Design. Fabrication and Characterization of Fiber Optic Sensors for Physical and Chemical Applications

Advent of lasers together with the advancement in fiber optics technology has revolutionized the sensor technology. Advancement in the telemetric applications of optical fiber based measurements is an added bonus. The present thesis describes variety of fiber based sensors using techniques like micro bending, long period grating and evanescent waves. Sensors to measure various physical and chemical parameters are described in this thesis.

Preparació i avaluació de microcàpsules de sílice mitjançant l'ús d'emulsions múltiples

Màster en Química Avançada: Química Física de Materials, Curs 2008-2009. Director: Francesc Mas Pujadas

Microcápsulas de sílice preparadas a partir de sistemas tensioactivos para la liberación de sustancias activas

Màster Experimental en Química: Química Física Curs: 2008-2009 Tutor: Francesc Mas Director: Carlos Rodríguez Abreu

A Study of the Physical and Engineering Behaviour of Cochin Marine Clays

With the increase in population, housing and construction of various facilities have been a problem with urbanization. Having exhausted all the trouble free hand, man is nowon the lookout for techniques to improve areas which were originally considered uninhabitable. Thus this study is based on the nature and engineering behavior of soft clays covering long stretches of coastal line and methods to improve their geotechnical properties .The main aim of the present investigation is to study in detail the physical and engineering behavior of the marine clays of Cochin. While it is well known that the marine clays have been posing numerous problems to foundation engineers all along, the relevant literature reveals that no systematic and comprehensive study has been attempted to date. The: knowledge gained through the study is suitably used to improve these properties with appropriate additives.

Influencia de la concentración de polielectrolito en el binding específico y electrostático de iones

Màster Experimental en Química: Química Física

First results of experimental and theoretical investigations on sextet states of doubly-excited five-electron ions

In continuation of our previous work on doubly-excited ions with three and four electrons we present the first results on optical transitions in the term system of doubly-excited ions with five electrons. Transitions between such sextet states were identified in beam-foil spectra of the ions nitrogen, oxygen and fluorine. Assignments were first established by comparison with Multi-Configuration Dirac-Fock calculations. Later assignments were aided by Multi-Configuration Hartree-Fock calculations (see the contribution by G. Miecznik et al. in this issue). Decay curves were recorded for all six candidate lines. The lifetime results are compared to theoretical values which confirm most of the assignments qualitatively.

Physical and psychological aggression in dating relationships in Spanish university students. 'Agresi??n f??sica y psicol??gica en las relaciones de noviazgo en universitarios espa??oles'

Resumen tomado de la publicaci??n. Resumen tambi??n en ingl??s

Nature Chemistry publica dos articles sobre les recerques dels investigadors del QBIS de la UdG

Publicar a la Nature Chemistry, revista que té un dels factors d'impacte més elevats i del prestigiós grup Nature, és extraordinàriament important i un autèntic succés per al grup de recerca i per a la carrera de l'investigador que ho aconsegueix. És per això que l'article fa referència a dos articles: un sobre la tesi doctoral d'Irene Prat i l'altre de la recerca en què treballa l'investigador Julio Lloret. En ambdós es mostren els resultats de la recerca del QBIS en aquest camp, el que s'han trobat a la frontera, que és la possibilitat d'utilitzar una variant del ferro extremament reactiva Fe(V) com a catalitzador per obtenir l'oxigen que conté l'aigua. Aquesta podria ser la primera etapa en la cursa per obtenir hidrogen a gran escala i a baix cost, 'una de les principals fonts d'energia del futur', asseguren

New Ruthenium complexes containing N, P and S-donor type of ligands: coordination chemistry, characterization and application to asymetric and non-asymetric catalysis

Síntesi de nous complexos de Ruteni amb lligands no quirals que tenen per fórmula [Ru(phen)([9]aneS3)X] (on X = H2O, py i MeCN). Caracterització espectroscòpica electroquímica i estructural d'aquesta família de complexos. Estudi de les seves propietats catalítiques en front a l'oxidació de substrats orgànics com l'alcohol benzílic en reaccions d'electrocatàlisi. Avaluació cinètica dels mecanismes de substitució entre els complexos Ru-py i Ru-MeCN. Generació d'un interruptor molecular foto-induït. Síntesi de nous complexos quirals de Ru atropoisomèricament purs amb lligands oxazolínics que tenen per fórmula [Ru(trpy)(Ph-box-R)X] on (X = Cl, H2O, py, MeCN, 2-OH-py). Caracterització estructural exhaustiva en estat sòlid (Raig-X) en solució (RMN) i en fase gas (càlculs DFT). Avaluació de la seva activitat catalítica en reaccions asimmetriques d'epoxidació de substrats proquirals. Síntesi de nous lligands polipiridílics quirals amb simetria C3. Estudi de la seva química de coordinació i avaluació de la seva activitat catalítica en reaccions asimmetriques d'oxidació i reducció.

Rhodium(I) catalyzed [2+2+2] cycloaddition reactions: experimental and theoretical studies

The [2+2+2] cycloaddition reaction involves the formation of three carbon-carbon bonds in one single step using alkynes, alkenes, nitriles, carbonyls and other unsaturated reagents as reactants. This is one of the most elegant methods for the construction of polycyclic aromatic compounds and heteroaromatic, which have important academic and industrial uses. The thesis is divided into ten chapters including six related publications. The first study based on the Wilkinson’s catalyst, RhCl(PPh3)3, compares the reaction mechanism of the [2+2+2] cycloaddition process of acetylene with the cycloaddition obtained for the model of the complex, RhCl(PH3)3. In an attempt to reduce computational costs in DFT studies, this research project aimed to substitute PPh3 ligands for PH3, despite the electronic and steric effects produced by PPh3 ligands being significantly different to those created by PH3 ones. In this first study, detailed theoretical calculations were performed to determine the reaction mechanism of the two complexes. Despite some differences being detected, it was found that modelling PPh3 by PH3 in the catalyst helps to reduce the computational cost significantly while at the same time providing qualitatively acceptable results. Taking into account the results obtained in this earlier study, the model of the Wilkinson’s catalyst, RhCl(PH3)3, was applied to study different [2+2+2] cycloaddition reactions with unsaturated systems conducted in the laboratory. Our research group found that in the case of totally closed systems, specifically 15- and 25-membered azamacrocycles can afford benzenic compounds, except in the case of 20-membered azamacrocycle (20-MAA) which was inactive with the Wilkinson’s catalyst. In this study, theoretical calculations allowed to determine the origin of the different reactivity of the 20-MAA, where it was found that the activation barrier of the oxidative addition of two alkynes is higher than those obtained for the 15- and 25-membered macrocycles. This barrier was attributed primarily to the interaction energy, which corresponds to the energy that is released when the two deformed reagents interact in the transition state. The main factor that helped to provide an explanation to the different reactivity observed was that the 20-MAA had a more stable and delocalized HOMO orbital in the oxidative addition step. Moreover, we observed that the formation of a strained ten-membered ring during the cycloaddition of 20-MAA presents significant steric hindrance. Furthermore, in Chapter 5, an electrochemical study is presented in collaboration with Prof. Anny Jutand from Paris. This work allowed studying the main steps of the catalytic cycle of the [2+2+2] cycloaddition reaction between diynes with a monoalkyne. First kinetic data were obtained of the [2+2+2] cycloaddition process catalyzed by the Wilkinson’s catalyst, where it was observed that the rate-determining step of the reaction can change depending on the structure of the starting reagents. In the case of the [2+2+2] cycloaddition reaction involving two alkynes and one alkene in the same molecule (enediynes), it is well known that the oxidative coupling may occur between two alkynes giving the corresponding metallacyclopentadiene, or between one alkyne and the alkene affording the metallacyclopentene complex. Wilkinson’s model was used in DFT calculations to analyze the different factors that may influence in the reaction mechanism. Here it was observed that the cyclic enediynes always prefer the oxidative coupling between two alkynes moieties, while the acyclic cases have different preferences depending on the linker and the substituents used in the alkynes. Moreover, the Wilkinson’s model was used to explain the experimental results achieved in Chapter 7 where the [2+2+2] cycloaddition reaction of enediynes is studied varying the position of the double bond in the starting reagent. It was observed that enediynes type yne-ene-yne preferred the standard [2+2+2] cycloaddition reaction, while enediynes type yne-yne-ene suffered β-hydride elimination followed a reductive elimination of Wilkinson’s catalyst giving cyclohexadiene compounds, which are isomers from those that would be obtained through standard [2+2+2] cycloaddition reactions. Finally, the last chapter of this thesis is based on the use of DFT calculations to determine the reaction mechanism when the macrocycles are treated with transition metals that are inactive to the [2+2+2] cycloaddition reaction, but which are thermally active leading to new polycyclic compounds. Thus, a domino process was described combining an ene reaction and a Diels-Alder cycloaddition.

Improvement of strategies for the management of fire blight (Erwinia amylovora). Evaluation and optimization of physical and chemical control methods, and use of decision support systems

El foc bacterià és una malaltia que afecta a plantes de la família de la rosàcies, causada pel bacteri Erwinia amylovora. El seu rang d'hostes inclou arbres fruiters, com la perera, la pomera o el codonyer, i plantes ornamentals de gran interès comercial i econòmic. Actualment, la malaltia s'ha dispersat i es troba àmpliament distribuïda en totes les zones de clima temperat del món. A Espanya, on la malaltia no és endèmica, el foc bacterià es va detectar per primer cop al 1995 al nord del país (Euskadi) i posteriorment, han aparegut varis focus en altres localitzacions, que han estat convenientment eradicats. El control del foc bacterià, és molt poc efectiu en plantes afectades per la malaltia, de manera que es basa en mesures encaminades a evitar la dispersió del patogen, i la introducció de la malaltia en regions no endèmiques. En aquest treball, la termoteràpia ha estat avaluada com a mètode d'eradicació d'E. amylovora de material vegetal de propagació asimptomàtic. S'ha demostrat que la termoteràpia és un mètode viable d'eradicar E. amylovora de material de propagació. Gairebé totes les espècies i varietats de rosàcies mantingudes en condicions d'humitat sobrevivien 7 hores a 45 ºC i més de 3 hores a 50 ºC, mentre que més d'1 hora d'exposició a 50 ºC amb calor seca produïa danys en el material vegetal i reduïa la brotació. Tractaments de 60 min a 45 ºC o 30 min a 50 ºC van ser suficients per reduir la població epífita d'E. amylovora a nivells no detectables (5 x 102 ufc g-1 p.f.) en branques de perera. Els derivats dels fosfonats i el benzotiadiazol són efectius en el control del foc bacterià en perera i pomera, tant en condicions de laboratori, com d'hivernacle i camp. Els inductors de defensa de les plantes redueixen els nivells de malaltia fins al 40-60%. Els intervals de temps mínims per aconseguir el millor control de la malaltia van ser 5 dies pel fosetil-Al, i 7 dies per l'etefon i el benzotiadiazol, i les dosis òptimes pel fosetil-Al i el benzotiadiazol van ser 3.72 g HPO32- L-1 i 150 mg i.a. L-1, respectivament. Es millora l'eficàcia del fosetil-Al i del benzotiadiazol en el control del foc bacterià, quan es combinen amb els antibiòtics a la meitat de la dosi d'aquests últims. Tot i que l'estratègia de barrejar productes és més pràctica i fàcil de dur a terme a camp, que l'estratègia de combinar productes, el millor nivell de control de la malaltia s'aconsegueix amb l'estratègia de combinar productes. Es va analitzar a nivell histològic i ultrastructural l'efecte del benzotiadiazol i dels fosfonats en la interacció Erwinia amylovora-perera. Ni el benzotiadiazol, ni el fosetil-Al, ni l'etefon van induir canvis estructurals en els teixits de perera 7 dies després de la seva aplicació. No obstant, després de la inoculació d'E. amylovora es va observar en plantes tractades amb fosetil-Al i etefon una desorganització estructural cel·lular, mentre que en les plantes tractades amb benzotiadiazol aquestes alteracions tissulars van ser retardades. S'han avaluat dos models (Maryblyt, Cougarblight) en un camp a Espanya afectat per la malaltia, per determinar la precisió de les prediccions. Es van utilitzar dos models per elaborar el mapa de risc, el BRS-Powell combinat i el BIS95 modificat. Els resultats van mostrar dos zones amb elevat i baix risc de la malaltia. Maryblyt i Cougarblight són dos models de fàcil ús, tot i que la seva implementació en programes de maneig de la malaltia requereix que siguin avaluats i validats per un període de temps més llarg i en àrees on la malaltia hi estigui present.

Physical and perceived noise levels within the neonatal intensive care unit of St. Louis Children's Hospital

This paper studies the success of the renovation of the Neonatal Intensive Care Unit at St. Louis Children's Hospital in reducing noise levels and improving the work environment.

Seasonal variations of the physical and optical characteristics of Saharan Dust: results from the Dust outflow and Deposition to the Ocean (DODO) experiment

North African dust is important for climate through its direct radiative effect on solar and terrestrial radiation and its role in the biogeochemical system. The Dust Outflow and Deposition to the Ocean project (DODO) aimed to characterize the physical and optical properties of airborne North African dust in two seasons and to use these observations to constrain model simulations, with the ultimate aim of being able to quantify the deposition of iron to the North Atlantic Ocean. The in situ properties of dust from airborne campaigns measured during February and August 2006, based at Dakar, Senegal, are presented here. Average values of the single scattering albedo (0.99, 0.98), mass specific extinction (0.85 m^2 g^-1 , 1.14 m^2 g^-1 ), asymmetry parameter (0.68, 0.68), and refractive index (1.53--0.0005i,1.53--0.0014i) for the accumulation mode were found to differ by varying degrees between the dry and wet season, respectively. It is hypothesized that these differences are due to different source regions and transport processes which also differ between the DODO campaigns. Elemental ratios of Ca/Al were found to differ between the dry and wet season (1.1 and 0.5, respectively). Differences in vertical profiles are found between seasons and between land and ocean locations and reflect the different dynamics of the seasons. Using measurements of the coarse mode size distribution and illustrative Mie calculations, the optical properties are found to be very sensitive to the presence and amount of coarse mode of mineral dust, and the importance of accurate measurements of the coarse mode of dust is highlighted.