Studio di fenomeni dinamici di rilevanza in catalisi attraverso l'utilizzo del sistema modello FE/TiOx/Pt(111)

This thesis is about the study of the SMSI effect on model catalysts such as Fe/TiOx/Pt (111). The study has involved the use of techniques such as TPD (Thermal Programmed Desorption), XPS (Xray Photoelectron Spectroscopy), LEED (Low Energy Electron Diffraction) and STM (Scanning Tunnelling Microscopy).openTESI.3644La copia a stampa della tesi e' disponibile presso la biblioteca con la collocazione indicat

Nanoscale molecular reorganization of the inhibitory postsynaptic density is a determinant of gabaergic synaptic potentiation

Gephyrin is a key scaffold protein mediating the anchoring of GABAA receptors at inhibitory synapses. Here, we exploited superresolution techniques combined with proximity-based clustering analysis and model simulations to investigate the single-molecule gephyrin reorganization during plasticity of inhibitory synapses in mouse hippocampal cultured neurons. This approach revealed that, during the expression of inhibitory LTP, the increase of gephyrin density at postsynaptic sites is associated with the promoted formation of gephyrin nanodomains. We demonstrate that the gephyrin rearrangement in nanodomains stabilizes the amplitude of postsynaptic currents, indicating that, in addition to the number of synaptic GABAA receptors, the nanoscale distribution of GABAA receptors in the postsynaptic area is a crucial determinant for the expression of inhibitory synaptic plasticity. In addition, the methodology implemented here clears the way to the application of the graph-based theory to single-molecule data for the description and quantification of the spatial organization of the synapse at the single-molecule level

Molecular plating of thin lanthanide layers with improved material properties for nuclear applications

In der vorliegenden Arbeit werden Experimente beschrieben, die zu einem vertieften Verständnis fundamentaler Prozesse bei der elektrochemischen Herstellung von Dünnschichten, sog. Targets, für kernphysikalische und -chemische Studien führten. Targets wurden mittels \u27Molecular Plating\u27 (MP) hergestellt, indem eine Elektrodeposition aus organischem Medium in der Regel bei konstantem Strom in Zwei-Elektroden-Zellen. Die Resultate erlaubten, optimierte Herstellungs-bedingungen zu ermitteln, welche die Produktion deutlich verbesserter Targets erlaubten. MP bei konstantem Strom ist ein massentransportkontrollierter Prozess. Der angelegte Strom wird durch einen konstanten Fluss elektroaktiver Spezies zur Kathode – auf der die Schicht wächst – und Anode aufrechterhalten. Die Untersuchungen zeigten, dass das Zellenpotential des Elektrodepositionsystems immer durch den Ohm\u27schen Spannungsabfall auf Grund des Widerstandes der verwendeten Lösung dominiert wurde. Dies erlaubte die Herleitung einer Beziehung zwischen dem Zellenpotential und der Konzentration der elektroaktiven Spezies. Die Beziehung erlaubt die Erklärung des gemessenen zeitlichen Verlaufs des Zellenpotentials während der Abscheidung als Funktion der Elektrolytkonzentration. Dies dient als Basis, auf der nun ein umfassenderes Bild der Prozesse, die für die charakteristischen Minima im Potentialverlauf einer Abscheidung verantwortlich sind, gewonnen werden kann. Es konnte gezeigt werden, dass die Minima mit der fast vollständigen Entfernung (durch Abscheidung) der aus einem gelösten Salz erzeugten Nd-Ionen korrespondieren. Die abgeschiedene Spezies wurde als Nd3+ identifiziert, vermutlich als Carboxylat, Oxid oder Hydroxid, was auf Grund der hohen negative Werte des Standardredoxpotentials der Lanthanide verständlich erscheint. Von den vorliegenden elektroaktiven Spezies tragen die Nd3+ Ionen nur zu knapp 20% zum Gesamtstrom bei. Durch Elektrolyse tragen auch die Lösungsmittelkomponenten zu diese Strom bei. Die Gegenwart von elektrolysiertem Lösungsmittel wurde in Analysen der Dünnschichten bestätigt. Diese waren immer mit chemi- und physisorbierten Lösungsmittelmolekülen bedeckt. Die Analyse der Dünnschichten zeigte, dass die Oberflächen von einem furchenartiges Netz durchzogen waren, und dass diese während des Trocknen der Schichten nach dem MP entstanden. Ob die Schichten an Luft oder in inerter Atmosphäre trockneten, hatte keinen Einfluss. Es wurden Experimente mit mehreren Lösungsmitteln durchgeführt, die sich deutlich in ihren physikalischen Eigenschaften, v.a. dem Siedepunkt, unterschieden. Furchenfreie Dünnschichten konnten insbesondere bei MP in N,N-dimethylformamide (DMF) erzeugt werden. Die Verwendung von DMF in Kombination mit einer Abscheidung auf sehr glatten Substraten erlaubte die Produktion von sehr homogenen, glatten und defektfreien Schichten. Diese waren vermutlich geringeren inneren Spannungen während des Trocknens ausgesetzt, als Schichten auf raueren Substraten oder solche, die aus flüchtigeren Lösungsmitteln hergestellt wurden. Die Oberflächenrauigkeit des Substrats und das gewählte Lösungsmittel wurden so als Schlüsselfaktoren für die Produktion hochqualitativer Schichten identifiziert. Es konnte gezeigt werden, dass mit MP eine sehr effiziente Methode zur Herstellung homogener Schichten mit exzellenter Ausbeute ist. In weiteren Experimenten mit dem primordialen Alpha-Emitter 147Sm als Modellisotop wurde die Eignung solcher Schichten als Alpha-Quelle untersucht. Sowohl die Energieauflösung als auch der Anteil der Alpha-Teilchen, die den Detektor erreichten, waren von den Quelleneigenschaften abhängig. Die Effekte wurden verschiedenen Variablen der Dünnschicht zugeordnet, welche die Alpha-Spektren beeinflussten. Dominant war die Wahl des Lösungsmittels und die Rauigkeit des Substrats. Dies beeinflusste Schichtdicke und -morphologie sowie die Art des Schichtwachstums und veränderte die Detektionseffizienz in Alpha-Messungen bis zu 15%. Nur homogene, ebene Schichten, die aus DMF auf glatten Substraten abgeschieden wurden, eignen sich optimal als Alpha-Quelle. Die gewonnenen Ergebnisse erlauben die optimierte Herstellung nuklearer Targets durch MP. Künftige Anwendungen beinhalten insbesondere die Herstellung von Targets für neutroneninduzierte Spaltexperimente und untergrundarmeAlpha-Messungen sehr kleiner Aktivitäten.This work describes experiments to gain an improved understanding of the processes associated with the electrochemical production of thin lanthanide layers for nuclear science investigations, i.e., nuclear targets. Nd, Sm, and Gd layers were prepared by means of the so-called molecular plating (MP) technique, where electrodeposition from an organic medium is usually performed in the constant current mode using two-electrode cells. The obtained results allowed the identification of optimized production conditions, which led to a significantly improved layer quality. Constant current density MP is a mass-transport controlled process. The applied current is maintained constant by constant fluxes of electroactive species towards the cathode – where the layer is grown – and the anode. The investigations showed the cell potentials of the electrodeposition systems to be always dominated by the ohmic drop produced by the resistance of the solutions used for the studies. This allowed to derive an expression relating cell potential with concentration of the electroactive species. This expression is able to explain the trends recorded with different electrolyte concentrations and it serves as a basis to get towards a full understanding of the reasons leading to the characteristic minima observed in the evolution of the cell potential curves with time. The minima were found to correspond to an almost complete depletion of the Nd ions obtained by dissolution of the model salt used for the investigations. Nd was confirmed to be deposited at the cathode as derivatives of Nd3+ – possibly as carboxylate, oxide or hydroxide. This fact was interpreted on the basis of the highly negative values of the standard redox potentials typical for lanthanide cations. Among the different electroactive species present in the complex MP solutions, the Nd3+ ions were found to contribute to less than 20% to the total current. Because of electrolysis, also the mixed solvent contributed to the applied costant current as an electroactive species. The presence of electrolyzed solvent was confirmed by the analysis of the produced deposits, which were always covered by both chemisorbed and physisorbed solvent molecules. Target characterizations showed the surfaces of the layers to present severe cracks, which were found to form during the drying time after completion of the MP. Different drying environments, i.e., air or Ar, did not affect the deposits. The drying-related nature of cracking and the solvent composition of the produced layers suggested to perform constant current density MPs using solvents with significantly different physical properties, most notably the boiling point. N,N-dimethylformamide (DMF), i.e., the highest boiling point solvent, proved to be very effective for the production of crack-free surfaces. DMF, in combination with the use of very smooth deposition substrates, allowed the growth of smooth, defectless layers, which likely underwent smaller stress during drying than the deposits produced by using rougher substrates and more volatile solvents. The roughness of the deposition substrate and the solvent used for the platings proved then to be core factors for the preparation of high quality layers. MP thus showed to be very effective for the production of uniform and homogeneous targets with excellent yield. Tests of the performance of layers produced by MP as α-particle sources were also carried out. 147Sm was used as model isotope for the α spectroscopy investigations. Both peak resolution and the fraction of α particles reaching the detector were found to be influenced by source effects. These effects were categorized according to different “layer variables”, i.e., variables influencing the α spectra by means of “layer effects”, and were found to be promoted by the plating solvent and the roughness of the deposition substrate used to perform the MPs. These parameters likely affected thickness, morphology, and growth mode of the layers. The layer variables proved to alter the relative detection efficiencies of the α measurements by as much as 15%. Only the uniform and homogeneous layers produced by MP from DMF using the smoothest deposition substrate available turned out to be optimum α-particle sources. The results obtained from this work open the way to an improved production of nuclear targets by means of molecular plating. Future applications include in particular the preparation of targets to be used in neutron-induced fission experiments and in low-background, low-activity α measurements

Studio di fenomeni dinamici di rilevanza in catalisi attraverso l'utilizzo del sistema modello FE/TiOx/Pt(111)

This thesis is about the study of the SMSI effect on model catalysts such as Fe/TiOx/Pt (111). The study has involved the use of techniques such as TPD (Thermal Programmed Desorption), XPS (Xray Photoelectron Spectroscopy), LEED (Low Energy Electron Diffraction) and STM (Scanning Tunnelling Microscopy)

Quantitative molecular plating of large-area 242Pu targets with improved layer properties

For measurements of the neutron-induced fission cross section of 242Pu, large-area (42cm2) 242Pu targets were prepared onTi-coated Si wafers by means of constant current density molecular plating. Radiochemical separations were performed prior tothe platings. Quantitative deposition yields (>95%) were determined for all targets by means of alpha-particles pectroscopy. Layer densities in the range of 100–150 μg/cm2 were obtained. The homogeneity of the targets was studied by radiographic imaging. A comparative study between the quality of the layers produced on the Ti-coated Si wafers and the quality of layers grown on normal Ti foils was carried out by applying scanning electronmicroscopy and energy dispersive X-ray spectroscopy. Ti-coated Si wafers resulted clearly superior to Ti foils in the production of homogeneous 242Pu layers with minimum defectivity.JRC.E.3-Materials researc

Locality-aware subgraphs for inductive link prediction in knowledge graphs

Recent methods for inductive reasoning on Knowledge Graphs (KGs) transform the link prediction problem into a graph classification task. They first extract a subgraph around each target link based on the -hop neighborhood of the target entities, encode the subgraphs using a Graph Neural Network (GNN), then learn a function that maps subgraph structural patterns to link existence. Although these methods have witnessed great successes, increasing often leads to an exponential expansion of the neighborhood, thereby degrading the GNN expressivity due to oversmoothing. In this paper, we formulate the subgraph extraction as a local clustering procedure that aims at sampling tightly-related subgraphs around the target links, based on a personalized PageRank (PPR) approach. Empirically, on three real-world KGs, we show that reasoning over subgraphs extracted by PPR-based local clustering can lead to a more accurate link prediction model than relying on neighbors within fixed hop distances. Furthermore, we investigate graph properties such as average clustering coefficient and node degree, and show that there is a relation between these and the performance of subgraph-based link prediction

Geolocation of Cultural Heritage Using Multi-view Knowledge Graph Embedding

Knowledge Graphs (KGs) have proven to be a reliable way of structuring data. They can provide a rich source of contextual information about cultural heritage collections. However, cultural heritage KGs are far from being complete. They are often missing important attributes such as geographical location, especially for sculptures and mobile or indoor entities such as paintings. In this paper, we first present a framework for ingesting knowledge about tangible cultural heritage entities from various data sources and their connected multi-hop knowledge into a geolocalized KG. Secondly, we propose a multi-view learning model for estimating the relative distance between a given pair of cultural heritage entities, based on the geographical as well as the knowledge connections of the entities

Vacuum Chromatography of Tl on SiO 2 at the Single-Atom Level

An isothermal vacuum chromatography setup for superheavy element chemistry studies was developed and tested online at the one-atom-at-a-time level. As a model system, the adsorption behavior of thallium on quartz was chosen with respect to a future chemical characterization of its superheavy homologue, element 113 (E113, Z = 113), using the described setup. Short-lived 184Tl (t1/2 = 10.1(5) s) was produced in the reaction 152Gd(35Cl, 3n)184Tl and delivered as a mass-separated ion beam to the chemistry experiment: A subsurface implantation and a subsequent fast thermal release from a metal matrix was followed by isothermal vacuum chromatography as the chemical separation stage. Single atomic species passing this chromatographic separation were finally identified by time- and energy-resolved event-by-event α-spectroscopy using a diamond-based solid-state detector. The derived adsorption enthalpy of −ΔHadsSiO2(Tl) = 158 ± 3 kJ·mol–1 significantly exceeds available data but correlates well with the adsorption of other elements studied on the same surface. The described technique enables chemical experiments with short-lived transactinide elements (t1/2 < 1 s), surpassing the rapidity of today’s state-of-the-art gas-phase experiments by at least 1 order of magnitude