Interrupted Imino‐Nazarov Cyclization of 1‐Aminopentadienyl Cation and Related Cascade Process

Facile 4π conrotatory imino‐Nazarov cyclization of a 1‐aminopentadienyl cation generated from condensation an aldehyde and secondary aniline in the presence of a catalytic amount of a Lewis acid has been developed. Silver(I)‐catalyzed intramolecular arene trapping of the resulting cyclic oxyallyl cation leads to formation of tricyclic indoline‐fused cyclopentanone. The use of lanthanide salts allows transformation after the initial trapping to afford tetrahydroquinoline‐fused cyclopentenone in a concise manner.     

Shear‐induced structuring kinetics in thermoplastic segmented polyurethanes monitored by rheological tools

Thermoplastic segmented polyurethanes (TPUs) are an important class of thermoplastic elastomers with a two‐phase microstructure arising from the thermodynamic incompatibility between hard (HSs) and soft segments. This microphase separation observed on cooling from a homogeneous state is often combined with the solidification of either or both types of segments. In this study, the structuring mechanism of two TPUs with HSs based on 4,4′‐diphenylmethane diisocyanate and 1,4‐butanediol was investigated from rheological measurements. Hence, in addition to the structuring temperature influence, the effect of an applied preshear flow in the melt polymer was analyzed, in particular. The results clearly show an enhancement of the solidification kinetics by the preshear. Indeed, the measured structuring time can be reduced by more than 1 decade. Rheo‐optical microscopy observations coupled with a shearing hot stage corroborated these results and showed the modification of the microstructure by the shear. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 190–201, 2010     

The low-frequency reflection and scattering of the S0 Lamb mode from a circular through-thickness hole in a plate: Finite Element,analytical and experimental studies

A study of the interaction of the S0 Lamb wave with a circular through-thickness hole in a plate is presented. The study is limited to the nondispersive frequency range of this wave, in which the distributions of stress and displacement are simple. This allows a Finite Element analysis to be undertaken using a two-dimensional membrane discretization. Predictions of the direct reflection of the S0 mode and the lateral scattering of the SH0 mode are made for a range of diameters of the hole. At the same time, an analytical solution based on modal superposition is developed, and this is also used to predict the reflection and scattering coefficients. Both sets of predictions are validated by experimental measurements. It is found that the trends of the reflection coefficients for different hole diameters, frequencies and distances from the hole satisfy a simple normalization. On a detailed scale, the functions exhibit undulations which are shown to result from the interference of the direct reflection with secondary reflections which arrive slightly later.     

Ultrasonic interferometry for the measurement of shear velocity and attenuation in viscoelastic solids

A method for the measurement of the shear properties of solid viscoelastic materials is presented. The viscoelastic material is cut into a cylindrical sample which is clamped between two rods. The transmission and reflection coefficient spectra of the fundamental torsional mode through the sample are measured by means of two pairs of piezoelectric transducers placed at the free ends of the rod-sample-rod system. Such spectra exhibit maxima and minima which occur approximately at the resonance frequencies of the free viscoelastic cylinder. Therefore, the shear velocity can be obtained by measuring the frequency interval between two consecutive maxima or minima. The shear attenuation is derived by best fitting the analytical expression of the reflection and transmission coefficients to the experimental spectra. The test is very quick to set up as the sample is simply clamped between the two rods.     

A remarkable [2.2.2]propellane

To explore the effects of fluorine substitution on the highly strained [2.2.2]propellane skeleton, a new representative of this ring system, perfluorotricyclo[2.2.2.01,4]octan-2-one ethylene ketal, was prepared by a rapid and quantitative [2+2] cycloaddition to the strained alkene perfluorobicyclo[2.2.0]hex-1(4)-ene. The propellane displays impressive thermal stability, and the vulnerable C-C bond joining the bridgeheads is very resistant to attack by electrophilic reagents. On the other hand, that electron-deficient bond is cleaved quickly at room temperature by a variety of nucleophiles and mild reducing agents. The behavior of this compound contrasts dramatically with that of the only known [2.2.2]propellane lacking fluorine substituents.     

Über binäre trilineare Formen

Ohne Zusammenfassung     

Oxidative dehydrogenation of propane under steady-state and transient regimes over alumina-supported catalysts prepared from mixed V_2W_4O_（19）~（4-） hexametalate precursors

An integrated approach combining the development of an innovative catalyst and the research of a set of adequate operating conditions for the propane oxidative dehydrogenation (ODH) is described. The experimental set-up, specially designed for steady-state and transient studies is presented. The preparation method, the characterization and the performances in steady-state and transient regimes of catalysts based on V_2W_4O_(19)~(4-) Lindqvist isopolyanion used as a precursor and supported on alumina are reported. The influence of the preparation method of the catalyst and the role of water in the feed gas are more particularly discussed.     

Trends in aircraft noise annoyance: the role of study and sample characteristics

Recently, it has been suggested that the annoyance of residents at a given aircraft noise exposure level increases over the years. The objective of the present study was to verify the hypothesized trend and to identify its possible causes. To this end, the large database used to establish earlier exposure-response relationships on aircraft noise was updated with original data from several recent surveys, yielding a database with data from 34 separate airports. Multilevel grouped regression was used to determine the annoyance response per airport, after which meta-regression was used to investigate whether study characteristics could explain the heterogeneity in annoyance response between airports. A significant increase over the years was observed in annoyance at a given level of aircraft noise exposure. Furthermore, the type of annoyance scale, the type of contact, and the response percentage were found to be sources of heterogeneity. Of these, only the scale factor could statistically account for the trend, although other findings rule it out as a satisfactory explanation. No evidence was found for increased self-reported noise sensitivity. The results are of importance to the applicability of current exposure-annoyance relationships for aircraft noise and provide a basis for decisions on whether these need to be updated.     

Chemical Evolution of a Bacterial Proteome

We have changed the amino acid set of the genetic code of Escherichia coli by evolving cultures capable of growing on the synthetic noncanonical amino acid L ‐β‐(thieno[3,2‐b]pyrrolyl)alanine ([3,2]Tpa) as a sole surrogate for the canonical amino acid L ‐tryptophan (Trp). A long‐term cultivation experiment in defined synthetic media resulted in the evolution of cells capable of surviving Trp→[3,2]Tpa substitutions in their proteomes in response to the 20 899 TGG codons of the E. coli W3110 genome. These evolved bacteria with new‐to‐nature amino acid composition showed robust growth in the complete absence of Trp. Our experimental results illustrate an approach for the evolution of synthetic cells with alternative biochemical building blocks.