Ab-initio study of hydrogen technology materials for hydrogen storage and proton conduction

This dissertation deals with two specific aspects of a potential hydrogen-based energy economy, namely the problems of energy storage and energy conversion. In order to contribute to the solution of these problems, the structural and dynamical properties of two promising materials for hydrogen storage (lithium imide/amide) and proton conduction (poly[vinyl phosphonic acid]) are modeled on an atomistic scale by means of first principles molecular dynamics simulation methods.rnrnrnIn the case of the hydrogen storage system lithium amide/imide (LiNH_2/Li_2NH), the focus was on the interplay of structural features and nuclear quantum effects. For these calculations, Path-Integral Molecular Dynamics (PIMD) simulations were used. The structures of these materials at room temperature were elucidated; in collaboration with an experimental group, a very good agreement between calculated and experimental solid-state 1H-NMR chemical shifts was observed. Specifically, the structure of Li_2NH features a disordered arrangement of the Li lattice, which was not reported in previous studies. In addition, a persistent precession of the NH bonds was observed in our simulations. We provide evidence that this precession is the consequence of a toroid-shaped effective potential, in which the protons in the material are immersed. This potential is essentially flat along the torus azimuthal angle, which might lead to important quantum delocalization effects of the protons over the torus.rnrnOn the energy conversion side, the dynamics of protons in a proton conducting polymer (poly[vinyl phosphonic acid], PVPA) was studied by means of a steered ab-initio Molecular Dynamics approach applied on a simplified polymer model. The focus was put on understanding the microscopic proton transport mechanism in polymer membranes, and on characterizing the relevance of the local environment. This covers particularly the effect of water molecules, which participate in the hydrogen bonding network in the material. The results indicate that these water molecules are essential for the effectiveness of proton conduction. A water-mediated Grotthuss mechanism is identified as the main contributor to proton conduction, which agrees with the experimentally observed decay on conductivity for the same material in the absence of water molecules.rnrnThe gain in understanding the microscopic processes and structures present in this materials can help the development of new materials with improved properties, thus contributing to the solution of problems in the implementation of fuel cells.

The velocity dispersion profile of the globular cluster 47Tucanae

Gli ammassi globulari rappresentano i laboratori ideali nei quali studiare la dinamica di sistemi ad N-corpi ed i suoi effetti sull’evoluzione stellare. Infatti, gli ammassi globulari sono gli unici sistemi astrofisici che, entro il tempo scala dell’età dell’Universo, sperimentano quasi tutti i processi di dinamica stellare noti. Questo lavoro di tesi si inserisce in un progetto a lungo termine volto a fornire una dettagliata caratterizzazione delle proprietà dinamiche degli ammassi globulari galattici. In questa ricerca, strumenti di fondamentale importanza sono il profilo di dispersione di velocità del sistema e la sua curva di rotazione. Per determinare le componenti radiali di questi profili cinematici in ammassi globulari galattici è necessario misurare la velocità lungo la linea di vista di un ampio campione di stelle membre, a differenti distanze dal centro. Seguendo un approccio multi-strumentale, è possibile campionare l’intera estensione radiale dell’ammasso utilizzando spettrografi multi-oggetto ad alta risoluzione spettrale nelle regioni intermedie/esterne, e spettrografi IFU con ottiche adattive per le regioni centrali (pochi secondi d’arco dal centro). Questo lavoro di tesi è volto a determinare il profilo di dispersione di velocità dell’ammasso globulare 47 Tucanae, campionando un’estensione radiale compresa tra circa 20'' e 13' dal centro. Per questo scopo sono state misurate le velocità radiali di circa un migliaio di stelle nella direzione di 47 Tucanae, utilizzando spettri ad alta risoluzione ottenuti con lo spettrografo multi-oggetto FLAMES montato al Very Large Telescope dell’ESO. Le velocità radiali sono state misurate utilizzando la tecnica di cross-correlazione tra gli spettri osservati e appropriati spettri teorici, e sono state ottenute accuratezze inferiori a 0.5km/s. Il campione così ottenuto (complementare a quello raccolto con strumenti IFU nelle regioni centrali) è fondamentale per costruire il profilo di dispersione di velocità dell’ammasso e la sua eventuale curva di rotazione. Questi dati, combinati col profilo di densità dell’ammasso precedentemente determinato, permetteranno di vincolare opportunamente modelli teorici come quelli di King (1966) o di Wilson (1975), e di arrivare così alla prima solida determinazione dei parametri strutturali e dinamici (raggi di core e di metà massa, tempo di rilassamento, parametro collisionale, etc.) e della massa totale e distribuzione di massa del sistema.

The floating mass transducer at the round window: direct transmission or bone conduction?

The round window placement of a floating mass transducer (FMT) is a new approach for coupling an implantable hearing system to the cochlea. We evaluated the vibration transfer to the cochlear fluids of an FMT placed at the round window (rwFMT) with special attention to the role of bone conduction. A posterior tympanotomy was performed on eleven ears of seven human whole head specimens. Several rwFMT setups were examined using laser Doppler vibrometry measurements at the stapes and the promontory. In three ears, the vibrations of a bone anchored hearing aid (BAHA) and an FMT fixed to the promontory (pFMT) were compared to explore the role of bone conduction. Vibration transmission to the measuring point at the stapes was best when the rwFMT was perpendicularly placed in the round window and underlayed with connective tissue. Fixation of the rwFMT to the round window exhibited significantly lower vibration transmission. Although measurable, bone conduction from the pFMT was much lower than that of the BAHA. Our results suggest that the rwFMT does not act as a small bone anchored hearing aid, but instead, acts as a direct vibratory stimulator of the round window membrane.

Velocity recovery cycles of human muscle action potentials in chronic renal failure

To test the hypothesis that muscle fibers are depolarized in patients with chronic renal failure, by measuring velocity recovery cycles of muscle action potentials as indicators of muscle membrane potential.

Muscle membrane dysfunction in critical illness myopathy assessed by velocity recovery cycles

To test the hypothesis that muscle fibers are depolarized in patients with critical illness myopathy by measuring velocity recovery cycles (VRCs) of muscle action potentials.

Incidence and predictors of atrioventricular conduction impairment after transcatheter aortic valve implantation

Atrioventricular (AV) conduction impairment is well described after surgical aortic valve replacement, but little is known in patients undergoing transcatheter aortic valve implantation (TAVI). We assessed AV conduction and need for a permanent pacemaker in patients undergoing TAVI with the Medtronic CoreValve Revalving System (MCRS) or the Edwards Sapien Valve (ESV). Sixty-seven patients without pre-existing permanent pacemaker were included in the study. Forty-one patients (61%) and 26 patients (39%) underwent successful TAVI with the MCRS and ESV, respectively. Complete AV block occurred in 15 patients (22%), second-degree AV block in 4 (6%), and new left bundle branch block in 15 (22%), respectively. A permanent pacemaker was implanted in 23 patients (34%). Overall PR interval and QRS width increased significantly after the procedure (p <0.001 for the 2 comparisons). Implantation of the MCRS compared to the ESV resulted in a trend toward a higher rate of new left bundle branch block and complete AV block (29% vs 12%, p = 0.09 for the 2 comparisons). During follow-up, complete AV block resolved in 64% of patients. In multivariable regression analysis pre-existing right bundle branch block was the only independent predictor of complete AV block after TAVI (relative risk 7.3, 95% confidence interval 2.4 to 22.2). In conclusion, TAVI is associated with impairment of AV conduction in a considerable portion of patients, patients with pre-existing right bundle branch block are at increased risk of complete AV block, and complete AV block resolves over time in most patients.

Chest pulse-wave velocity: a novel approach to assess arterial stiffness

Pulse-wave velocity (PWV) is considered as the gold-standard method to assess arterial stiffness, an independent predictor of cardiovascular morbidity and mortality. Current available devices that measure PWV need to be operated by skilled medical staff, thus, reducing the potential use of PWV in the ambulatory setting. In this paper, we present a new technique allowing continuous, unsupervised measurements of pulse transit times (PTT) in central arteries by means of a chest sensor. This technique relies on measuring the propagation time of pressure pulses from their genesis in the left ventricle to their later arrival at the cutaneous vasculature on the sternum. Combined thoracic impedance cardiography and phonocardiography are used to detect the opening of the aortic valve, from which a pre-ejection period (PEP) value is estimated. Multichannel reflective photoplethysmography at the sternum is used to detect the distal pulse-arrival time (PAT). A PTT value is then calculated as PTT = PAT - PEP. After optimizing the parameters of the chest PTT calculation algorithm on a nine-subject cohort, a prospective validation study involving 31 normo- and hypertensive subjects was performed. 1/chest PTT correlated very well with the COMPLIOR carotid to femoral PWV (r = 0.88, p < 10 (-9)). Finally, an empirical method to map chest PTT values onto chest PWV values is explored.

Muscle ischaemia in patients with orthostatic hypotension assessed by velocity recovery cycles

Patients with orthostatic hypotension may experience neck pain radiating to the occipital region of the skull and the shoulders while standing (so-called coat-hanger ache). This study assessed muscle membrane potential in the trapezius muscle of patients with orthostatic hypotension and healthy subjects during head-up tilt (HUT), by measuring velocity recovery cycles (VRCs) of muscle action potentials as an indicator of muscle membrane potential.

Velocity recovery cycles of human muscle action potentials: Repeatability and variability

Velocity recovery cycles (VRCs) of human muscle action potentials have been proposed as a new technique for assessing muscle membrane function in myopathies. This study was undertaken to determine the variability and repeatability of VRC measures such as supernormality, to help guide future clinical use of the method.