Toward phenanthridin-2-ylidene: electrophilicity versus acidity in planar-constrained C-aryl iminium salts

A phenanthridinium salt was prepared in four steps, including an intramolecular CH-arylation and a hydride abstraction reaction. Treatment with sterically demanding bases does not lead to the corresponding carbene, but rather to addition products: the planar-constrained geometry significantly enhances the electrophilicity over the acidity of C-aryl iminium salts.     

A telescope illumination system for a wide-field endoscope

Endoscopic illumination systems conduct light down a built-in fibre-optic bundle to illuminate the object. Many modern endoscopes employ wide-field imaging optical systems and therefore require an illuminating beam of large divergence. This is commonly provided by placing a strong diverging lens at the far end of the fibre bundle, but it results in a poor uniformity of illumination in the object space. This paper describes the design of a telescopic illumination system to overcome this problem.     

Site segregation in size-mismatched nanoalloys: Application to Cu-Ag

In order to determine the energetic driving forces for surface segregation in bimetallic clusters, we use a combined approach coupling numerical simulations within an N-body interatomic potential and a lattice-gas model. This approach, which has been used successfully to study both the superficial segregation in semi-infinite alloys and the intergranular segregation, allows us to determine the relative contributions of the three elementary driving forces for the different sites of the cluster surface (vertices, edges and facets) in both dilute limits for the Cu-Ag system. We show that the segregation hierarchy based on broken-bond arguments (preferential segregation to the vertex sites, less to edge sites, and least to facet sites) is not at all universal. In particular, unusual hierarchies are predicted when the sizes of the constituents are strongly different. Furthermore, we compare the segregation driving forces for cubo-octahedral and icosahedral clusters. They are similar for the vertex sites and edge sites, whereas they differ significantly for the sites of the triangular facets. The segregation of the species with the largest atomic radius (Ag) is indeed largely enhanced in the icosahedral structure due to dilations of the orthoradial distances.     

Blackett Memorial Lecture: the nuclear option—human factors in safety

The UK nuclear industry is currently undergoing a series of dramatic changes. Important, among many is the establishment of the Nuclear Decommissioning Authority (NDA) with an associated impact on service delivery. At the same time, the debate on the future of our energy supply in the UK is increasingly focused on the question of the nuclear option. Issues of safety and reliability are paramount for the nuclear industry given both the nature of the hazard and the associated public perceptions of the associated risks. This paper explores linked developments in human factors and the management of safety in the nuclear industry in the context of unprecedented change.     

Reliable determination of interpolating polynomials

This paper addresses a fundamental problem in mathematics and numerical analysis, that of determining a polynomial interpolant to specified data. The data is taken as consisting of a set of points (abscissae), at each of which is specified a function value. Additionally, at each point, any number of leading derivative values of the function may be given. Mathematically, this problem is solved. The classical Lagrangian interpolation formula applies in the derivative-free case, and the Newton form of the interpolating polynomial in general.Numerically, few reliable algorithms are available; most published algorithms concentrate on speed of computation. This paper describes an algorithm that delivers the required polynomial in Chebyshev form. It is based on the repeated use of the Newton representation, with a data ordering strategy and iterative refinement to improve accuracy, using a carefully devised merit function to measure success. The algorithm attempts to provide a polynomial that is stable in the sense of backward error analysis, i.e. that is exact for slightly perturbed data.Implementations of the algorithm have been in use since the early 1980s in the NAG Library and NPL's Data Approximation Subroutine Library (DASL). In addition to providing polynomial interpolants in their own right, these implementations are used as computational modules in the NAG and DASL routines for constrained least-squares polynomial data fitting.This paper constitutes the first detailed presentation of the algorithm.     

Muon spin resonance and repolarization in amorphous silicon monoxide (a-SiO)

Studies of the muonium fractions in the amorphous oxide a-SiO have been carried out by RF resonance at TRIUMF, Canada and LF repolarization techniques at RAL, U.K. The resonance measurements confirm the presence of the interstitial Mu centre in this intermediate oxide of silicon. Analysis of the data gathered at RAL, using a recently-developed fitting technique, reveals that the Mu^* state is present here as well, but with lower relative fractions than in a-Si. However, as in the latter material, but in contrast to c-Si, this bond-centre species appears to be stable up to room temperature.     

Complex polymer architectures through dimethoxymethyl 1,1‐diphenylethylene derivatives

The reactions of polystyryllithium and potassium on dimethoxymethyl 1,1‐diphenylethylene derivatives were studied in different solvents. In a polar medium, A₃ and A₆ star types were formed according to the stoichiometry, whereas in a nonpolar medium, hyperbranched structures were synthesized. Extensions of an already proposed mechanism in polar and nonpolar media were examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3329–3335, 2003     

An amylopectin tris(phenylcarbamate) chiral stationary phase for high performance liquid chromatography

Amylopectin tris(phenylcarbamate) has been evaluated as a chiral stationary phase for HPLC; the influence on its cptical resolving capabilities of mobile phase composition and nature of the alcohol used as modifier has been studied. Separation and resolution of twelve arylalcohol racemates were examined. In most instances, the stationary phase exhibited high optical resolving capacity.