Los prospectos Las Bellas y Don Bernardo se ubican en la Región Metropolitana, Comuna de Alhué, 40 km al sur de Melipilla y 10 km al WSW del distrito mesotermal polimetálico rico en Au y Ag Alhué. Las rocas más antiguas que afloran en estos prospectos corresponden a rocas volcánicas pertenecientes a la Formación Lo Valle. Estas rocas están intruidas, en orden temporal, por un granitoide de grano grueso, de composición tonalítica, y por cuerpos emplazados en forma de diques, sills y stocks, de composición monzogranítica. Finalmente, intruyen diques de pórfido félsico que contienen a la mineralización. Las estructuras están representadas por fallas de rumbos desde N20ºW hasta N30ºE, de carácter preferentemente subvertical. La mineralización de interés económico se presenta en ambos prospectos en forma de 10 estructuras observables en superficie, que siguen las fallas antes mencionadas. Estas estructuras consisten en diques de pórfido fracturado y en parte brechizado con alteración cuarzo-sericítica y menor propilítica (clorita + calcita ± epidota - adularia), y alteración supérgena sobreimpuesta, representada por argilización y por la presencia de boxwork regulares y, óxidos e hidróxidos de hierro. Las estructuras, de disposición subverticales a 70ºE, presentan potencias observadas entre 10 y 30 m, largos reconocidos entre 100 y 2000 m, y una profundidad de al menos 250 m en Las Bellas y de 625 m en Don Bernardo (basado en diferencias de cota). Los estilos de mineralización corresponden a vetas, brechas hidrotermales, sheeted veins, stockwork y diseminación. La mineralogía de las vetas corresponde a cuarzo, pirita, calcopirita y, en menor proporción, galena, covelina y Au nativo. Las brechas hidrotermales son del tipo matriz soportante, cuya matriz está constituida por cuarzo, magnetita, hematita, goethita, jarosita y diseminación de boxwork regulares y pirita fina; y fragmentos angulosos de pórfido félsico consistente en cuarzo, pirita, hematita, magnetita y menor bornita, calcosina. Las vetillas de las sheeted-veins y stockwork, de 1 - 10 mm de espesor, presentan hematita, magnetita, limonitas, jarosita y relictos de pirita. En un muestreo tipo chip sampling en los diques en la zona de estudio y su posterior análisis geoquímico mostraron valores anómalos de metales preciosos, con rangos de concentraciones de Au entre 0,5 y 7823 ppb y de Ag entre 0,5 y 271 ppm, y de metales base (Cu, Mo, Pb, Zn) sumado a los tipos y estilos de mineralización y a la alteración hidrotermal sugieren un modelo de depósito mesotermal polimetálico, en zona de ebullición (brechas hidrotermales y stockwork) y transición entre epitermal de baja sulfidización y pórfido. Además, comparando la litología y la diferencia de cota en que afloran las vetas en los prospectos en estudio y el distrito minero Alhué, indican que el nivel estructural en Las Bellas y Don Bernardo es más profundo que Alhué, sin embargo pertenecen al mismo metalotecto. Con lo anterior se concluye que Las Bellas y Don Bernardo son importantes prospectos ricos en Au y Ag del Cretácico Superior, que además poseen un gran potencial de mineralización tipo pórfido de metales base en profundidad. Finalmente, los prospectos en estudio, junto con los yacimientos en transición epitermal - mesotermal del tipo adularia - sericita El Bronce de Petorca, Cerro Cantillana y Distrito Minero Chancón y, los yacimientos mesotermales Distrito Minero Alhué y Distrito Minero Las Palmas, debido a su similar marco geológico, edad, estilos de mineralización, minerales de mena y alteración, definen una franja en transición epitermal - mesotermal vetiforme polimetálica rica en oro y plata del Cretácico Superior en Chile Central.

Master of Science / Department of Geology / Matthew E. Brueseke / Mid-Miocene epithermal Au-Ag ores of the northern Great Basin USA are related to magmatism associated with the inception of the Yellowstone hotspot. The geochemical chemical connection between these ores and spatially and temporally related volcanism is not well understood, but has been suggested (Kamenov, 2007; Saunders et al., 2015). These Cu- and Pb- isotope studies show that the ore and associated gangue minerals have different sources of Pb, which supports evidence that the metal(loids) originate from a deep magmatic source (Saunders et al., 2008). Cu isotopes as a tool for exploring linkages between ore deposits and related volcanic rocks is a new and evolving field. A suite of mid-Miocene Northern Great Basin (NGB) and Snake River Plain (SRP) volcanic rocks was analyzed by aquaregia leach for their δ⁶⁵Cu compositions. These samples have all been previously characterized and include basalts, trachybasalt, basaltic andesites, and basaltic trachyandesites that are representative of regional flood basalt magmatism and younger basalt eruptions in central Idaho. Included are rocks from the Santa Rosa-Calico volcanic field, NV (e.g., Buckskin-National district); Owyhee Mountains, ID (Silver City District); Midas, NV region, near Jarbidge, NV; and a locality proximal to Steens Mountain, OR. Also included are two Pleistocene basalts from the central Snake River plain unequivocally related to the Yellowstone hotspot volcanism (McKinney Basalt and Basalt of Flat Top Butte), and one Eocene basalt from the Owyhee Mountains that is related to pre-hotspot arc volcanism. International rock standards ranging from ultramafic to intermediate were also analyzed in this study for comparison. Our new δ⁶⁵Cu data greatly expands the range of known Cu isotopic compositions for basalts, with values ranging from -0.84‰ to +2.61‰. These values overlap with the δ⁶⁵Cu of regional ores, further suggesting a link between the source(s) of the ores and the NGB rocks. The range of δ⁶⁵Cu values also overlaps with mantle rock values, suggesting that the Cu isotopic composition may be a signature derived from the mantle source. Fractionation mechanisms that cause such a broad range in Cu isotopes are still unclear but liquid-vapor transitions and mantle metasomatism are being explored. Furthermore, δ⁶⁵Cu values of international rock standards reported in this study did not agree with previously reported data (Archer and Vance, 2004; Bigalke et al., 2010; Moeller et al., 2012; Liu et al., 2014, 2015) suggesting that aquaregia leach may not be a preferable technique when analyzing volcanic rocks.

El distrito Cerro Negro está ubicado en el noroeste del Macizo del Deseado, a unos 50 km al sureste de la localidad de Perito Moreno, en la provincia de Santa Cruz (Patagonia, Argentina). Comprende un conjunto de mineralizaciones vetiformes epitermales de Au-Ag con reservas calculadas en 6,7 Moz Au eq., que posicionan actualmente a Cerro Negro como el más importante proyecto epitermal de oro y plata de la región y como uno de los más importantes descubrimientos epitermales a nivel mundial. En el sector oeste del distrito se alojan los depósitos más importantes que son la veta Eureka y el sistema de vetas Marianas-San Marcos. En este sector es donde se han desarrollado los estudios de esta tesis doctoral. La geología del sector oeste del distrito está dominada por una secuencia volcánica del Jurásico superior correspondiente al Complejo Volcánico Bahía Laura, apoyada sobre un basamento metamórfico no aflorante con una edad máxima de depositación de ~379 Ma (Devónico superior) equivalente a la Formación La Modesta (Macizo del Deseado) y al Complejo Metamórfico Andino Oriental (Argentina-Chile). El vulcanismo está representado por un ciclo inicial denominado Sección Inferior, que se asigna a la Formación Bajo Pobre, conformado por intercalaciones de lavas y niveles piroclásticos de flujo de composiciones andesíticas a dacíticas y cuerpos intrusivos subvolcánicos de similares composiciones. Todas estas unidades están relacionadas genéticamente a través de un tren evolutivo co-magmático de composiciones mayormente intermedias, y se interpreta que formarían parte de un aparato volcánico de naturaleza poligenética y posiblemente de larga vida (>3 Ma). Con posterioridad, y como consecuencia de un alto gradiente térmico, se generaron las condiciones para el emplazamiento de un campo geotermal-hidrotermal de unos 15 km2. Los fluidos hidrotermales se focalizaron en sitios de mayor permeabilidad como son las zonas extensivas de grandes fallas, posiblemente heredadas del basamento (Eureka) y en fracturas secundarias (sistema Marianas-San Marcos), generando depósitos epitermales de Au-Ag. En niveles someros (zonas de descarga) se distinguen depósitos de brechas de erupción hidrotermal con niveles de retrabajamiento intercalados, alteraciones hidrotermales de naturaleza ácida y depósitos de hot spring. Luego se desarrolla un ciclo tardío agrupado en la Sección Superior, que se asigna a las formaciones Chon Aike y La Matilde, caracterizado por una secuencia mayormente ácida, formada por tobas y tufitas, ignimbritas y domos extrusivos de composiciones riolíticas, que no muestran una relación co-magmática con las unidades previas. Esta parte de la secuencia marca una declinación en la frecuencia del vulcanismo, que se desarrolla de manera más episódica y relacionada a la evolución de complejos de domos, posiblemente vinculados a un vulcanismo de naturaleza mayormente monogenética. Las mineralizaciones corresponden a cuerpos vetiformes de rumbo NO, ONO y EO con longitudes, espesores y contenidos en metales preciosos excepcionales. Eureka es la veta más importante del distrito y del Macizo del Deseado, con una longitud de hasta 5 km y espesores de hasta 20 metros. En el extremo oeste, conocido como clavo Eureka West, se reconocieron tres etapas: hidrotermal, tectónica, y supergénica. En la etapa hidrotermal predominan los bandeados crustifome-coloformes de cuarzo-calcedonia, adularia y carbonatos de Fe-Mn con un progresivo aumento de sílice y una disminución en el tamaño de las bandas. Los minerales de mena constituyen el 1% del volumen de la veta, concentrados en bandas de tipo ginguro compuestas por sulfuros y sulfosales de plata junto a sulfuros de metales base y electrum (Au40Ag60). Vetillas de calcita cortan al episodio mineralizante principal. El episodio tectónico está representado por cuerpos de brechas de falla con clastos de veta bandeada que por sectores aportan elevados tenores de plata. Una importante etapa supergénica desarrollada hasta 400 metros de profundidad, modifica los minerales primarios reemplazándolos por una nueva asociación mineral secundaria concentrando los metales preciosos, asociados a microfracturas ricas en óxidos de hierro. La signatura geoquímica de la veta está caracterizada por Au, Ag, Pb, Zn, Cu y As, con una relación Ag:Au de ~17:1. La alteración hidrotermal incluye cuarzo, adularia, illita, esmectita y clorita. Las inclusiones fluidas indican que el fluido mineralizante con evidencias de ebullición alcanzó temperaturas de 260°C y salinidades de entre 1-2% de NaCl eq. Los datos de isótopos estables establecen un origen meteórico para las aguas con un importante aporte magmático para el principal evento mineralizante, y para episodios tardíos composiciones que evidencian la presencia de aguas calentadas por fase vapor. El episodio hidrotermal principal arrojó una edad de ~156 Ma mostrando la coetaneidad con el vulcanismo andesítico-dacítico de la Sección Inferior. El clavo Eureka West se clasifica como un depósito epitermal de metales preciosos de tipo sulfuración intermedia a baja, tipología frecuente en el Macizo del Deseado (e.g. San José, Manantial Espejo y Martha). El sistema Marianas-San Marcos está conformado por vetas epitermales de cuarzo-adularia-esmectita con mineralización de Au y Ag, compuesto mayormente por texturas coloformes-crustiformes agrupadas en 4 episodios principales, siendo 3 de naturaleza hidrotermal y el último de tipo tectónico-hidrotermal. La mineralización principal de metales preciosos se encuentra asociada a bandas tipo ginguro ricas en sulfuros y sulfosales de plata con metales base. La signatura geoquímica de las vetas corresponde a Au, Ag, As, Sb, Zn, Pb, Se y Hg, con una relación Ag:Au <10:1. La alteración hidrotermal incluye cuarzo, adularia, illita, esmectita, illita-esmectita y clorita, conformando un halo de minerales de mayor temperatura alrededor de las vetas. Cerca de la superficie, y asociado a depósitos de brechas de erupción hidrotermal, se identifican alteraciones de tipo ácida que indican el paleo nivel freático. Las inclusiones fluidas indican que el fluido mineralizante alcanzó temperaturas entre 220-300°C y salinidades de 1-3% de NaCl eq. Los datos de isótopos estables establecen un origen meteórico para los fluidos del principal evento mineralizante e indican un origen magmático para los metales. Además, en forma tardía se registraron aguas calentadas por fase vapor que percolaron durante episodios de pausa en el hidrotermalismo, representadas por vetillas de calcita tardía que diluyen la mineralización principal. Las texturas de las vetas, los estudios de inclusiones fluidas y la presencia de brechas de erupción hidrotermal encima de las vetas Marianas, revelan ebullición con procesos de flashing como mecanismos de formación de las vetas. Las vetas se formaron a ~155 Ma durante las últimas etapas del vulcanismo andesítico-dacítico de la Sección Inferior. Las vetas Marianas-San Marcos se clasifican como depósitos epitermales de metales preciosos de tipo baja sulfuración comparables en el Macizo del Deseado con el depósito Cerro Vanguardia y con Hishikari (Japón), Round Mountain, Sleeper, McLaughlin y Midas (oeste de EEUU), y Martha Hill Favona (Nueva Zelanda). Este sistema de vetas puede clasificarse como un sistema epitermal de tipo hot spring formado cerca del paleo nivel freático. El depósito epitermal de Cerro Negro representa el mejor ejemplo de depósitos de Au-Ag de alta ley pertenecientes al Modelo Geotermal del Macizo del Deseado, con preservación de los dos subtipos (proximal y distal a intrusivos), aportando gran variedad de características mineralógicas, geoquímicas y de exploración hasta ahora no reconocidas en la provincia metalogénica del Deseado.

La lignine est un des polymères naturels les plus abondants et le seul constituant de la biomasse basé sur des unités aromatiques et, à ce titre, représente une ressource renouvelable prometteuse pour la production durable de molécules organiques plus complexes. Les travaux de cette thèse portent sur le développement de matériaux catalytiques capables de transformer sélectivement la lignine en molécules fonctionnelles de base, hautement oxygénées, et l'étude de leur mise en oeuvre en condition alcaline oxydante en utilisant le peroxyde d'hydrogène comme donneur d'oxygène. Différentes familles de matériaux hybrides de type SBA-15 à base de titane, Au/titane, Ag/titane et Fe(TAML) ont tout d'abord été synthétisées et entièrement caractérisées. Des études catalytiques comparatives ont ensuite été réalisées afin d'évaluer leurs performances en termes de degré de dépolymérisation et distribution de produits. Le catalyseur présentant le plus fort potentiel, le matériau TiO2 supporté sur SBA-15, a ensuite été soumis à des études de réactivité plus poussées afin d'optimiser les différents paramètres réactionnels (température, temps de réaction et quantité d'oxydant) permettant d'atteindre en présence d'un excès d'oxydant jusqu'à 90 %pds de conversion de la lignine et à 80°C un rendement en bio-huile de 50%pds constituée principalement d'acides carboxyliques et molécules aromatiques potentiellement valorisables / Lignin is one of the most abundant natural polymers and the only biomass constituent based on aromatic units and as such represents a promising renewable resource for the sustainable production of complex organic molecules. This dissertation reports on the development of catalytic materials capable of selectively transform lignin into basic functional molecules with high oxygen content and the study of their performance under alkaline oxidative conditions, using hydrogen peroxide as oxygen donner. Different families of hybrid materials based on the SBA-15 scaffold were first synthesized by incorporation of titanium, Au/titanium, Ag/titanium and Fe-TAML and completely characterized. Comparative catalytic studies were then accomplished in order to evaluate their performance in terms of degree of depolymerization and product distribution. The catalyst with the highest potential, the TiO2 based SBA-15 material, was then submitted to further reactivity studies in order to optimize the different reaction parameters (temperature, reaction time and quantity of oxidant). In the presence of an excess of oxidant, conversions up to 90 wt. % were obtained, whereas a temperature of 80 °C allowed to obtain a yield in bio-oil of 50 wt. %, which is mainly composed of carboxylic acids and aromatic molecules with potential to be further valorized

La majeure partie des équipements électroniques qui nous entourent fonctionne dans des environnements plutôt cléments où les variations thermiques sont d’amplitudes faibles à modérées. En aéronautique, l’utilisation d’équipements fonctionnant dans des milieux beaucoup plus hostiles que les environnements traditionnellement rencontrés en électronique pourrait permettre d’améliorer considérablement les performances des aéronefs, notamment en terme de poids, de consommation de carburant et de coût de maintenance. Toutefois, l’utilisation d’assemblages électroniques « classiques » dans des environnements où les variations thermiques sont fortes pose des problèmes techniques majeurs : les hautes températures peuvent faire fondre les alliages de brasure courants et la fatigue thermomécanique peut très rapidement provoquer la défaillance des assemblages. Pour pallier ces problèmes, les composants électroniques peuvent être reportés par frittage d’argent dans les circuits. En effet, cette technologie d’assemblage permet de remplacer les brasures usuelles par un matériau ayant un point de fusion nettement plus élevé : l’argent pur (Tfus=962°C). Cependant, le frittage a tendance à produire des matériaux poreux et la porosité peut avoir un effet néfaste sur le vieillissement des joints d’attache des composants électroniques. Par conséquent, dans cette thèse, les liens existant entre profil thermique de frittage et porosité ainsi que ceux existant entre porosité et résistance aux cycles thermiques (-65°C/+200°C) ont été étudiés. Par ailleurs, la question des interactions métallurgiques pouvant se produire à hautes températures entre l’argent fritté et certaines métallisations usuelles de composants et de substrats a également été abordée. / Most of usual electronic devices operate in environments where the amplitude of temperature changes is limited. The use of electronic equipment operating in harsh environments in aircrafts could however improve their performances, especially their weight, their gas consumption and their cost of maintenance. Unfortunately the use of classical electronic assembly technologies in environments where wide amplitude thermal variations take place raises major technical issues: the high temperatures reached in some parts of aircrafts can melt usual brazing materials and thermomechanical fatigue can induce early failure of the assemblies. To prevent these problems from happening, electronic components can be attached using silver sintering. One of the strengths of this technology is that it allows the replacement of traditional brazing material by a high melting point material: pure silver (Tm=962°C). Silver sintering nevertheless leads to a porous material and porosity can have a negative impact on the ageing of the attachment joints of electronic components. One of the goals of this PhD thesis is therefore to study the link between the sintering temperature profile and the porosity of silver. Furthermore the impact of different rates of porosity on the mechanical behavior of silver has been assessed. These investigations have mainly been focused on the fatigue behavior of porous silver electrical junctions under thermal cycling (-65°C/+200 °C). The question of the metallurgical interactions that may exist at high temperatures between silver and some of the usual metallization of components and/or substrates has lastly been addressed.

Doctor of Philosophy / Department of Chemistry / Kenneth J. Klabunde / This is an account of the synthesis of several drastically different forms of silver nanoparticles: Bare metal nanoparticles, dry nanoparticulate powders, aqueous soluble particles, and organic ligand coated monodisperse silver nanoparticles were all produced. The synthetic method was adapted from previous studies on gold nanoparticles and investigated to understand the optimal conditions for silver nanoparticle synthesis. Also the procedure for refinement of the nanoparticles was studied and applied to the formation of alloy nanoparticles. This extraordinary procedure produces beautifully colored colloids of spherical metal nanoparticles of the highest quality which under suitable conditions self-assemble into extensive three dimensional superlattice structures. The silver nanoparticle products were later tested against several biological pathogens to find dramatic increases in antimicrobial potency in comparison to commercially available silver preparations.

Deposition of noble metal and semiconductor nanocrystalline thin films has received much attention. CdS and CdSe are important semiconductors used in optical devices. A wet chemical route which uses the interface of two immiscible liquids to control the growth and deposition of nanocrystalline thin films forms the basis of the current study. In this method, a metal precursor dissolved in toluene or decane is held in contact with a water layer containing a reducing or sulphiding agent. The reaction proceeds at the interface of the liquids and results in deposits adhering to the interfacial region. The products of such reactions typically consist of nanocrystals forming a thin film. Stable sols of Au, Ag were found to metathesize on contact with alkylamine in oil to form monolayer films that spread across large areas at the water/oil interface. The nature and properties of interfacial thin films depend on the alkylamine. Nanocrystalline thin films consisting of CdS adhering to the interface starting with a polydispersed aqueous sol of crystallites and alkylamine were obtained. The optical band gaps of the films formed are dependent on the alkylamine chain length, with the shortest chain yielding the largest gap. A systematic increase in particle diameters following adsorption is responsible for changes in the electronic structure of films. The formation of nanocrystalline films of CdS adhering at the interface using a toluene solution of cadmium diethyldithiocarbamate and aqueous Na2S solution, in the presence of tetraoctylammonium bromide (TOAB) in the aqueous phase, was investigated under various reaction parameters, while CdSe was obtained using Na2SeSO3 solution and the influences of deposition temperature and solution concentration were studied. A ternary water/decane/2-butoxyethanol /salt system was used to grow deposits of CdSe and CdS. Nanostructured thin films were obtained at the upper interface of the ternary system, between the emulsive middle layer and oil rich top phase. The influence of deposition conditions such as precursor concentrations and temperature, as well as the nature of the medium on the properties of the deposits was studied. Deposits grown using the ternary system were compared with those obtained using water/decane and water/toluene systems. Reaction parameters such as temperature, solution concentration and the size of CdS and CdSe were controlled. A thin film of CdS and CdSe nanocrystals was formed at the interface. The grain size was found to be dependent on reaction temperature and solution concentration, with higher temperatures and solution concentration resulting in larger grains. The nature of thin films obtained at the interface of two immiscible liquids and of a water/decane/2-butoxyethanol/salt ternary system were studied using Scanning and Transmission electron microscopy, X-ray diffraction and UV-visible spectroscopy.

Nanoscience dominates virtually every field of science and technology in the 21st century. Nanoparticles are of fundamental interest since they possess unique size- dependent properties (optical, electrical, mechanical, chemical, magnetic etc.), which are quite different from the bulk and the atomic state. Bimetallic nanoparticles are of particular interest since they combine the advantages of the individual monometallic counterparts. The present study focuses on bimetallic nanoparticles containing gold as one of the constituents. Au-Pd, Au-Pt and Au-Ag bimetallic/alloy nanoparticles have been prepared by four different synthetic methods, and characterised by a variety of techniques, with an emphasis on Au-Ag alloy systems in the solution phase as well as in the form of nanostructured films on solid substrates. Au- Ag alloy nanoparticles have been used to demonstrate two different applications. The first is the use of Au-Ag monolayer protected alloy clusters in demonstrating single electron charging events in the solution phase as well as in the dry state. Single electron transfer events involving nanosized particles are being probed extensively due to their potential applications in the field of electronics. The second is an analytical application, involving the use of trisodium citrate capped Au-Ag alloy hydrosols as substrates for surface enhanced Raman and resonance Raman scattering [SE(R)RS] studies. The sols have been used for single molecule detection purposes. Various organic molecules such as quinones, phthalocyanines and methyl violet have been self- assembled in a stepwise manner on the nanoparticulate as well as bulk Au, Ag and Au-Ag surfaces, and characterised extensively by spectroscopic, electrochemical and spectroelectrochemical techniques.

Atualmente, aplicações de nanopartículas de magnetita (NPs-Fe3O4) têm sido comumente reportadas em inúmeros trabalhos descritos na literatura. Catálise, ferrofluidos e dispositivos de armazenamento de dados são algumas delas. Além disso, aplicações biomédicas têm sido demonstradas. Para esse último, têm-se os exemplos de magneto-hipertermia, liberação controlada de fármacos, agente de contraste em imagens de ressonância magnética e o controle de reações bioeletrocatalíticas envolvendo enzimas redox. Nesta tese, NPs-Fe3O4 foram aplicadas em duas vertentes inéditas. Dessa forma, tendo em vista uma melhor compreensão, a sua escrita foi dividida em dois capítulos, nos quais abordam separadamente cada uma dessas vertentes. O primeiro capítulo descreve a obtenção, modificação e funcionalização de NPs-Fe3O4 a afim de usá-las como uma plataforma para a imobilização do citocromo c (Cyt c); uma proteína redox de comportamento modelo dotada de um grupo prostético heme em sua estrutura terciária. Em seguida, após um efetivo processo de imobilização do Cyt c sobre as NPs-Fe3O4 com superfície modificada, o uso de um campo magnético externo possibilitou a deposição do mesmo na interface eletródica, estabelecendo a reação de transferência direta de elétrons entre o grupo heme e a superfície metálica do eletrodo de trabalho. Além disso, por meio da permuta entre os estados comutáveis switch on e switch off, obteve-se o controle magnético comutável da reação de transferência direta de elétrons do Cyt c quando imobilizado na superfície das NPs-Fe3O4 com superfície modificada. Já para o segundo capítulo, NPs-Fe3O4 foram utilizadas como adesivo magnético a fim de capturar nanoestruturas metálicas hollow (nanocages bimetálicos de Au/Ag) dispersas em suspensão aquosa. Dessa forma, por meio da influência de um campo magnético constante, os aglomerados formados entre esses dois nanomateriais foram depositados sobre uma máscara litográfica, levando a formação de padrões de litografia magnética dispostos sobre a superfície de um substrato de ITO (vidro recoberto com óxido de estanho dopado com índio). Imagens de microscopia eletrônica de varredura (MEV) comprovaram que a metodologia utilizada para o preparo dos padrões litográficos foi eficaz, apresentando um alto rendimento na obtenção dos mesmos. Além disso, realizou-se com sucesso o mapeamento químico de infravermelho dos padrões litográficos dispostos sobre o ITO. Para isso, empregou-se como alvo os modos vibracionais do polímero polivinilpirrolidona (PVP) utilizado na funcionalização dos nanocages bimetálicos de Au/Ag. Por fim, acredita-se que os padrões litográficos arranjados em macroescala, juntamente com os aglomerados de nanocages bimetálicos alinhados na forma de microfios, possuem potencial aplicação em estudos de espectroscopia de absorção no infravermelho intensificado por superfície (SEIRA). / Currently, applications of magnetite nanoparticles (Fe3O4-NPs) have been commonly reported in many studies in the literature. Catalysis, ferrofluids and data storage devices are some of them. Moreover, biomedical applications have been demonstrated. For the latter, there are the following examples, such as magneto-hyperthermia, controlled release of drugs and the control of bioelectrocatalysis of the enzymatic reactions. In this thesis, Fe3O4-NPs were used in two new applications. Therefore, towards a better understanding its writing was divided into two chapters, which each one of them reports separately these two applications. The first chapter describes the synthesis, modification and functionalization of Fe3O4-NPs in order to use them as a platform for the immobilization of cytochrome c (Cyt c); model redox protein which possess a heme prosthetic group in its tertiary structure. Then, after an effective immobilization of Cyt c on surface-modified Fe3O4-NPs, the use of an external magnetic field permitted the deposition of this redox protein on the electrode interface, establishing the reaction of direct electron transfer between heme prosthetic group and the metallic surface of the working electrode. Furthermore, by the exchange between ON and OFF switch modes was obtained the magnetic control of the direct electron transfer of Cyt c when immobilized on the surface-modified Fe3O4-NPs. For the second chapter, Fe3O4-NPs were used as magnetic adhesive to capture hollow metallic nanostructures (Au-Ag bimetallic nanocages) dispersed in aqueous suspension. Thus, by use of a constant magnetic field, the agglomerates formed between these two nanomaterials were deposited on a lithographic mask, leading to formation of magnetolithograph patterns on the surface of ITO substrate (glass coated with oxide tin-doped indium). Scanning electron microscopy images (SEM) showed that the methodology used for the high-yield preparation of lithographicpatterns was effective. Furthermore, the FTIR chemical mapping of the lithographic patterns arranged on the ITO\'s surface was successfully performed. For this, the CH2 and C-N, C=O vibrational modes of the polyvinylpyrrolidone polymer (PVP) used for the functionalization of Au-Ag bimetallic nanocages were employed as target. Finally, we believed that magnetolithograph patterns arranged in microscale on the ITO surface, and also the clusters of the bimetallic nanocages aligned as micro-wires show potential application in surface-enhanced infrared absorption (SEIRA).

Atualmente, aplicações de nanopartículas de magnetita (NPs-Fe3O4) têm sido comumente reportadas em inúmeros trabalhos descritos na literatura. Catálise, ferrofluidos e dispositivos de armazenamento de dados são algumas delas. Além disso, aplicações biomédicas têm sido demonstradas. Para esse último, têm-se os exemplos de magneto-hipertermia, liberação controlada de fármacos, agente de contraste em imagens de ressonância magnética e o controle de reações bioeletrocatalíticas envolvendo enzimas redox. Nesta tese, NPs-Fe3O4 foram aplicadas em duas vertentes inéditas. Dessa forma, tendo em vista uma melhor compreensão, a sua escrita foi dividida em dois capítulos, nos quais abordam separadamente cada uma dessas vertentes. O primeiro capítulo descreve a obtenção, modificação e funcionalização de NPs-Fe3O4 a afim de usá-las como uma plataforma para a imobilização do citocromo c (Cyt c); uma proteína redox de comportamento modelo dotada de um grupo prostético heme em sua estrutura terciária. Em seguida, após um efetivo processo de imobilização do Cyt c sobre as NPs-Fe3O4 com superfície modificada, o uso de um campo magnético externo possibilitou a deposição do mesmo na interface eletródica, estabelecendo a reação de transferência direta de elétrons entre o grupo heme e a superfície metálica do eletrodo de trabalho. Além disso, por meio da permuta entre os estados comutáveis switch on e switch off, obteve-se o controle magnético comutável da reação de transferência direta de elétrons do Cyt c quando imobilizado na superfície das NPs-Fe3O4 com superfície modificada. Já para o segundo capítulo, NPs-Fe3O4 foram utilizadas como adesivo magnético a fim de capturar nanoestruturas metálicas hollow (nanocages bimetálicos de Au/Ag) dispersas em suspensão aquosa. Dessa forma, por meio da influência de um campo magnético constante, os aglomerados formados entre esses dois nanomateriais foram depositados sobre uma máscara litográfica, levando a formação de padrões de litografia magnética dispostos sobre a superfície de um substrato de ITO (vidro recoberto com óxido de estanho dopado com índio). Imagens de microscopia eletrônica de varredura (MEV) comprovaram que a metodologia utilizada para o preparo dos padrões litográficos foi eficaz, apresentando um alto rendimento na obtenção dos mesmos. Além disso, realizou-se com sucesso o mapeamento químico de infravermelho dos padrões litográficos dispostos sobre o ITO. Para isso, empregou-se como alvo os modos vibracionais do polímero polivinilpirrolidona (PVP) utilizado na funcionalização dos nanocages bimetálicos de Au/Ag. Por fim, acredita-se que os padrões litográficos arranjados em macroescala, juntamente com os aglomerados de nanocages bimetálicos alinhados na forma de microfios, possuem potencial aplicação em estudos de espectroscopia de absorção no infravermelho intensificado por superfície (SEIRA). / Currently, applications of magnetite nanoparticles (Fe3O4-NPs) have been commonly reported in many studies in the literature. Catalysis, ferrofluids and data storage devices are some of them. Moreover, biomedical applications have been demonstrated. For the latter, there are the following examples, such as magneto-hyperthermia, controlled release of drugs and the control of bioelectrocatalysis of the enzymatic reactions. In this thesis, Fe3O4-NPs were used in two new applications. Therefore, towards a better understanding its writing was divided into two chapters, which each one of them reports separately these two applications. The first chapter describes the synthesis, modification and functionalization of Fe3O4-NPs in order to use them as a platform for the immobilization of cytochrome c (Cyt c); model redox protein which possess a heme prosthetic group in its tertiary structure. Then, after an effective immobilization of Cyt c on surface-modified Fe3O4-NPs, the use of an external magnetic field permitted the deposition of this redox protein on the electrode interface, establishing the reaction of direct electron transfer between heme prosthetic group and the metallic surface of the working electrode. Furthermore, by the exchange between ON and OFF switch modes was obtained the magnetic control of the direct electron transfer of Cyt c when immobilized on the surface-modified Fe3O4-NPs. For the second chapter, Fe3O4-NPs were used as magnetic adhesive to capture hollow metallic nanostructures (Au-Ag bimetallic nanocages) dispersed in aqueous suspension. Thus, by use of a constant magnetic field, the agglomerates formed between these two nanomaterials were deposited on a lithographic mask, leading to formation of magnetolithograph patterns on the surface of ITO substrate (glass coated with oxide tin-doped indium). Scanning electron microscopy images (SEM) showed that the methodology used for the high-yield preparation of lithographicpatterns was effective. Furthermore, the FTIR chemical mapping of the lithographic patterns arranged on the ITO\'s surface was successfully performed. For this, the CH2 and C-N, C=O vibrational modes of the polyvinylpyrrolidone polymer (PVP) used for the functionalization of Au-Ag bimetallic nanocages were employed as target. Finally, we believed that magnetolithograph patterns arranged in microscale on the ITO surface, and also the clusters of the bimetallic nanocages aligned as micro-wires show potential application in surface-enhanced infrared absorption (SEIRA).