alcohol or that of the monomer by NHC^tBu.     

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.     

Water-dispersible sugar-coated iron oxide nanoparticles. An evaluation of their relaxometric and magnetic hyperthermia properties

Synthesis of functionalized magnetic nanoparticles (NPs) for biomedical applications represents a current challenge. In this paper we present the synthesis and characterization of water-dispersible sugar-coated iron oxide NPs specifically designed as magnetic fluid hyperthermia heat mediators and negative contrast agents for magnetic resonance imaging. In particular, the influence of the inorganic core size was investigated. To this end, iron oxide NPs with average size in the range of 4-35 nm were prepared by thermal decomposition of molecular precursors and then coated with organic ligands bearing a phosphonate group on one side and rhamnose, mannose, or ribose moieties on the other side. In this way a strong anchorage of the organic ligand on the inorganic surface was simply realized by ligand exchange, due to covalent bonding between the Fe(3+) atom and the phosphonate group. These synthesized nanoobjects can be fully dispersed in water forming colloids that are stable over very long periods. Mannose, ribose, and rhamnose were chosen to test the versatility of the method and also because these carbohydrates, in particular rhamnose, which is a substrate of skin lectin, confer targeting properties to the nanosystems. The magnetic, hyperthermal, and relaxometric properties of all the synthesized samples were investigated. Iron oxide NPs of ca. 16-18 nm were found to represent an efficient bifunctional targeting system for theranostic applications, as they have very good transverse relaxivity (three times larger than the best currently available commercial products) and large heat release upon application of radio frequency (RF) electromagnetic radiation with amplitude and frequency close to the human tolerance limit. The results have been rationalized on the basis of the magnetic properties of the investigated samples.     

Purification and structure elucidation of three naturally bioactive molecules from the new terrestrial Streptomyces sp. TN17 strain

Thirty litres of fermentation broth was extracted from the newly isolated Streptomyces sp. strain TN17 and various separation and purification steps led to the isolation of three pure bioactive compounds (1-3). Compound 1: cyclo (L-Leu-L-Arg), a diketopiperazine 'DKP' derivative; 2: di-(2-ethylhexyl) phthalate, a phthalate derivative; and 3: cyclo 1-[2-(cyclopentanecarbonyl-3-phenyl-propionyl]-pyrrolidine-2-carboxylic acid (1-carbamoyl-propyl)-amide, a cyclic tetrapeptide derivative. The chemical structure of these three active compounds was established on the basis of spectroscopic studies (MS and NMR) and by comparison with data from the literature. According to our biological studies, the pure compounds (1-3) possess antibacterial and antifungal activities.     

The total synthesis of the crinine alkaloid hamayne via a Pd[0]-catalyzed intramolecular alder-ene reaction

The racemic form of the title alkaloid, 1, has been prepared in 13 steps from the ring-fused gem-dibromocyclopropane 7. Key transformations include the thermally induced electrocyclic ring-opening of compound 7, the Pd[0]-catalyzed intramolecular Alder-ene (IMAE) reaction of the derived sulfonamide (±)-12, and the conversion of the ensuing C-3a-arylhexahydroindole (±)-16 into (±)-hamayne via a Pictet-Spengler reaction.