Assessing the use of NMR chemical shifts for prediction of VLE in non-ideal binary liquid mixtures

A method of estimating vapour liquid equilibrium (VLE) using NMR chemical shift data has been proposed by Xu et al. (2012). This method is based on the concept that the average local composition around each species is determined by the thermodynamics of the system, and also determines the screening of the NMR active groups within that molecule, and so their NMR chemical shifts. Xu et al.‘s method has been replicated and verified; results are confirmed to be accurate for alcohol + hydrocarbon mixtures, giving VLE predictions of comparable accuracy to the UNIFAC, generally considered the best predictive activity coefficient model available. However, for more strongly non-ideal mixtures, the method becomes less reliable, giving significantly less accurate predictions of total pressure than UNIFAC. Several causes for this are identified. The model proposed by Xu et al. (2012) is unable to fit minima or maxima in chemical shifts, which are observed experimentally in some binary mixtures. Different NMR resonances within the same molecule lead to different predictions of VLE, clearly an un-physical result. The thermodynamics of strongly non-ideal mixtures are determined by more complex interactions than a simple description of average local composition around each component in the mixtures, for example strong and directional hydrogen bonds. Different groups within the same molecule may have different local compositions in their immediate vicinity; for example in the case of alcohol + water mixtures, one would expect a clustering of water molecules around the hydroxyl group but not the aliphatic group. Hence, the concept of a simple local composition model is not valid for these more complex cases, and it is therefore not surprising that a model based on this simple concept is often not effective in predicting VLE.C. D’Agostino would like to acknowledge Wolfson College, Cambridge, for supporting his research activities.This is the accepted manuscript. The final version is available from Elsevier at http://www.sciencedirect.com/science/article/pii/S0009250914004461

Regional flow-ecology relationships in small, temperate rivers

Flow–ecology relationships within river systems are an important area of ongoing investigation, because of potential applications such as understanding the ecological impact of flow alteration at modified sites. This study analyses relationships between flow characteristics and benthic macroinvertebrates from 18 streams of similar size and typology within Northern England, to develop quantitative flow–ecology relationships applicable at regional scale. High and low flow event frequencies displayed statistically significant relationships with the ecological metrics of LIFE Score, Shannon's Diversity and a velocity flow affinity trait score. Results suggest that flow event frequencies have a significant role in influencing ecology within the river network system. Hence, this indicates that future flow regime design in the region may be enhanced if this variable is considered

A Computational Tool for the Microstructure Optimization of a Polymeric Heart Valve Prosthesis.

Styrene-based block copolymers are promising materials for the development of a polymeric heart valve prosthesis (PHV), and the mechanical properties of these polymers can be tuned via the manufacturing process, orienting the cylindrical domains to achieve material anisotropy. The aim of this work is the development of a computational tool for the optimization of the material microstructure in a new PHV intended for aortic valve replacement to enhance the mechanical performance of the device. An iterative procedure was implemented to orient the cylinders along the maximum principal stress direction of the leaflet. A numerical model of the leaflet was developed, and the polymer mechanical behavior was described by a hyperelastic anisotropic constitutive law. A custom routine was implemented to align the cylinders with the maximum principal stress direction in the leaflet for each iteration. The study was focused on valve closure, since during this phase the fibrous structure of the leaflets must bear the greatest load. The optimal microstructure obtained by our procedure is characterized by mainly circumferential orientation of the cylinders within the valve leaflet. An increase in the radial strain and a decrease in the circumferential strain due to the microstructure optimization were observed. Also, a decrease in the maximum value of the strain energy density was found in the case of optimized orientation; since the strain energy density is a widely used criterion to predict elastomer's lifetime, this result suggests a possible increase of the device durability if the polymer microstructure is optimized. The present method represents a valuable tool for the design of a new anisotropic PHV, allowing the investigation of different designs, materials, and loading conditions.The authors thank the British Heart Foundation for financial support for this work under Grant NH/11/4/29059 and SP/15/5/31548

Evaluation of an aortic valve prosthesis: Fluid-structure interaction or structural simulation?

Bio-inspired polymeric heart valves (PHVs) are excellent candidates to mimic the structural and the fluid dynamic features of the native valve. PHVs can be implanted as prosthetic alternative to currently clinically used mechanical and biological valves or as potential candidate for a minimally invasive treatment, like the transcatheter aortic valve implantation. Nevertheless, PHVs are not currently used for clinical applications due to their lack of reliability. In order to investigate the main features of this new class of prostheses, pulsatile tests in an in-house pulse duplicator were carried out and reproduced in silico with both structural Finite-Element (FE) and Fluid-Structure interaction (FSI) analyses. Valve kinematics and geometric orifice area (GOA) were evaluated to compare the in vitro and the in silico tests. Numerical results showed better similarity with experiments for the FSI than for the FE simulations. The maximum difference between experimental and FSI GOA at maximum opening time was only 5%, as compared to the 46.5% between experimental and structural FE GOA. The stress distribution on the valve leaflets clearly reflected the difference in valve kinematics. Higher stress values were found in the FSI simulations with respect to those obtained in the FE simulation. This study demonstrates that FSI simulations are more appropriate than FE simulations to describe the actual behaviour of PHVs as they can replicate the valve-fluid interaction while providing realistic fluid dynamic results

Automated quantitative MRI volumetry reports support diagnostic interpretation in dementia: a multi-rater, clinical accuracy study

OBJECTIVES: We examined whether providing a quantitative report (QReport) of regional brain volumes improves radiologists' accuracy and confidence in detecting volume loss, and in differentiating Alzheimer's disease (AD) and frontotemporal dementia (FTD), compared with visual assessment alone. METHODS: Our forced-choice multi-rater clinical accuracy study used MRI from 16 AD patients, 14 FTD patients, and 15 healthy controls; age range 52-81. Our QReport was presented to raters with regional grey matter volumes plotted as percentiles against data from a normative population (n = 461). Nine raters with varying radiological experience (3 each: consultants, registrars, 'non-clinical image analysts') assessed each case twice (with and without the QReport). Raters were blinded to clinical and demographic information; they classified scans as 'normal' or 'abnormal' and if 'abnormal' as 'AD' or 'FTD'. RESULTS: The QReport improved sensitivity for detecting volume loss and AD across all raters combined (p = 0.015* and p = 0.002*, respectively). Only the consultant group's accuracy increased significantly when using the QReport (p = 0.02*). Overall, raters' agreement (Cohen's κ) with the 'gold standard' was not significantly affected by the QReport; only the consultant group improved significantly (κs 0.41➔0.55, p = 0.04*). Cronbach's alpha for interrater agreement improved from 0.886 to 0.925, corresponding to an improvement from 'good' to 'excellent'. CONCLUSION: Our QReport referencing single-subject results to normative data alongside visual assessment improved sensitivity, accuracy, and interrater agreement for detecting volume loss. The QReport was most effective in the consultants, suggesting that experience is needed to fully benefit from the additional information provided by quantitative analyses. KEY POINTS: • The use of quantitative report alongside routine visual MRI assessment improves sensitivity and accuracy for detecting volume loss and AD vs visual assessment alone. • Consultant neuroradiologists' assessment accuracy and agreement (kappa scores) significantly improved with the use of quantitative atrophy reports. • First multi-rater radiological clinical evaluation of visual quantitative MRI atrophy report for use as a diagnostic aid in dementia

Governance, regulation and financial market instability: the implications for policy

Just as the 1929 Stock Market Crash discredited Classical economic theory and policy and opened the way for Keynesianism, a consequence of the collapse of confidence in financial markets and the banking system—and the effect that this has had on the global macro economy—is currently discrediting the ‘conventional wisdom’ of neo-liberalism. This paper argues that at the heart of the crisis is a breakdown in governance that has its roots in the co-evolution of political and economic developments and of economic theory and policy since the 1929 Stock Market Crash and the Great Depression that followed. However, while many are looking back to the Great Depression and to the theories and policies that seemed to contribute to recovery during the first part of the twentieth century, we argue that the current context is different from the earlier one; and there are more recent events that may provide better insight into the causes and contributing factors giving rise to the present crisis and to the implications for theory and policy that follow