An approach to triquinane synthesis using the Pauson-Khand reaction

Tricyclic skeletons have been generated from acyclic enyne precursors by using an intramolecular Pauson-Khand reaction in combination with aldol, Michael and alkylation reactions.     

A Language for Teaching Discrete-event Simulation

Courses which teach discrete-event simulation are based on many different simulation languages. The requirements for a language to support teaching simulation are discussed. In particular, it is recommended that such languages separate into distinct modules those aspects of simulation which are taught as separate topics. Implementation of the separation is discussed. The SEESIM language, developed as a teaching aid, is described, and examples of its use are given. Straightforward use of SEESIM can be learned quickly, yet the language provides facilities for a staged introduction to advanced concepts of simulation.     

On Congruence of Complex Matrices

For each of a standard set of normal forms for (n × n) complex matrices under the relation of congruence, explicit matrices are exhibited which transform, via congruence, the normal form to its transpose.     

Reduction of Entrained Hydroxy Species in Ormosil Films for Integrated Optics

Organically modified silicates (ormosils) have been viewed as possible materials for optical signal processing devices for communications networks. One significant problem obstructing their use in this application is the absorption of infrared light by hydroxy species (present for example in silanol groups (SiOH) and water) around the communications wavelengths (1310 and 1550 nm). We have investigated several ormosil compositions, synthesised via an aqueous sol-gel method, to determine if residual hydroxy groups can be removed more effectively via reducing the connectivity of the material by increasing the number of organic groups (such as Si—CH₃). Furthermore, we have investigated the effect of different inert atmospheres on the drying process. It was found that reducing the connectivity does promote the removal of hydroxy absorption, mainly via the condensation of residual silanol groups, but also by removal of residual water, depending on the other precursors in the system. It was also found that the drying atmosphere used (nitrogen or helium) had no effect on the drying process.     

Electron energy loss spectroscopy; history and related matters

This paper begins with some historical remarks regarding the author’s early interest in the use of electron energy loss spectroscopy to probe dynamical phenomena on crystal surfaces. We then discuss the physical nature of the interactions responsible for vibrational and spin waves losses, with attention to their role in related phenomena. PACS 61.14.-x; 68.35.Ja; 68.49.Jk; 68.49.Uv     

Characterisation of the photocatalyst Pilkington Activ™: a reference film photocatalyst?

Pilkington Glass Activ™ represents a possible suitable successor to P25 TiO₂, especially as a benchmark photocatalyst film for comparing other photocatalyst or PSH self-cleaning films. Activ™ is a glass product with a clear, colourless, effectively invisible, photocatalytic coating of titania that also exhibits PSH. Although not as active as a film of P25 TiO₂, Activ™ vastly superior mechanical stability, very reproducible activity and widespread commercial availability makes it highly attractive as a reference photocatalytic film. The photocatalytic and photo-induced superhydrophilitic (PSH) properties of Activ™ are studied in some detail and the results reported. Thus, the kinetics of stearic acid destruction (a 10⁴ electron process) are zero order over the stearic acid range 4–129 monolayers and exhibit formal quantum efficiencies (FQE) of 0.7×10⁻⁵ and 10.2×10⁻⁵ molecules per photon when irradiated with light of 365±20 and 254 nm, respectively; the latter appears also to be the quantum yield for Activ™ at 254 nm. The kinetics of stearic acid destruction exhibit Langmuir–Hinshelwood-like saturation type kinetics as a function of oxygen partial pressure, with no destruction occurring in the absence of oxygen and the rate of destruction appearing the same in air and oxygen atmospheres. Further kinetic work revealed a Langmuir adsorption type constant for oxygen of 0.45±0.16 kPa⁻¹ and an activation energy of 19±1 kJ mol⁻¹. A study of the PSH properties of Activ™ reveals a high water contact angle (67°) before ultra-bandgap irradiation reduced to 0° after prolonged irradiation. The kinetics of PSH are similar to those reported by others for sol–gel films using a low level of UV light. The kinetics of contact angle recovery in the dark appear monophasic and different to the biphasic kinetics reported recently by others for sol–gel films [J. Phys. Chem. B 107 (2003) 1028]. Overall, Activ™ appears a very suitable reference material for semiconductor film photocatalysis.     

Optimized prefactored compact schemes

The numerical simulation of aeroacoustic phenomena requires high-order accurate numerical schemes with low dispersion and dissipation errors. In this paper we describe a strategy for developing high-order accurate prefactored compact schemes, requiring very small stencil support. These schemes require fewer boundary stencils and offer simpler boundary condition implementation than existing compact schemes. The prefactorization strategy splits the central implicit schemes into forward and backward biased operators. Using Fourier analysis, we show it is possible to select the coefficients of the biased operators such that their dispersion characteristics match those of the original central compact scheme and their numerical wavenumbers have equal and opposite imaginary components. This ensures that when the forward and backward stencils are added, the original central compact scheme is recovered. To extend the resolution characteristic of the schemes, an optimization strategy is employed in which formal order of accuracy is sacrificed in preference to enhanced resolution characteristics across the range of wavenumbers realizable on a given mesh. The resulting optimized schemes yield improved dispersion characteristics compared to the standard sixth- and eighth-order compact schemes making them more suitable for high-resolution numerical simulations in gas dynamics and computational aeroacoustics. The efficiency, accuracy and convergence characteristics of the new optimized prefactored compact schemes are demonstrated by their application to several test problems.     

Ferrocene derivatives XXVIII. The metallation of phenylazoferrocene and the synthesis of phenylazocyclopentadienyl derivatives of other metals

Phenylazoferrocene undergoes nickelation and palladation exclusively on the phenyl group. Lithium phenylazocyclopentadienide has been converted into derivatives of Mo, Mn, Fe, Ru and Rh.