First principle study of ions in water and ionic liquids

Die beiden in dieser Arbeit betrachteten Systeme, wässrige Lösungen von Ionen und ionische Flüssigkeiten, zeigen vielfältige Eigenschaften und Anwendungsmöglichkeiten, im Gegensatz zu anderen Systemen. Man findet sie beinahe überall im normalen Leben (Wasser), oder ihre Bedeutung wächst (ioinische Flüssigkeiten). Der elektronische Anteil und der atomare Anteil wurden getrennt voneinander untersucht und im Zusammenhang analysiert. Mittels dieser Methode konnten die in dem jeweiligen System auftretenden Mechanismen genauer untersucht werden. Diese Methode wird "Multiscale Modeling" genannt, dabei werden die Untereinheiten eines Systems genauer betrachtet, wie in diesem Fall die elektronischen and atomaren Teilsystem. Die Ergebnisse, die aus den jeweiligen Betrachtungen hervorgehen, zeigen, dass, im Falle von hydratisierten Ionen die Wasser-Wasser Wechselwirkungen wesentlich stärker sind als die elektrostatischen Wechselwirkung zwischen Wasser und dem Ion. Anhand der Ergebnisse ergibt sich, dass normale nicht-polarisierbare Modelle ausreichen, um Ionen-Wasser Lösungen zu beschreiben. Im Falle der ionischen Flüssigkeiten betrachten wir die elektronische Ebene mittels sehr genauer post-Hartree-Fock Methoden und DFT, deren Ergebnisse dann mit denen auf molekularer Ebene (mithilfe von CPMD/klassischer MD) in Beziehung gesetzt werden. Die bisherigen Ergebnisse zeigen, dass die Wasserstoff-Brückenbindungen im Fall der ionischen Flüssigkeiten nicht vernachässigt werden können. Weiterhin hat diese Studie herausgefunden, dass die klassischen Kraftfelder die Elektrostatik (Dipol- und Quadrupolmomente) nicht genau genug beschreibt. Die Kombination des mikroskopischen Mechanismus und der molekularen Eigenschaften ist besonders sinnvoll um verschiedene Anhaltspunkte von Simualtionen (z.B. mit klassische Molekular-Dynamik) oder Experimenten zu liefern oder solche zu erklären.

Evaluation of slope stability under water and seismic load through the Minimum Lithostatic Deviation method

The main objective of this thesis is to obtain a better understanding of the methods to assess the stability of a slope. We have illustrated the principal variants of the Limit Equilibrium (LE) method found in literature, focalizing our attention on the Minimum Lithostatic Deviation (MLD) method, developed by Prof. Tinti and his collaborators (e.g. Tinti and Manucci, 2006, 2008). We had two main goals: the first was to test the MLD method on some real cases. We have selected the case of the Vajont landslide with the objective to reconstruct the conditions that caused the destabilization of Mount Toc, and two sites in the Norwegian margin, where failures has not occurred recently, with the aim to evaluate the present stability state and to assess under which conditions they might be mobilized. The second goal was to study the stability charts by Taylor and by Michalowski, and to use the MLD method to investigate the correctness and adequacy of this engineering tool.

Crowdsensing and proximity services for impaired mobility

La tesi si occupa della creazione di una piattaforma virtuale, composta da un sito web e da una applicazione Android, a supporto di persone con handicap motori. La piattaforma e composta da una mappa interattiva che permette agli utenti di inserire nuovi locali o di commentarne esistenti, e di fare lo stesso per le barriere architettoniche. Per questi motivi il progetto e dettato da una continua comunicazione tra client e server, rendendo la piattaforma aggiornata e dinamica, anche alla vista degli utenti. La parte web viene implementata attraverso Spring MVC, utilizzando delle View .jsp ed AJAX per la comunicazione remota con il server. La parte mobile e stata implementata basandosi principalmente sulle classi di geolocalizzazione di Android, oltre alle librerie osmdroid ed osmbonuspack, fornendo compatitiblita con OSM. Questa fornisce anche un servizio di calcolo del percorso, cercando di evitare il numero maggiore di ostacoli. L'applicazione Android appoggia le proprie comunicazioni sulla libreria Robospice. La parte di persistenza e stata implementata adottando un approccio ad alto livello, grazie ad Hibernate e JPA.

Diagnostic performance and accuracy of 3-D spoiled gradient-dual-echo MRI with water- and fat-signal separation in liver-fat quantification: comparison to liver biopsy

To prospectively evaluate a 3-dimensional spoiled gradient-dual-echo (3D SPGR-DE) magnetic resonance imaging (MRI) sequence for the qualitative and quantitative analysis of liver fat content (LFC) in patients with the suspicion of fatty liver disease using histopathology as the standard of reference.

The relationship between extravascular lung water and oxygenation in three patients with influenza A (H1N1)-induced respiratory failure

This case series reports the correlation between extravascular lung water (EVLW) and the partial arterial oxygen pressure/fractional inspiratory oxygen (PaO(2)/FiO(2)) ratio in three patients with severe influenza A (H1N1)-induced respiratory failure. All patients suffered from grave hypoxia (PaO(2), 26-42 mmHg) and were mechanically ventilated using biphasic airway pressure (PEEP, 12-15 mmHg; FiO(2), 0.8-1) in combination with prone positioning at 12 hourly intervals. All patients were monitored using the PICCO system for 8-11 days. During mechanical ventilation, a total of 62 simultaneous determinations of the PaO(2)/FiO(2) ratio and EVLW were performed. A significant correlation between EVLW and the PaO(2)/FiO(2) ratio (Spearman-rho correlation coefficient, -0.852; p < 0.001) was observed. In all patients, a decrease in EVLW was accompanied by an improvement in oxygenation. Serum lactate dehydrogenase levels were elevated in all patients and significantly correlated with EVLW during the intensive care unit stay (Spearman-rho correlation coefficient, 0.786; p < 0.001). In conclusion, EVLW seems increased in patients with severe H1N1-induced respiratory failure and appears to be closely correlated with impairments of oxygenatory function.

Magnetization exchange with water and T(1) relaxation of the downfield resonances in human brain spectra at 3.0 T

The use of water suppression for in vivo proton MR spectroscopy diminishes the signal intensities from resonances that undergo magnetization exchange with water, particularly those downfield of water. To investigate these exchangeable resonances, an inversion transfer experiment was performed using the metabolite cycling technique for non-water-suppressed MR spectroscopy from a large brain voxel in 11 healthy volunteers at 3.0 T. The exchange rates of the most prominent peaks downfield of water were found to range from 0.5 to 8.9 s(-1), while the T(1) relaxation times in absence of exchange were found to range from 175 to 525 ms. These findings may help toward the assignments of the downfield resonances and a better understanding of the sources of contrast in chemical exchange saturation transfer imaging.

Comparison of Model Chemistry and Density Functional Theory Thermochemical Predictions with Experiment for Formation of Ionic Clusters of the Ammonium Cation Complexed with Water and Ammonia; Atmospheric Implications

The G2, G3, CBS-QB3, and CBS-APNO model chemistry methods and the B3LYP, B3P86, mPW1PW, and PBE1PBE density functional theory (DFT) methods have been used to calculate ΔH° and ΔG° values for ionic clusters of the ammonium ion complexed with water and ammonia. Results for the clusters NH4+(NH3)n and NH4+(H2O)n, where n = 1−4, are reported in this paper and compared against experimental values. Agreement with the experimental values for ΔH° and ΔG° for formation of NH4+(NH3)n clusters is excellent. Comparison between experiment and theory for formation of the NH4+(H2O)n clusters is quite good considering the uncertainty in the experimental values. The four DFT methods yield excellent agreement with experiment and the model chemistry methods when the aug-cc-pVTZ basis set is used for energetic calculations and the 6-31G* basis set is used for geometries and frequencies. On the basis of these results, we predict that all ions in the lower troposphere will be saturated with at least one complete first hydration shell of water molecules.

Transport of Hydraulic Fracturing Water and Wastes in the Susquehanna River Basin, Pennsylvania

The development of the Marcellus Shale gas play in Pennsylvania and the northeastern United States has resulted in significant amounts of water and wastes transported by truck over roadways. This study used geographic information systems (GIS) to quantify truck travel distances via both the preferred routes (minimum distance while also favoring higher-order roads) as well as, where available, the likely actual distances for freshwater and waste transport between pertinent locations (e. g., gas wells, treatment facilities, freshwater sources). Results show that truck travel distances in the Susquehanna River Basin are greater than those used in prior life-cycle assessments of tight shale gas. When compared to likely actual transport distances, if policies were instituted to constrain truck travel to the closest destination and higher-order roads, transport mileage reductions of 40-80% could be realized. Using reasonable assumptions of current practices, greenhouse gas (GHG) emissions associated with water and waste hauling were calculated to be 70-157 MT CO2 eq per gas well. Furthermore, empty so-called backhaul trips, such as to freshwater withdrawal sites or returning from deep well injection sites, were found to increase emissions by an additional 30%, underscoring the importance of including return trips in the analysis. The results should inform future life-cycle assessments of tight shale gases in managed watersheds and help local and regional governments plan for impacts of transportation on local infrastructure. (C) 2013 American Society of Civil Engineers.

Assessment of water and sanitation infrastructure at primary schools in Rakai District, Uganda

“Addressing water problems will help improve sanitation.” This relationship identified by a primary school teacher in Rakai District, Uganda, was a key component in understanding how water and sanitation technologies interact and how identified successes, challenges, and improvements would enhance schools’ water and sanitation condition. In this study, researchers and Ugandan counterparts visited 49 primary schools in Rakai District to assess the existing water and sanitation infrastructure of government and private schools. Researchers were specifically interested in learning which technologies were being used and why they were working or not. Through the development of a unique water and sanitation assessment tool, schools have been placed in to four relationship quadrants to rate existing water and latrine use standards. Recommendations including improved rainwater use and sanitation through composting have been offered to schools sampled.