Time-resolved gas-phase kinetic study of the germylene addition reaction, CH3C CCH3

Time-resolved kinetic studies of the reaction of germylene, GeH2, generated by laser. ash photolysis of 3,4-dimethyl-1-germacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reaction with 2-butyne, CH3C CCH3. The reaction was studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas, at five temperatures in the range 300-556 K. The second order rate constants obtained by extrapolation to the high pressure limits at each temperature, fitted the Arrhenius equation: log(k(infinity)/cm(3) molecule(-1) s(-1)) = (-10.46 +/- 10.06) + (5.16 +/- 10.47) kJ mol(-1)/ RT ln 10 Calculations of the energy surface of the GeC4H8 reaction system were carried out employing the additivity principle, by combining previous quantum chemical calculations of related reaction systems. These support formation of 1,2-dimethylvinylgermylene (rather than 2,3-dimethylgermirene) as the end product. RRKM calculations of the pressure dependence of the reaction are in reasonable agreement with this finding. The reactions of GeH2 with C2H2 and with CH3CRCCH3 are compared and contrasted.

Spatiotemporal behavior of the TIGGE medium-range ensemble forecasts

Using the recently-developed mean–variance of logarithms (MVL) diagram, together with the TIGGE archive of medium-range ensemble forecasts from nine different centres, an analysis is presented of the spatiotemporal dynamics of their perturbations, showing how the differences between models and perturbation techniques can explain the shape of their characteristic MVL curves. In particular, a divide is seen between ensembles based on singular vectors or empirical orthogonal functions, and those based on bred vector, Ensemble Transform with Rescaling or Ensemble Kalman Filter techniques. Consideration is also given to the use of the MVL diagram to compare the growth of perturbations within the ensemble with the growth of the forecast error, showing that there is a much closer correspondence for some models than others. Finally, the use of the MVL technique to assist in selecting models for inclusion in a multi-model ensemble is discussed, and an experiment suggested to test its potential in this context.

Effect of intensive vs. free range production on the fat and fatty acid composition of whole birds and edible portions of retail chickens in the UK

The primary objective was to compare the fat and fatty acid contents of cooked retail chickens from intensive and free range systems. Total fat comprised approximately 14, 2.5, 8, 9 and 15 g/100 g cooked weight in whole birds, skinless breast, breast with skin, skinless leg and leg meat with skin, respectively, with no effect of intensive compared with free range systems. Free range breast and leg meat contained significantly less polyunsaturated fatty acids (n-6 and n-3) than did those from intensive rearing and had a consistently higher n-6/n-3 ratio (6.0 vs. 7.9). Generally, the concentrations of long chain n-3 fatty acids were considerably lower than those reported in earlier research studies. Overall, there was no evidence that meat from free range chickens had a fatty acid profile that would be classified as healthier than that from intensively reared birds and indeed, in some aspects, the opposite was the case. (C) 2011 Elsevier Ltd. All rights reserved.

Benchmarking and valuation issues in measuring depreciation for European office markets

Purpose – The paper addresses the practical problems which emerge when attempting to apply longitudinal approaches to the assessment of property depreciation using valuation-based data. These problems relate to inconsistent valuation regimes and the difficulties in finding appropriate benchmarks. Design/methodology/approach – The paper adopts a case study of seven major office locations around Europe and attempts to determine ten-year rental value depreciation rates based on a longitudinal approach using IPD, CBRE and BNP Paribas datasets. Findings – The depreciation rates range from a 5 per cent PA depreciation rate in Frankfurt to a 2 per cent appreciation rate in Stockholm. The results are discussed in the context of the difficulties in applying this method with inconsistent data. Research limitations/implications – The paper has methodological implications for measuring property investment depreciation and provides an example of the problems in adopting theoretically sound approaches with inconsistent information. Practical implications – Valuations play an important role in performance measurement and cross border investment decision making and, therefore, knowledge of inconsistency of valuation practice aids decision making and informs any application of valuation-based data in the attainment of depreciation rates. Originality/value – The paper provides new insights into the use of property market valuation data in a cross-border context, insights that previously had been anecdotal and unproven in nature.

The first international workshop on the role and impact of mathematics in medicine: a collective account

The First International Workshop on The Role and Impact of Mathematics in Medicine (RIMM) convened in Paris in June 2010. A broad range of researchers discussed the difficulties, challenges and opportunities faced by those wishing to see mathematical methods contribute to improved medical outcomes. Finding mechanisms for inter- disciplinary meetings, developing a common language, staying focused on the medical problem at hand, deriving realistic mathematical solutions, obtaining

Cognitive follow up of a small cohort of Huntington's disease patients over a 5 year period

A small group of patients with manifest Huntington's disease (HD) were followed longitudinally to assess cognitive decline in relation to time from disease diagnosis. This article looks at performance on a range of computerised and pencil and paper cognitive tasks in patients 5 years post diagnosis, who were assessed annually for a 5 year follow up period. The almost universal cognitive decline reported in other longitudinal studies of HD was not replicated in this study. It was proposed that longitudinal follow up in HD is complicated by the varying degree to which different tasks are able to withstand repeated administration; a finding which would have significant implications on study design in future trials of cognitive enhansing interventions.

Comparison of MODIS broadband albedo over an agricultural site with ground measurements and values derived from Earth observation data at a range of spatial scales

Land surface albedo is dependent on atmospheric state and hence is difficult to validate. Over the UK persistent cloud cover and land cover heterogeneity at moderate (km-scale) spatial resolution can also complicate comparison of field-measured albedo with that derived from instruments such as the Moderate Resolution Imaging Spectrometer (MODIS). A practical method of comparing moderate resolution satellite-derived albedo with ground-based measurements over an agricultural site in the UK is presented. Point measurements of albedo made on the ground are scaled up to the MODIS resolution (1 km) through reflectance data obtained at a range of spatial scales. The point measurements of albedo agreed in magnitude with MODIS values over the test site to within a few per cent, despite problems such as persistent cloud cover and the difficulties of comparing measurements made during different years. Albedo values derived from airborne and field-measured data were generally lower than the corresponding satellite-derived values. This is thought to be due to assumptions made regarding the ratio of direct to diffuse illumination used when calculating albedo from reflectance. Measurements of albedo calculated for specific times fitted closely to the trajectories of temporal albedo derived from both Systeme pour l'Observation de la Terre (SPOT) Vegetation (VGT) and MODIS instruments.

In vitro evaluation of the antimicrobial activity of a range of probiotics against pathogens: Evidence for the effects of organic acids

The aim of this study was to investigate the antimicrobial properties of fifteen selected strains belonging to the Lactobacillus, Bifidobacterium, Lactococcus, Streptococcus and Bacillus genera against Gram-positive and Gram-negative pathogenic bacteria. In vitro antibacterial activity was initially investigated by an agar spot method. Results from the agar spot test showed that most of the selected strains were able to produce active compounds on solid media with antagonistic properties against Salmonella Typhimurium, Escherichia coli, Enterococcus faecalis, Staphylococcus aureus and Clostridium difficile. These results were also confirmed when cell-free culture supernatants (CFCS) from the putative probiotics were used in an agar well diffusion assay. Neutralization of the culture supernatants with alkali reduced the antagonistic effects. These experiments are able to confirm the capacity of potential probiotics to inhibit selected pathogens. One of the main inhibitory mechanisms may result from the production of organic acids from glucose fermentation and consequent lowering of culture pH. This observation was confirmed when the profile of organic acids was analysed demonstrating that lactic and acetic acid were the principal end products of probiotic metabolism. Furthermore, the assessment of the haemolytic activity and the susceptibility of the strains to the most commonly used antimicrobials, considered as basic safety aspects, were also studied. The observed antimicrobial activity was mainly genus-specific, additionally significant differences could be observed among species.

The potential for skill across the range of the seamless weather-climate prediction problem: a stimulus for our science

Predictability is considered in the context of the seamless weather-climate prediction problem, and the notion is developed that there can be predictive power on all time-scales. On all scales there are phenomena that occur as well as longer time-scales and external conditions that should combine to give some predictability. To what extent this theoretical predictability may actually be realised and, further, to what extent it may be useful is not clear. However the potential should provide a stimulus to, and high profile for, our science and its application for many years.

Grid warehousing of molecular dynamics protein unfolding data

With the increasing awareness of protein folding disorders, the explosion of genomic information, and the need for efficient ways to predict protein structure, protein folding and unfolding has become a central issue in molecular sciences research. Molecular dynamics computer simulations are increasingly employed to understand the folding and unfolding of proteins. Running protein unfolding simulations is computationally expensive and finding ways to enhance performance is a grid issue on its own. However, more and more groups run such simulations and generate a myriad of data, which raises new challenges in managing and analyzing these data. Because the vast range of proteins researchers want to study and simulate, the computational effort needed to generate data, the large data volumes involved, and the different types of analyses scientists need to perform, it is desirable to provide a public repository allowing researchers to pool and share protein unfolding data. This paper describes efforts to provide a grid-enabled data warehouse for protein unfolding data. We outline the challenge and present first results in the design and implementation of the data warehouse.