In silico study of reaction mechanisms and design principles for water oxidation catalysts

Throughout the last decades the water oxidation process has been extensively investigated. However, open questions remain on the reaction mechanism and the possible intermediates in the catalytic cycle. Indeed, different catalysts can function through different reaction routes. Some of them work in a proton-coupled electron transfer (PCET) pathway, while other catalysts have a non-PCET behaviour. Some of these problems lie in the very short lifetime of intermediates, which makes it difficult to characterize them experimentally. Within this context, DFT calculations represent a very useful tool. In fact quantum-mechanical computational tools allow exploring and analyzing the possible intermediates and study and compare different reaction pathways in order to find the energetically most likely one. In the same way the thermodynamics of the catalytic cycle and the kinetics of the reaction coordinates can be analyzed. The specific aim of this thesis is the study of different catalysts and reaction pathways to find clues about the mechanism of the reaction and develop guiding principles for the design of efficient water oxidation complexesUBL - phd migration 201

Self-assembly of Clicked Star-Shaped Triazines into Functional Nanostructures

Two non-amphiphilic star-shaped 2, 4, 6-tris(1, 2, 3-triazol-4-yl)-1, 3, 5-triazines showing different behavior in terms of self-assembly and luminescent properties are described. They aggregate in the liquid phase to form low-dimensional nanostructures with a variety of morphologies, such as spherical particles, one-hole hollow spheres, toroids, twisted fibers or helical nanotubes, just by varying the conditions of a straightforward reprecipitation method. Aggregation has an opposite effect concerning the fluorescent properties of the proposed compounds, either causing the enhancement or the quenching of the emission after the self-assembly. Quantum chemical calculations have been also performed to assist in the structural and electronic characterization of the two star-shaped compounds

Holocene alluvial sequence in the val de zaragoza (Los Monegros) in the palaeoenvironmental context of the ebro basin (Ne Spain)

Flat-bottomed valleys formed by Holocene fills are the most characteristic landforms in the center of the Ebro basin. This paper analyzes, within a regional framework, a small fluvial basin located in the north of the Alcubierre Range. Three Holocene morphosedimentary units (H1-H3) and a sub-functional level (H4) are identified. These units are representative of the regional geomorphological evolutionary process in the Ebro basin. New chronological insights on climate and landscape management are provided by a study of the Bastarás weir, a construction made for water flow management during the Little Ice Age (LIA). The integration of Val de Zaragoza radiocarbon datings into the regional framework enables the authors to identify the main formation stages, as well as the influence of climatic and human factors on its evolution. The intensification of human pressure in the territory is reflected in a progressive increase in sediment accumulation rates in the valleys, peaking during Roman times and the Little Ice Age. Los valles de fondo plano formados por rellenos holocenos constituyen los paisajes más característicos del sector central de la cuenca del Ebro. En este trabajo se analiza una pequeña cuenca fluvial localizada en el norte de la Sierra de Alcubierre, en la que se han identificado tres unidades morfosedimentarias holocenas (H1-H3) y un nivel subfuncional (H4), que son representativos de la evolución geomorfológica regional de la Cuenca del Ebro. Uno de los aspectos más relevantes del valle lo constituye el azud de Bastarás, construcción realizada durante la Pequeña Edad del Hielo para el aprovechamiento del agua, que aporta nuevos datos cronológicos sobre dicha época y acerca de la gestión del territorio. La integración de las dataciones radiocarbónicas obtenidas en la Val de Zaragoza en un marco regional ha permitido precisar las principales etapas de formación de los valles de fondo plano, así como la importancia de los factores climáticos y humanos en su evolución. La intensificación de la presión humana sobre el territorio queda reflejada en un progresivo aumento en las tasas de acumulación de sedimentos en los valles, alcanzando sus picos máximos en Época Romana y en la Pequeña Edad del Hielo

Curvature effects on the surface thickness and tension at the free interface of 4^4He systems

The thickness $W$ and the surface energy $\sigma_A$ at the free interface of superfluid $^4$He are studied. Results of calculations carried out by using density functionals for cylindrical and spherical systems are presented in a unified way, including a comparison with the behavior of planar slabs. It is found that for large species $W$ is independent of the geometry. The obtained values of $W$ are compared with prior theoretical results and experimental data. Experimental data favor results evaluated by adopting finite range approaches. The behavior of $\sigma_A$ and $W \sigma_A$ exhibit overshoots similar to that found previously for the central density, the trend of these observables towards their asymptotic values is examined.Comment: 35 pages, TeX, 5 figures, definitive versio

Viability of competing field theories for the driven lattice gas

It has recently been suggested that the driven lattice gas should be described by a novel field theory in the limit of infinite drive. We review the original and the new field theory, invoking several well-documented key features of the microscopics. Since the new field theory fails to reproduce these characteristics, we argue that it cannot serve as a viable description of the driven lattice gas. Recent results, for the critical exponents associated with this theory, are re-analyzed and shown to be incorrect.Comment: 4 pages, revtex, no figure

Prediction of the in vivo mechanical behavior of biointegrable acrylic macroporous scaffolds

[EN] This study examines a biocompatible scaffold series of random copolymer networks P(EA-HEA) made of Ethyl Acrylate, EA, and 2-Hydroxyl Ethyl Acrylate, HEA. The P(EA-HEA) scaffolds have been synthesized with varying crosslinking density and filled with a Poly(Vinyl Alcohol), PVA, to mimic the growing cartilaginous tissue during tissue repair. In cartilage regeneration the scaffold needs to have sufficient mechanical properties to sustain the compression in the joint and, at the same time, transmit mechanical signals to the cells for chondrogenic differentiation. Mechanical tests show that the elastic modulus increases with increasing crosslinking density of P(EA-HEA) scaffolds. The water plays an important role in the mechanical behavior of the scaffold, but highly depends on the crosslinking density of the proper polymer. Furthermore, when the scaffold with hydrogel is tested it can be seen that the modulus increases with increasing hydrogel density. Even so, the mechanical properties are inferior than those of the scaffolds with water filling the pores. The hydrogel inside the pores of the scaffolds facilitates the expulsion of water during compression and lowers the mechanical modulus of the scaffold. The P(EA-HEA) with PVA shows to be a good artificial cartilage model with mechanical properties close to native articular cartilage.This work was funded by the Spanish Ministry of Economy and Competitiveness (MINECO) through the project MAT2013-46467-C4-1-R (including the FEDER financial support). CIBER-BBN is an initiative funded by the VI National R&D&i Plan 2008-2011, Iniciativa Ingenio 2010, Consolider Program. CIBER actions are financed by the Instituto de Salud Carlos III with assistance from the European Regional Development Fund. The authors acknowledge the assistance and advice of Electron Microscopy Service of the UPV.Vikingsson, L.; Antolinos Turpín, CM.; Gómez-Tejedor, JA.; Gallego Ferrer, G.; Gómez Ribelles, JL. (2016). Prediction of the in vivo mechanical behavior of biointegrable acrylic macroporous scaffolds. Materials Science and Engineering: C. 61:651-658. https://doi.org/10.1016/j.msec.2015.12.068S6516586

Twenty five years after KLS: A celebration of non-equilibrium statistical mechanics

When Lenz proposed a simple model for phase transitions in magnetism, he couldn't have imagined that the "Ising model" was to become a jewel in field of equilibrium statistical mechanics. Its role spans the spectrum, from a good pedagogical example to a universality class in critical phenomena. A quarter century ago, Katz, Lebowitz and Spohn found a similar treasure. By introducing a seemingly trivial modification to the Ising lattice gas, they took it into the vast realms of non-equilibrium statistical mechanics. An abundant variety of unexpected behavior emerged and caught many of us by surprise. We present a brief review of some of the new insights garnered and some of the outstanding puzzles, as well as speculate on the model's role in the future of non-equilibrium statistical physics.Comment: 3 figures. Proceedings of 100th Statistical Mechanics Meeting, Rutgers, NJ (December, 2008

In silico study of reaction mechanisms and design principles for water oxidation catalysts

Throughout the last decades the water oxidation process has been extensively investigated. However, open questions remain on the reaction mechanism and the possible intermediates in the catalytic cycle. Indeed, different catalysts can function through different reaction routes. Some of them work in a proton-coupled electron transfer (PCET) pathway, while other catalysts have a non-PCET behaviour. Some of these problems lie in the very short lifetime of intermediates, which makes it difficult to characterize them experimentally. Within this context, DFT calculations represent a very useful tool. In fact quantum-mechanical computational tools allow exploring and analyzing the possible intermediates and study and compare different reaction pathways in order to find the energetically most likely one. In the same way the thermodynamics of the catalytic cycle and the kinetics of the reaction coordinates can be analyzed. The specific aim of this thesis is the study of different catalysts and reaction pathways to find clues about the mechanism of the reaction and develop guiding principles for the design of efficient water oxidation complexe