Effect of weak hydrogen bonding and included solvent on the crystal structure of the square-planar complex trans-Pt{PPh2(C16H15)}(2)Cl-2

Crystallisation of the square-planar complex trans-Pt{PPh2(C16H15)}(2)Cl-2 from dichloromethane-diethyl ether (1:1) affords two different solvates; trans-Pt{PPh2(C16H15)}(2)Cl-2. CH2Cl2 1 and trans-Pt{PPh2(C16H15)}(2)Cl-2. Et2O 2; the CH2Cl2 forms H-bonding interactions with the complex whereas the Et2O participates only in weak van der Waals interactions; these differences arise from the different hydrogen-bonding characteristics of each solvent.

Volumetric properties, viscosity and refractive index of the protic ionic liquid, pyrrolidinium octanoate, in molecular solvents

Densities ([rho]) and viscosities ([eta]) of binary mixtures containing the Protic Ionic Liquid (PIL), pyrrolidinium octanoate with five molecular solvents: water, methanol, ethanol, n-butanol, and acetonitrile are determined at the atmospheric pressure as a function of the temperature and within the whole composition range. The refractive index of all mixtures (nD) is measured at 298.15†K. The excess molar volumes VE and deviation from additivity rules of viscosities [eta]E and refractive index [Delta][phi]n, of pyrrolidinium octanoate solutions were then deduced from the experimental results as well as apparent molar volumes V[phi]i, partial molar volumes and thermal expansion coefficients [alpha]p. The excess molar volumes VE are negative over the entire mole fraction range for mixture with water, acetonitrile, and methanol indicating strong hydrogen-bonding interaction for the entire mole fraction. In the case of longest carbon chain alcohols (such as ethanol and n-butanol)†+†pyrrolidinium octanoate solutions, the VE variation as a function of the composition describes an S shape. The deviation from additivity rules of viscosities is negative over the entire composition range for the acetonitrile, methanol, ethanol, and butanol, and becomes less negative with increasing temperature. Whereas, [eta]E of the {[Pyrr][C7CO2]†+†water} binary mixtures is positive in the whole mole fraction range and decreases with increasing temperature. the excess Gibbs free energies of activation of viscous flow ([Delta]G*E) for these systems were calculated. The deviation from additivity rules of refractive index [Delta][phi]n are positive over the whole composition range and approach a maximum of 0.25 in PIL mole fraction for all systems. The magnitude of deviation for [Delta][phi]n describes the following order: water†>†methanol†>†acetonitrile†>†ethanol. Results have been discussed in terms of molecular interactions and molecular structures in these binary mixtures.

Assessment of the impact speed and angle conditions for the EN1317 barrier tests

Roadside safety barriers designs are tested with passenger cars in Europe using standard EN1317 in which the impact angle for normal, high and very high containment level tests is 20°. In comparison to EN1317, the US standard MASH has higher impact angles for cars and pickups (25°) and different vehicle masses. Studies in Europe (RISER) and the US have shown values for the 90th percentile impact angle of 30°–34°. Thus, the limited evidence available suggests that the 20° angle applied in EN 1317 may be too low.
The first goal of this paper is to use the US NCHRP database (Project NCHRP 17–22) to assess the distribution of impact angle and collision speed in recent ROR accidents. Second, based on the findings of the statistical analysis and on analysis of impact angles and speeds in the literature, an LS-DYNA finite element analysis was carried out to evaluate the normal containment level of concrete barriers in non-standard collisions. The FE model was validated against a crash test of a portable concrete barrier carried out at the UK Transport Research Laboratory (TRL).
The accident data analysis for run-off road accidents indicates that a substantial proportion of accidents have an impact angle in excess of 20°. The baseline LS-DYNA model showed good comparison with experimental acceleration severity index (ASI) data and the parametric analysis indicates a very significant influence of impact angle on ASI. Accordingly, a review of European run-off road accidents and the configuration of EN 1317 should be performed.

Reactivity of the 4d transition metals toward N hydrogenation and NH dissociation: A DFT-based HSAB analysis

The density functional theory (DFT) based hard-soft acid-base (HSAB) reactivity indices, including the electrophilicity index, have been successfully applied to many areas of molecular chemistry. In this work we test the applicability of such an approach to fundamental surface chemistry. We have considered, as prototypical surface reactions, both the hydrogenation of atomic nitrogen and the dissociative adsorption of the NH molecular radical. By use of a DFT methodology, the minimum energy reaction pathways, and corresponding reaction barriers, of the above reactions over Zr(001), Nb(110), Mo(110), Tc(001), Ru(001), Rh(111), and Pd(111) have been determined. By consideration of the chemical potential and chemical hardness of the surface metal atoms, and the principle of electronegativity equalization, it is found that the charge transferred to the NH radical during the process of dissociative adsorption correlates very well with that determined by Mulliken population analysis. Furthermore, it is found that the stability of the NH/surface transition state complex relates directly to this charge transfer and that the trend in transition state stability predicted by a HSAB; treatment correlates very strongly with that determined by DFT calculations. With regards to N hydrogenation, we find that during the course of the reaction, H loses cohesion to the surface, as it must migrate from a 3-fold hollow site to either a bridge or top site, to react with N. Partial density of states (PDOS) and Mulliken population analysis reveal that this loss of bonding is accompanied by charge transfer from H to the surface metal atoms. Moreover, by simple modeling, we show that the reaction barriers are directly proportional to this mandatory charge transfer. Indeed, it is found that the reaction barriers correlate very well with the electrophilicity index of the metal atoms.

Can less be more? Comparison of an 8-item placement quality measure with the 50-item Dundee Ready Educational Environment Measure (DREEM)

Clinical clerks learn more than they are taught and not all they learn can be measured. As a result, curriculum leaders evaluate clinical educational environments. The quantitative Dundee Ready Environment Measure (DREEM) is a de facto standard for that purpose. Its 50 items and 5 subscales were developed by consensus. Reasoning that an instrument would perform best if it were underpinned by a clearly conceptualized link between environment and learning as well as psychometric evidence, we developed the mixed methods Manchester Clinical Placement Index (MCPI), eliminated redundant items, and published validity evidence for its 8 item and 2 subscale structure. Here, we set out to compare MCPI with DREEM. 104 students on full-time clinical placements completed both measures three times during a single academic year. There was good agreement and at least as good discrimination between placements with the smaller MCPI. Total MCPI scores and the mean score of its 5-item learning environment subscale allowed ten raters to distinguish between the quality of educational environments. Twenty raters were needed for the 3-item MCPI training subscale and the DREEM scale and its subscales. MCPI compares favourably with DREEM in that one-sixth the number of items perform at least as well psychometrically, it provides formative free text data, and it is founded on the widely shared assumption that communities of practice make good learning environments.

The validity of the MacNew Quality of Life Questionnaire in heart disease.

Background A previous review suggested that the MacNew Quality of Life Questionnaire was the most appropriate disease-specific measure of health-related quality of life among people with ischaemic heart disease. However, there is ambiguity about the allocation of items to the three factors underlying the MacNew and the factor structure has not been confirmed previously among the people in the UK. Methods The MacNew Questionnaire and the SF-36 were administered to 117 newly admitted patients to a tertiary referral centre in Northern Ireland. All patients had been diagnosed with ischaemic heart disease. Results A confirmatory factor analysis was conducted on the factor structure of the MacNew and the model was found to be an inadequate fit of the data. A quantitative and qualitative analysis of the items suggested that a five factor solution was more appropriate and this was validated by confirmatory factor analysis. This new structure also displayed strong evidence of concurrent validity when compared to the SF-36. Conclusion We recommend that researchers should submit scores obtained from items on the MacNew to secondary analyses after being grouped according to the factor structure proposed in this paper, in order to explore further the most appropriate grouping of items.

Preliminary investigation of the application of Raman spectroscopy to the prediction of the sensory quality of beef silverside

The potential of Raman spectroscopy for the determination of meat quality attributes has been investigated using data from a set of 52 cooked beef samples, which were rated by trained taste panels. The Raman spectra, shear force and cooking loss were measured and PLS used to correlate the attributes with the Raman data. Good correlations and standard errors of prediction were found when the Raman data were used to predict the panels' rating of acceptability of texture (R-2 = 0.71, Residual Mean Standard Error of Prediction (RMSEP)% of the mean (mu) = 15%), degree of tenderness (R-2 = 0.65, RMSEP% of mu = 18%), degree of juiciness (R-2 = 0.62, RMSEP% of mu = 16%), and overall acceptability (R-2 = 0.67, RMSEP% of mu = 11%). In contrast, the mechanically determined shear force was poorly correlated with tenderness (R-2 = 0.15). Tentative interpretation of the plots of the regression coefficients suggests that the alpha-helix to beta-sheet ratio of the proteins and the hydrophobicity of the myofibrillar environment are important factors contributing to the shear force, tenderness, texture and overall acceptability of the beef. In summary, this work demonstrates that Raman spectroscopy can be used to predict consumer-perceived beef quality. In part, this overall success is due to the fact that the Raman method predicts texture and tenderness, which are the predominant factors in determining overall acceptability in the Western world. Nonetheless, it is clear that Raman spectroscopy has considerable potential as a method for non-destructive and rapid determination of beef quality parameters.

Hydrochemical and isotopic tracing of mixing dynamics and water quality evolution under pumping conditions in the mine shaft of the abandoned Frances Colliery, Scotland.

Since 1995, when pumps were withdrawn from deep mines in East Fife (Scotland), mine waters have been rebounding throughout the coalfield. Recently, it has become necessary to pump and treat these waters to prevent their uncontrolled emergence at the surface. However, even relatively shallow pumping to surface treatment lagoons of the initially chemically-stratified mine water from a shaft in the coastal Frances Colliery during two dynamic step-drawdown tests to establish the hydraulic characteristics of the system resulted in rapid breakdown of the stratification within 24 h and a poor pumped water quality with high dissolved Fe loading. Further, data are presented here of hydrochemical and isotopic sampling of the extended pump testing lasting up to several weeks. The use in particular of the environmental isotopes d18O, d2H, d34S, 3H, 13C and 14C alongside hydrochemical and hydraulic pump test data allowed characterisation of the Frances system dynamics, mixing patterns and water quality sources feeding into this mineshaft under continuously pumped conditions. The pumped water quality reflects three significant components of mixing: shallow freshwater, seawater, and leakage from the surface treatment lagoons. In spite of the early impact of recirculating lagoon waters on the hydrochemistries, the highest Fe loadings in the longer-term pumped waters are identified with a mixed freshwater–seawater component affected by pyrite oxidation/melanterite dissolution in the subsurface system.