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Environmental and energy issues have stimulated renewed interest in utilizing both water and methanol as reagents and reaction mediums. Our current interest is to evaluate the scope of group nine organometallics and establish thermodynamic parameters for their reactivity in aqueous solvent. A comprehensive thermodynamic database for a wide scope of organo-rhodium transformations in a range of reaction media including benzene, water, and methanol has been well established by our group. Aqueous solutions of rhodium porphyrin have been determined to manifest an exceptional range of substrate reactions with carbon monoxide, dihydrogen, olefins, methanol and aldehydes. This study will focus on expansion of the thermodynamic database to all the group nine metals, particularly the iridium porphyrin systems in both water and methanol. Substrate reactivity and development of new mechanistic strategies for the conversion of carbon monoxide, alkanes, and alkenes to organic oxygenates are central objectives. Water/Methanol soluble porphyrin iridium complexes including iridium tetrakis(p-sulfonatophenyl)porphyrin ((TSPP)Ir) and iridium tetrakis(3,5-sulfonatomesityl)porphyrin ((TMPS)Ir) derivatives can be prepared by sulfonation of tetra phenyl porphyrin (H2TPP) and tetra mesityl porphyrin (H2TMP). The reactivity of dihydrogen with aqueous solutions of iridium(III) tetrakis(p-sulfonatophenyl)porphyrin ((TSPP)Ir(III)) complexes produce equilibrium distributions between six iridium species including iridium hydride ([(TSPP)Ir-D(D2O)]-4), iridium(I) ([(TSPP)IrI(D2O)]-5), and iridium (II) dimer ([(TSPP)IrII(D2O)]2-8) complexes. Each of these types of iridium porphyrin species including Ir(I), Ir(II), Ir(III), Ir-H, and Ir-OH function as precursors for a range of organometallic substrate reactions. A primary objective is to define the quantitative relationships pertaining to the distribution of species in aqueous solution as a function of the dihydrogen and hydrogen ion concentrations through direct measurement of five equilibrium constants along with free energy changes of coordinated water and free energy changes of reactions of dihydrogen in water. Reactivity, kinetics and evaluation of equilibrium thermodynamics, including the reactions of iridium hydroxide and methoxide with olefins to produce beta-hydroxyalkyl and beta-methoxyalkyl complexes, reactions of iridium hydride and olefins to produce iridium alkyl complexes, and reactions of iridium hydride with carbon monoxide to produce iridium formyl [Ir-CHO] complexes are also objectives of this research. Another research goal is the design and synthesis of diporphyrin ligands that form dimetal complexes capable of preorganizing transition states for substrate reactions that involve two metal centers. Dirhodium dimetalloradical complexes are observed to manifest large rate increases over mono-metalloradical activation reactions of hydrogen, methane, and other small molecule substrates. In this study, synthesis of diporphyrin (bisporphyrin) ligands and other ligands which will permit dimetallo complexes like anti-aromatic [14]annulene and low steric porphine ligands will be also be examined. / Chemistry

The objective of the present study was to acquire a better understanding of parameters controlling the species generation and transport from compartment fires. The experiments were performed in a half-scale ISO 9705 compartment and a 6.1 m long hallway connected in a head-on configuration. The buoyancy driven propane fire was provided by a burner and a continuous gaseous fuel supply system. All the measurements were obtained during the steady state of the fire. The ventilation conditions were fixed and three different fire source elevations were studied for heat release rates ranging from 20 kW to 150kW. The species yields were obtained from performing detailed mapping measurements at the compartment and hallway exit planes. The measurements included local specie mole fractions of oxygen, carbon dioxide, carbon monoxide and unburned hydrocarbons. The local temperature and the local pressure (for local gas velocity calculations) were also measured. In addition, visual observations of the flow dynamic were performed through a window and the vents to give useful insights and lead to a better understanding of the combustion process. The data obtained from the species generation study was analyzed using previously developed methods. The method based on equivalence ratio was presented and determined inappropriate for the present study where the global equivalence ratio was not equal to the plume equivalence ratio due to the complexity of the fire dynamic taking place. The method consisting of correlating the species yields based on the combustion within the compartment as a function of a non dimensional heat release rate allowed qualitative conclusions to be made. The non-dimensional heat release rate was based on the fuel load and the geometric parameters of the compartment. This methodology revealed similarities in the species production between the three fire source elevations investigated. A correlation of the data was obtained based on experimental data. The transport of species to remote locations was studied for the three fire source elevations and fixed ventilation conditions. Species mole fractions and yields were obtained at the compartment exit plane (compartment/hallway interface) and at the hallway exit plane. The results were compared for various heat release rates and showed differences for some scenarios attributed to mixing along the hallway and oxidation reactions outside the compartment. / Master of Science

The purpose of this study was to investigate the supported catalyst of the type CuO-Al₂O₃ which has been described by Lockwood and Frazer (13). This type of catalyst is unique in that it has a high activity at low temperatures, is suitable for use at high temperatures and has been reported to be truly catalytic in the oxidation of carbon monoxide. Lockwood and Frazer (15) have described the preparation of a catalyst of this type. Their description of the method of preparation and of the quantities of materials used is rather inadequate for an exact duplication of the catalyst which they prepared and studied. The method of procedure used in the study of this catalyst has been to vary both the composition and heat treatment of the catalysts and to observe the subsequent change in catalytic activity. 1. Increasing the copper oxide content of the copper oxide-aluminum catalysts increases the activity of the catalysts at least over the composition range studied. 2. Increasing the temperature to which the copper oxide-aluminum oxide catalysts are heated increases the activity. 3. The temperatures required for the catalysts to exhibit 100% activity are all above 270°C. 4. It was found impossible to reproduce the copper oxide-aluminum catalyst which was prepared by Lockwood and Frazer. 5. A catalyst prepared from pure copper oxide was more active than any of the catalysts which were studied. / M.S.

Tesis por compendio / La presente tesis doctoral titulada “Complejos metálicos de transición para la detección cromo-fluorogénica de monóxido de carbono en aplicaciones medioambientales y biomédicas” se basa en la utilización de los principios de la Química de la Coordinación para el diseño y desarrollo de nuevos compuestos químicos capaces de detectar monóxido de carbono en aire mediante cambios de color y/o de fluorescencia. La primera familia de sondas colorimétricas que se presenta en el capítulo 3 está basada en unos complejos dinucleares de rodio hexacoordinados con ligandos trifenilfosfina y distintos ácidos carboxílicos. Primeramente, se expone el trabajo desarrollado con el complejo A de fórmula [Rh2(C6H4PPh2)2(O2CCH3)2]·(HO2CCH3)2 capaz de detectar selectivamente y con alta sensibilidad CO tanto en disolución como en aire. En presencia de CO se produce un cambio de color de morado a amarillo, debido a la coordinación del CO en las posiciones axiales del complejo. A continuación se amplia el trabajo con una colección de cinco complejos de rodio (II) B-F adsorbidos en gel de sílice y se estudia su uso como sondas para la detección de CO en aire mediante cambios de color visibles a simple vista. En tercer lugar, se procede a depositar los complejos en papel de celulosa para facilitar su aplicación en la detección práctica de CO. Se elige el complejo D [Rh2[(C6H4)P(C6H5)2]2(O2CCF3)2]· (CF3CO2H)2 como el más sensible a CO en este nuevo soporte y se inserta dentro de un sistema opto-electrónico capaz de cuantificar el CO presente en el aire; mediante la transducción del cambio de color del complejo en una señal eléctrica, y esta señal en un valor de concentración de CO determinado. Finalmente, teniendo en cuenta el papel del CO como agente terapéutico y aprovechando que la coordinación de CO en los complejos de rodio presentados es reversible; se seleccionan los dos complejos dicarbonílicos con cinéticas de liberación de CO en disolución más lentas A·(CO)2 y F·(CO)2 de fórmulas [Rh2[(C6H4)P(C6H5)2]2(O2CCH3)2]·(CO)2 y [Rh2[(m-CH3C6H3)P(m- CH3C6H4)2]2(O2CCH3)2]·(CO)2) como posibles moléculas liberadoras de CO (CO-RMs) a utilizar en estudios sobre inhibición de agentes indicadores de inflamación celular (ver capítulo 4). En la segunda parte de esta tesis doctoral se ha preparado una colección de vinil complejos de rutenio y de osmio G-K funcionalizados con grupos dadores de electrones (pireno, tolueno y benceno) y con un grupo aceptor de electrones (2,1,3-benzotiadiazol (BTD)). Estos complejos son coloreados, ya que presentan una banda de transferencia de carga. En presencia de CO se produce el desplazamiento del BTD con el consiguiente cambio de color (ver capítulo 5). En primer lugar, para posibilitar la detección fluorogénica de CO, se ha preparado el complejo G mediante el anclaje del fluoróforo pirenilvinilo como ligando dador de electrones del complejo de rutenio (II). En presencia de CO y mediante el desplazamiento del BTD se consigue un aumento de fluorescencia observable incluso a simple vista. Para concluir la segunda parte de la tesis se han sintetizado cuatro complejos más, H-K, dos de rutenio y dos de osmio; que han sido utilizados también para detectar CO en aire. Para la preparación de estas sondas también se ha utilizado gel de sílice como soporte. En presencia de CO se produce el desplazamiento del BTD (colorante) y los complejos metálicos cambian de color, permitiendo así la semicuantificación del CO en los rangos de concentración en que el CO es altamente tóxico incluso para exposiciones cortas. / Moragues Pons, ME. (2014). Transition metal complexes for chromo-fluorogenic detection of carbon monoxide in environmental and biomedical applications [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/48453 / Premios Extraordinarios de tesis doctorales / Compendio