Labile Interactions Defined in Crystalline Metal Complexes

The problems involved in identifying and quantifying labile interactions considered to influence complex compound structures are highlighted through the assessment of four different families of metal complexes for which extensive crystallographic data are available. Modification of the charge distribution within a ligand molecule as a result of coordination is one factor with a number of ramifications. A detailed analysis of evidence for both intra- and inter-molecular attractions in dimethylsulfoxide complexes of metal perchlorates is used to provide a basis for the consideration of weak interactions between complex ions involving forces including phenyl-group attractions, hydrogen bonding and cavity inclusion.     

Fields for which the projective schur subgroup is the whole Brauer group

LetBr(K) denote the Brauer group of a fieldK andPS(K) the projective Schur subgroup. 1. LetK be a finitely generated infinite field. ThenPS(K)=Br(K) if and only ifK is a global field. 2.|LetK be a finitely generated infinite field, and letK((t)) denote the field of formal power series int overK. ThenPS(K((t)))=Br(K((t))) if and only ifK=ℚ.     

Monte Carlo determinations of the beta dose rate to tooth enamel

The results of Monte Carlo simulations of the beta dose rate to enamel are presented. The dose rates are the most comprehensive to date, incorporating the beta spectrum from 21 different radionuclides, all internal conversion and Auger electrons, the majority of the bremsstrahlung radiation, effects due to radon loss in the uranium series, and variations in the moisture content of the sediment. Applications to a new dating technique in archaeology using electron spin resonance and beta-gradient isochrons are discussed.     

Bayesian Prediction Analysis for Growth Curve Model Using Noninformative Priors

We apply a Bayesian approach to the problem of prediction in an unbalanced growth curve model using noninformative priors. Due to the complexity of the model, no analytic forms of the predictive densities are available. We propose both approximations and a prediction-oriented Metropolis-Hastings sampling algorithm for two types of prediction, namely the prediction of future observations for a new subject and the prediction of future values for a partially observed subject. They are illustrated and compared through real data and simulation studies. Two of the approximations compare favorably with the approximation in Fearn (1975, Biometrika, 62, 89–100) and are very comparable to the more accurate Rao-Blackwellization from Metropolis-Hastings sampling algorithm.     

A short synthesis of (±)-tecomanine via a Pauson-Khand-based route

The N-carboethoxy precursor to (±)-tecomanine has been prepared in 11 steps from 2-methyl-1-buten-3-yne. The key step, Pauson-Khand cyclization of a methylated 5-aza-6-nonen-1-yne succeeds, but only in low yield, a consequence of the dialkyl substitution about the azaenyne framework. Nevertheless, the overall sequence to that point is one of the more efficient to be described.     

Allocating energy in a first-to-n match

This paper models a decision where a player must allocate limitedenergy over a contest of uncertain length. The motivating exampleis a squash match where one of the players is not as fit asthe other. Should a player's energy be concentrated in the earlygames of the match? Should it be spread evenly over all possiblegames? Or should it be conserved for the end of the match? Wemodel this as a decision problem where, in each game, the decision-makermust determine how much energy to expend. We assume that thereare only a small number of discrete energy choices for eachgame and that the more energy the decision-maker expends, themore likely he is to win that game. We solve for the optimaldecision with dynamic programming. With only two possible energychoices for each game, we show that it does not matter how energyis expended. In the case where there are three or more energychoices, we show how to take advantage of the structure of theproblem to determine the optimal sequence of decisions. As forpractical advice, the model suggests that when the decision-makerfalls behind in a match, he ought to switch to a more conservativeapproach by dividing his remaining energy evenly among all thepossible remaining games. Received 14 May 2003. Revised 5 January 2004.     

On‐line Determination of Particle Size Distributions in Flowing Dispersions

Emulsions are of great importance to industry. They are involved in many engineering operations, including chemical reactions, extraction, emulsification and suspension polymerization, etc. However, an important problem for these processes is how to control the size distribution of the dispersed phase. Indeed, off‐line analysis of the emulsion may generate uncertainties due to sampling and dilution of the product, which are likely to change the dispersion state and physico‐chemical properties. In this work, an on‐line optical method is proposed to characterize dispersed media in real flowing conditions. This method is based on the time‐analysis of back‐scattered light fluctuations. The present paper deals with the development of this method and its application to dispersions of alumina in water. The results obtained with the on‐line optical method are compared with those acquired by classical laser light scattering and microscopy.     

The effect of nanoparticle shape on polymer‐nanocomposite rheology and tensile strength

Nanoparticles can influence the properties of polymer materials by a variety of mechanisms. With fullerene, carbon nanotube, and clay or graphene sheet nanocomposites in mind, we investigate how particle shape influences the melt shear viscosity η and the tensile strength τ, which we determine via molecular dynamics simulations. Our simulations of compact (icosahedral), tube or rod‐like, and sheet‐like model nanoparticles, all at a volume fraction ? ≈ 0.05, indicate an order of magnitude increase in the viscosity η relative to the pure melt. This finding evidently can not be explained by continuum hydrodynamics and we provide evidence that the η increase in our model nanocomposites has its origin in chain bridging between the nanoparticles. We find that this increase is the largest for the rod‐like nanoparticles and least for the sheet‐like nanoparticles. Curiously, the enhancements of η and τ exhibit opposite trends with increasing chain length N and with particle shape anisotropy. Evidently, the concept of bridging chains alone cannot account for the increase in τ and we suggest that the deformability or flexibility of the sheet nanoparticles contributes to nanocomposite strength and toughness by reducing the relative value of the Poisson ratio of the composite. The molecular dynamics simulations in the present work focus on the reference case where the modification of the melt structure associated with glass‐formation and entanglement interactions should not be an issue. Since many applications require good particle dispersion, we also focus on the case where the polymer‐particle interactions favor nanoparticle dispersion. Our simulations point to a substantial contribution of nanoparticle shape to both mechanical and processing properties of polymer nanocomposites. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1882–1897, 2007     

Growth of masking as a measure of response growth in hearing-impaired listeners

Growth-of-masking functions were obtained from 19 normal and 5 hearing-impaired listeners using a simultaneous-masking paradigm. When masker and probe frequency are identical, the slope of masking approximates 1.0 for both normal-hearing and impaired listeners. For masker frequencies less than or greater than probe frequency, the slopes for impaired listeners are shallower than those of normals. These findings are consistent with previously reported physiological data (single-fiber rate versus level and AP masking functions) for animals with induced cochlear lesions. Results are discussed in terms of a potential masking technique to estimate the growth of response in normal and impaired ears.     

Metaheuristics can solve sudoku puzzles

In this paper we present, to our knowledge, the first application of a metaheuristic technique to the very popular and NP-complete puzzle known as ‘sudoku’. We see that this stochastic search-based algorithm, which uses simulated annealing, is able to complete logic-solvable puzzle-instances that feature daily in many of the UK’s national newspapers. We also introduce a new method for producing sudoku problem instances (that are not necessarily logic-solvable) and use this together with the proposed SA algorithm to try and discover for what types of instances this algorithm is best suited. Consequently we notice the presence of an ‘easy-hard-easy’ style phase-transition similar to other problems encountered in operational research.