128 research outputs found

    Imaging Molecular Structure through Femtosecond Photoelectron Diffraction on Aligned and Oriented Gas-Phase Molecules

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    This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump-probe setup combining optical lasers and an X-ray Free-Electron Laser. We present results of two experiments aimed at measuring photoelectron angular distributions of laser-aligned 1-ethynyl-4-fluorobenzene (C8H5F) and dissociating, laseraligned 1,4-dibromobenzene (C6H4Br2) molecules and discuss them in the larger context of photoelectron diffraction on gas-phase molecules. We also show how the strong nanosecond laser pulse used for adiabatically laser-aligning the molecules influences the measured electron and ion spectra and angular distributions, and discuss how this may affect the outcome of future time-resolved photoelectron diffraction experiments.Comment: 24 pages, 10 figures, Faraday Discussions 17

    Subsecond Morphological Changes in Nafion during Water Uptake Detected by Small-Angle X-ray Scattering

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    The ability of Nafion® membrane to absorb water rapidly and create a network of hydrated interconnected water domains provides this material with an unmatched ability to conduct ions through a chemically and mechanically robust membrane. The morphology and composition of these hydrated membranes significantly affects their transport properties and performance. This work demonstrates that differences in interfacial interactions between the membranes exposed to vapor or liquid water can cause significant changes in kinetics of water uptake. In-situ small-angle X-ray scattering (SAXS) experiments captured the rapid swelling of the membrane in liquid water with nanostructure rearrangement on the order of seconds. For membranes in contact with water vapor, morphological changes are four-orders-of-magnitude slower than in liquid water, suggesting that interfacial resistance limits the penetration of water into the membrane. Also, upon water absorption from liquid water, a structural rearrangement from a distribution of spherical and cylindrical domains to exclusively cylindrical-like domains is suggested. These differences in water-uptake kinetics and morphology provide a new perspective into Schroeder’s Paradox, which dictates different water contents for vaporand liquid-equilibrated ionomers at unit activity. The findings of this work provide critical insights into the fast kinetics of water absorption of Nafion membrane, which can aid in the design of energy conversion devices that operate under frequent changes in environmental conditions

    Aneurysm Ostium Angle: A Predictor of the Need for Stent as Assistance for Endovascular Aneurysm Coiling in Internal Carotid Artery Sidewall Aneurysms

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    BACKGROUND AND PURPOSE: There is no satisfactory parameter that can predict the need for assistant devices for endovascular aneurysm coiling. Our aim was to evaluate the utility of MOA as a predictor of the need for stent-assisted coiling in ICA sidewall aneurysms

    Prednisolone is associated with a worse lipid profile than hydrocortisone in patients with adrenal insufficiency

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    Objective: Prednisolone is used as glucocorticoid replacement therapy for adrenal insufficiency (AI). Recent data indicate that its use in AI is associated with low bone mineral density. Data on risk factors for cardiovascular disease in patients with AI treated with prednisolone are scarce, despite this condition being the predominant cause of excess mortality. We aimed to address this question using real-world data from the European Adrenal Insufficiency Registry (EU-AIR). // Design/methods: EU-AIR, comprising of 19 centres across Germany, the Netherlands, Sweden and the UK, commenced enrolling patients with AI in August 2012. Patients receiving prednisolone (3–6 mg/day, n = 50) or hydrocortisone (15–30 mg/day, n = 909) were identified and grouped at a ratio of 1:3 (prednisolone:hydrocortisone) by matching for gender, age, duration and type of disease. Data from baseline and follow-up visits were analysed. Data from patients with congenital adrenal hyperplasia were excluded. // Results: Significantly higher mean ± S.D. total (6.3 ± 1.6 vs 5.4 ± 1.1 mmol/L; P = 0.003) and low-density lipoprotein (LDL) cholesterol levels (3.9 ± 1.4 vs 3.2 ± 1.0 mmol/L; P = 0.013) were identified in 47 patients on prednisolone vs 141 receiving hydrocortisone at baseline and at follow-up (P = 0.005 and P = 0.006, respectively). HbA1c, high-density lipoprotein and triglyceride levels, body mass index, systolic and diastolic blood pressure and waist circumference were not significantly different. // Conclusions: This is the first matched analysis of its kind. Significantly higher LDL levels in patients receiving prednisolone relative to hydrocortisone could predict a higher relative risk of cardiovascular disease in the former group

    Data-Driven Robust Control for Type 1 Diabetes Under Meal and Exercise Uncertainties

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    We present a fully closed-loop design for an artificial pancreas (AP) which regulates the delivery of insulin for the control of Type I diabetes. Our AP controller operates in a fully automated fashion, without requiring any manual interaction (e.g. in the form of meal announcements) with the patient. A major obstacle to achieving closed-loop insulin control is the uncertainty in those aspects of a patient's daily behavior that significantly affect blood glucose, especially in relation to meals and physical activity. To handle such uncertainties, we develop a data-driven robust model-predictive control framework, where we capture a wide range of individual meal and exercise patterns using uncertainty sets learned from historical data. These sets are then used in the controller and state estimator to achieve automated, precise, and personalized insulin therapy. We provide an extensive in silico evaluation of our robust AP design, demonstrating the potential of this approach, without explicit meal announcements, to support high carbohydrate disturbances and to regulate glucose levels in large clusters of virtual patients learned from population-wide survey data.Comment: Extended version of paper accepted at the 15th International Conference on Computational Methods in Systems Biolog

    Urine steroid metabolomics for the differential diagnosis of adrenal incidentalomas in the EURINE-ACT study: a prospective test validation study

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    Strukturanalyse organischer Verbindungen

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    Material and signal flow

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