Enhanced regioselectivity of Yang photocyclization in the crystalline state

[reaction: see text] In contrast to the solution state, where Yang photocyclization of ketones of general structure 1 leads to equal amounts of cyclobutanols 2 and 3 (by abstraction of HA and HB, respectively), irradiation in the crystalline state is much more regioselective, favoring either 2 or 3 depending on the nature of the substituent X. X-ray crystallography and molecular mechanics calculations reveal the source of this remarkable solid-state regioselectivity.     

Investigation of ultrafast laser-driven radiative blast waves

We have examined the evolution of cylindrically symmetric blast waves produced by the deposition of femtosecond laser pulses in gas jets. In high- Z gases radiative effects become important. We observe the production of an ionization precursor ahead of the shock front and deceleration parameters below the adiabatic value of 1/2 (for a cylinder), an effect expected when the blast wave loses energy by radiative cooling. Despite significant radiative cooling, the blast waves do not appear to develop thin shell instabilities expected for strongly radiative waves. This is believed to be due to the stabilizing effect of a relatively thick blast wave shell resulting in part from electron thermal conduction effects.     

Phase Separation and Organisation of Colloidal Spheres Suspended in Sheared Lyotropic Liquid‐Crystalline Polymers

Summary: Organisation behaviours of spherical particles suspended in sheared, lyotropic, liquid‐crystalline polymer solutions have been investigated using polarizing optical microscopy. We find that in a nematic phase the particles phase separate and adopt anisotropic chain‐like structures along the director. An earring defect is observed around a single particle whereas a cross or strings defect between neighbouring particles is found to serve as a repulsive barrier to prevent the particles from contacting each other. A theoretical analysis is presented to explain this new phenomenon.

An optical micrograph of 0.01 wt.‐% glass spheres suspended in a nematic solution of 40 wt.‐% ethyl cellulose in chloroform under an external shear force.     

The bis(η-cyclopentadienyl)titanium(IV) – salicylate system revisited and the characterisation of two 3,5-di-t-butylsalicylate analogues. The molecular structure of [Cp2Ti(sal)], (sal = O2CC6H4O2−)

The Cp₂Ti^IV – salicylate system has been re-examined and procedures for the syntheses of [Cp₂Ti(salH)₂] and [Cp₂Ti(sal)] explored, [salH = (O₂CC₆H₄OH-2)^–; sal = (O₂CC₆H₄O-2)^2–]. The new 3,5-di-t-butylsalicylate analogues have been prepared and characterised. An X-ray structure determination of [Cp₂Ti(sal)] confirms the chelating nature of the sal ligand which is bonded to the metal through the phenolic and one of the carboxylate oxygen atoms.     

High accuracy non-contact ultrasonic thickness gauging of aluminium sheet using electromagnetic acoustic transducers.

Aluminium sheet thickness has been calculated from ultrasonic data obtained using a send-receive, radially polarised electromagnetic acoustic transducer (EMAT). Sheets in the thickness range between 0.1 and 0.5 mm have been measured using this non-contact approach at a stand-off of up to 1.5 mm. Normal incidence shear waves generated and detected in the sheet and the resultant waveforms have been processed using transit time measurements and Fourier analysis. Two broad band EMAT systems have been used to perform the measurements with centre frequencies of approximately 5 MHz and frequency content up to 10 and 20 MHz respectively. The most accurate measurements of thickness on thin sheets have been made using Fourier analysis and have yielded measurements accurate to within 0.2% (or 0.4 microm) for 280 microm thick aluminium sheets. Discrete shear wave echoes can be observed for sheets down to a thickness of 250 microm using the higher frequency EMAT system. However temporal measurements of these signals yield lower accuracy results when compared to the Fourier analysis method which is capable of sub-micron accuracy.     

FT‐Raman spectroscopy of pigments on a Hindu statue,Kali Walking on Siva

FT‐Raman spectroscopic analysis of eight pigmented specimens from an important Hindu statue group, Kali Walking on Siva, acquired in 1895 but of indeterminate age and now in the Horniman Museum, London, has revealed some interesting and unusual combinations of coloured pigments including cinnabar, minium, lapis lazuli and red ochre. Several specimens showed evidence of organic additives, which have been attributed to shellac resins commonly believed to have been used on this type of statuary. The Raman spectroscopic results confirm that the predominant black pigment on the Kali figure is lamp black or soot, in contrast to the SEM‐EDX data that suggests the origin of this pigment as from bone black or ivory black from the presence of phosphorus. An eclectic range of white pigments have been identified in this group including lead white, barytes, calcite and anhydrite; rutile and anatase found on one specimen on the jackal in this group have been ascribed to recent unrecorded restoration. Copyright © 2006 John Wiley & Sons, Ltd.     

Monodomain Liquid Crystal Main Chain Elastomers by Photocrosslinking

A new synthetic strategy for the preparation of macroscopically oriented smectic main chain liquid crystal elastomers (MC‐LCE) by the photocrosslinking of laterally functionalized polyesters is presented. X‐ray measurements proved the formation of the monodomain and allowed a quantitative determination of the order parameter. The thermo‐actuation of our material at the phase transition from the liquid‐crystalline to the isotropic phase was demonstrated by temperature dependent measurements of the sample length, showing a fully reversible shape change of ≈40%. Mechanical measurements showed that the sample can be stretched by up to 60% along the smectic layer normal without any reorientation of the structure, in contrast to earlier experiments and theoretical predictions. The results are discussed in the context of limited smectic layer correlation in different types of smectic materials.

     

Numerical study of dispersing pollutant clouds in a built-up environment

In this paper, we study numerically the dispersion of a passive scalar released from an instantaneous point source in a built-up (urban) environment using a Reynolds-averaged Navier–Stokes method. A nonlinear k–? turbulence model [Speziale, C.G., 1987. On nonlinear k–l and k–? models of turbulence. J. Fluid Mech., 178, 459–475] was used for the closure of the mean momentum equations. A tensor diffusivity model [Yoshizawa, A., 1985. Statistical analysis of the anisotropy of scalar diffusion in turbulent shear flows. Phys. Fluids, 28, 3226–3231] was used for closure of the scalar transport equations. The concentration variance was also calculated from its transport equation, for which new values of Yoshizawa’s closure coefficients are used, in order to account for the instantaneous tracer release and the complex geometry. A new dissipation length-scale model, required for the modelling of the dissipation rate of concentration variance, is also proposed. The numerical results for the flow, the pollutant concentration and the concentration variance, are compared with experimental data. This data was obtained from a water-channel simulation of a full-scale field experiment of tracer dispersion through a large array of building-like obstacles known as the Mock Urban Setting Trial (MUST).