The use of temporary tethers in the meta photocycloaddition reaction

The use of temporary tethers in facilitating meta photocycloaddition reactions between phenol and allyl alcohol derivatives has been investigated. The merits of silicon, carbonate and methylene acetal tethers were assessed, whilst considering strategies for the preparation of the natural products gymnomitrol and gelsemine. The photoadducts were epoxidised, and then subjected to acid catalysed fragmentation with concomitant cleavage of the tether. Depending on whether water or methanol was used during the fragmentation stage of the methylene tethers, the methylene group was either removed altogether or transformed into a MOM group.     

An unusual 1,2-N→C acyl migration in urea derivatives of α-aminoorganolithiums

Transmetalation of urea derivatives of α-aminoorganostannanes with alkyllithiums provides α-aminoorganolithiums which undergo rapid N to C acyl migration to afford α-aminocarboxamides. The stereochemical course of the transmetalation/migration process depends on the substituents on the urea and varies from complete retention of configuration to complete racemization.     

A novel method for automated grid generation of ice shapes for local‐flow analysis

Modelling a complex geometry, such as ice roughness, plays a key role for the computational flow analysis over rough surfaces. This paper presents two enhancement ideas in modelling roughness geometry for local flow analysis over an aerodynamic surface. The first enhancement is use of the leading‐edge region of an airfoil as a perturbation to the parabola surface. The reasons for using a parabola as the base geometry are: it resembles the airfoil leading edge in the vicinity of its apex and it allows the use of a lower apparent Reynolds number. The second enhancement makes use of the Fourier analysis for modelling complex ice roughness on the leading edge of airfoils. This method of modelling provides an analytical expression, which describes the roughness geometry and the corresponding derivatives. The factors affecting the performance of the Fourier analysis were also investigated. It was shown that the number of sine–cosine terms and the number of control points are of importance. Finally, these enhancements are incorporated into an automated grid generation method over the airfoil ice accretion surface. The validations for both enhancements demonstrate that they can improve the current capability of grid generation and computational flow field analysis around airfoils with ice roughness. Copyright © 2004 John Wiley & Sons, Ltd.     

Time resolved spectroscopic NMR imaging using hyperpolarized Xe

We have visualized the melting and dissolution processes of xenon (Xe) ice into different solvents using the methods of nuclear magnetic resonance (NMR) spectroscopy, imaging, and time resolved spectroscopic imaging by means of hyperpolarized ¹²⁹Xe. Starting from the initial condition of a hyperpolarized solid Xe layer frozen on top of an ethanol (ethanol/water) ice block we measured the Xe phase transitions as a function of time and temperature. In the pure ethanol sample, pieces of Xe ice first fall through the viscous ethanol to the bottom of the sample tube and then form a thin layer of liquid Xe/ethanol. The xenon atoms are trapped in this liquid layer up to room temperature and keep their magnetization over a time period of 11 min. In the ethanol/water mixture (80 vol%/20%), most of the polarized Xe liquid first stays on top of the ethanol/water ice block and then starts to penetrate into the pores and cracks of the ethanol/water ice block. In the final stage, nearly all the Xe polarization is in the gas phase above the liquid and trapped inside the pores. NMR spectra of homogeneous samples of pure ethanol containing thermally polarized Xe and the spectroscopic images of the melting process show that very high concentrations of hyperpolarized Xe (about half of the density of liquid Xe) can be stored or delivered in pure ethanol.     

Dynamics of capture and fusion in heavy ion collisions

The effect of entrance channel on decrease of the complete fusion cross sections and on the yield of reaction products are associated with the quasifission which depends on the mass asymmetry and shell structure of colliding nuclei. In reactions of massive projectile and target nuclei, the competition between complete fusion and quasifission appears at the stage of compound nucleus formation, in addition to the increase of the fission probability. It is shown that the yield of quasifission products may be symmetric or asymmetric in dependence on peculiarities of shell structure of reaction fragments. Marima of mass or charge distributions are connected with the peculiarities of shell structure of reaction fragments.     

The response of thermally and optically stimulated luminescence from Al2O3:C to high-energy heavy charged particles

The thermoluminescence (TL) and optically stimulated luminescence (OSL) response of Al₂O₃ dosimeters to high-energy heavy charged particles (HCP) has been studied using the heavy ion medical accelarator at Chiba, Japan. The samples were Al₂O₃ single-crystal chips, of the type usually known as TLD-500, and Luxel^TM dosimeters (Al₂O₃:C powder in plastic) from Landauer Inc. The samples were exposed to ⁴He (150 MeV/u), ¹²C (400 MeV/u), ²⁸Si (490 MeV/u) and ⁵⁶Fe (500 MeV/u) ions, with linear energy transfer values covering the range from 2.26 to 189 keV/μm in water and doses from 1 to 100 mGy (to water). A ⁹⁰Sr/⁹⁰Y beta source, calibrated against a ⁶⁰Co secondary standard, was used for calibration purposes. For OSL, we used both continuous-wave OSL measurements (CW-OSL, using green light stimulation at 525 nm) and pulsed OSL measurements (POSL, using 532 nm stimulation from a Nd:YAG Q-switched laser). The efficiencies (η_HCP,γ) of the different HCPs at producing OSL or TL were observed to depend not only upon the linear energy transfer (LET) of the HCP, but also upon the sample type (single crystal chip or Luxel^TM) and the luminescence method used to define the signal—i.e. TL, CW-OSL initial intensity, CW-OSL total area, or POSL. Observed changes in shape of the decay curve lead to potential methods for extracting LET information of unknown radiation fields. A discussion of the results is given, including the potential use of OSL from Al₂O₃ in the areas of space radiation dosimetry and radiation oncology.     

New developments in X-ray storage phosphors

We found a significant PSL effect in Eu²⁺-doped fluorozirconate glasses (ZBLAN) which were additionally doped with Br⁻ or Cl⁻ ions. The PSL is attributed to the characteristic emission of Eu²⁺ present in nano-crystallites of BaBr₂ or BaCl₂, which form in the glass upon annealing. The metastable hexagonal form of BaX₂ (X=Br,Cl) is always formed first before it is converted into the stable orthorhombic form. The particle size increases upon annealing and so does the PSL efficiency of the glass ceramic. However, there is a saturation of the PSL efficiency, which is for Br⁻ doping about 9% and for Cl⁻-doping about 80% of the Eu-doped BaFBr standard. The particle size was determined by transmission electron microscopy (TEM). The TEM results show a clear tendency for bigger particles for longer annealing at the expense of its number. The particle size for the most efficient phosphor is about 100 nm.     

New data on the ternary fission of 252Cf from the Gammasphere facility

Ternary fission of ²⁵²Cf was studied at Gammasphere using eight ΔE×E particle telescopes. Helium, beryllium, boron, and carbon light charged particles (LCPs) emitted with kinetic energy more than 9, 21, 26, and 32 MeV, respectively, were identified. The 3368-keV γ transition from the first 2⁺ excited state in ¹⁰Be was found and the population probability ratio N(2⁺)/N(0⁺) = 0.160 ± 0.025 was estimated. No evidence was found for 3368-keV γ rays emitted from a triple molecular state. For the first time, charge distributions are obtained for ternary fission fragments emitted with helium, beryllium, and carbon LCPs.