Dissertations / Theses on the topic 'Pigment Spectroscopy'

Cette thèse porte sur l’étude de l’interface entre électrodes et cellules épithéliales de la rétine : l’épithélium pigmenté. Les cellules RPE (Retinal Pigment Epithelium) qui le constitue forment une monocouche qui à confluence est constituée de cellules de forme polygonale. Elles sont juxtaposées et en contact intime les unes avec les autres par la présence de jonctions serrées. Un épithélium pigmenté endommagé est souvent associé à des pathologies de la vision. La spectroscopie d’impédance est une méthode de mesure qui permet d’étudier de manière non destructive un milieu composé d’éléments diélectriques et conducteurs. Cette mesure s’applique particulièrement bien aux cellules épithéliales. On applique ceci à l’étude du tapis cellulaires. Les membranes cellulaires remplissent le rôle de milieu diélectrique alors que les milieux ioniques intra et extracellulaires peuvent être considérés conducteurs. On peut en première approche analyser le module de l’impédance mesurée à une fréquence donnée afin de suivre le développement des tissus. Par exemple dans le domaine des implants à électrodes les fréquences autour de 1 KHz sont couramment citées. On peut par la suite mesurer l’impédance dans une gamme de fréquence plus importante et appliquer un modèle composé de dipôles électriques aux mesures. L’analyse des paramètres extraits peut donner une interprétation plus fine de l’état du tapis cellulaire. Deux notions seront principalement abordées dans cette thèse. Tout d’abord l’étude de l’utilisation de l’élément à constante de phase (CPE) dans la représentation du tapis cellulaire. Ensuite dans le cadre de ce modèle on va étudier le tapis cellulaire face à différentes perturbations
This manuscript focuses on studying the interface between an electrode and epithelial cells of the retina: the Retinal Pigment Epithelium (RPE). The cells that are part of this epithelium develops until they form a monolayer of juxtaposed cells with close lateral contact involving the presence of tight junctions. A damaged epithelium is often associated with sight alterations.Impedance spectroscopy is a measurement method that allows to study materials containing both conducting and dielectric elements in a non–destructive way. We apply this technique to the RPE cells layer. Cells membranes are the dielectric part while the intra and extracellular mediums are the conductive parts of this material. In a first stage one can measure the impedance at a fixed frequency as a way to follow tissues development. As an example, the 1 KHz frequency is often considered in characterizing electrodes from implanted devices. One can also measure the impedance over a wider bandwidth and apply an electric model circuit to the data. The extracted parameters can give a better interpretation of the state of the cell layer. In this work, two part will be mainly investigated. First we will evaluate the use of a constant phase element in part of the electrical model describing the cell layer. Second, and considering the same model, we will observe the reaction of the model when the cells are subject to various perturbations

Ces dernières années, les matériaux fonctionnels hybrides ont commencé à être employés pour des applications de la haute technologie, allant des senseurs bio/médicaux, à la production d’énergie renouvelable. Pour cette raison, ils sont devenus le centre de plusieurs études dans le domaine des sciences des matériaux. Simultanément, des molécules conjuguées ont été examinée intensément à cause de leurs propriétés venant de leurs longs systèmes π, allant de la possibilité de conduire l’électricité, à leur capacité d’absorber la lumière dans une grande fenêtre spectrale. Le travail de cette thèse se concentre sur l’introduction de tels systèmes dans deux sortes de matériaux hybrides, les dispositifs photovoltaïques pour la production d’électricité (en particuliers les cellules solaires à pigment photosensible) et de carburants alternatifs (hydrogène), et pour les hydrogels biocompatibles sensibles aux stimuli (capables de conduire l’électricité et de réagir sous irradiation), et sur l’étude de leur influence sur les caractéristiques du matériau final
In recent years hybrid functional materials began to be employed in a series of technologically advanced applications spanning from bio/medical sensors, to renewable energy generation. For this reason, they became the focus of several studies in the field of materials science. At the same time, conjugated molecules have also been intensively investigated, due to the properties arising by the presence of long π-conjugated systems, from the possibility to conduct electricity to the ability to absorb light in a wide range of wavelengths. This PhD work focused on the introduction of such systems in two different kinds of hybrid materials, namely photovoltaic devices for the production of electricity (in particular Dye Sensitzed Solar Cells) and alternative fuels (hydrogen), and biocompatible stimuli-responsive hydrogels (capable to conduct electricity and to react upon irradiation), and on the study of their influence on the characteristics of the final material

The Maya of Central America developed a complex society: among their many achievements they developed a writing system, complex calendar and were prolific builders. The buildings of their large urban centres, such as Copan in Honduras, were decorated with painted stucco, moulded masks, carving and elaborate murals, using a range of coloured pigments. In this study the paints used on the buildings of Copan and some ceramic sherds have been investigated, non-destructively, using micro-Raman spectroscopy, micro-ATR infrared spectroscopy, environmental scanning electron microscopy with energy dispersive X-ray analysis (ESEM-EDX) and FTIR-ATR imaging spectroscopy. The paint samples come from four buildings and one tomb covering three time periods in the four hundred year history of Copan. The main pigment used in the red paint on these samples was identified as haematite, and the stucco as a mixture of calcite particles dispersed throughout a calcite-based lime wash stucco. The composition and physical nature of the stucco changed through time, indicating a refining of production techniques over this period. A range of minor mineral components have been identified in each of the samples including rutile, quartz, clay and carbon. The presence and proportion of these and other minerals differed in each sample, leading to unique mineral signatures for the paint from each time period. Green and grey paints have also been identified on one of the buildings, the Rosalila Temple. The green pigment was identified as a celadonite-based green earth, and the grey pigment as a mixture of carbon and muscovite. The combination of carbon and mica to create a reflective paint is a novel finding in Maya archaeology. The high spatial resolution of the micro-FTIR-ATR spectral imaging system has been used to resolve individual particles in tomb wall paint and to identify their mineralogy from their spectra. This system has been used in combination with micro-Raman spectroscopy and ESEM-EDX mapping to characterize the paint, which was found to be a mixture of haematite and silicate particles, with minor amounts of calcite, carbon and magnetite particles, in a sub-micron haematite and calcite matrix. The blending of a high percentage of silicate particles into the haematite pigment is unique the tomb sample. The stucco in this tomb wall paint has finely ground carbon dispersed throughout the top layer providing a dark base for the paint layer. Changing paint mixtures and stucco composition were found to correlate with changes in paint processing techniques and building construction methods over the four hundred years of site occupation.

Ausgangspunkt dieser Arbeit war die Frage, inwieweit die zur Herstellung von Compositmaterialien aus leitfähigen Polymerfilmen (Polythiophen, Polypyrrol) und Metalloxidschichten (anodisch oxidiertes Titan, chemisch oxidiertes Silicium bzw. Aluminium) entwickelte Präparationsmethode auf die Herstellung hybrider Core - Shell - Partikel (Core: Metalloxidpartikel; Shell: leitfähiges Polymer) übertragbar ist. Die erfolgreiche Beschichtung dispergierter Oxidpartikel mit leitfähigen Poly- meren zeigte, dass nicht nur eine analoge Verfahrensweise (Adsorption des Monomers auf der Substratoberfläche und anschließende Zugabe des Oxidationsmittels) verwendet werden konnte, sondern dass bei der Pulverbeschichtung infolge der großen spezifischen Oberfläche der Materialien auch ohne Einsatz spezieller Haftvermittler, hervorragende Schichtqualitäten (hohe Haftfestigkeit, hoher Be- deckungsgrad) erreicht wurden, und die auf diesem Wege hergestellten Verbundmaterialien in Pulverform in beliebiger Menge, Partikelgröße und Zusam-mensetzung verfügbar waren. Der durch die Verkapselung der Oxidteilchen mit intrinsich leitfähigen Polymeren bewirkte enge Kontakt zwischen Polymer- und Oxidphase und die auf diesem Wege realisierte Oberflächenmodifizierung führte zu einem im Vergleich zu den reinen Komponenten wesentlich veränderten Eigenschaftsspektrum. Durch die Herstellung von Compositen waren die leitfähigen Polymere leichter dispergierbar, und konnten kathaphoretisch in guter Qualität, auch auf großen Substratflächen abgeschieden werden
Starting with the question about the possibility of producing composites based on conducting polymer films (polythiophene, polypyrrole) and metal oxide layers (anodically oxidized titanium, chemical oxidized silicon or aluminium) it was the goal of this work to transfer and modify this method for the preparation of hybrid core - shell - particles (core: metal oxide particle; shell: conducting polymer). By the successfully covering of dispersed oxide particles it was shown, that not only an analogous procedure (adsorption of the monomer on the substrate surface and the following addition of an oxidant) can be used, but that in the case of powder covering because of the high specific surface area of the oxide powders, outstanding layer qualities without using adhesion promotors can be produced. Following this way, powder-like compound materials can be ordered and designed in any quantity, particle size and composition. Through the encapsulation of the oxide particles with intrinsic conducting polymers a narrow contact between the polymer and the oxide phase and a surface modification were made by a very simple way. By this surface modification a totally different behaviour of the composites, compared to their components was realized. The producing of composites allowes a better dispersibility of conducting polymers and their cathaphoretically deposition with a good quality, also on larger substrate surfaces

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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
Neste trabalho foram estudadas amostras do Centro de Museologia, Antropologia e Arqueologia da FCT - UNESP de Presidente Prudente, o qual é coordenado pela professora Dra. Ruth Kunzli. As amostras foram caracterizadas por espectroscopia vibracional via espalhamento micro-Raman e a absorção no infravermelho com transformada de Fourier (FTIR), análise térmica por termogravimetria (TG) e energia dispersiva de raio-X (EDX). O objetivo principal do trabalho foi identificar os pigmentos utilizados na fabricação dos artefatos cerâmicos encontrados no sítio arqueológico Lagoa São Paulo - 02, Presidente Epitácio, SP, bem como os aditivos incorporados ao corpo cerâmico para entender como os arteftos foram confeccionados. Para o pigmento vermelho os resultados de Raman, FTIR, EDX e TG sugerem a utilização de hematia, um óxido de ferro consistente com o que podia ser encontrado nas rochas avermelhadas das encostas dos rios que eram desgastadas pela água. O pigmento preto apresenta bandas Raman características do carvão, provavelmente, este pigmento era encontrado na natureza como o produto da queima de material orgânico, possivelmente de origem vegetal. Para o pigmento branco, os espectros de FTIR e as curvas de TG sugerem o uso de caulim pela presença das bandas de absorção e do pico endotérmico em 550ºC aracterístico da caulinita, o que é consistente com os dados arqueológicos. Os aditivos identificados foram o carvão e o quartzo, sendo este último encontrado nas rochas presentes na região do sítio arqueológico. Tais aditivos são adicionados na confecção das cerâmicas para evitar o rachamento quando do cozimento, facilitar uma secagem homogênea e, ao mesmo tempo, reduzir a porosidade e a plasticidade. O processo de queima das amostras foi investigado via TG revelaram que todas elas passaram por processos de queima. Entretanto, os resultados sugerem que a amostra...
In this study samples from the Centro de Museologia, Antropologia e Arqueologia (CEMAARQ) of the UNESP Unip Estadual Paulista in Presidente Prudente, São Paulo State, Brazil, coordinated by professor Dra. Ruth Künzli, were investigated. The samples were characterized by vibrational spectroscopy via micro-Roman scattering and Fourier transform infrared absorption (FTIR), thermal analysis by termogravimetry (TG) and energy dispersive X-ray (EDX). The main objective was to identify the pigments used in the manufacture of ceramic artifacts found in the archaeological site Lagoa Sao Paulo - 02, Presidente Epitácio, SP, and the additives incorporated to the ceramic body to understand how the artifacts were made. For the red pigment of the results of Raman, FTIR, EDX e TG suggested the use of hematite, an iron oxide consistent with that found in the red rocks of the river banks eroded by water. The black pigment has Roman bands characteristic of charcol, probably, this pigment was found in nature as the product of burning organic material, possibly from vegetable. For the white pigment, the FTIR spectra and TG curves suggest the use of Kaolin by the presence of the absorption bands and the endothermic peak at 550ºC, characteristic of kaolinite, which is consistent with the archaeological data. The additives were identified as charcoal and quartz, the latter being found in rocks present in the archeological site. These additives are added in the manufacture of ceramics to prevent cracking when buring, to promote a homogeneous drying and to reduce porosity and plasticity. The burning process of the samples was investigated by TG and revealed that all of them were submitted to burning processes. However, the results suggest that the sample ... (Complete abstract click electronic access below)

Ausgangspunkt dieser Arbeit war die Frage, inwieweit die zur Herstellung von Compositmaterialien aus leitfähigen Polymerfilmen (Polythiophen, Polypyrrol) und Metalloxidschichten (anodisch oxidiertes Titan, chemisch oxidiertes Silicium bzw. Aluminium) entwickelte Präparationsmethode auf die Herstellung hybrider Core - Shell - Partikel (Core: Metalloxidpartikel; Shell: leitfähiges Polymer) übertragbar ist. Die erfolgreiche Beschichtung dispergierter Oxidpartikel mit leitfähigen Poly- meren zeigte, dass nicht nur eine analoge Verfahrensweise (Adsorption des Monomers auf der Substratoberfläche und anschließende Zugabe des Oxidationsmittels) verwendet werden konnte, sondern dass bei der Pulverbeschichtung infolge der großen spezifischen Oberfläche der Materialien auch ohne Einsatz spezieller Haftvermittler, hervorragende Schichtqualitäten (hohe Haftfestigkeit, hoher Be- deckungsgrad) erreicht wurden, und die auf diesem Wege hergestellten Verbundmaterialien in Pulverform in beliebiger Menge, Partikelgröße und Zusam-mensetzung verfügbar waren. Der durch die Verkapselung der Oxidteilchen mit intrinsich leitfähigen Polymeren bewirkte enge Kontakt zwischen Polymer- und Oxidphase und die auf diesem Wege realisierte Oberflächenmodifizierung führte zu einem im Vergleich zu den reinen Komponenten wesentlich veränderten Eigenschaftsspektrum. Durch die Herstellung von Compositen waren die leitfähigen Polymere leichter dispergierbar, und konnten kathaphoretisch in guter Qualität, auch auf großen Substratflächen abgeschieden werden.
Starting with the question about the possibility of producing composites based on conducting polymer films (polythiophene, polypyrrole) and metal oxide layers (anodically oxidized titanium, chemical oxidized silicon or aluminium) it was the goal of this work to transfer and modify this method for the preparation of hybrid core - shell - particles (core: metal oxide particle; shell: conducting polymer). By the successfully covering of dispersed oxide particles it was shown, that not only an analogous procedure (adsorption of the monomer on the substrate surface and the following addition of an oxidant) can be used, but that in the case of powder covering because of the high specific surface area of the oxide powders, outstanding layer qualities without using adhesion promotors can be produced. Following this way, powder-like compound materials can be ordered and designed in any quantity, particle size and composition. Through the encapsulation of the oxide particles with intrinsic conducting polymers a narrow contact between the polymer and the oxide phase and a surface modification were made by a very simple way. By this surface modification a totally different behaviour of the composites, compared to their components was realized. The producing of composites allowes a better dispersibility of conducting polymers and their cathaphoretically deposition with a good quality, also on larger substrate surfaces.

La Norvegia è il leader mondiale per la produzione di salmone dell’Atlantico (Salmo salar). Il salmone norvegese è la specie più commercializzata in Europa e la terza specie ittica più consumata nel mondo (EUMOFA, 2016). La qualità del pesce è un concetto complesso che coinvolge diversi fattori come sicurezza, qualità nutrizionale, disponibilità, convenienza e altri attributi come colore e freschezza (Botta, 1995; Cardello, 1995). La pigmentazione muscolare nei salmonidi d'allevamento è considerata il parametro di qualità più importante dopo la freschezza (García-Chavarría et al., 2013). Studi sul comportamento del consumatore hanno dimostrato che la colorazione di questo prodotto viene inconsciamente relazionata con valore nutritivo, salubrità, freschezza e gusto. Difatti, al momento dell’acquisto, i consumatori hanno affermato che il colore è un parametro molto influente e sono disposti a pagare di più per un salmone più “rosso” (Anderson, 2000; García-Chavarría et al., 2013). La tipica colorazione rosata che caratterizza i salmonidi è dovuta ai carotenoidi (Shahidi et al., 1998). L’alimentazione con questi pigmenti è considerata la pratica di allevamento più importante per il salmone (Moe, 1990). Per questo motivo, ci sono diversi studi al riguardo. Lo scopo di questa tesi è sviluppare una metodologia per estrarre ed analizzare i principali carotenoidi presenti nel tessuto muscolare e negli organi dei salmonidi, tramite l’utilizzo della Risonanza Magnetica Nucleare ad alta risoluzione (HR 1H-NMR).

Obtention de données structurales sur la dimension du cœur porphyrique et l'angle de la liaison fe-o-fe par l'étude de composes modèles, mu-oxo tetraporphyrine et mu-oxo deuteroporphyrine. Adoption d'une structure coudée pour la liaison fe-o-fe, se traduisant en spectrométrie Raman par des profils d'excitation très différents pour les modes caractéristiques de l'entité mu-oxo

Orientador: Carlos José Leopoldo Constantino
Banca: Henrique de Santana
Banca: Ruth Kunzli
O Programa de Pós-Graduação em Ciência e Tecnologia de Materiais POSMAT, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi da UNESP
Resumo: Neste trabalho foram estudadas amostras do Centro de Museologia, Antropologia e Arqueologia da FCT - UNESP de Presidente Prudente, o qual é coordenado pela professora Dra. Ruth Kunzli. As amostras foram caracterizadas por espectroscopia vibracional via espalhamento micro-Raman e a absorção no infravermelho com transformada de Fourier (FTIR), análise térmica por termogravimetria (TG) e energia dispersiva de raio-X (EDX). O objetivo principal do trabalho foi identificar os pigmentos utilizados na fabricação dos artefatos cerâmicos encontrados no sítio arqueológico Lagoa São Paulo - 02, Presidente Epitácio, SP, bem como os aditivos incorporados ao corpo cerâmico para entender como os arteftos foram confeccionados. Para o pigmento vermelho os resultados de Raman, FTIR, EDX e TG sugerem a utilização de hematia, um óxido de ferro consistente com o que podia ser encontrado nas rochas avermelhadas das encostas dos rios que eram desgastadas pela água. O pigmento preto apresenta bandas Raman características do carvão, provavelmente, este pigmento era encontrado na natureza como o produto da queima de material orgânico, possivelmente de origem vegetal. Para o pigmento branco, os espectros de FTIR e as curvas de TG sugerem o uso de caulim pela presença das bandas de absorção e do pico endotérmico em 550ºC aracterístico da caulinita, o que é consistente com os dados arqueológicos. Os aditivos identificados foram o carvão e o quartzo, sendo este último encontrado nas rochas presentes na região do sítio arqueológico. Tais aditivos são adicionados na confecção das cerâmicas para evitar o rachamento quando do cozimento, facilitar uma secagem homogênea e, ao mesmo tempo, reduzir a porosidade e a plasticidade. O processo de queima das amostras foi investigado via TG revelaram que todas elas passaram por processos de queima. Entretanto, os resultados sugerem que a amostra ... (Resumo completo, clicar acesso eletrônico abaixo)
Abstract: In this study samples from the "Centro de Museologia, Antropologia e Arqueologia (CEMAARQ)" of the "UNESP Unip Estadual Paulista" in Presidente Prudente, São Paulo State, Brazil, coordinated by professor Dra. Ruth Künzli, were investigated. The samples were characterized by vibrational spectroscopy via micro-Roman scattering and Fourier transform infrared absorption (FTIR), thermal analysis by termogravimetry (TG) and energy dispersive X-ray (EDX). The main objective was to identify the pigments used in the manufacture of ceramic artifacts found in the archaeological site "Lagoa Sao Paulo - 02", Presidente Epitácio, SP, and the additives incorporated to the ceramic body to understand how the artifacts were made. For the red pigment of the results of Raman, FTIR, EDX e TG suggested the use of hematite, an iron oxide consistent with that found in the red rocks of the river banks eroded by water. The black pigment has Roman bands characteristic of charcol, probably, this pigment was found in nature as the product of burning organic material, possibly from vegetable. For the white pigment, the FTIR spectra and TG curves suggest the use of Kaolin by the presence of the absorption bands and the endothermic peak at 550ºC, characteristic of kaolinite, which is consistent with the archaeological data. The additives were identified as charcoal and quartz, the latter being found in rocks present in the archeological site. These additives are added in the manufacture of ceramics to prevent cracking when buring, to promote a homogeneous drying and to reduce porosity and plasticity. The burning process of the samples was investigated by TG and revealed that all of them were submitted to burning processes. However, the results suggest that the sample ... (Complete abstract click electronic access below)
Mestre

Various chromone derivatives have been used in asthma therapy, and their biological activity is apparently related to certain chemical features which include conformation and acidity. In the present study, substituent effects on conformation and acidity have been explored in chromone systems with potential biological activity. A range of variously substituted symmetrical chromone-2-carboxamides (including a series of N,N-dimethylchromone-2-carboxamides) have been prepared via chromone-2-carboxylic acids, which, in turn, were prepared from the corresponding o-hydroxyacetophenones. The N,N-dimethylchromone-2-carboxamides were prepared by reacting the appropriate chromone-2-carbonyl chlorides with dimethylammonium chloride in pyridine, in an approach which resolved various problems encountered in the preparation of these compounds. Substituent effects on the conformation of chromone-2-carboxamides have been explored using dynamic NMR spectroscopy, and the observed splitting of the N-alkyl signals has been attributed to slow site-exchange of the N-alkyl substituents. Dynamic NMR frequency separations and coalescence temperatures have been used to calculate rotational energy barriers, and substituent effects on these rotational energy barriers have been analysed. The possible implication of ring-opening of chromones in chromone pharmacology has also been examined. A range of 3-(2-hydroxybenzoyl)acrylamides has been prepared via the dimethylamine-mediated ring-opening of N,N-dimethylchromone-2-carboxamides and the E-double-bond configuration of the ring-opened products has been unambiguously established by single crystal analysis of the parent system. The configuration and conformation of the crystal structure of the parent system have been shown, using IR and NMR spectroscopic, and molecular graphics techniques, to be maintained in solution and to characterise the whole series. ¹H and ¹³C NMR spectroscopy have also been used to study the dimethylamine-mediated ring-opening of disodium cromoglycate. The kinetics of the dimethylamine-mediated ring-opening of N,N-dimethylchromone-2-carboxamides have been studied using UV spectroscopy. These reactions have been shown to follow third-order kinetics overall and a mechanism accommodating the observed third-order kinetics has been proposed. Substituent effects have been further investigated by the potentiometric determination of the pKa (pK [subscript a]) values for a series of chromone-2-carboxylic acids. The relationship between acidity and the observed rate constants has been explored and has verified that the observed rate constants are sensitive to the influence of meta-substituents on the stability of the phenoxide ion "leaving group" rather than C-2 electrophilicity.

The use of UV-visible, mid infrared, near infrared (NIR) and Raman spectrometries for monitoring the milling of polymer-pigment dispersions was investigated. Experiments showed that both NIR and Raman showed possibility for in-situ monitoring of particle size reduction and were both investigated further. A fundamental investigation of the information content of NIR spectra was completed, showing the influence of particle size on the scattering properties of the pigment dispersions. This was used to rationalise observations made from spectra collected in-situ during particle size reduction experiments on different scales. Cyan, magenta and yellow pigment dispersion NIR spectra, collected in-situ, during milling, showed an increase in baseline offset as pigment size was reduced. Experimentation was performed on < 1 kg scale to develop and assess the technique before applying to larger scale 10 kg and 200 kg milling experiments. Qualitative and quantitative, univariate and multivariat e, modelling approaches were explored for monitoring experiments performed on different scales. < 1 kg scale milling experiments showed errors in prediction of between 0.90 -7.96 % for samples at the end point of milling (with particle sizes ranging from 100 to 114 nm). A calibration model derived from < 1 kg experiments was applied to 10 kg milling experiments with an error of prediction of 4.14 % for particles of 110 nm. Qualitative univariate modelling of 200 kg pigment dispersion milling experiments was able to show where faults occurred and where particle size reduction was no longer progressing. The work has demonstrated that in situ NIR measurements could potentially replace the current off-line particle size method. Raman spectroscopy also showed potential for following particle size reduction processes (< 1 kg scale) for cyan and yellow pigment dispersions using a wide area illumination Raman probe. Issues with fluorescence were encountered for magenta pigments and alternative s were explored to remove this.

Since the mid 1980s, Raman and X-ray fluorescence spectroscopy have become instrumental techniques that can be easily and successfully applied to chemical analysis. In this respect, scientific studies of works of art and the materials used in their creation are one of the fields that have received great impulse.
Several reasons for the spectroscopic investigation of antiquities and art objects can be pointed out. One of them is the interest in the materials and techniques in use during a certain period or region. This knowledge may be utilized for roughly dating the art object (retrieving pigments with a known date of invention may indicate that the artifact dates from a more recent period). Another reason is that this analysis is a useful source of information during a restoration or conservation treatment, and signs of a previous restoration, retouching or even forgeries can be found.

At the beginning of this century investigation in cultural heritage became an important research field that posed great scientific interest, requiring unprecedented interdisciplinary knowledge of a wide spectrum of areas such as history, archaeology, physics, chemistry, engineering, chemometrics and many other disciplines. On the other hand, improvements in the instrumental techniques used have been the goal of many important studies. Even more, in this decade the investigation has been focalized on the development of a new generation of instruments which allows the combination of complementary analytical techniques along with the advantage of portable instrumentation. Both improvements permit a robust and non-destructive chemical analysis of works of art which are difficult or impossible to study in a laboratory (highly valuable masterpieces, large paintings, and wall paintings).
Chemometrics methods are the necessary complement to these instrumental improvements. In order to maximize the robustness of these instruments, automatic and robust data processing tools are needed to obtain the maximum possible information from a work of art.
This doctoral thesis presents a framework to perform data-fusion systems for classification analysis of pigments investigated in the field of cultural heritage. These systems were developed and evaluated within a European Community research project, the main objective of which was to develop a portable micro Raman and micro X-ray fluorescence instrument (PRAXIS).

The general aim of this doctoral thesis is to study different strategies for the implementation of Raman-XRF data-fusion systems, in order to improve classification analysis of pigments investigated in the field of cultural heritage. This study takes into account the nature of the different interferences usually encountered in these types of signals and its elimination by developing dedicated algorithms. Moreover, this study evaluates automation in classification analysis by developing inference systems.


In order to reach that global aim these particular objectives are defined:

1) To study the nature of stochastic events and signal interferences present in Raman and XRF spectroscopy in order to enable the implementation of chemometrics techniques for classification. This is done in more detail for Raman data, due to the fact that this technique is mainly used in this field for "fingerprint" analysis. The methodology used is Wavelet transform and the improvements achieved in this area are presented in a paper entitled Noise and background removal in Raman spectra of ancient pigments using wavelet transform.
2) To establish the capabilities of a fuzzy logic system for automatic pigment identification. This issue is presented in a paper entitled Fuzzy logic for identifying pigments studied by Raman spectroscopy.
3) To review the current state-of-art of data-fusion in analytical chemistry and to establish actual data-fusion methodologies onto a Raman-XRF sensor fusion system. The performance of each data-fusion architecture is discussed in a paper entitled Micro Raman and X-ray fluorescence spectroscopy data fusion for the classification of ochre pigments.
4) To improve data-fusion methodologies by dual-domain analysis achieved by Wavelet transform. The achievements are presented in two papers Data fusion and dual-domain classification analysis of pigments studied in works of art and Data fusion in the wavelet domain by means of fuzzy aggregation connectives.
5) To define the necessary parameters and propose a methodology to implement data-fusion strategies in Raman and XRF spectroscopy.

Structure

The thesis has been structured in different chapters, each one containing the following information:

Chapter 1 is a theoretical chapter; the first part gives an overview of the basic concepts and latest advances in the fields of micro-Raman spectroscopy and micro-X ray fluorescence spectrometry. The characteristics of a new instrument which combines both techniques are presented along with the improvements achieved in that area. In the second part, the background of chemometrics techniques used in this work is presented.

Chapter 2 introduces the framework for the study of ancient pigments. It describes the nature of samples analyzed and gives an overview of the different techniques used in the creation of works of art throughout the years. Finally, the instruments used in this doctoral thesis for preliminary and final validation analysis are described.

Chapter 3 deals with the data pre-treatment needed before applying chemometric techniques, both for classification and data-fusion. In that respect, the first part focuses on the principles of Wavelet transform as a tool to eliminate signal interferences. This chapter includes a paper in which the development of an innovative method to eliminate noise and background signals from Raman spectra simultaneously is presented. It has been successfully applied for Raman spectra of ancient pigments.

Chapter 4 presents a preliminary study of automatic analysis of pigments by means of soft computing solutions such as Fuzzy logic. A published paper is presented in which Fuzzy logic is used to perform an automatic system for pigment identification. This study is extended to a fusion model and X-ray fluorescence analysis data is incorporated in the developed identification system. The ability of fuzzy logic to process imprecise information is described in the last part of this chapter.

Chapter 5 deals with three data-fusion architectures and their analysis by means of hard computing solutions as Principal components analysis (PCA) and Partial least squares - discriminant analysis (PLS-DA). The models are implemented for the classification of a set of ancient pigments from Byzantine iconography. Benefits and drawbacks of each method are pointed out.

Chapter 6 incorporates a new innovative strategy for data-fusion. The fusion of data in the wavelet domain is discussed and two approaches are presented for Raman and X-ray fluorescence data-fusion: Mid-level and High level dual domain data-fusion. Both are used and successfully applied for the automatic identification of pigments in classification problems with different levels of difficulty. Two papers are included in which both methods are used for the classification of ancient pigments, which face difficult identification problems. These two methods combine the benefits described in the previous chapters of this thesis with the consequent improvement of classification results. The developed systems are suitable to perform a rapid and automatic classification of ancient pigments.

Chapter 7 presents a review of the state of the art regarding data-fusion. The different steps necessary to achieve a proper data fusion are discussed.

Finally, Chapter 8 presents the conclusions of the thesis and suggests some possible issues for future research.




Fusión de datos en espectroscopias Raman y de fluorescencia de rayos X para la identificación de pigmentos en trabajos de arte
Desde mediados de los años 80s, las espectroscopias Raman y de fluorescencia de rayos X (XRF) se pueden considerar técnicas instrumentales de fácil aplicación en el análisis químico. Uno de los ámbitos de gran aplicación de dichas técnicas se centra en el estudio científico de una obra de arte y de los materiales utilizados en su creación.
Existen varias razones para la investigación de antigüedades y objetos de arte por medio de técnicas espectroscópicas. Una de ellas es el estudio de los materiales y técnicas aplicados durante un cierto período o en una determinada región. Este conocimiento puede ser muy útil para ubicar aproximadamente un objeto de arte en una determinada época o periodo. Otra razón es que este análisis es una importante fuente de información para la restauración o el tratamiento de conservación, y permite encontrar señales de una restauración anterior, de repintado o de falsificaciones.

Desde el comienzo de este siglo, la investigación en el patrimonio cultural se sitúa como un campo de la investigación importante con un gran interés científico. Esta investigación, requiere un importante trabajo multidisciplinario que implica a especialistas en áreas como historia, arqueología, física, química, ingeniería, quimiometría y otras disciplinas. Por otro lado, el objetivo de muchos trabajos científicos y estudios importantes, ha sido el desarrollo y las mejoras en estas técnicas instrumentales de análisis. Más aun, en esta década la investigación está enfocada en el desarrollo de una nueva generación de instrumentos que permiten la combinación de técnicas analíticas complementarias junto con la ventaja de una instrumentación portátil. Ambas mejoras permiten un análisis químico robusto y no destructivo de los objetos de arte, en especial de aquellos en los que resulta difícil o casi imposible de estudiar en un laboratorio. Como por ejemplo obras de arte de gran valor y pertenecientes al patrimonio cultural del país, pinturas de grandes dimensiones y pinturas realizadas en murales.

Los métodos Quimiométricos de análisis son el complemento necesario a estas mejoras instrumentales. Con objeto de aumentar al máximo la robustez de estos instrumentos, es necesario proveerlos de herramientas de procesamiento automáticas y robustas para obtener el máximo de información del objeto bajo estudio.
Esta tesis doctoral, presenta un marco de referencia para realizar fusión de datos para la clasificación e identificación de pigmentos estudiados en el campo de patrimonio cultural. Estos sistemas se desarrollan y evalúan dentro de un proyecto de investigación de la comunidad europea. El objetivo principal de este proyecto ha sido desarrollar un instrumento portátil para realizar espectroscopias Raman y de fluorescencia de rayos-X (PRAXIS).

El objetivo general de esta tesis doctoral es estudiar diferentes estrategias para el desarrollo de sistemas de fusión de datos Raman y XRF para mejorar la clasificación de pigmentos. Este estudio contempla la naturaleza de las distintas interferencias que habitualmente se encuentran en estos tipos de mediciones (espectros) y su eliminación por medio del desarrollo de metodologías adecuadas. También, se evalúa la posibilidad de automatización en el proceso de clasificación.


Para alcanzar este objetivo global, se definen los siguientes objetivos particulares:

1) Estudiar la naturaleza de eventos estocásticos (ruido) e interferencias habitualmente presentes en espectroscopia Raman y XRF, con el fin de facilitar la aplicación de técnicas quimiométricas de clasificación. Este estudio se realiza más profundamente para los espectros obtenidos por espectroscopia Raman, ya que es la técnica principalmente utilizada en este campo para una identificación del tipo "huella digital." La metodología usada es la transformada Wavelet y las mejoras logradas se presentan en un artículo titulado "Ruido y eliminación de señales de fondo en espectros Raman de pigmentos antiguos por medio de la transformada Wavelet".
2) Establecer un sistema de lógica difusa para la identificación automática de pigmentos. Este estudio se presenta en un articulo titulado "Lógica difusa para identificar pigmentos estudiados por espectroscopia Raman".
3) Estudiar la situación actual de aplicaciones y desarrollos de fusión de datos en química analítica y establecer las metodologías de fusión de datos reales en un instrumento Raman-XRF. Los resultados obtenidos en distintos modelos de fusión de datos se discute en un articulo titulado "Fusión de espectros Raman y de fluorescencia de rayos X para la clasificación de pigmentos ocres".
4) Mejorar las metodologías de fusión de datos por medio del análisis en el dominio dual dado por la transformada Wavelet. Los logros obtenidos se presentan en dos artículos "Fusión de espectros y análisis de clasificación en el dominio dual de pigmentos estudiados en obras de arte" y "Fusión de datos en el dominio Wavelet por medio de conectores de agregado difuso".
5) definir los parámetros necesarios y proponer a una metodología llevar a cabo las estrategias de fusión de espectros en espectroscopias Raman y XRF.

Estructura

La tesis ha sido la estructura en capítulos diferentes, donde cada uno contiene la siguiente información:

El capítulo 1 es un capítulo teórico; donde en una primera parte se da una apreciación global de los conceptos básicos y de los últimos adelantos en espectroscopias Raman y de fluorescencia de rayos X. Las características de un nuevo instrumento que combina ambas técnicas se presentan junto con las mejoras logradas en él. En una segunda parte, se describen las técnicas quimiométricas usadas en este trabajo.

El capítulo 2 describe la naturaleza de las muestras estudiadas y de su uso en la creación de obra de arte. Finalmente, se describen instrumentos Raman y XRF usados en esta tesis doctoral.

El capítulo 3 presenta el tratamiento necesario en los datos antes de aplicar las técnicas quimiométricas, ya sea para la clasificación y/o fusión de datos. En ese sentido, se presenta un estudio de la aplicación de la transformada Wavelet como una herramienta para eliminar las interferencias señaladas. Este capítulo incluye un artículo en el que nosotros presentamos el desarrollo de un método innovador para eliminar simultáneamente las señales de ruido y fondo es espectros Raman.

El capítulo 4 presenta un estudio preliminar del análisis automático de pigmentos por medio de la lógica difusa. Se presenta artículo donde la lógica difusa es utilizada para realizar un sistema automático de identificación de pigmentos. Este estudio se extiende a un modelo de fusión y por el cuál la información obtenida por XRF es incorporada en el sistema de identificación desarrollado.

El capítulo 5 presenta tres arquitecturas de fusión de datos y el posterior análisis por medio de técnicas quimiométricas como el análisis de componentes Principal (PCA) y la regresión por mínimos cuadrados parciales para análisis discriminante (PLS-DA). Los modelos se llevan a cabo con el estudio de pigmentos antiguos referidos a la iconografía bizantina. Esta parte acaba señalando los beneficios y desventajas de cada método.

El capítulo 6 presenta una nueva estrategia para la fusión de datos, que es la fusión de datos en el dominio del wavelet. Se discuten los fundamentos y se presentan dos modelos de fusión de datos Raman y XRF en el dominio wavelet: El nivel medio y el nivel alto, ambos se aplican a la identificación automática de pigmentos. Dos artículos son incluidos, donde se describen ambos métodos y se presenta su aplicación para la clasificación de pigmentos antiguos.

El Capítulo 7 presenta un estudio sobre el estado actual en la investigación de fusión de datos y su aplicación en química analítica. Las etapas necesarias para desarrollar métodos apropiados de fusión de análisis.

Finalmente, en el capítulo 8 presenta las conclusiones de la tesis y propone posibles trabajos de investigación futura.

Ce travail porte sur le traitement de surface de pigments, d’oxyde d’aluminium, de fer et de titane par des polyesters acrylique et l’analyse des propriétés qui en résultent. Les mesures d’angle de mouillage montrent que le traitement rend les pigments plus hydrophobes. Ces traitements sont ils complets, avec un recouvrement homogène de la surface et quels sont les types de liaisons formées ? L’analyse quantitative a été menée par thermogravimétrie et spectroscopie infrarouge après traitement et lavages par différents solvants. Les résultats cohérents montrent que les molécules sont fixées sur les trois oxydes de fer, une partie des molécules seulement sur l’oxyde de titane, avec une plus faible fraction fixée sur l’alumine. Des liaisons chimiques sont détectées par spectroscopie infrarouge, assisté par un modèle de mécanique quantique. Cependant l’AFM et l’XPS montrent que le traitement de la surface n’est pas homogène, le polymère se dépose sous forme d’îlots. L’observation directe par AFM sur des plaquettes d’alumine est décisive. Elle montre que ce mode de dépôt résulte de la conformation des molécules en pelotes. Cette hétérogénéité est inhérente à la structure macromoléculaire, dont la contribution entropique empêche le dépôt planaire sur la surface. Nous préconisons l’utilisation de molécules plus petites ou une polymérisation in-situ
This work is devoted to the surface treatment by acrylic polyesters of aluminum, iron and titanium oxides pigments and of the resulting properties. The wetting angle measurements show out hydrophobic character of pigments after their treatment. Which is the polymer fraction applied on then surface, the homogeneity of covering and the character of bonds formed by the polymer with the surface? An almost complete polymer deposit is observed by thermogravimetry and by infrared spectroscopy which can be partly removed by a solvent as a function of surface oxide. A small part of the polymer remains on alumina, a larger part on titanium oxide and is fixed on the various iron oxide pigments. Chemical bonds are observed by infrared spectroscopy thanks to quantum mechanics attributions. The surface treatment is inhomogeneous on the surface, as shown by AFM and XPS, with the aspect of small islands of polymer. AFM direct observation on alumina is decisive for the discussion. Each island results from a statistic coil conformation of the polymer chains. The inhomogeneous covering is inherent on entropic contribution on energy of polymer chains which inhibit a planar covering of molecules on the oxide surfaces. The use of shorter molecules or in-situ polymerization should be favored

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
O clareamento dental é uma técnica que surgiu no inicio do século XIX. Desde então, e em função dos resultados obtidos ao longo do tempo, esta foi sendo alterada de maneira a reduzir os riscos do procedimento e ao mesmo tempo melhorar o resultado estético obtido. Com o aparecimento das fontes de luz para uso odontológico, novas e interessantes possibilidades surgiram e permitiram a utilização de métodos de aceleração que respeitem a fisiologia pulpar, que diminuam o tempo de exposição do paciente aos agentes peróxidos e promovam ainda a obtenção de bons resultados estéticos. Nos dias de hoje, pode-se observar na literatura importantes questionamentos acerca da contribuição efetiva da luz visível no processo e, os efeitos dos agentes peróxidos nas estruturas cristalinas dos dentes, materiais restauradores em geral e tecidos moles. Estas preocupações foram o cerne da motivação para a realização desta pesquisa, sendo assim, este trabalho vem propor uma série de metodologias inovadoras que avaliem através de tecnologias modernas os mecanismos básicos de interação da luz visível com o peróxido de hidrogênio e com os pigmentos orgânicos. Os experimentos aqui demonstrados abordam os fatores críticos relacionados com a eficiência do processo em diferentes substratos por meio de análise de transmitância, de fluorescência e imagens digitais. Com estes estudos pretendemos responder de maneira objetiva algumas das questões que foram observadas serem de fundamental importância no esclarecimento da real eficiência e eficácia da luz no clareamento dental.
The dental bleaching is a technique that appeared in the beginning of the XIX century. Since then, and in function of the obtained results a long the time, this has been altered in way to reduce the procedure risks and at the same time improve the aesthetic results. With the rise of light sources to be used in dentistry, new and exciting possibilities appeared and allowed the use of catalytic methods that respect the pulpal physiology, which diminishes the exposure time of the patients to the bleaching agents and provides good aesthetic results. In nowadays, it is possible to observe in the literature important questionings over the real contribution of light in the process and, the effects of the peroxide over the crystalline structure of the teeth, restorative materials and soft tissues. These concerning were the major motivation to the realization of this research, in this way, this work proposes a new series of methods that asses by the use of new technologies the basic mechanisms of visible light interaction with the hydrogen peroxide and with the organic pigments. The experiments here demonstrated study the critical factors related with the process efficiency in different substrates by digital images, transmittance and fluorescence. With these studies we pretend to respond in objective way some questions that were observed to be of fundamental importance in the understanding of the light efficiency and efficacy to the dental bleaching.

Orientador: Osmir Batista de Oliveira Júnior
Banca: Vanderlei Salvador Bagnato
Banca: Carlos EduardoFrancci
Resumo: O clareamento dental é uma técnica que surgiu no inicio do século XIX. Desde então, e em função dos resultados obtidos ao longo do tempo, esta foi sendo alterada de maneira a reduzir os riscos do procedimento e ao mesmo tempo melhorar o resultado estético obtido. Com o aparecimento das fontes de luz para uso odontológico, novas e interessantes possibilidades surgiram e permitiram a utilização de métodos de aceleração que respeitem a fisiologia pulpar, que diminuam o tempo de exposição do paciente aos agentes peróxidos e promovam ainda a obtenção de bons resultados estéticos. Nos dias de hoje, pode-se observar na literatura importantes questionamentos acerca da contribuição efetiva da luz visível no processo e, os efeitos dos agentes peróxidos nas estruturas cristalinas dos dentes, materiais restauradores em geral e tecidos moles. Estas preocupações foram o cerne da motivação para a realização desta pesquisa, sendo assim, este trabalho vem propor uma série de metodologias inovadoras que avaliem através de tecnologias modernas os mecanismos básicos de interação da luz visível com o peróxido de hidrogênio e com os pigmentos orgânicos. Os experimentos aqui demonstrados abordam os fatores críticos relacionados com a eficiência do processo em diferentes substratos por meio de análise de transmitância, de fluorescência e imagens digitais. Com estes estudos pretendemos responder de maneira objetiva algumas das questões que foram observadas serem de fundamental importância no esclarecimento da real eficiência e eficácia da luz no clareamento dental.
Abstract: The dental bleaching is a technique that appeared in the beginning of the XIX century. Since then, and in function of the obtained results a long the time, this has been altered in way to reduce the procedure risks and at the same time improve the aesthetic results. With the rise of light sources to be used in dentistry, new and exciting possibilities appeared and allowed the use of catalytic methods that respect the pulpal physiology, which diminishes the exposure time of the patients to the bleaching agents and provides good aesthetic results. In nowadays, it is possible to observe in the literature important questionings over the real contribution of light in the process and, the effects of the peroxide over the crystalline structure of the teeth, restorative materials and soft tissues. These concerning were the major motivation to the realization of this research, in this way, this work proposes a new series of methods that asses by the use of new technologies the basic mechanisms of visible light interaction with the hydrogen peroxide and with the organic pigments. The experiments here demonstrated study the critical factors related with the process efficiency in different substrates by digital images, transmittance and fluorescence. With these studies we pretend to respond in objective way some questions that were observed to be of fundamental importance in the understanding of the light efficiency and efficacy to the dental bleaching.
Mestre

Anbaubegleitende spektral-optische Analysen direkt an der Pflanze haben zunehmend Bedeutung für die gartenbauliche Produktion. Veränderungen individueller Pflanzeninhaltsstoffe können mit Hilfe optischer Sensoren unmittelbar und beliebig oft erfasst werden, wodurch Pflanzenreaktionen auf veränderte Umgebungs- und Kulturbedingungen instrumentell messbar sind. Im Konzept eines Präzisionsgartenbau könnten diese zusätzlichen Informationen adaptiven Kulturmaßnahmen dienen und zur effizienten Nutzung von Ressourcen in der Produktion von Obst und Gemüse beitragen. Die wellenlängenspezifische Lichtabsorption pflanzlicher Gewebe ermöglicht zerstörungsfreie Reflexions- oder Transmissionsmessungen und die Adressierung von Pigmentgruppen im ultravioletten und sichtbaren Bereich des elektromagnetischen Spektrums. Auf Grund veränderlicher Gehalte während des Wachstum und der Entwicklung pflanzlicher Gewebe, sind Pigmente zudem wichtige Indikatoren für den physiologischen Zustand von Obst und Gemüse. Präzise zerstörungsfreie Spektralanalysen werden allerdings durch komplexe optische Eigenschaften biologischen Materials, besonders im Hinblick auf die Reifeentwicklung von Obst und Gemüse erschwert. Zur Lösung dieser Problematik wurde ein neuer iterativer Ansatz (iMLR) entwickelt, der überlagerte in-situ und in-vivo Spektren individueller Pigmente aus einem Summenmessspektrum separiert. Dieser Algorithmus wurde in eine eigenständige Applikation überführt. Eine Datenbank enthält spektrale Signaturen von Chlorophyll a und b, Lycopin, β-Carotin, α-Carotin, Lutein und Violaxanthin. Obwohl die spektrale Analyse einzelner Pigmente durch optische Störgrößen in komplex aufgebauten biologischen Geweben und Pigmentgemischen erschwert ist, konnte ein neuer Ansatz erarbeitet und validiert werden. Diese Methode minimiert spektrale Überlagerung von in-situ und in-vivo aufgezeichneten Messsummensignalen und analysiert Pigmentgehalte in Farbstoffgemische zuverlässig.
Spectral measurements on plants have already been introduced in practice through extensive research and through the recent increase in the availability of low-cost devices. It can be expected that optical sensor systems may contribute to an economic and sustainable use of natural resources as a part of the concept for precision horticulture. In terms of phytomonitoring approaches, such technologies which address variable amounts of individual chromophoric plant components become more important. Their wavelength-selective light absorption makes pigments specifically responsive to reflection or transmission recordings in the ultraviolet and visible range of the electromagnetic spectrum. Additionally, pigments serve as indicators for physiological stages of leaf and fruit. Consequently, the instrumental recording of variable pigment contents has high potential with regards to dynamic plant-adapted processes during the production of fruit and vegetables. Solving the known issues of non-destructive spectroscopy, a new approach was figured out in the present work to obtain a more precise analysis of individual pigment contents, which vary during the cultivation of horticultural crops. The tool is based on an iterative algorithm (iMLR), that separates coinciding in-situ and in-vitro spectra from sum signals of individual pigments. Finally, the algorithm was integrated into a stand-alone application containing a library of chlorophyll a and b, as well as signatures of lycopene, β-carotene, α-carotene, lutein and violaxanthin. It can be pointed out that individual pigment compositions are suitable indicators of the physiological stage of horticultural products. However, the spectral analysis of single pigment levels is challenging due to complex interactions of coinciding absorption and diffuse light scattering in natural pigment mixtures or in fruit extracts. From this, an improved method for the reliable decomposition of spectral signals was developed.

La connaissance des matériaux de l'art participe à la conservation et à la restauration des oeuvres du patrimoine. A cette fin la tomographie par cohérence optique (OCT), technique d'imagerie interférentielle développée initialement pour l'étude des tissus biologiques, a été détournée ici de son application première pour l'étude des pigments des couches picturales en utilisant l'extension récente de l'OCT à la spectroscopie par transformée de Fourier résolue spatialement. Nous disposons d'un dispositif OCT plein champ fonctionnant dans le domaine temporel, utilisant un objectif de Mirau et une source émettant dans le domaine du visible. Le système introduit des effets d'ouverture conduisant à décaler les spectres vers les grandes longueurs d'onde. Après avoir défini un protocole nous permettant de corriger ces effets, nous avons validé avec succès la mesure de réflectivité d'échantillons d'or plans. Les particules de pigments sont des particules diffusantes et absorbantes de forme et de taille aléatoires de l'ordre du micromètre. A partir du cas sphérique nous avons établi théoriquement et expérimentalement que la mesure spectrale par OCT dépend des caractéristiques morphologiques de chaque particule analysée. La dispersion des mesures au sein d'un échantillon rend alors impossible la distinction de deux particules de matériaux différents. Cependant, le calcul de la moyenne sur un grand nombre de particules de même type permet de discriminer deux couches juxtaposées ou superposées, ce qui a été vérifié expérimentalement sur pigments jaunes et rouges. En couplant l'analyse spectroscopique à l'imagerie, on améliore ainsi la caractérisation d'un échantillon

The application of spectroscopic techniques is crucial for art historians and conservators who require knowledge of materials used in works of art (pigments, dyes, binders, additives, ...) in particular instances. In this sense, the knowledge of pigments which were in use on the ancient artists' palettes is fundamental to preserve the art works. In addition, this knowledge is important to determine correct conservation approaches, to study degradation processes or authenticity-related issues. For instance, the proper interpretation of molecular signatures from a vibrational spectroscopy gives valuable information about the materials used by the artists. In this regard, the spectral identification is one of the essential interpretations to be performed, which is generally carried out by visual comparison between the unknown spectra with an appropriate database of reference spectra. This identification approach while being simple and intuitive may turn out a complex task which usually requires an experienced analyst and inevitably introduces an element of subjectivity linked to the intervention of the investigator. Besides, these analyses can be limited due to interferences from other phenomena like noises or admixtures. This task is further complicated when the spectra are to be interpreted by a software system. Hence, the noise impact must be reduced to have an effective identification and a robust strategy for processing multi-component spectra needs to be implemented. Clearly, a fully-automated data processing system for a reliable spectral interpretation is of practical interest. Several automated methodologies were designed, developed and analysed in this Ph.D. Thesis for the purposes of art works analysis through Raman spectroscopy. In this sense, the usage of mathematical morphology together with p-spline fitting demonstrated to be a consistent combination in the application of data enhancement Raman spectra from artistic pigments. Besides, a generalised identification methodology to identify single- and multi- component spectra was developed. This identification method relies on automated spectral matching based on principal component analysis (PCA) and independent components analysis (ICA), being computationally efficient and conceptually simple. Moreover, a supervised classification methodology to automatically distinguish between Raman spectra showing small differences was developed. According to predefined reference training sets, the classification method is able to classify unknown Raman spectra relying on PCA and multiple discriminant analysis (MDA). Both the identification and classification methodologies successfully work using a single spectral observation for the unknown Raman spectra, with no user intervention or previous knowledge of the analysed sample. The designed, developed and analysed automated methodologies for noise filtering and identification and classification of artistic pigments are integrated in a global system for the automated data interpretation of spectra from art works analysis implemented in this Ph.D. Thesis, namely PigmentsLab. This software platform together with the integrated methodologies can play a good auxiliary role in the analysts' endpoint interpretation, providing insight from the raw spectral measurements into pigments. The system implementation provides an easy-to-use software platform and straightforward to update when new spectral data become available. The robust, reliable and consistent results obtained on Raman spectra demonstrated the competitiveness of the implemented data processing solutions. The system has great potential as an accurate and practical method for the automated interpretation of Raman spectra for not only pigment analysis, but essentially for any material group.
La aplicación de técnicas espectroscópicas es crucial para los conservadores de arte que requieren el conocimiento de los materiales utilizados en obras de arte (pigmentos, aglutinantes, aditivos, ...) en casos particulares. En este sentido, el conocimiento del uso de los diferentes pigmentos en las paletas de los artistas es fundamental para preservar las obras de arte. Este conocimiento es importante para determinar las estrategias de conservación correctas, para estudiar los procesos de degradación o problemas relacionados con la autenticidad de las obras de arte. Por ejemplo, la interpretación adecuada de las firmas moleculares de una espectroscopia vibracional proporciona información valiosa sobre los materiales utilizados por los artistas. La identificación espectral es una de las interpretaciones esenciales a realizar, y generalmente se lleva a cabo mediante la comparación visual entre los espectros desconocidos con una base de datos adecuada de los espectros de referencia. Esta estrategia de identificación, a pesar de ser sencilla e intuitiva, puede resultar una tarea compleja que requiere generalmente de un analista experimentado e inevitablemente introduce un elemento de subjetividad vinculado a la intervención del investigador. Además, estos análisis pueden verse limitados debido a interferencias de otros fenómenos como ruido o mezclas de pigmentos. Esta tarea se complica aún más cuando los espectros deben ser interpretados por un computador. Por tanto, el impacto del ruido debe ser reducido para tener una identificación eficaz, y se debe implementar una estrategia robusta para el procesado de espectros de múltiples componentes. El desarrollo de un sistema de procesado de datos totalmente automatizado para una interpretación espectral fiable es de evidente interés práctico. Varias metodologías automatizadas han sido diseñadas y desarrolladas en esta tesis doctoral, focalizadas en el análisis de arte mediante espectroscopia Raman. En este sentido, el uso de morfología matemática junto con el ajuste basado en p-splines demostró ser una combinación consistente en la aplicación de mejora de la calidad de espectros Raman de pigmentos artísticos. Además, se ha desarrollado una metodología de identificación generalizada para identificar los espectros Raman compuestos tanto de un solo pigmento como de múltiples pigmentos. Este método de identificación se basa en la búsqueda de coincidencia espectral automatizada basada en el análisis por componentes principales (PCA) y el análisis por componentes independientes (ICA), siendo un método computacionalmente eficiente y conceptualmente simple. Por otra parte, se ha desarrollado una metodología de clasificación supervisada para distinguir entre espectros Raman que muestran pequeñas diferencias entre ellos. A partir de conjuntos de referencia predefinidos de datos de entrenamiento, el método de clasificación es capaz de clasificar los espectros Raman desconocidos mediante PCA y el análisis discriminante múltiple (MDA). Tanto la metodología de identificación como la de clasificación funcionan correctamente utilizando una sola observación espectral para los espectros Raman desconocidos, sin intervención del usuario ni el conocimiento previo de la muestra analizada. Las metodologías automatizadas diseñadas y desarrolladas para el filtrado de ruido y la identificación y clasificación de pigmentos artísticos están integradas en un sistema global para la interpretación automatizada de datos a partir de espectros medidos en obras de arte que ha sido implementado en esta tesis doctoral, llamado PigmentsLab. Esta plataforma software puede representar un buen papel auxiliar en la interpretación de punto final de los analistas, proporcionando valor a partir de las medidas espectrales en bruto de pigmentos artísticos. Los resultados obtenidos en los espectros Raman analizados, siendo robustos y consistentes, demuestran la competitividad de las soluciones de tratamiento de señal implementadas.

Neste estudo amostras coletadas de pinturas rupestres foram analisadas para identificação do material utilizado; análises da sua interação e de processos eventuais de degradação, além de atribuições quanto à sua origem, foram também feitas através da espectroscopia Raman. Pigmentos encontrados em pinturas rupestres em Minas Gerais foram identificados, junto a produtos de degradação microbiológica. A partir dos resultados, foi feita uma caracterização da transformação de desidratação do pigmento amarelo de goetita (α-FeOOH) a hematita (α-Fe2O3) por espectroscopia Raman na tentativa de contextualizá-la no problema da origem da hematita encontrada nas representações. Foram identificados os pigmentos calcita (CaCO3) para o branco, carvão vegetal para o preto, goetita (α-FeOOH) para o amarelo e hematita (α-Fe2O3) para o vermelho, que constituem basicamente a paleta de cores desse período. Produtos de degradação microbiológica foram identificados por espectroscopia Raman e no infravermelho por ATR como sendo whewellita (CaC2O4.H2O) e weddelita(CaC2O4.2H2O). A transformação topotática de goetita a hematita por aquecimento foi acompanhada por espectroscopia Raman in situ e ex-situ e infravermelho, na tentativa de caracterizar o processo quanto às fases formadas, possíveis marcadores, de maneira a complementar resultados da literatura que utilizaram outras técnicas, como difração de raio-X (XRD) e microscopia eletrônica de transmissão (TEM). Esse estudo foi realizado na tentativa de determinar a existência de possível manipulação térmica desses materiais como sugerido em trabalhos anteriores. Em particular, nos espectros Raman, o comportamento diferenciado da banda em torno de 660 cm-1 e a maior largura das bandas de uma maneira geral, presentes na chamada hematita desordenada, perfil que as amostras naturais coletadas apresentam, são marcadores do efeito de temperatura, uma vez que parecem estar ligados mais estreitamente ao deslocamento catiônico dos íons Fe do que ao rearranjo da gaiola octaédrica de oxigênios ao redor destes, durante a transição a partir de goetita. Esse comportamento dos espectros Raman é confirmado pelos padrões dos difratogramas de raio-X. Concluiu-se que esse desordenamento, entretanto, não é causado somente pela temperatura e, dessa forma, não pode ser usado para atestar inequivocamente como sendo resultado de processamento dos materiais (goetita).
This dissertation reports the investigation carried out on samples collected from rupestrian paintings, aiming at the identification of materials used, their interaction and degradation. The technique of choice was Raman microscopy as it is a non-destructive tool, which provides the spatial resolution necessary for the study of heterogeneous samples. Pigments were identified together with products of microbiological degradation. Thermal convertion of goethite (yellow) to hematite (red) was followed by Raman spectroscopy in a tentative to address the issue of the provenance of red pigments (natural hematite or heated goethite) found in the paintings. White pigments were identified as calcite (CaCO3), whereas charcoal was used as black, goethite (α-FeOOH) as yellow and hematite (α-Fe2O3) as red. These pigments are usually found in rock art palletes. Degradation products from microbiological activity were identified by Raman microscopy and ATR infrared spectroscopy as being whewellite (CaC2O4.H2O) and weddelite (CaC2O4.2H2O). The topotatic transition from goethite to hematite was followed by in situ and ex-situ Raman and infrared spectroscopy, regarding the characterization of the phases formed, possible markers, aiming to complement the previous results reported in the literature using other techniques such as X-ray diffractometry (XRD) and transmission eletron microscopy (TEM). The main goal of the study of temperature effect on the Raman spectrum of goethite was to determine whether hematite was used as found in nature or was obtained by goethite heating as suggested in previous investigations. Particularly, the behavior of the 660 cm-1 band and a larger linewidth for bands in the spectrum, present in the disordered hematite and in the red pigments analysed, are markers of the thermal processing. These features seem to be related to the movement of iron ions and to the rearrangment of the octahedrical cage formed by oxygen atoms around them. Such conclusions are in agreement with X-ray data. Unfortunately, temperature is not the only factor to cause such structural disorder and, hence, it cannot be used as an unequivocal marker of thermal processing.

Les ukiyo-e désignent les estampes produites au Japon entre le XVIIe et le XIXe siècle. Elles sont le reflet des changements sociaux et économiques de la société japonaise pendant la période d’Edo (1615-1868), ère de paix et de prospérité, et adoptent une nouvelle iconographie représentant des scènes de la vie quotidienne et des plaisirs de la vie. Les techniques et les matériaux employés par les artistes évoluent également. Les premières estampes colorées apparaissent au début du XVIIIe siècle et au XIXe siècle, avec l’ouverture économique du Japon, des pigments chimiques importés d’Occident enrichissent la palette chromatique disponible. La collection Torralba (Musée de Saragosse, Espagne) comprend un fonds d’estampes ukiyo-e représentatives du XVIIIe et XIXe siècle. L’accès à ce corpus nous donne l’opportunité d’étudier les matériaux utilisés grâce à des méthodes adaptées, non invasives et sans contact, afin de suivre l’évolution de la technique et/ou des matériaux (locaux ou importés) employés. Un développement méthodologique est impératif afin d’analyser et de caractériser ces matériaux (pigments, colorants, liants, support), notamment les colorants organiques, difficiles à identifier. Les techniques de spectroscopie de réflectance dans l’infrarouge et d’imagerie hyperspectrale sont théoriquement capables de discriminer les matériaux organiques et inorganiques. Cependant les œuvres analysées sont souvent des systèmes complexes et les données obtenues sont la plupart du temps difficiles à interpréter de manière certaine. Il est donc indispensable de mettre en place une stratégie multi analytique afin de croiser les données et d’obtenir un maximum d’informations pour permettre l’identification des matériaux. L’étude de l’évolution des matériaux au cours du temps permet ainsi d’obtenir des informations importantes du point de vue de l’histoire de l’art et des techniques, reflets notamment des évolutions culturelles et sociétales au Japon au cours du XIXe siècle
Ukiyo-e means the prints produced in Japan between the 17th and 19th centuries. They reflect the social and economic changes in Japanese society during the Edo period (1615-1868), era of peace and prosperity, and adopt a new iconography depicting scenes of everyday life and the pleasures of life. The techniques and materials used by artists are also changing. The first coloured prints appear in the early 18th century. From the 19th century, with Japan's economic opening, chemical pigments imported from the West enrich the available color palette. The Federico Torralba Collection (Museum of Zaragoza, Spain) includes ukiyo-e prints representative of the 18th and 19th centuries. Access to this corpus gives us the opportunity to study the materials used, through appropriate non-invasive and contactless methods, and to follow the evolution of technologies and/or materials (local or imported) used. A methodological development is imperative to analyse and characterise these materials (pigments, dyes, binders), including organic dyes which are difficult to identify. Reflectance spectroscopy techniques in the infrared (FORS) and Hyperspectral Imaging (HSI) are theoretically capable of distinguishing organic from inorganic materials. However, the analysed works are often complex systems and the data obtained are difficult to interpret with certainty for the most of the time. It is therefore essential to establish a multianalytical strategy to cross the data in order to get maximum information allowing the identification of materials. The study of the evolution of materials over time gives the opportunity to obtain important information in art history and history of technology, reflecting the cultural and societal evolution in 19th century Japan

Neste trabalho foi investigado o efeito exercido por microambientes sobre a estabilidade química e fotoquímica de corantes. Em particular, estudaram-se os fatores responsáveis pelo aumento da estabilidade química e fotoquímica de índigo quando em interação com paligorsquita, que compõem o pigmento histórico Azul Maia, sobre o qual ainda havia controvérsias na literatura. Os corantes investigados foram índigo, dehidroíndigo, alizarina, purpurina, luteolina e β-caroteno; os microambientes foram proporcionados pelas argilas paligorsquita, sepiolita, montmorilonita, laponita e HDL de Al3+ e Mg2+ (3:1). Paligorsquita e a sepiolita são as únicas argilas que apresentam microporos em sua estrutura. As técnicas de caracterização empregadas neste trabalho foram: espectroscopia vibracional (Raman e absorção no infravermelho), espectroscopia de absorção no UV-VIS, difratometria de raios X, análise térmica (TG e DSC), CG-MS, HLPC-MS, medidas de área superficial por isoterma de adsorção de N2 e SEM. Duas técnicas com resolução temporal em escala de sub-picosegundos (absorção de transiente e infravermelho resolvido no tempo) foram utilizadas. O sistema índigo+paligorsquita corresponde à mistura dos dois sólidos, seguida de aquecimento, sendo que a partir de 70 °C a coloração da mistura adquire tonalidade esverdeada e também apresenta maior estabilidade química e fotoquímica. Essa estabilidade e também a alteração na cor aumentam com a temperatura de aquecimento da mistura e o intervalo considerado engloba as temperaturas de perda de água zeolítica (70 - 150 °C) e coordenada (170 - 280 °C) da estrutura da argila. Os resultados de espectroscopia vibracional e eletrônica dos simulantes de Azul Maia indicam que o índigo interage através de ligações de hidrogênio com as moléculas de água coordenada. Essa interação, entretanto, só é possível com a remoção da água zeolítica, o que ocorre a partir de 70 °C. Com aquecimento em temperaturas acima de 170 °C o comportamento do espectro eletrônico e vibracional se altera, indicando a formação direta de complexos com os metais presentes nas bordas internas dos microporos. Os resultados de espectroscopia Raman indicam que com a interação por ligação de hidrogênio a simetria molecular do índigo diminua. Os estudos por espectroscopia com resolução temporal mostraram que o índigo apresenta transferência de próton no estado excitado (ESIPT) de um dos amino grupos para a carbonila adjacente; após esta transferência, há a formação da espécie mono-enol a qual relaxa ao estado fundamental após 120 ps, através de intersecção cônica, o que explica a alta fotoestabilidade do corante. No caso da mistura aquecida a 130 °C os resultados, obtidos pela primeira vez para uma molécula imobilizada em argila, confirmam que o índigo encontra-se em um ambiente hidrofílico, considerando o tempo de vida de decaimento do estado excitado (3,0 ps), comparável ao do índigo carmim em solução aquosa (2,7 ps). O tempo de vida também é muito curto, comparado ao em solução de DMSO (120 ps) o que pode explicar a alta estabilidade do corante quando dentro do microcanal da argila. Finalmente, constatou-se que o dehidroíndigo não é responsável pela coloração de simulantes de Azul Maia, a qual resulta de alterações no espectro de absorção no visível do corante que ocorrem com a interação com a argila
In this work, the role played by the microenvironment on the chemical and photochemical stability of dyes was investigated. The factors responsible for the enhanced stability of indigo when interacting with palygorskite were detailed studied; the indigo and palygorskite system constitutes a simulant of Maya Blue, a historical pigment with properties which are controversially described in the literature. The dyes here investigated were indigo, dehydroindigo, alizarin, purpurin, luteolin and β-carotene; the microenvironment was provided by palygorskite, sepiolite, montmorillonite, laponite and a layered double hydroxide (Al3+ e Mg2+, 3:1). Palygorskite and sepiolite are the only clays with micropores in their structure. Several characterization techniques were employed, namely vibrational spectroscopy (Raman and infrared), UV-VIS electronic absorption spectroscopy, X-ray diffractometry, thermal analysis (TG and DSC), CG-MS, HPLC-MS, surface area and porosity determination (N2 isotherm adsorption) and scanning electron microscopy. Two sub-picosecond time resolved techniques (transient absorption and infrared absorption) were also used. The indigo+palygorskite system corresponds to the intimate mixture of both solids, followed by heating; from 70 °C the mixture attains a greenish hue and an enhanced chemical and photochemical stability. Both stability and color change increase with the heating temperature, which also leads to loss of zeolitic and coordinated water (70 to 150 °C and 170 to 280 °C, respectively). Vibrational and electronic spectroscopies indicate that, in the Maya Blue simulants, the dye interacts with the clay through hydrogen bonds with the coordinated water molecules. Such interaction, however, is only possible with the removal of the zeolitic water, which starts at 70 °C. At temperatures above 170 °C, both vibrational and electronic spectral profiles change, indicating that the interaction is now proceeding directly with the metals that are at the internal borders of the micropores. Results from Raman spectroscopy suggest that with the hydrogen bond and metal interaction a symmetry lowering occurs. Time resolved spectroscopy results show that indigo present an excited state intramolecular proton transfer from one of the NH to the adjacent carbonyl group, originating a mono-enol species, which decays to the ground state after 120 ps through a conical intersection. Such fast decay explains the high photochemical stability of indigo. In the case of the ind+paly mixture heated at 130 °C, the time resolved data obtained for the first time for a dye+clay system confirms that indigo is in a hydrophilic environment, taking into account the excited state lifetime (3.0 ps), comparable to indigo carmine in aqueous solution (2.7 ps). The excited state lifetime of indigo in the clay is also very short when compared to the experimental data for the dye in DMSO solution (120 ps), which is possibly an explanation for the dye high stability when inside the clay micropores. Finally, dehydroindigo was not found to be responsible for the color of Maya Blue simulants, which results from the spectral changes in the dye absorption spectrum originated by the interaction with the clay.

La plupart des peintures pariétales du Paléolithique supérieur sont rouges (hématite naturelle pure ou en mélange avec des argiles) ou noirs (charbon ou oxyde de manganèse). Ces pigments ont été préparés par broyage, mélange et peut-être chauffage. Les analyses physico-chimiques permettent de déterminer la nature du matériau, son mode de préparation et éventuellement sa provenance.
Les diverses phases d'oxyde de manganèse se distinguent par leur composition chimique, leur structure et l'état de valence de l'ion Mn (II, III, IV). La transformation structurale des oxydes lors d'un traitement thermique a été suivie par MET. Ce travail nous a conduit à déterminer des stigmates caractéristiques d'un chauffage, comme des pores dans la bixbyite (Mn2O3).
L'analyse d'échantillons archéologiques provenant de France et d'Espagne a permis d'évaluer le niveau technique des Préhistoriques. La matière picturale est constituée de pigment brut ou mélangé. Cependant aucun pigment noir chauffé n'a été identifié dans les prélèvements analysés.

La LIBS est une technique d’analyse élémentaire encore peu utilisée pour l'analyse de terrain du patrimoine culturel. Trois grandes problématiques ont été le sujet de cette thèse, afin de mieux maîtriser son utilisation dans ce domaine :Passage du laboratoire vers le terrain : la faisabilité de l’identification de pigments sur un chantier de restauration a été illustrée. La complémentarité LIBS-spectroscopie Raman a été démontrée pour l’identification de pigments et les études stratigraphiques. Impact visuel de l’analyse LIBS sur l’œuvre : les dimensions du cratère d'ablation sont contrôlées par la mise en forme et la focalisation du faisceau laser. Les décolorations périphériques observées sont dues à des dépôts oxydés. Des seuils de perception ont été établis en fonction de l’énergie délivrée, ce qui donne la possibilité d'éviter ces décolorations. Effets de matrice : la normalisation de droites d'étalonnage de Cu dans diverses matrices métalliques par la quantité de matière ablatée, la température et la densité électronique du plasma ne corrige pas complètement les variations entre matériaux. Pour les expliquer, la proportion d'atomes ablatés présents sous forme de vapeur atomique dans le plasma est déterminée. Ce paramètre dépend de la nature et de la concentration de l'élément, ainsi que de la matrice considérée, ce qui implique que l'émission du plasma ne semble pas représentative de la composition du matériau et qu'une quantification fiable ne peut être menée qu'à l'aide d'étalons.

La couleur des végétaux verts est un des critères importants d’appréciation de la qualité des aliments. Elle est due notamment aux chlorophylles, aux caroténoïdes et à leurs dérivés, molécules au rôle nutritionnel important. Les procédés culinaires ou de l’industrie alimentaire conduisent à des modifications des molécules qui composent les systèmes pigmentaires. Des études scientifiques récentes n’ayant pas retrouvé, dans certains conditions, de corrélation entre la couleur (déterminée par colorimétrie) et le contenue en pigments, on a étudié les modifications de la couleur et du contenu en pigments de « haricots verts », c’est-à-dire de gousses immatures de Phaseolus vulgaris L. Lors de divers traitements, thermiques ou non (culinaires et industriels). Des échantillons été étudiés à la fois au laboratoire et sur site industriel. Dans les deux cas, la couleur des gousses entières a été déterminée par colorimétrie tristimulus (système L*a*b*). Le contenu en pigments a été déterminé par deux méthodes mise au point au cours du travail et qui ont fait l’objet de publications. Sur site industriel, la composition en pigments a été déterminée par chromatographie quantitative sur couches minces, grâce à un traitement numérique d’images numérisées des couches minces produites. Par cette méthode rapide, peu coûteuse, répétable et qui révèle jusqu’à certains isomères structuraux des chlorophylles, on a étudié les étapes préliminaires des traitements industriels. Pour les analyses au laboratoire, on a mis au point deux méthodes spectroscopiques qui évitent toute séparation chromatographique préalable : la spectroscopie UV-Vis avec régression linéaire multiple, d’une part, et la résonance magnétique nucléaire quantitative, d’autre part. La première méthode est rapide, et facile à utiliser, mais la RMN quantitative donne plus d’information sur les isomères structuraux des pigments (épimères des chlorophylles et isomères cis/trans des caroténoïdes).

L'évaluation des capacités non-destructives de la Microscopie Raman en Archéologie est la ligne directrice de ce travail de recherche. Trois domaines ont été choisis afin d'estimer les avantages et les limites d'une telle technique d'analyse ; il s'agit de l'étude 1) des pigments issus des peintures préhistoriques, 2) des produits de corrosion de métaux d'origine archéologique et 3) des vitraux (le verre, la coloration et l'altération). Les résultats plus ou moins « positifs » selon les domaines, mettent en
évidence, par exemple, les capacités de la MR à distinguer les oxydes de Mn du carbone dans les peintures noires préhistoriques ou encore, la facile identification de l'hématite ; ils permettent également de distinguer assez facilement les différentes phases
d'altérations existantes sur les métaux corrodés (sulfates, oxydes, chlorures...). Enfin, si l'étude du verre et des colorations en surface offrent des résultats assez positifs (complexes de type : PbCrO4.PbO), l'identification de la coloration dans la masse des vitraux par des colloï des métalliques reste plus complexe. La fluorescence constitue
également un des désavantages certain de cette méthode. Toutefois, la réussite de cette technique, dans le domaine de l'archéometrie, où elle est encore peu appliquée, permet d'entrevoir un avenir prospère et une utilité incontestable pour les archéologues,
restaurateurs et conservateurs.

Esta Tese trata da investigação do efeito da nanoestruturação sobre algumas propriedades espectroscópicas de óxido de ferro(III), um dos mais importantes pigmentos vermelhos usados em bens culturais, o que foi conduzido por meio do estudo da cor de pigmentos de hematita (α-Fe2O3). A formação de eflorescências em duas pinturas (têmpera sobre tela e mural) foi também investigada visando compreender o papel da composição química e de fatores ambientais no desencadeamento de processos de degradação. Pigmentos naturais e sintéticos (cores de vermelho à púrpura) com morfologia definida foram caracterizados por espectroscopia de reflectância difusa (RD) no UVVIS-NIR, espectroscopia Raman (radiações excitantes em 532 nm, 632,8 nm, 785 nm e 1064 nm) e SEM-EDS. Alterações nas propriedades ópticas de hematitas com morfologias diferentes e após tratamento térmico foram correlacionadas com as alterações observadas nos espectros de RD no UV-VIS-NIR (principalmente abaixo de 500 nm e acima de 800 nm) e nos espectros Raman. Os resultados obtidos permitiram excluir o tamanho de partícula como fator determinante da cor de pigmentos de hematita, um argumento bastante usado na literatura ainda atualmente. Com o objetivo de avaliar o desempenho de equipamentos Raman miniaturizados, frequentemente empregados em investigações de bens culturais, espectros Raman de Fe2O3 amorfo obtidos em equipamento Raman portátil foram comparados com resultados obtidos em equipamentos de bancada. A necessidade do uso de maior potência de laser para compensar o pior desempenho desses equipamentos foi considerada como um fator importante para as alterações observadas nos espectros registrados. Esse fato é mais grave quando se emprega radiação de maior energia (532 nm), que pode afetar o espectro mesmo com potências mais baixas. A pintura Barco com bandeirinhas e pássaros (têmpera, 1955) de Alfredo Volpi, pertencente ao Museu de Arte Contemporânea da Universidade de São Paulo (MAC-USP), que apresentava sinais de eflorescências em sua superfície, foi analisada dentro do período de 3 anos em diferentes campanhas de amostragem. Os materiais coletados foram analisados por microscopia Raman, SEM-EDS e microscopia óptica. Os resultados indicaram que o material eflorescente apresentava natureza proteica, provavelmente proveniente da camada pictórica (têmpera), da camada de preparação (gelatina) ou de proteínas associadas a microorganismos (biodeterioração). Foi ainda considerada a hipótese da migração de aglutinante proteico da base de preparação da pintura para sua superfície como um fator inicial que poderia ter levado ao posterior surgimento de microorganismos na superfície da obra. As eflorescências salinas presentes na pintura mural da Sala do Trono do Palácio Nacional de Mafra, Portugal (séc. XVIII XIX) foram analisadas por microscopia Raman, µ-FTIR, µ-XRD, microscopia óptica, análise microbiológica, e identificadas como CaCO3, provavelmente formados devido à alta umidade verificada na região degradada da pintura. Fungos do gênero Cladosporium e Penicillium, usualmente associados à presença de fissuras e destacamentos, foram identificados nesta mesma região da pintura.Os resultados obtidos a partir dos estudos de casos das pinturas demonstraram a importância da parceria entre museus e órgãos públicos com laboratórios de pesquisa para a implementação de tecnologia dedicada ao monitoramento ambiental e detecção de processos de degradação em estágios iniciais.
This thesis presents the investigation of nanostructuration effects on some spectroscopic properties of iron oxides, one of the most important red pigments found in cultural heritage objects, which was conducted by studying the color of hematite pigments (α-Fe2O3). Two different paintings (tempera on canvas and mural painting) showing signs of efflorescence were investigated aiming to contribute to the understanding of the role played by microenvironment chemical composition and environment factors in triggering degradation processes. Natural and synthetic pigments (red to purple colors) with a defined morphology, were characterized by UV-VIS-NIR diffuse reflectance spectroscopy, Raman spectroscopy (532 nm, 632.8 nm, 785 nm and 1064 nm) and SEM-EDS. Changes in the optical properties of hematite with different morphologies and after heat treatment were correlated with the changes observed in the diffuse reflectance spectra (observed below 500 nm and above 800 nm) and in the Raman spectra. This allowed the particle size to be excluded as the main factor to affect the color of hematite pigments. In order to evaluate the performance of miniaturized Raman equipment, frequently used in cultural property investigations, amorphous Fe2O3 Raman spectra obtained with portable Raman equipment were compared with results from benchtop equipment. The need to use higher laser power to compensate for the poorer performance of these devices was considered as an important factor for the changes observed in the recorded spectra. This fact is more significant when using higher energy radiation (532 nm), which can affect the spectrum even at lower powers. The painting \"Barco com banderinhas e pássaros\" (tempera, 1955) by Alfredo Volpi, belonging to the Museum of Contemporary Art of the University of São Paulo (MACUSP), which showed signs of efflorescence on its surface, was analyzed during 3 years in different campaigns to sampling efflorescent material. The collected materials were analyzed using Raman microscopy, SEM-EDS and optical microscopy. The results indicated that the efflorescent material had a protein nature, probably from the pictorial layer (tempering), the preparation layer (gelatin) or proteins associated with microorganisms (biodeterioration). Nevertheless the results suggest that protein binder migration from the paint preparation layer to the surface may have occurred, which could possibly have led to the subsequent proliferation of microorganisms. The saline efflorescence presented in the mural painting of the Throne Room of the National Palace of Mafra, Portugal (18th-19th century) was analyzed using Raman microscopy, µ-FTIR, µ-XRD, UV-VIS optical microscopy and microbiological analysis. Saline efflorescence was identified as calcium carbonate, which was probably formed due to the moisture in the microenvironment of the degraded region. Fungi of the genus Cladosporium and Penicillium, usually associated to the presence of fissures and detachments, were identified in the same region of the painting. The results obtained from the case studies of the paintings demonstrated the importance of collaborations between museums and public agencies with research laboratories for the implementation of technology dedicated to environmental monitoring and detection of early stages of degradation processes.

The focus of this study was analytical investigations of Egyptian paintings, mainly Coptic icons and Islamic wooden ceilings, dating from 1300-1900 using multiinstrumental techniques. Twenty three Coptic icons and three wooden ceilings dated from different periods and painted by different painters in case of icons were examined. The materials used including pigments, media, varnishes, ground layers and gold layers. The surface stratigraphy of paint samples, their layered structured and the composition of materials used in each layer were analysed. Variations in painting techniques, pigments palettes, paint media and varnishes applied in Egyptian paintings according to painters, time and type of paintings were revealed. A total of twenty-eight organic and inorganic pigments were identified in this study, of which nine have never been previously included as a part of the Egyptian pigment palettes, namely; smalt, lapis lazuli, indigo, pararealgar, Prussian blue, chrome yellow, barium yellow, barium white and hydromagnesite. The identification of hydromagnesite, which has never been to date considered as a pigment either in Egypt or elsewhere and the identification of smalt from the mid-14th century, whose reported earliest large scale use was in the 16th century. Two types of resins were identified as a constituent of the oil/resin varnish applied on Coptic icons of which Venice turpentine has been identified for the first time as an ingredient of Egyptian varnishes. The identification of mosaic gold in an 18th C. icon, a novel usage of dammar resin and the multilayered structure of the white ground layers were revealed.
Egyptian Ministry of Higher Educations

The focus of this study was analytical investigations of Egyptian paintings, mainly Coptic icons and Islamic wooden ceilings, dating from 1300-1900 using multi-instrumental techniques. Twenty three Coptic icons and three wooden ceilings dated from different periods and painted by different painters in case of icons were examined. The materials used including pigments, media, varnishes, ground layers and gold layers. The surface stratigraphy of paint samples, their layered structured and the composition of materials used in each layer were analysed. Variations in painting techniques, pigments palettes, paint media and varnishes applied in Egyptian paintings according to painters, time and type of paintings were revealed. A total of twenty-eight organic and inorganic pigments were identified in this study, of which nine have never been previously included as a part of the Egyptian pigment palettes, namely; smalt, lapis lazuli, indigo, pararealgar, Prussian blue, chrome yellow, barium yellow, barium white and hydromagnesite. The identification of hydromagnesite, which has never been to date considered as a pigment either in Egypt or elsewhere and the identification of smalt from the mid-14th century, whose reported earliest large scale use was in the 16th century. Two types of resins were identified as a constituent of the oil/resin varnish applied on Coptic icons of which Venice turpentine has been identified for the first time as an ingredient of Egyptian varnishes. The identification of mosaic gold in an 18th C. icon, a novel usage of dammar resin and the multilayered structure of the white ground layers were revealed.

Ce travail concerne l'influence de la température sur la structure et la dynamique des protéines collectrices de lumière des bactéries pourpres dans leur environnement natif, les membranes intracytoplasmiques.
Pour mener à bien ces études, nous avons développé au laboratoire une approche de “calorimétrie fonctionnelle” dans les membranes intracytoplasmiques par des techniques de spectroscopie d'absorption, de dichroïsme circulaire et de Raman de résonance. Nous avons analysé l'effet de la température sur les propriétés spectrales de la protéine LH1 en utilisant les molécules de bactériochlorophylles comme marqueur naturel de l'assemblage des polypeptides transmembranaires, constituant l'anneau de LH1. Il existe dans la littérature de nombreuses études sur les processus d'auto-assemblage de ces protéines antennes, mais toutes réalisées après solubilisation en présence de détergent. C'est pourquoi nos études ont été réalisées sans ajout de détergent ou autres agents chaotrophes, mais directement sur les membranes intracytoplasmiques contenant la protéine LH1 surexprimée naturellement, dans le but de comparer les chemins de dissociation-réassociation de ces protéines selon qu'elles sont extraites ou non de leur milieu natif.
Nous avons montré que la variation de température autour de valeurs proches des conditions physiologiques révèle la dynamique de la structure des protéines LH1 et LH2. Ces résultats mettent en évidence l'existence d'un équilibre entre deux formes spectrales démontrant une flexibilité conformationnelle des protéines antennes dans leur environnement natif.
A des températures élevées, nous montrons qu'il est possible de dissocier de manière réversible la protéine LH1, mais que le processus de dissociation et réassociation de la protéine suit un chemin différent de celui observé à partir de la protéine solubilisée.
Ces études montrent l'importance des interactions entre bactériochlorophylles pour l'oligomérisation et le fonctionnement des protéines antennes dans leur “milieu naturel”

A travers l’étude par fluorescence X et diffraction de rayons X de trois grottes ornées Paléolithiques en rapport avec les questionnements des archéologues, c’est un travail de recherche physico-chimique autant que méthodologique qui est présenté au lecteur. La complexité analytique qu’il y a derrière l’étude in situ et non-invasive d’un art rupestre, a guidé notre réflexion sur le développement de procédures de traitement quantitatif des données, adaptées au site étudié (nature des pigments analysés, condition de conservation des œuvres). Cette complexité vient du fait qu’une couche picturale, tracée sur un support rocheux, est discontinue et ne recouvre pas uniformément la roche. Elle est de plus généralement peu épaisse. Pour ces raisons, une forte contribution de la paroi se retrouve dans l’information physico-chimique propre au pigment.Trois approches différentes ont ainsi été proposées pour approcher la matière picturale des grottes de Rouffignac et de Font-de-Gaume, situées en Périgord dans le sud-ouest de la France, et de la grotte de La Garma, localisée dans la région Cantabrique dans le nord de l’Espagne. L’une consiste en la semi-quantification d’oxydes discriminant le pigment de la paroi, bouclés à cent pourcent, permettant de s’affranchir de paramètres propres aux conditions expériences ; une deuxième est une semi-quantification par rapport à l’élément calcium, de sorte que la contribution de la paroi à travers la couche picturale reste la même d’un point de mesure à l’autre ; la dernière adopte une approche par simulation Monte Carlo afin de séparer clairement les informations de la paroi de celles du pigment. L’application de ces approches quantitatives a permis d’enrichir la connaissance stylistique que les archéologues en avaient, en apportant une vision physico-chimique à l’organisation des œuvres au sein de la grotte et des relations qu’elles entretiennent les unes avec les autres. Ce travail s’ouvre également au milieu karstique lui-même en intégrant à l’étude de l’art pariétal, un travail sur la genèse des faciès des parois. Le but étant d’acquérir le recul nécessaire pour mieux évaluer les interactions entre support et œuvres, et l’évolution des supports ornés, resituées dans leur contexte karstique général
The present study is a physicochemical research as well as a methodological work, carried out through the study of three Palaeolithic caves by X-ray fluorescence and X-ray diffraction. The analytical complexity behind in situ and non-invasive study of rock art, has guided our reflexion about the development of quantitative procedures of data processing, in order to adjust them appropriately to the specificity of the site and its rock art (specific constitution of the analysed pigment and conservation condition of the ornamented wall). This complexity is due to the fact that pigment layers don’t cover uniformly the rock surface. Also, the layers are generally very thin. For this reason, in the pigment signal, the proportion of the physicochemical information specific to the substrate is very high.Three approaches have been tested in the caves of Rouffignac, Font-de-Gaume and La Garma to characterise their Palaeolithic rock art. The two first are located in the Périgord region in the south-west of France, the last one in the Cantabrian region of Spain. One is related to the semi-quantification of oxides which discriminate the pigment from the substrate, allowing to not taking account experimental condition parameters; the second is a semi-quantification related to Ca, in order that the contribution in the concentration of the substrate detected through the paint layer remains the same for each measurement point; the last one is based on a Monte Carlo simulations method to separate distinctly the pigment information to those from the wall. These quantitative approaches enhanced the stylistic knowledge of archaeologists, bringing new physicochemical insights into the organisation of the representations and their relationship with the others inside the cave. Also, this work is concerned by the karstic environment; incorporating a research on wall taphonomy to the pigment study. The aim is to access to a better appreciation of the pigment-wall interactions and their evolution during time, given their global environmental context

O grande desafio da Implantodontia é alcançar resultados a longo prazo com maior preservação dos tecidos ósseos, resposta adequada dos tecidos conjuntivos e manutenção da estabilidade secundária adequada para a retenção de próteses. Estes fatores evitam a perda indesejável tanto do tratamento reabilitador quanto dos tecidos ósseos de suporte. A região extraoral apresenta menores espessuras ósseas em comparação às regiões de maxila e mandíbula, especialmente no osso temporal. Portanto, os seguintes aspectos foram investigados: (i) Análise pelo Método dos Elementos Finitos (FEA) de 16 modelos virtuais, com aplicação de forças estáticas de tensão e compressão nos pontos médios entre os implantes. Três implantes maxilofaciais extraorais foram posicionados no osso temporal, onde um deles foi posicionado sobre o processo mastóide. Este estudo foi totalmente realizado em ambiente computacional. Foram empregados dois tipos de conexões protéticas e intermediários retos de conicidades 20º e 45º, posicionados virtualmente no modelo de osso temporal, com paralelismo entre eles. Foi desenhada uma barra virtual para retenção protética do tipo barra-clipe da prótese auricular. Foram consideradas as melhores configurações aquelas apresentando distribuição uniforme e branda das tensões de von Mises sobre o tecido ósseo adjacente aos implantes. (ii) Confecção de corpos de prova com graus variáveis de pigmentação para (a) melhorar a reprodutibilidade da coloração (b) entender e reduzir o processo de descoloração para melhorar a longevidade das próteses. Um elastômero maxilofacial tipo A foi pigmentado intrinsecamente de acordo com os seis tons da Escala de Fitzpatrick. Uma técnica de pigmentação foi desenvolvida a partir dos resultados obtidos a partir de uma Escala de Fitzpatrick impressa em papel e dos pigmentos intrínsecos de cores primárias. Este dimetil-metilvinil-siloxano reforçado por platina A 223-30 (Factor II, Inc., Lakeside, AZ, USA) apresenta dureza \"Shore-A\" 30. As amostras foram expostas a fotoenvelhecimento acelerado, e sua degradação mapeada com Espectroscopia UV/Vis/NIR. Concluiu-se que: (i) Os implantes com conexão cone Morse plataforma 3.7 tem melhor comportamento biomecânico com intermediários de 45o e altura de 2mm. Sugere-se planejamento cirúrgico visando a instalação a 3 horas para o temporal esquerdo e 9 horas para o temporal direito, mais 6 horas (mastóide). Implantes com conexão cone Morse plataforma 4.0 apresentaram comportamento biomecânico desejável com intermediários de 20o e alturas de 2mm or 4mm. Para implantes com conexão cone Morse plataforma 4.0, sugere-se a instalação a 6-9-12 horas para o temporal direito, e 12-6-3 para o esquerdo, visando comportamento biomecânico adequado. Sugere-se que os implantes extraorais Brånemark hexágono externo com plataforma 4.1 regular ou expandida sejam preferencialmente empregados com intermediários de 20o. (ii) O SiO2 5% pode ser adicionado à preparação do silicone para retardar o desbotamento da prótese maxilofacial. O TiO2 traz mudanças visuais significativas e pode ser considerado como opacificador.
Major challenges in Implantology include: achieving longevity of implants, bone tissue preservation, connective tissue suitable answer and maintenance of secondary stability in order to retain prosthesis. These factors avoid the undesirable loss of both rehabilitation treatment and supporting bone tissues. The extraoral region has less bone depth compared to the maxilla and mandible regions, especially for the temporal bone. Therefore, the following aspects were investigated: (i) Finite Elements Analysis (FEA) of 16 virtual models, with static application of tension and compression forces in medium points between implants. Three extraoral maxillofacial implants were placed on the temporal bone, which one of them was placed on the mastoid process. This study was made entirely in a computational environment. Two prosthetic connection types and straight Intermediários were employed, with conicities of 20º and 45º, placed virtually on the temporal bone model, mutually parallel. A virtual bar for bar-clip prosthetic retention of auricular prosthesis was designed. The best configurations were considered to be the ones presenting uniform and mild von Mises tension distribution over the bone tissue around the implants. (ii) Generation of samples with varying degree of pigmentation to (a) improve the reproducibility of the colouration (b) understand and minimise the discolouration process to improve prosthetics longevity. A maxillofacial elastomer type A was intrinsically pigmented according to the six tones of the Fitzpatrick Scale. A pigmentation technique was developed from spectroscopy outcomes of paper printed Fitzpatrick Scale and the primary colors pigments. This platinum reinforced dimethyl methylvinyl siloxane A 223-30 (Factor II, Inc., Lakeside, AZ, USA) presents \"Shore-A\" hardness 30. The samples were exposed to accelerated photo aging, and their degradation mapped with UV/Vis/NIR Spectroscopy. The effects of exclusion of oxygen and inclusion of nanoparticle fillers during prosthetic formulation were investigated. It was concluded that: (i) Morse taper prosthetic connection 3.7 platform implants, should be employed with 45o abutments with 2mm height. The surgical planning shall be for placement 3 hours for the left temporal bone and 9 hours for the right, and in 6 hours (mastoid). Morse taper prosthetic connection 4.0 platform implants behaved biomechanically desirably with 20o abutments in 2mm or 4mm heights. For the Morse taper connection 4.0 platform implants, their placement shall be in 6-9-12 hours, for the right temporal, and 12-3-6, for the left temporal, in order to achieve proper biomechanical behaviour. The Brånemark extraoral external hexagon implant, with 4.1 platform (normal or expanded) should preferrably be used with 20o abutments. (ii) The SiO2 5% may be added to the silicone preparation in order to slow maxillofacial prosthesis colour fading. The TiO2 brings visually significant changes and may be considered as an opacifier.

We investigate the ultrafast electronic excitation dynamics of phycobiliproteins from cryptophyte algae using two-dimensional electronic spectroscopy and frequency-resolved transient absorption spectroscopy. We detail the development of a transient absorption spectrometer that utilizes balanced and fast detection methods to reduce noise and maintain high temporal and spectral resolution. We observe coherent oscillations and attribute them to vibrational coherences using the wave packet formalism. Analysis of the dynamic Stokes shift and motion of the wave packet on the potential-energy surface indicate the coherences are predominantly situated in the excited electronic state of the protein. These measurements imply that the ultrafast energy transfer within phycobiliproteins is coupled to the vibrational motion of its constituent chromophores. We demonstrate the capability and necessity of multiple ultrafast spectroscopic techniques for determining the origin of coherent motion in photosynthetic light-harvesting complexes.

碩士
國立陽明大學
生醫光電工程研究所
92
The purpose of this study was to know whether the melanin in retinal pigment epithelium (RPE) would interfere with retina or not on Raman spectrum; to measure the contents of melanin and to determine the distribution of melanin in RPE. First of all, we tested the Raman spectrum of melanin powder which was synthesized. We got the range of spectrum of melanin powder from 1550cm-1 to 1600cm-1. We tried to measure the Raman spectrum of pig's RPE. The result of spectrum of pig's RPE had the same profile as melanin from 1550cm-1 to 1600cm-1, but the Raman intensity was not equal to melanin. We compared the signal of RPE, sclera, and RPE with sclera. We discover that the spectrum of sclera did not affect the signal of RPE, and we can see that the profile of RPE was the same as that of sclera. We found that the distribution of melanin in RPE didn't present regular model, and the difference of melanin contents was about 800 a.u. on Raman intensity. In the experiment about whether melanin would interfere the retina's Raman signal, we still catch the signal of melanin with and without retina covered on the RPE. The profiles of them were the same but the intensity was not. It would be due to the melanin accumulate at the apical part of RPE cell which surround with photoreceptor outer segment. Therefore, when we make laser light focused on the retina, melanin was easily in the tight focused area. Then we obtain the spectrum of melanin.