Esta Tese de doutorado teve por objetivo aumentar a compreensão dos aspectos sinérgicos na corrosão de bens culturais feitos com chumbo (Pb) e avaliar a agressividade ambiental sobre bens culturais em igrejas e museus brasileiros para a proposição de estratégias de conservação. Neste contexto, foram investigados, em microambientes simulados, os efeitos sinérgicos entre formaldeído e ácido acético, ácido fórmico ou dióxido de carbono na corrosão de Pb; foi feita a síntese e caracterização de diferentes formiatos gerados nos processos de corrosão de Pb por formaldeído ou ácido fórmico; foi avaliada a agressividade ambiental sobre bens culturais da Igreja de São Francisco (São Paulo, ambiente urbano industrial), da Igreja dos Freis Carmelitas (Santos, ambiente urbano industrial costeiro), do Museu de Arte Contemporânea da USP (MAC, São Paulo, reserva técnica da nova sede) e do Museu de Arqueologia e Etnologia da USP (MAE, São Paulo, reserva técnica), através de cupons metálicos (chumbo e cobre) expostos nos ambientes interno e externo dessas instituições e através do uso de monitores miniaturizados; foi feita a otimização destes monitores e, finalmente, foi considerado o desenvolvimento de um nariz eletrônico (EN) baseado em microbalanças de quartzo (QCMs) para o uso em conservação preventiva. Nestas investigações microscopia Raman foi a principal técnica empregada, sendo que as demais foram FTIR-ATR, µ-FTIR-ATR, µ-FTIR, nano-FTIR (SINS), s-SNOM, AFM, SEM, SEM-EDX, XRD e SR-XRD. Os resultados apontaram para a necessidade de individualização dos objetos artísticos tanto para a proposição de estratégias de conservação quanto para o entendimento de sua reatividade, mostraram a agressividade ambiental de todas as instituições investigadas, indicaram a potencialidade de ENs em conservação preventiva e demonstraram a utilidade de técnicas de alta resolução lateral, como nano-FTIR, em investigações de corrosão metálica. Mais especificamente, as investigações de sinergia entre poluentes aumentaram o entendimento da reatividade de Pb e permitiram a proposição de esquemas mais completos de sua reatividade, levando a discussões acerca da conservação desses bens. A agressividade química ambiental das igrejas e museus a bens culturais foi inferida pela caracterização de cupons metálicos expostos em seus interiores e exteriores, enquanto que a agressividade relacionada a fatores físicos, como temperatura e umidade relativa, foi inferida através do uso de monitores miniaturizados expostos somente nas igrejas. Com esse monitoramento, estratégias de conservação foram propostas. Para a devida caracterização dos cupons metálicos, expostos nas igrejas e museus ou nos microambientes simulados, a síntese e a caracterização de diferentes formiatos de Pb foi essencial. Por fim, visando melhorar o desempenho dos monitores miniaturizados e ampliar sua aplicabilidade (com seu futuro uso como EN), um novo dispositivo foi construído e um estágio na Universidade de Aveiro, em Portugal, foi realizado para o desenvolvimento de um EN baseado em QCMs. / The objective of this doctoral thesis was to increase the understanding of synergistic aspects in the corrosion of cultural objects made with lead (Pb) and to assess the environmental aggressiveness on cultural objects of Brazilian churches and museums in order to propose conservation strategies. In this context, in simulated micro-environments, the synergistic effects between formaldehyde and acetic acid, formic acid or carbon dioxide in Pb corrosion were investigated; the syntheses and characterization of different formates generated by formaldehyde or formic acid in Pb corrosion processes was conducted; the environmental aggressiveness on cultural objects of the church of São Francisco (São Paulo, urban industrial environment), of the church of the Carmelite Friars (Santos, urban industrial littoral environment), of the Museum of Contemporary Art of the USP (MAC, São Paulo, new site) and of the Museum of Archaeology and Ethnology of the USP (MAE, São Paulo) was assessed exposing metal coupons (lead and copper) in their internal and external environments and using miniaturized monitors; these monitors were optimized and finally, the development of an \'electronic nose\' (EN) based on quartz crystal microbalances (QCMs) was considered for preventive conservation. In these investigations the principal technique employed was Raman microscopy, and FTIR-ATR, µ-FTIR-ATR, µ-FTIR, nano-FTIR (SINS), s-SNOM, AFM, SEM, SEM-EDX, XRD and SR-XRD were also used. The results pointed out to the necessity of individualization of the artistic objects when investigating their reactivity or when proposing conservation strategies, showed the environmental aggressiveness of all the investigated institutions, indicated the potential of ENs in preventive conservation and demonstrated the utility of techniques of high lateral resolution such as nano-FTIR for the investigation of metal corrosion. More specifically, the investigations of synergistic effects between gaseous pollutants increased the understanding of Pb reactivity and allowed to propose more completed schemes of its reactivity, which allowed discussions on the conservation of these objects. The aggressiveness related to the environmental chemical composition of the churches and museums was inferred through the characterization of metal coupons exposed in their indoor and outdoor environments, whilst the aggressiveness related to physical factors such as temperature and relative humidity was inferred through the use of miniaturized monitors exposed only in the churches. With this monitoring, conservation strategies were proposed. For the well characterization of the metal coupons, exposed in the churches and museums or in simulated microenvironments, the syntheses and characterization of different Pb formates were essential. Finally, aiming at still improving the performance of the miniaturized monitors and increasing their applicability (in their future use as EN), a new device was constructed, and an internship was considered in the University of Aveiro, Portugal, for the development of an EN based on QCMs.

Um estudo refinado dos filmes derivados do gel de pentóxido de vanádio foi realizado por meio de técnicas espectroscópicas e microscópicas visando compreender melhor as características deste material na escala microscópica. Foi demonstrado que o gel de pentóxido de vanádio é uma suspensão de nanopartículas anisotrópicas que se mantêm estáveis mesmo em altas concentrações. As propriedades estruturais e espectroscópicas destas nanopartículas foram revistas e discutidas no estado da arte. Em paralelo foi possível investigar fenômenos como a transição de fase induzida por laser e desenvolver aplicações tecnológicas em áreas como litografia e sensoriamento de gases. Ficou destacada nesta tese o grande potencial de investigação da microscopia Raman confocal na área de nanomateriais. / A refined study of films derived from vanadium pentoxide gel was carried out based on spectroscopic and microscopic techniques, aiming a better understanding of this material on a microscopic scale. It was demonstrated that the vanadium pentoxide gel consists of a suspension of anisotropic nanoparticles which remains stable even at high concentrations. The structural and spectroscopic properties of such nanoparticles were reviewed and discussed, providing new insights at the state of the art. It was also investigated the occurrence of some relevant phenomena, such as the laser induced phase transition, and to develop new technological applications in areas such as gas sensing and lithography. The collection of results described in thesis highlighted a great research potential of confocal Raman microscopy, in the field of nanomaterials.

Les bois sont une combinaison complexe de très fortes hétérogénéités multi-échelles, avec une trame de fond par espèce qui caractérise ses trois plans d'anisotropie. Les propriétés macroscopiques des bois dépendent de l'ensemble des échelles inférieures d'hétérogénéités : les cernes de croissance, les cellules, ainsi que l'organisation et la concentration des composés chimiques des parois cellulaires. Alors que l'effet des microfibrilles de cellulose cristalline de la phase solide sur les propriétés macroscopiques a été étudié, l'un des défis actuels consiste à évaluer le déterminisme des arrangements moléculaires au sein des parois sur les propriétés des cellules au sein d'un tissu. Dans ce contexte, le présent travail de thèse se développe selon deux axes : (i) La collecte d'informations sur les organisations pariétales à travers la diversité des cellules, et (ii) la caractérisation des propriétés micro-mécaniques à l'échelle du tissu, avec la prise en compte des échelles inférieures d'hétérogénéités. L'essentiel des descriptions sub-pariétales a été réalisé à l'aide d'un micro-spectromètre confocal Raman, et d'outils d'analyses dédiés qui ont été développés dans le cadre de cette étude. Les résultats obtenus ont par exemple permis de caractériser la paroi d'une cellule en formation (thylle), l'installation de la paroi secondaire dans des fibres, l'influence de stimuli environnementaux sur l'organisation sub-pariétale, ou encore le caractère continu de l'organisation spatiale des microfibrilles dans l'épaisseur des parois de différents types de cellules matures. La caractérisation mécanique a été réalisée selon la direction longitudinale des cellules, dans des essais de traction sur des éprouvettes de très faibles dimensions (épaisseur inférieure à 100 µm). La mise en évidence des phénomènes complexes en jeu dans le comportement mécanique a fait l'objet d'une étude sur la variation des propriétés structurales et mécaniques à l'intérieur d'un cerne. Les différentes phases de la relation contrainte-déformation ont été discutées, et une modélisation simplifiée par homogénéisation multi-échelle a notamment permis de poser un ensemble de pistes de réflexions sur le déterminisme de l'organisation sub-pariétale sur les propriétés mécaniques des cellules au sein d'un tissu. / Woods are a highly complex combination of multi-scale heterogeneities. Macroscopic properties of wood depend on all smaller scales of heterogeneity: growth rings, cells, as well as organization and concentration of cell wall chemical compounds. While the effect of the crystalline elements (microfibrils) of the solid phase on the macroscopic properties has been studied, one of the challenges is to estimate the determinism of the cell-wall molecular arrangements on the cells' properties inside a tissue. In this context, the present study is developed along two lines: (i) The collection of information on cell wall organization across the diversity of cells, and (ii) the characterization of micro-mechanical properties at the tissue level, with the consideration of smaller scales of heterogeneity. Most sub-cell wall descriptions were performed using a confocal Raman micro-spectrometer, and tools of analysis that were developed in this study. For example, obtained results have highlighted the cell wall of a living cell (thyllose), the cell wall formation in poplar fibers close to the cambial region, the impact of environmental stimuli on sub-cell wall organization, or else the continuous variation of the spatial organization of crystalline compounds in wall of different mature cells. The mechanical characterization was realized in the longitudinal direction on small samples (thickness below 100µm). The understanding of complex phenomena involved in the mechanical behavior was approached through a study on the variation of structural and mechanical properties within a ring. The different parts of the stress-strain curve have been discussed, and a simplified homogenization model has help to highlighted the determinism of sub-cell wall organization on the mechanical properties of cells at the tissue level.

Um estudo refinado dos filmes derivados do gel de pentóxido de vanádio foi realizado por meio de técnicas espectroscópicas e microscópicas visando compreender melhor as características deste material na escala microscópica. Foi demonstrado que o gel de pentóxido de vanádio é uma suspensão de nanopartículas anisotrópicas que se mantêm estáveis mesmo em altas concentrações. As propriedades estruturais e espectroscópicas destas nanopartículas foram revistas e discutidas no estado da arte. Em paralelo foi possível investigar fenômenos como a transição de fase induzida por laser e desenvolver aplicações tecnológicas em áreas como litografia e sensoriamento de gases. Ficou destacada nesta tese o grande potencial de investigação da microscopia Raman confocal na área de nanomateriais. / A refined study of films derived from vanadium pentoxide gel was carried out based on spectroscopic and microscopic techniques, aiming a better understanding of this material on a microscopic scale. It was demonstrated that the vanadium pentoxide gel consists of a suspension of anisotropic nanoparticles which remains stable even at high concentrations. The structural and spectroscopic properties of such nanoparticles were reviewed and discussed, providing new insights at the state of the art. It was also investigated the occurrence of some relevant phenomena, such as the laser induced phase transition, and to develop new technological applications in areas such as gas sensing and lithography. The collection of results described in thesis highlighted a great research potential of confocal Raman microscopy, in the field of nanomaterials.

<p dir="ltr">This thesis describes advancements in both chemical imaging and optical manipulation methodologies for their application in tandem monitoring and control of biochemical processes. We developed a fast acquisition multimodal nonlinear imaging platform based on pulse-picking to minimize photoperturbation to the sample during imaging. By frequency doubling the imaging source, through acousto-optic modulation and simple comparator circuitry, we developed a comprehensive platform that uses chemical specific signals generated during imaging to control the pixel location for laser activation for reaction control. This feedback loop allows for advanced decision logic on a pixel by pixel basis.</p>

This thesis broadly describes the construction of two kinds of spectroscopic set-ups to analyze properties of various materials. In the first part, construction of a Raman spectrometer and a high-throughput in-vivo detection for early plant abiotic stress responses is described. Following which, the set-up is modified into a microscope employed to study Murine blood components with samples varying in age. Initial Raman set-up is also improvised using a polarizer in order to gain deeper understanding of the vibrational and rotational bonds in water. The second part of the thesis explains the construction of a laser-induced fluorescence (LIF) sensor module. Performance testing and experiments were carried out with the sensor module to monitor stress in vegetation and fruits and also detect toxins found in corn and carcinogenic compounds in gasoline. The module was further mounted to an unmanned aerial vehicle for field surveys and preliminary testing in flight is described.

No / A comprehensive study has been undertaken into a 13th century Coptic-Byzantine icon from the St. Mercurius Church, St. Mercurius monastery, Old Cairo, Egypt. The layered structure, pigment composition and varnish identification were revealed by means of optical and Raman microscopy and gas chromatography¿mass spectrometry (GC¿MS). The structure of the icon comprised six layers; wooden panel, canvas, white ground, two bole layers and a single paint layer. Azurite (2CuCO3·Cu(OH)2), cinnabar (mercuric (II) sulfide ¿-HgS), yellow ochre (Fe2O3·H2O), hydromagnesite Mg5(CO3)4(OH)2·4H2O and lamp black (carbon, C) are the pigments identified in the icon. The green paint area is of interest as it is applied neither with a green pigment nor with a mixture of a blue and yellow pigment. Instead, a yellow layer of dammar resin was applied on top of blue azurite to obtain the green colour. Pinaceae sp. resin mixed with drying oil was used as a protective varnish.

Chapter 1 gives a general introduction into plastic polymer and microplastics including concepts, sources and distribution in the environment, microplastic sampling and analytical methods, and sampling area descriptions. Chapter 2 represents all methods and followed equipment used in the thesis. A double-filtration procedure preferable to Raman microscopy technique was developed to collect marine microplastics in brackish water from Can Gio and seawater from the East Sea. Chapter 3 is a comprehensive guideline on IR and Raman spectra interpretation of PE, PP, PVC, PS, PMMA, and polymer textiles, which is especially useful if the automatic library is not available. This chapter represents how to identify polymer type, predict sources and chemical behaviours of microplastics with the smallest size of 15 μm based on microscopic and spectroscopic data. Also, this chapter evaluates the sample handling workflows for salt, water and sand samples. Chapter 4 demonstrates the change in microplastic pollution from 250 MPs/L in Saigon urban canals (the center of Ho Chi Minh City), through UNESCO Can Gio Mangrove Biosphere Reserve (10 – 20 MPs/L), to estuaries of Saigon-Đong Nai River, Soai Rap River, Long Tau River (Ganh Rai Gulf), and eventually to the East Sea (3 – 5 MPs/L). Chapter 5 highlights the correlation of microplastic properties and compositions in beach sand and seawater in the coastal environment, particularly at Can Gio 30 April Tourist Beach. This is a pilot study to identify the differences and similarities in morphologies and compositions of microplastics accumulated in beach sand and distributed in seawater, thereby, concluding sources and transport routes of microplastics in the coastal environment. The results show that microplastics accumulated at concentrations from 0 to 92.56 MPs/kg from the surface to 20-cm sand layers. The seawater at Can Gio Beach and Đong Tranh Cape contained 6.44 and 3.75 MPs/L of microplastics, respectively. White polyethylene fragments predominated, and all the microplastics comprised small secondary microplastics with a minimum size of 25 µm and a maximum size of 260 µm for fragments and a length of 640 µm for fibers. The proportions of PE, PP, PS and PMMA were similar. The differing percentages of other compositions in sand and seawater are attributed to the morphology and density of the microplastics. Chapter 6 deals with the detection and determination of microplastics in Vietnamese sea salts. As a result, there was a higher fluctuation in microplastic amount amongs non-branded salts compared with branded salts. An average of 133.62 MPs/kg salt, corresponding to 487.71 microplastics entering the human body per year via salt consumption. More importantly, this chapter provides a convincing evidence for microplastic contamination in marine salts from the seawater. There are similarities in percentage, shape, size and colour of microplastics, especially PE, PET and PP extracted from sea salt and seawater collected in 3 different regions in Southern Vietnam (Can Gio Reserve and Vung Tau).:Chapter 1. Introduction 1.1. Synthetic polymers and plastic products 1.1.1. Overview of polymers and plastics 1.1.2. Plastic applications and global productions 1.1.2.1. Conventional plastics 1.1.2.2. Bioplastics 1.1.3. The life cycle of plastics and plastic pollution 1.2. Microplastics – definitions, sources and fate 1.2.1. Definition and classification of microplastics 1.2.2. Sources and pathways of microplastics into the environments 1.2.3. Global distribution and behaviours of microplastics in the environment 1.2.3.1. Physical behaviours: temporal and spatial accumulations 1.2.3.2. Chemical behaviours: Degradation and Adsorption 1.2.3.3. Biobehaviours: Ingestion, Translocation and Biodegradation 1.3. Effects and bioavailability of plastics on ecosystems, creatures and humans 1.3.1. Aquatic ecosystem 1.3.2. Terrestrial ecosystem 1.3.3. Food safety and human healths 1.4. Microplastic sampling techniques and analytical methods 1.4.1. Microplastic sampling techniques 1.4.1.1. Water sampling 1.4.1.2. Sediment sampling 1.4.2. Sample preparations for microplastic analysis 1.4.2.1. Matrix removal – oxidation and tissue digestion 1.4.2.2. Microplastic separation – density flotation and filtration 1.4.3. Microplastic qualification and quantification methods 1.4.3.1. Visual identification methods 1.4.3.2. Spectroscopic identification methods 1.4.3.3. Destructive thermal techniques 1.4.3.4. Summarized workflow from samples to the results on microplastics 1.4.3.5. Data expression Chapter 2. Materials and Methods 2.1. Materials 2.2. Microscopy-spectroscopy for microplastic quantification and qualification 2.3. Quality assurances (QA) and quality controls (QC) 2.4. Collected and interviewed data on the study areas 2.5. Water samples 2.6. Sand samples 2.7. Marine salt samples Chapter 3. The comprehensive guideline on micro-spectroscopic interpretation and sample preparations for microplastic analysis 3.1. Abstract 3.2. Visual characterizations of microplastics 3.3. Interpretation of IR and Raman spectra for plastic identification 3.4. The specificity of spectroscopies for identifying polymer type and chemical behaviours of sampled microplastics 3.4.1. Poly-Ethylene (PE) 3.4.2. Poly-Propylene (PP) 3.4.3. Poly-Vinyl Chloride (PVC) 3.4.4. Poly-Styrene (PS) 3.4.5. Poly Methyl Metacrylate (PMMA) 3.4.6. Poly-Ethylene Terephthalate (PET) 3.4.7. Poly-Amides-6, Nylon-6 (PA-6) 3.4.8. Similarity in Raman bands of pure plastics and sampled microplastics 3.5. The evaluation of sample treatment procedures 3.5.1. Salt samples 3.5.2. Sand samples 3.5.3. Water samples Chapter 4. Assessing microplastic prevalence and spatial dispersion from Saigon urban river network to East Sea by µ-Raman spectroscopy 4.1. Abstract 4.2. Microplastic pollution in the freshwater at Saigon urban canals 4.3. Microplastic pollution in the seawater at Can Gio Biosphere Reserve 4.4. Spatial and vertical dispersion of microplastics in the East Sea of Vietnam 4.5. Conclusions Chapter 5. Comparison of Microplastic Pollution in Beach Sediment and Seawater at UNESCO Can Gio Mangrove Biosphere Reserve 5.1. Abstract 5.2. Microplastic pollution in the sand at Can Gio Beach 5.2.1. Spatial variation in the microplastic amounts along the tidal lines 5.2.2. The abundance and composition of microplastics accumulated in sand layers 5.3. Microplastic pollution in seawater at Can Gio Beach and Đong Tranh Cape 5.4. Comparison of microplastic pollution between seawater and beach sand 5.5. Conclusions and recommendations Chapter 6. Microplastic contamination in Vietnamese sea salts 6.1. Abstract 6.2. The microplastics abundance in commercial sea salts 6.3. Microplastic pollution in the seawater taken at salt pans in Vietnam 6.4. Microplastic contamination in the sea salt collected at salt pans in Vietnam 6.5. Comparison of characteristics of microplastics in the seawater and sea salt 6.6. The enhanced toxicity of microplastics-contaminated salt consumption 6.7. Conclusions and recommendations Final Conclusions and Future Recommendations List of references Appendix Statistical data Photos taken on the sampling trips

Les besoins de nouvelles technologies en télécommunications motivent la recherche de matériaux participant à la formation de composants optiques. Dans ce but, l’étude de la photostructuration de nouvelles formulations de verres possédant des propriétés optiques ajustables a été réalisée. Deux cas ont été étudiés : la modification du réseau vitreux ou l’introduction d’ions photosensibles au sein du verre. - Des verres oxysulfures de germanium et de gallium ont été élaborés sous forme de massif, et sous forme de couche mince. Leurs propriétés optiques sont intermédiaires à celles des composés purs Ge(Ga)O2 et Ge(Ga)S2. La photosensibilité des verres diminue avec l’augmentation de la valeur du rapport O/S des matériaux. - L’ajout d’ions argent au sein de verres phosphates de zinc a été étudié. Plusieurs techniques de réduction de l’ion argent dans ces verres ont été explorées comme l’irradiation par faisceau électronique, par rayonnement gamma ou par Laser. Dans le cas particulier d’une irradiation par laser femtoseconde de cadence de 8 Mhz et émettant à 1030 nm, il a été possible de créer des structures optiques de 85 nm environ, donc bien inférieur à la longueur d’onde utilisée pour l’écriture. Ces premiers résultats offrent une nouvelle alternative à la création dans le futur de structures photoniques composites. / The increment of the need of new technologies in photonics is a perfect vector for the research and development of new components for integrated optics. The photostructuration of new glassy materials with novel optical properties is proposed. Two approaches have been conducted : Modification of the glass matrix or addition of photosensitive ions. - Germanium and gallium oxysulfide glasses have been elaborated into bulk glasses as well as amorphous thin films. They exhibit optical properties in between their respective pure sulphide or oxide counterpart in the Ge(Ga)O2 - Ge(Ga)S2 system. The photosensitivity of the oxysulfide glasses lowers as the oxygen/sulphur ratio of the glasses is increased. - The photosensitivity of silver ions within silver phosphate glasses was studied as well. Several techniques were used in order to trigger the reduction of silver such as gamma ray or electron beam irradiation, or laser beam exposure. Under a femtosecond laser with a repetition rate of 8 Mhz, emitting at 1030 nm, it was possible to create optical objects, below the diffraction limit, of about 85 nm. Those results are a new alternative for the creation of photonic composite structures.

Esta tese tem como objetivo contribuir para o conhecimento e desenvolvimento das células solares sensibilizadas por corantes, através da elaboração de novas espécies supramoleculares e de estudos fundamentais de caracterização do filme de TiO2-P25 e da interface TiO2-Corante pela técnica de microscopia Raman confocal. Os estudos de microcopia Raman confocal da distribuição das fases cristalinas rutilo e anatase em filmes de TiO2-P25 (Degussa) mostraram que a fase rutilo está presente em agregados de diferentes tamanhos (de 250 nm a 3 &#181;m) distribuídos na fase anatase e que estes agregados permaneceram mesmo após os processos de preparação da suspensão coloidal. Na presença do corante N3, verificou-se que a irradiação com laser em 532 nm, usando potência acima de 25 mW cm-2, provoca a absorção e posterior combustão do filme interfacial, com drásticas mudanças na morfologia visualizadas por microscopia Raman confocal, revelando a ocorrência da transformação de anatase em rutilo na região de incidência do feixe de laser. Outro ponto investigado nesta tese, foi a síntese e aplicação de novos sensibilizadores supramoleculares em células solares sensibilizadas por corante (DSC), visando diminuir os processos de recombinação e melhor aproveitamento do espectro solar através da estabilização do corante foto-oxidado e da transferência vetorial de elétron/energia. Além dos trabalhos com novas porfirinas supramoleculares, reproduzidas no apêndice, esta tese apresenta um estudo detalhado de uma série, formada por três espécies diméricas, constituídas pelas unidades [Ru(dcbH2)Cl]+ e [Ru(dmb)2Cl]+, unidas por ligantes ponte com dimensões lineares crescentes, isto é: bpy, bpe e bpeb (dcbH2= ácido-2,2\'-bipiridina-4,4\'-dicarboxílico, dmb= 4,4\'-dimetil-2,2\'- bipiridina, bpy= 4,4\'-bipiridina, bpe= trans-1,2-bis(4-piridil)-etileno e bpeb= trans-1,4- bis[2-(piridil)etenil]-benzeno). O rendimento global das DSCs correspondentes cresceram com o aumento do tamanho da ponte, passando de 2,78 % para o corante dim-Ru-bpy, para 2,89 e 3,25 % nos corantes dim-Ru-bpe e dim-Rbpeb, respectivamente. Foi observado que os valores de Jsc e &#951; têm correlação linear com a distância de separação do buraco e da superfície do eletrodo de TiO2, ratificando que o processo de retardação da recombinação de carga, causado pelo aumento da ponte, é um fator muito importante para esta classe de compostos. Os resultados de IPCE mostraram que a unidade [Ru(dmb)2Cl(P)]+ também é responsável pela fotoinjeção de elétrons no TiO2. Assim, a excitação de qualquer uma das unidades, sempre acaba formando a espécie TiO2(e-)-Ru-Ru(h+) no filme interfacial. Os resultados confirmam as expectativas esperadas no planejamento energético vetorial, no qual o HOMO foi centrado na unidade distante da superfície e o LUMO ficou sobre a dcbH2 diretamente ancorada no superfície do TiO2. / This thesis encompasses our efforts to improve the knowledge and contribute to the development of dye-sensitized solar cells, by focusing on supramolecular design of new dyes and on critical aspects of the morphology of the TiO2-P25 and TiO2-Dye interfaces, as probed by confocal Raman microscopy. According to Raman imaging of the crystalline phase distribution of TiO2-P25 (Degussa) rutile was present as aggregates of different sizes (from 250 nm to 3 &#181;m) dispersed in the 25 nm anatase powder, persisting even after applying criterious procedures for generating uniform colloidal suspensions. In addition, the irradiation of TiO2-P25 films containing adsorbed N3 dye, using a 532 nm laser (power over to 25 mW cm-2) led to the absorption and instantaneous combustion of the dye, promoting drastic local changes associated with the anatase to rutile conversion. The design and application of new supramolecular sensitizers in DSC has also been pursued, aiming an improvement of efficiency by slowing down the electron-hole recombination process, while enhancing the light harvesting effects in the visible range by means of vectorial electron/energy transfer. Studies concerning another efficient supramolecular porphyrin dye, have also been performed and published (Appendix). As the main subject, a series of dimeric species have been reported. They were based on the [Ru(dcbH2)Cl]+ and [Ru(dmb)2Cl]+ units connected by linear bridging ligands of increasing lengths, such as: bpy, bpe and bpeb (dcbH2= 2,2\'-bipyridine-4,4\'-dicarboxylic acid, dmb= 4,4\'-dimethyl-2,2\'-bipyridine, bpy= 4,4\'-bipyridine, bpe= trans-1,2-bis(4- pyridyl)-ethylene e bpeb= trans-1,4-bis[2-(4-pyridyl)ethenyl]-benzene). The overall yield of the corresponding DSCs increased with the bridging ligand length, from 2.78 % for dim-Ru-bpy, to 2.89 % and 3.25 % for dim-Ru-bpe and dim-Ru-bpeb, respectively. The electrochemical parameters associated with the short circuit current exhibited a linear correlation with the hole separation distance between the TiO2 electrode and the binuclear dye terminal, confirming that the retardation of charge recombination through the increasing distance is indeed a relevant factor for this series of compounds. The IPCE results indicated that the [Ru(dmb)2Cl(P)]+ unit is also involved in electron transfer, such that the dye excitation always leads the TiO2(e-)-Ru-Ru(h+) species. This conclusion confirmed the success of the supramolecular design and vectorial transfer strategy, in which the HOMO center was placed far away from the surface, but in communication with the LUMO center located at the dcbH2 group anchored on TiO2.