Etude de l'obtention d'enoxysilanes par action du triethylsilane sur des cetones enolisables,aliphatiques ou cyclaniques,en presence de catalyseurs au nickel

The preparion of alkoxysilanes and alkenoxysilanes has been achieved by the reaction of enolizable aliphatic or cyclic ketones with triethylsilane in the presence of nickel catalysts. For some catalysts, the reaction can be directed to give exclusively one or the other of these derivatives. The use of certain nickel catalysts gives very high yields of alkenoxysilanes, and this has been closely investigated.     

Bis phenylene flattened 13-membered tetraamide macrocyclic ligand (TAML) for square planar cobalt(III)*

Abstract

The preparation, characterization, and evaluation of a cobalt(III) complex with 13-membered tetraamide macrocyclic ligand (TAML) is described. This is a square-planar (X-ray) S = 1 paramagnetic (¹H NMR) compound, which becomes an S = 0 diamagnetic octahedral species in excess d₅-pyridine. Its one-electron oxidation at an electrode is fully reversible with the lowest E_½ value (0.66 V vs SCE) among all investigated Co^III TAML complexes. The oxidation results in a neutral blue species which is consistent with a Co^III/radical-cation ligand. The ease of oxidation is likely due to the two benzene rings incorporated in the ligand structure (whereas there is just one in many other Co^III TAMLs). The oxidized neutral species are unexpectedly EPR silent, presumably due to the π-stacking aggregation. However, they display eight-line hyperfine patterns in the presence of excess of 4-tert-butylpyridine or 4-tert-butyl isonitrile. The EPR spectra are more consistent with the Co^III/radical-cation ligand formulation rather than with a Co^IV complex. Attempts to synthesize a similar vanadium complex under the same conditions as for cobalt using [V^VO(OCHMe₂)₃] were not successful. TAML-free decavanadate was isolated instead.     

pH-gradient ion-exchange chromatography: an analytical tool for design and optimization of protein separations

This work demonstrates that a highly linear, controllable and wide-ranged pH-gradient can be generated through an ion-exchange chromatography (IEC) column. Such a pH-gradient anion-exchange chromatography was evaluated with 17 model proteins and found that acidic (pI<6) and basic (pI>8) proteins elute roughly at their pI, whereas neutral proteins (pI 6-8) elute at pH 8-9 regardless their pI values. Because of the flat nature of protein titration curves from pH approximately 6 to approximately 9, neutral proteins indeed exhibit nearly zero net charge at pH approximately 9. The elution-pH in pH-gradient IEC or the titration curve, but not the pI, was identified as the key parameter for pH optimization of preparative IEC in a fast and rational way. The pH-gradient IEC was also applied and found to be an excellent analytical tool for the fractionation of crude protein mixtures.     

Frequency shifts with age in click-evoked otoacoustic emissions of preterm infants

An anechoic wind tunnel dedicated to fan self-noise studies has been designed and constructed at the von Karman Institute The multi-chamber, mass flow driven design allows for all fan performance characteristics, aerodynamic quantities (e.g., wake turbulence measurements), and acoustic properties to be assessed in the same facility with the same conditions. The acoustic chamber performance is assessed using the optimum reference method and found to be within the ISO 3745 standards down to 150 Hz for pure tone and broadband source mechanisms. The additional influence of installation effects of an aerodynamic inlet was found to create a scattered sound field only near the source location, while still providing good anechoic results at more distant sound pressure measurement positions. It was found to have inflow properties, span-wise uniformity, and low turbulence intensity, consistent with those desired for fan self-noise studies.     

Subcritical, nontypical and period-doubling bifurcations of a delta wing in a low speed wind tunnel

Limit Cycle Oscillations (LCOs) involving Delta wings are an important area of research in modern aeroelasticity. Such phenomena can be the result of geometric or aerodynamic nonlinearity. In this paper, a flexible half-span Delta wing is tested in a low speed wind tunnel in order to investigate its dynamic response. The wing is designed to be more flexible than the models used in previous research on the subject in order to expand the airspeed range in which LCOs occur. The experiments reveal that this wing features a very rich bifurcation behavior. Three types of bifurcation are observed for the first time for such an aeroelastic system: subcritical bifurcations, period-doubling/period-halving and nontypical bifurcations. They give rise to a great variety of LCOs, even at very low angles of attack. The LCOs resulting from the nontypical bifurcation display Hopf-type behavior, i.e. having fundamental frequencies equal to one of the linear modal frequencies. All of the other LCOs have fundamental frequencies that are unrelated to the underlying linear system modes.     

Characterization and Quantification of Nanoparticle-Antibody Conjugates on Cells Using C(60) ToF SIMS in the Event-By-Event Bombardment/Detection Mode

Cluster C(60) ToF-SIMS (time-of-flight secondary ion mass spectrometry) operated in the event-by-event bombardment-detection method has been applied to: a) quantify the binding density of Au nanoparticles (AuNPs)-antiCD4 conjugates on the cell surface; b) identify the binding sites between AuNPs and antibody. Briefly, our method consists of recording the secondary ions, SIs, individually emitted from a single C(60) (1,2+) impact. From the cumulative mass spectral data we selected events where a specific SI was detected. The selected records revealed the SIs co-ejected from the nanovolume impacted by an individual C(60) with an emission area of ~ 10nm in diameter as an emission depth of 5-10 nm. The fractional coverage is obtained as the ratio of the effective number of projectile impacts on a specified sampling area (N(e)) to the total number of impacts (N(0)). In the negative ion mass spectrum, the palmitate (C(16)H(31)O(2) (-)) and oletate (C(18)H(33)O(2) (-)) fatty acid ions present signals from lipid membrane of the cells. The signals at m/z 197 (Au(-)) and 223 (AuCN(-)) originate from the AuNPs labeled antibodies (antiCD4) bound to the cell surface antigens. The characteristic amino acid ions validate the presence of antiCD4. A coincidence mass spectrum extracted with ion at m/z 223 (AuCN(-)) reveals the presence of cysteine at m/z 120, documenting the closeness of cysteine and the AuNP. Their proximity suggests that the binding site for AuNP on the antibody is the sulfur-terminal cysteine. The fractional coverage of membrane lipid was determined to be ~23% of the cell surfaces while the AuNPs was found to be ~21%. The novel method can be implemented on smaller size NPs, it should thus be applicable for studies on size dependent binding of NP-antibody conjugates.     

Optimization of the Microwave-Assisted Ortho Ester Claisen Rearrangement: Application to Monoterpenols

Two monoterpenols, perillyl alcohol and nerol, have been converted into their γ,δ-unsaturated ester derivatives following a modified process of microwave-assisted ortho ester Claisen rearrangement. The yields obtained (>90%) are better than those previously obtained. The optimized process needs less reaction time (5 min), smaller amount of reagent, and no solvent.