Orientador: Alexandre Zirpoli Simões / Banca: Elson de Campos / Banca: Filiberto González Garcia / Resumo: Por ser um gás tóxico, inodoro, insípido e incolor, ou seja, imperceptível ao ser humano, o monóxido de carbono (CO) apresenta um sério risco à saúde, sendo necessário um sensor eficiente que alerte sua presença. Assim, filmes espessos foram depositados manualmente sobre substratos de alumina a partir de nanopartículas de dióxido de cério (CeO2) puro e dopadas com európio sintetizadas pelo método hidrotermal assistido por micro-ondas (HAM), visando a sua aplicação como sensores de gás. As nanopartículas fabricadas pelo método HAM foram caracterizadas por Difração de Raios-X (DRX), Espectroscopia Raman, Espectroscopia de Absorção no Ultravioleta-Visível (UV-Vis), área de superfície específica (SBET), entre outros, enquanto os filmes sensores foram caracterizados morfologicamente por Microscopia Eletrônica de Varredura (MEV) e tiveram suas propriedades sensoriais quantificadas. Os difratogramas das amostras apresentaram todos os picos referentes à estrutura tipo fluorita do CeO2. Valores de área de superfície específica maiores que os encontrados na literatura foram obtidos. As micrografias (MEV) obtidas mostram que os filmes espessos são porosos e depositados sem laminações sobre o substrato de alumina, com espessura da ordem de 45 55 μm. As medidas elétricas mostram uma temperatura de trabalho entre 350 e 400°C, intervalo no qual a resposta ao monóxido de carbono foi maior. Os filmes apresentaram excelentes tempos de resposta e de recuperação, principalmente para a amostra co... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: As a toxic, odorless, tasteless and colorless gas, therefore imperceptible by humans, carbon monoxide (CO) is life-threatening and an efficient sensor is necessary to warn us about its presence in the environment. Therefore, thick films were manually deposited on alumina substrates from pure and europium doped cerium dioxide (CeO2) nanoparticles synthesized by the microwave-assisted hydrothermal method (MAH), aiming their application as gas sensors. The nanoparticles synthesized by the MAH method were characterized by X-Ray Diffraction (XRD), Raman spectroscopy, Ultraviolet-Visible spectroscopy (UV-Vis), specific surface area (SBET), among other techniques, while the sensor films were morphologically characterized by Scanning Electron Microscopy (SEM) and had their properties as gas sensors measured. The X-ray diffraction pattern of the samples showed every peak belonging to the fluorite-type structure of CeO2. Specific surface area values higher than the ones commonly found in the literature were obtained. The SEM micrographies show that the thick films are porous and were deposited with no laminations on the alumina substrates, with thickness of 60 μm. The electrical measurements showed an operating temperature between 350 and 400°C, in which the response to carbon monoxide was higher. The films had remarkable response and recovery time, especially for the sample with the stoichiometry Ce1-(3/4)xEuxO2 (x=0,08), which presented a response time of 0.9 second after the exposure to CO. The results obtained in this work are significant and they are an evidence of the quality of the sensor films fabricated with nanoparticles synthesized by the HAM method / Mestre

Este trabalho apresenta a síntese e a caracterização de quatro complexos trinucleares de acetato de rutênio, de fórmula geral [Ru3O(CH3COO)6(L)2(CO)] nos quais L são ligantes N-heterocíclicos 4-aminopiridina, isonicotinamida, 4-(dimetil)aminopiridina e 2,6-dimetilpirazina com características -aceptoras ou -doadoras. Os derivados de rutênio foram sintetizados de acordo com adaptações de rotas sintéticas já reportadas na literatura, e caracterizados por meio de técnicas de cunho espectroscópico, eletroquímico e outras, a saber: análise elementar, 1H RMN, absorção UV-vis, infra-vermelho, voltametria cíclica e difração de raios-X. Foi investigada a liberação fotoinduzida de monóxido de carbono proveniente dos complexos trinucleares em acetonitrila, por meio de acompanhamento espectrofotométrico. O rendimento quântico envolvido na liberação do CO foi calculado por meio de actinometria química. Foi estudada a interação entre os complexos com as biomoléculas HSA e o DNA de timo de bezerro por meio das técnicas espectroscópicas de fluorescência, UV-vis e dicroísmo circular. Além disso, foram realizados ensaios preliminares in vitro para avaliar a citotoxicidade dos complexos frente a uma linhagem de células de melanoma murinho (B16F10) e foi avaliada a atividade tripanocida dos complexos sobre a forma amastigota do parasita Tripanossoma cruzi. / This work describes the synthesis and characterization of four ruthenium trinuclear complex of general formula [Ru3O(CH3COO)6(CO)(L)2] where L = 2,6-dimethylaminopyridine; isonicotinamide; 4-aminopyridine and 4-dimethylpyrazine (N-heterocyclic ligands with -acceptor or -donor characteristics). The ruthenium derivatives were synthesized according to adaptations of synthetic routes already reported in literature and characterized by spectroscopic and electrochemical techniques such as nuclear magnetic ressonance (NMR), UV-vis, infrared, cyclic voltammetry, X-ray diffraction and elemental analysis. The photoinduced release of carbon monoxide in acetonitrile was investigated by means of spectrophotometric monitoring. The quantum yield involved in the CO release was calculated by chemical actinometry. It was studied the interaction between the complexes with the biomolecules HSA and calf thymus DNA by spectroscopic techniques of fluorescence, UV-vis and circular dichroism. In addition, preliminary tests were performed in vitro in order to evaluate the cytotoxicity of the complexes against a murine melanoma cell line (B16F10) and trypanocidal activity of the complexes over the amastigote form of the parasite Trypanosoma cruzi.

Carbon monoxide (CO) is now well established as one of the signaling molecules in higher organisms, including humans. Due to its physiological roles, CO is now accepted as a potential therapeutic agent. The use of CO gas has been studied in multiple clinical trials. Vasodilation, anti-inflammatory, anti-apoptotic, anti-proliferative and cytoprotective effects are just a few of the pharmacological actions attributed to CO gas in various models of diseases. Use of inhaled CO gas as a therapeutic has many limitations which necessitate the development of a new approach for CO delivery. In order to handle CO safely, compounds that release CO (CO-releasing molecules, CORMs) have been developed. CORMs that release CO only when triggered, and with the ability to target certain tissue sites, are of particular interest. Our lab is developing molecules that release CO only when illuminated with visible light (photoCORMs). These photoCORMs are based on a motif found in naturally-occurring flavonols, which are chemical compounds found in wide variety of foods including fruits, vegetables, tea and dark chocolate. The research presented in this dissertation outlines the results of studies on extended flavonols as CO release agents. The specific studies described herein focus on understanding visible light-induced CO-releasing flavonols in terms of their: a) structure/reactivity relationships, especially in biological environments; b) interactions with metal ions and proteins; c) reaction pathway of CO release; and d) their properties when combined with a CO-sensing motif.

Abstract not available

<p>The work has been done in cooperation with the Swedish Road Administration.Snowmobiles has been around for many decades, but it wasn’t until the 1960s they got the name snowmobile. There are about 260 000 snowmobiles registered in Sweden today and this paper maps the environmental impact the emissions from those snowmobiles have. The result comes from literature surveys and data from traffic records, U.S. Environmental Protection Agency, EPA and The International Snowmobile Manufacturers Association, ISMA. There are three common types of snowmobile engines: conventional two-stroke engines, direct injected two-stroke engines and four-stroke engines. The conventional one has been in use since the beginning, the other two types where employed much later during the beginning of the 21th century. The conventional engine is responsible for the great majority of carbon monoxide and hydrocarbon emissions from snowmobiles in Sweden today. The conventional accounts for 81 % of the total emissions of carbon dioxide and 83 % of the total emissions of hydrocarbon. There should be some form of regulation in order to expedite the phasing out of conventional engines in the future.</p> / <p>Arbetet är utfört i samarbete med Vägverket. Snöskotrar är en terrängfordonstyp som körs på snö. Snöskotrar har funnit sedan 1960 talet, även tidigare, men först under 1960-talet fick de namnet snöskotrar. Det finns ungefär 260 000 snöskotrar registrerade i Sverige. Med detta arbete kartläggs vilken miljöpåverkan från avgasutsläpp från snöskotrar det finns idag i Sverige. Resultatet kommer från litteraturundersökning och data från trafikregister, U.S. Environmental Protection Agency, EPA och The International Snowmobile Manufacturers Association, ISMA. Det finns tre olika typer av motorer som användas för snöskotrar: tvåtakts konventionell, tvåtakts direktsprutad och fyrtakts. Konventionell är den motortyp som har funnits allt sedan början; de två andra kommer mycket senare, först i början av 2000-talet. Konventionell motor är den som bidrar till största utsläppet av kolmonoxid och kolväte jämfört med de två andra motorerna som används idag i Sverige. De konventionell står för 81 % av det totala utsläppet av kolmonoxid och 83 % av kolväte. Det bör finnas någon form av reglering för att kunna minska på snöskotrars utsläpp i framtiden, som via styrmedel ta bort den konventionella motortypen</p>

<p>The usefulness of low concentrations (typically 10 to 100 <i>µ</i>M) of [¹¹C]carbon monoxide and aryl triflates as substrates in ¹¹C-carbonylation using different nucleophiles in the presence of lithium bromide was investigated. The reactions were performed in a micro autoclave of 200 <i>µ</i>L volume and catalysed (mediated) by palladium(0). </p><p>A peripheral type benzodiazepine receptor (PBR) ligand, 1-(2-chlorophenyl)-<i>N</i>-methyl-<i>N</i>-(1-methylpropyl)isoquinoline-3-carboxamide (PK11195) and its structural analogues including an irreversible ligand for PBR, some other amides, ketones and carboxylic acids, were all labelled with ¹¹C using this approach. The [<i>carbonyl</i>-¹¹C]PK11195, analogues and other amides were prepared from aryl triflates and amines, and the [<i>carbonyl</i>-¹¹C]ketones were prepared from aryl triflates and organoboranes. In the synthesis of [<i>carboxyl</i>-¹¹C]carboxylic acids, water was utilised as nucleophile. The decay-corrected radiochemical yields were 10 to 55% for [¹¹C]PK11195 and analogues, 2 to 63% for other [¹¹C]amides, 10 to 75% for [¹¹C]ketones and 25 to 65% for [¹¹C]carboxylic acids. The specific radioactivity of the labelled compounds was in the range of 150 to 900 GBq/<i>µ</i>mol. </p><p>Some [¹¹C]amines were prepared by a reductive amination of the corresponding [carbonyl-¹¹C]ketones. These reactions were performed using different amines in the presence of TiCl₄ and NaBH₃CN. The radiochemical yields of the [¹¹C]amines varied from 2 to 78% (determined by analytical HPLC). </p><p>In order to confirm the labelling position, synthesis of selected ¹³C-substituted compounds were performed. For each substance group/ synthesis method, a selected compound was synthesised using (¹³C)carbon monoxide and the ¹³C-substituted compound was then analysed by ¹³C NMR.</p><p>A synthetic route was developed for the preparation of 1-(2-chloro-phenyl)-isoquinolin-3-yl trifluoromethanesulfonate used as the precursor in the synthesis of [<i>carbonyl</i>-¹¹C]PK11195 and analogues.</p>

Near-infrared (NIR) absorption spectroscopy with tunable diode lasers allows the simultaneous detection of the three most important isotopologues of carbon dioxide (<SUP>12</SUP>CO<SUB>2</SUB>, <SUP>13</SUP>CO<SUB>2</SUB>, <SUP>12</SUP>C<SUP>18</SUP>O<SUP>16</SUP>O) and carbon monoxide (<SUP>12</SUP>CO, <SUP>13</SUP>CO, <SUP>12</SUP>C<SUP>18</SUP>O). The flexible and compact fiber-optic tunable diode laser absorption spectrometer (TDLAS) allows selective measurements of CO<SUB>2</SUB> and CO with high isotopic resolution without sample preparation since there is no interference with water vapour. For each species, linear calibration plots with a dynamic range of four orders of magnitude and detection limits (LOD) in the range of a few ppm were obtained utilizing wavelength modulation spectroscopy (WMS) with balanced detection in a Herriott-type multipass cell. The high performance of the apparatus is illustrated by fill-evacuation-refill cycles.

The performance of a home-built tunable diode laser (TDL) spectrometer, aimed at multi-line detection of carbon dioxide, has been evaluated and optimized. In the regime of the (30<SUP>0</SUP>1)<SUB>III</SUB> / (000) band of <SUP>12</SUP>CO<SUB>2</SUB> around 1.6 μm, the dominating isotope species <SUP>12</SUP>CO<SUB>2</SUB>, <SUP>13</SUP>CO<SUB>2</SUB>, and <SUP>12</SUP>C<SUP>18</SUP>O<SUP>16</SUP>O were detected simultaneously without interference by water vapor. Detection limits in the range of few ppmv were obtained for each species utilizing wavelength modulation (WM) spectroscopy with balanced detection in a long-path absorption cell set-up. High sensitivity in conjunction with high precision —typically ±1‰ and ±6‰ for 3% and 0.7% of CO<SUB>2</SUB>, respectively— renders this experimental approach a promising analytical concept for isotope-ratio determination of carbon dioxide in soil and breath gas. For a moderate <SUP>12</SUP>CO<SUB>2</SUB> line, the pressure dependence of the line profile was characterized in detail, to account for pressure effects on sensitive measurements.

This work deals with radiochemistry and new approaches to develop novel PET tracers labelled with the radionuclide 11C. Two methods for the synthesis of 11C-labelled acrylamides have been explored. First, [1-11C]-acrylic acid was obtained from a palladium(0)-mediated 11C-carboxylation of acetylene with [11C]carbon monoxide; this could be converted to the corresponding acyl chloride and then combined with benzylamine to form N-benzyl[carbonyl-11C]acrylamide. In the second method, the palladium(0)-mediated carbonylation of vinyl halides with [11C]carbon monoxide was explored. This latter method, yielded labelled acrylamides in a single step with retention of configuration at the C=C double bond, and required less amine compared to the acetylene method. The vinyl halide method was used to synthesize a library of 11C-labelled EGFr-inhibitors in 7-61% decay corrected radiochemical yield via a combinatorial approach. The compounds were designed to target either the active or the inactive form of EGFr, following computational docking studies. The rhodium(I)-mediated carbonylative cross-coupling of an azide and an amine was shown to be a very general reaction and was used to synthesize a library of dual VEGFr-2/PDGFrβ inhibitors that were 11C-labelled at the urea position in 38-78% dc rcy. The angiotensin II AT1 receptor antagonist eprosartan was 11C-labelled at one of the carboxyl groups in one step using a palladium(0)-mediated carboxylation. Autoradiography shows specific binding in rat kidney, lung and adrenal cortex, and organ distribution shows a high accumulation in the intestines, kidneys and liver. Specific binding in frozen sections of human adrenal incidentalomas warrants further investigations of this tracer. Three angiotensin II AT2 ligands were 11C-labelled at the amide group in a palladium(0)-mediated aminocarbonylation in 16-36% dc rcy. One of the compounds was evaluated using in vitro using autoradiography, and in vivo using organ distribution and animal PET. The compound was metabolized fast and excreted via urine. High radioactivity was also found in the liver, meaning that more metabolically stable compounds are desirable for future development.

Vehicles powered by proton exchange membrane (PEM) fuelcells are approaching commercialisation. Being inherently cleanand efficient sources of power, fuel cells constitute asustainable alternative to internal combustion engines to meetfuture low-emission legislation. The PEM fuel cell may befuelled directly by hydrogen, but other alternatives appearmore attractive at present, due to problems related to theproduction, transportation and handling of hydrogen. Fuelling with an alcohol fuel, such as methanol, which isoxidised directly at the anode, offers certain advantages.However, the efficiency of the direct-methanol fuel cell (DMFC)is still significantly lower than that of the conventionalhydrogen-fuelled PEM fuel cell, due to some technical problemsremaining unsolved. Hence, indirect fuelling by a reformedliquid fuel may be the most feasible option in the early stagesof the introduction of fuel cell vehicles. The work presented in this thesis concerns the developmentof catalysts for production of hydrogen from methanol bypartial oxidation, steam reforming or a combination thereof.The work contributes to the understanding of how thepreparation route affects catalyst morphology and howphysicochemical properties determine catalytic behaviour andreaction pathways. The thesis is a summary of seven papers published inscientific periodicals. The first paper (Paper I) reviews thecurrent status of catalytic hydrogen generation from methanol,focusing on the fuel cell application. Paper II investigatesthe partial oxidation of methanol over Cu/ZnO catalystsprepared in microemulsion and by a conventionalco-precipitation technique. The activity for methanolconversion in the low-temperature regime is found to besignificantly higher over the former materials and the workcontinues by determining the nature of possible Cu-ZnOinteractions in the catalysts by studying their physicochemicalproperties more thoroughly (Paper III). In Paper IV, thepathways for methanol conversion via both partial oxidation andsteam reforming are elucidated. In Paper V, partial oxidation of methanol is studied overPd/ZnO catalysts prepared by microemulsion technique and againcompared to conventional materials. This investigationdemonstrates that although possessing high methanol conversionactivity, palladium-based catalysts are not suitable forreforming in fuel cell applications due to the considerableamounts of carbon monoxide formed. In Paper VI, methanol reforming is investigated over acommercial Cu/ZnO/Al2O3 catalyst. The mechanisms for carbonmonoxide formation and strategies for its suppression arediscussed, as well as reactor design aspects. The study alsoincludes some simple kinetic modelling. Finally, Paper VIIdescribes the optimisation of catalyst composition and processconditions to reach high hydrogen production efficiency at lowoperating temperatures and with minimum carbon monoxideformation. <b>Keywords:</b>PEM fuel cells, hydrogen, methanol, reforming,(partial) oxidation, reaction pathways, carbon monoxide,catalyst, microemulsion, Cu/ZnO, Pd/ZnO, copper, redoxproperties, oxidation state