The chemical profiling, characterization of Aloe products and phytochemical properties of Aloe vera were studied. The adulteration of commercial products derived from medicinal plants has been a major muddle for both the society and the pharmaceuticalindustry. Economically motivated adulteration includes the potential for contaminated, sub‐potent or counterfeit medication to enter the supply chain at several levels, from the production of raw ingredients through to the point of retail sale. Darwin’s theory of evolution states that, species undergo genetic variation with time to adapt to environmental changes. Therefore, the same species growing in widely different habitats may drift from the original genetic makeup as a mechanism of adaptation and that may result in them having different chemical profiles. Therefore this study aimed at investigating the phytochemical properties of Aloe vera growing in South Africa. Also, this study aims to utilize Thin Layer Chromatography to profile this plant, as well as use Infra Red spectroscopy to characterize commercial Aloe vera products. A large quantity of Aloe vera plant was collected from AloeWay, Iphofolo Game Farm, Polokwane in the Limpopo province of South Africa. The identity of the plant was confirmedrom literature and authenticated by Professor DS Grierson of Botany Department, University of Fort Hare, Alice. The plant leaves were divided into two portions. One portion was extracted fresh while the other was cut into pieces and oven dried at 400C then and milled to a homogenous powder once dried completely. The phytochemical composition of the gel and leaf extracts revealed the presence of alkaloids, flavonoids, saponins, tannins and phenols at different concentrations. Results showed that the dry plant material yielded more phytochemicals than the fresh plant material. In particular, it was found that the acetone extract showed much more amounts ofphychemicals than the dichloromethane and aqueous extracts. The percentage compositions of phenols (71.86), flavonols (36.61), proanthocyanidins (82.71), saponins (37.73) and alkaloids (13.29) were significantly high in the acetone extract, followed by the dichloromthane extract with values of 46.85, 37.73, 49.51, 89.0 and 11.11 respectively, while the least composition was found in the aqueous extract. Furthermore, flavonoids were somewhat high in composition in both the aqueous extract of the dried and of the fresh plant material while others were very low. Tannins levels were significantly very low in all the solvent extracts. It was found that the acetone extract showed great amounts of phytochemicals than dichloromethane and aqueous extracts. Since A. vera is used in the treatment of different ailments such as skin wounds and abrasions, eczema, constipation, rheumatoid arthritis etc, the medicinal uses of this plant could be associated to such analysed bioactive compounds. Acetone, hexane, ethanol, water and dichloromethane were used to extract the Aloe vera leaf and the best solvent extract was determined. Thin layer chromatography was used to profile the leaf extracts with the aim of documenting the main phytochemicals present in the Aloe vera growing in South Africa. The best spraying reagent was determined. Fourier transform infrared spectrophotometer was used to validate the presence of Aloe vera ingredients in commercial products. The yield extraction ability of the solvent was the order: water>ethanol> hexane >dichloromethane and acetone for the dry portion. However, for the plant extracted fresh, the order of yield produced was ethanol-acetone-dichloromethane > and water. The different solvent systems separated the compounds differently. Hexane: acetone: ethanol (20 : 5: 2) and Benzene: ethanol: ammonium (80): ethanol (10): ammonium solvent systems were noted to be the best mobile phase as they gave the best separation compared to other systems.EMW [ethyl acetate (81): methanol (11): water (8)] showed better separation than the other two separating solvent systems. Vanillin- sulphuric acid spray was seen to be the best spraying reagent as compared to vanillin- phosphoric acid. Fourier transform infrared spectrophotometer validated the presence aloe ingredients in aloe vera commercial products.

Pentameric ligand-gated ion channels (pLGICs) are membrane bound receptors found in the nervous system. They are responsible for detecting neurotransmitters released from neurons and subsequently mediating responses of the cells on which they are found. Thus, pLGICs play an invaluable role in communication between cells of the nervous system and understanding their function is pivotal to understanding how the nervous system works in general. One factor which is known to mediate pLGIC function is lipids found in the membrane environment in which pLGICs are embedded. This dissertation explores the various ways in which lipids interact with and modulate the function of pLGIC. Potential mechanisms and biological consequences of this modulation will be presented and discussed within the context of our current state of knowledge of pLGIC and nervous system function.

Les travaux exposés dans ce manuscrit concernent le développement de spectromètres laser pour la mesure in-situ de CH4, CO2 et H2O dans l'atmosphère moyenne ainsi que la spectroscopie associée, l'inversion des données atmosphériques et les premières campagnes ballon. La première partie de ce manuscrit décrit le contexte scientifique qui a conduit au développement des spectromètres laser et donne un état de l'art en matière instrumentale. La seconde partie décrit deux études spectroscopiques portant sur le multiplet R(6) du méthane à 3.24µm et sur les transitions R18e et R20e du dioxyde de carbone à 2.68µm pour l'inversion des mesures atmosphériques. La troisième partie de ce manuscrit porte sur le développement des spectromètres PicoSDLA-CH4 dédié à la mesure de CH4 dans l'atmosphère à 3.24µm, utilisant une source laser à différence de fréquence, et PicoSDLA-CO2 dédié à la mesure de CO2 à 2.68µm avec une diode à antimoniure. Ces spectromètres ont réalisé plusieurs vols sous ballons stratosphériques en 2010, 2011 et 2012. Les résultats de ces campagnes sont exposés dans la quatrième partie du manuscrit. / This thesis reports the development of laser spectrometers dedicated to in-situ measurements of CH4, CO2 et H2O in the middle atmosphere. It includes the development of the prototypes, the associated spectroscopy, the concentration data retrieval as well as the first balloon campaigns. The first part of the thesis describes the scientific framework and it further gives a state of art of the instrumental field. The second part gives the results from a spectroscopic study on the R(6) manifold of CH4 at 3.24µm and on the R18e and R20e lines of CO2 at 2.68µm in order to allow an accurate concentration retrieval. The third part details the development of the PicoSDLA-CH4 spectrometer dedicated to the in-situ measurements of CH4 at 3.24µm, using a difference frequency generation (DFG) laser source, and the development of PicoSDLA-CO2, a sensor dedicated to measurements of CO2 at 2.68µm using antimonide laser diodes. Both spectrometers were involved in three balloon campaigns in 2010, 2011 and 2012; the results are presented in the fourth part of the thesis.

Introduction: Dupuytren's disease (DD) is an ill-defined fibroproliferative disorder affecting the palms of the hands of certain patient groups. Whether changes in DD fibroblasts are due to genetic alterations alone or related to metabolic dysregulation has not yet been investigated. Hypotheses: 1. DD is a disease of several networks rather than of a single gene. 2. DD may be investigated more effectively by employing systems biology. 3. Strict definition of cell passage number is important for the revelation of any DD phenotype. 4. Some of the differences between DD and healthy tissues reside in a difference in their respiratory metabolism. 5. Any such differences are akin the Warburg effect noted for tumour cells in the literature. Methods: We induced hypoxia in healthy and disease cells to test whether the difference in disease cell types and healthy is the same as the difference in control fibroblasts cultured in normoxia and hypoxia. We investigated both at the metabolic level (intracellular and extracellular) and at the transcript level. This study also employed Fourier transform infrared spectroscopy to permit profiling of cells: (1) DD cords and nodules against the unaffected transverse palmar fascia (internal control), (2) those (1) with carpal ligamentous fascia (external controls) (3) those in (1) against DD fat surrounding the nodule, and skin overlying the nodule. We then compared metabolic profiles of the above to determine the effect of serial passaging by assessment of reproducibility. Subsequently, a novel protocol was employed in carefully controlled culture conditions for the parallel extraction of the metabolome and transcriptome of DD-derived fibroblasts and control at normoxic and hypoxic conditions to investigate this hypothesis. Gas chromatography-mass spectrometry combined with microarrays was employed to identify metabolites and transcript characteristic for DD tissue phenotypes. The extracellular metabolome was also studied for a selected subset. The metabolic and transcriptional changes were then integrated employing a network approach. Results: Carefully controlled culture conditions combined with multivariate statistical analyses demonstrated metabolic differences in DD and unaffected transverse palmar fascia, in addition to the external control. Differences between profiles of the four DD tissue phenotypes were also demonstrated. In addition early passage (0-3) metabolic differences were observed where a clear separation pattern in clusters was observed. Subsequent passages (4-6) displayed asynchrony, losing distinction between diseased and non-diseased sample phenotypes. A substantial number of dysregulated metabolites involved in amino acid metabolism, carbohydrate metabolism and also metabolism of cofactors and vitamins including downregulated cysteine and aspartic acid have been identified from the integrative analyses. Metabolic and transcriptional differences were revealed between fibroblast cell samples (passage number 3) cultured in 1% and 21% oxygen. The hypothesis that the difference in disease and healthy cells maybe akin to the differences in healthy cells in normoxia and hypoxia was rejected as only a very small number of significant molecules from these studies coincided in perturbed fascia and disease samples. No lactic acid was observed and little difference in the pyruvate concentrations. Yet, upon perturbation several of these transcripts and metabolites involved in the afore-mentioned pathways were significantly dysregulated. Conclusion: Early, but not late, passage numbers of primary cells provide representative metabolic and transcript fingerprinting for investigating DD. A unique parallel analysis of transcript and metabolic profiles of DD fibroblasts and control, enabled a robust characterization of DD and correlation of parameters across the various levels of systemic description. The tools that should facilitate our understanding of these complex systems are immature, but the pleiotropy of the difference between healthy and DD tissue suggest the aetiology of a network-based disease.

Nous couplons des sources de rayonnement infrarouge et un spectromètre à transformée de Fourier (FTIR) avec un microscope optique en champ proche (SNOM) à pointe diffusante pour sonder les propriétés optiques locales de la matière avec une résolution spatiale sub-longueur d'onde.Nous étudions l'émission thermique de champ proche d'un échantillon constitué d'une couche d'or recouvrant partiellement du carbure de silicium, puis d'un empilement de nano-couches semi-conductrices. Nous révélons expérimentalement la présence d'ondes de surface se propageant aux différentes interfaces de ces échantillons, en imagerie et en spectroscopie. Nous sondons l'évolution spatiale du spectre de la densité locale d'états électromagnétiques grâce à l'imagerie hyperspectrale super-résolue de l'émission thermique de champ proche. Nous montrons que la résolution spatiale et le contraste entre les structures diminuent lorsque la distance à laquelle la sonde effectue les balayages augmente.Nous couplons notre SNOM et un FTIR avec le rayonnement synchrotron et démontrons la capacité d'un tel couplage de mener des études de nanospectroscopie dans l'infrarouge moyen en l'illustrant sur les échantillons précédemment mentionnés. Nous démontrons l'imagerie térahertz super-résolue à l'aide du rayonnement synchrotron.Nous étudions expérimentalement l'influence de l'illumination sur les images obtenues en SNOM et montrons que la détection de l'émission thermique de champ proche permet d'obtenir des images exemptes de distorsions et donc plus simples à interpréter que celles obtenues en utilisant un laser monochromatique ou l'émission thermique de champ lointain. Nous développons un mode d'imagerie 3D. / We couple infrared sources with a scattering near-field scanning optical microscope (SNOM) combined with a Fourier transform infrared spectrometer (FTIR) in order to probe the local optical properties of matter with sub-wavelength spatial resolution. We study the near-field thermal emission of a surface made of silicon carbide and gold, and then of a semiconductor-based multilayer. We reveal experimentally the presence of surface waves propagating at the different interfaces of these samples, by imaging and spectroscopy. We probe the spatial evolution of the electromagnetic local density of states spectrum thanks to super-resolved hyperspectral imaging of the near-field thermal emission. We show that spatial resolution and contrast between the structures decrease as the distance at which the probe performs the scans increases. We couple our SNOM and FTIR with synchrotron radiation and demonstrate the capability of such coupling to perform nanospectroscopy studies in the mid-infrared range by investigating the samples mentioned above. We demonstrate super-resolved terahertz imaging using synchrotron radiation. We experimentally study the influence of the illumination on the images obtained in SNOM and show that the detection of the near-field thermal emission provides distortion-free images and therefore are easier to interpret than those obtained using a monochromatic laser source or far-field thermal emission. We also develop a 3D imaging technique.

Orientador: Ronei Jesus Popi / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-18T17:27:36Z (GMT). No. of bitstreams: 1 Maretto_DaniloAlthmann_D.pdf: 2617064 bytes, checksum: 1ebea2b6ab73ef552155cd9b79b6fd1b (MD5) Previous issue date: 2011 / Resumo: O objetivo desta tese de doutorado foi de utilizar o algoritmo Máquinas de Vetores de Suporte (SVM) em problemas de classificação e calibração, onde algoritmos mais tradicionais (SIMCA e PLS, respectivamente) encontram problemas. Foram realizadas quatro aplicações utilizando dados de espectroscopia no infravermelho. Na primeira o SVM se mostrou ser uma ferramenta mais indicada para a determinação de Carbono e Nitrogênio em solo por NIR, quando estes elementos estão em solos sem que se saiba se há ou não a presença do mineral gipsita, obtendo concentrações desses elementos com erros consideravelmente menores do que a previsão feita pelo PLS. Na determinação da concentração de um mineral em polímero por NIR, que foi a segunda aplicação, o PLS conseguiu previsões com erros aceitáveis, entretanto, através da análise do teste F e o gráfico de erros absolutos das previsões, foi possível concluir que o modelo SVM conseguiu chegar a um modelo mais ajustado. Na terceira aplicação, que consistiu na classificação de bactérias quanto às condições de crescimento (temperaturas 30 ou 40°C e na presença ou ausência de fosfato) por MIR, o SIMCA não foi capaz de classificar corretamente a grande maioria das amostras enquanto o SVM produziu apenas uma previsão errada. E por fim, na última aplicação, que foi a diferenciação de nódulos cirróticos e de hepatocarcinoma por microespectroscopia MIR, a taxa das previsões corretas para os conjuntos de validação do SVM foram maiores do que do SIMCA. Nas quatro aplicações o SVM produziu resultados melhores do que o SIMCA e o PLS, mostrando que pode ser uma alternativa aos métodos mais tradicionais de classificação e calibração multivariada / Abstract: The objective of this thesis was to use the algorithm Support Vector Machines (SVM) in problems of classification and calibration, where more traditional algorithms (SIMCA and PLS, respectively) present problems. Four applications were developed using data for infrared spectra. In the first one, the SVM proved to be a most suitable tool for determination of carbon and nitrogen in soil by NIR, when these elements are in soils without knowledge whether or not the presence of the gypsum mineral, obtaining concentrations of these elements with errors considerably smaller than the estimated by the PLS. In the determination of the concentration of a mineral in a polymer by NIR, which was the second application, the PLS presented predictions with acceptable errors, however, by examining the F test and observing absolute errors of predictions, it was concluded that the SVM was able to reach a more adjusted model. In the third application, classification of bacteria on the different growth conditions (temperatures 30 or 40 ° C and in the presence or absence of phosphate) by MIR, the SIMCA was not able to correctly classify the majority of the samples while the SVM produced only one false prediction. Finally, in the last application, which was the differentiation of cirrhotic nodules and Hepatocellular carcinoma by infrared microspectroscopy, the rate of correct predictions for the validation of sets of SVM was higher than the SIMCA. In the four applications SVM produced better results than SIMCA and PLS, showing that it can be an alternative to the traditional algorithms for classification and multivariate calibration / Doutorado / Quimica Analitica / Doutor em Ciências

No sistema imune de artrópodes, em contraste com o dos vertebrados, não ocorre uma resposta a antígenos por meio da produção de imunoglobulinas específicas contra agentes infecciosos. Portanto, a imunidade adaptativa está ausente, sendo que o sistema imune nesses animais baseia-se somente numa resposta inata. Os mecanismos presentes na resposta imune inata dos artrópodes incluem: (i) o sistema de coagulação; (ii) a cascata da profenoloxidase; (iii) a liberação de moléculas que possuem ação direta contra microorganismos dentre elas, os peptídeos antimicrobianos (PAMs). Estas moléculas podem ser constitutivas, como observado em aracnídeos, ou terem sua expressão induzida após desafio imune, como observado em alguns insetos. PAMs são moléculas anfipáticas, geralmente catiônicas e compostas por 9 a 100 resíduos. O estudo desses peptídeos, além de possibilitar a descoberta de novas moléculas que tenham modo de ação alternativo aos antibióticos convencionais, permite uma compreensão mais ampla do sistema imunológico de diferentes grupos de animais, bem como a origem dos seus mecanismos na história evolutiva. Neste trabalho foi utilizado o opilião Acutisoma longipes como modelo experimental para a caracterização de PAMs presentes na sua hemolinfa, tendo em vista que não há registros de estudos dessa natureza que utilizaram representantes da ordem Opiliones. Primeiramente, foi demonstrada a ocorrência de diversas frações, obtidas da purificação da hemolinfa, com atividade anti-M. luteus, consistidas por peptídeos que aparentemente são constitutivos. Uma das frações mostrou-se pura e apresentou um peptídeo de 2,1 kDa cuja estrutura primária, composta por 18 resíduos, foi completamente elucidada (SGYLPGKEYVYKYKGKVF) por sequenciamento de novo e sequenciamento do N-terminal. Este peptídeo linear foi nomeado longipina. O peptídeo sintético apresentou atividade antimicrobiana contra as bactérias Escherichia coli e Micrococcus luteus, e as leveduras Candida albicans e C. tropicalis, além de não apresentar atividade hemolítica na máxima concentração testada (100 mM). Foi demonstrado que a longipina liga-se preferencialmente a vesículas unilamelares grandes (LUVs), constituídas de fosfolipídios aniônicos (POPG), que mimetizam as cargas da superfície das células de microorganismos. A ligação do peptídeo a LUVs compostas, na razão molar de 1:1, por POPG e POPC (zwiteriônico) provoca o extravasamento de marcadores (carboxifluoresceína) aprisionados nos seus interiores. Esse peptídeo encontra-se majoritariamente desestruturado em solução ou na presença de sistema mimético composto somente por POPC. Porém, na sua ligação com POPG:POPC 1:1, adota estruturas b e estrutura relacionada à presente em agregados intermoleculares de fibras amiloides. / The arthropods immune system, in contrast to the vertebrates one, lacks a response to antigens through the production of specific immunoglobulins to fight against infectious agents. Therefore, the adaptive immunity is absent, and their immune system is only supported by an innate response. The mechanisms present in the arthropods innate immune response include: (i) the clotting system; (ii) the prophenoloxidase cascade; (ii) the release of molecules that can directly act against microorganisms among them, the antimicrobial peptides (AMPs). These molecules can be constitutive, as observed in arachnids, or have their expression induced upon imune challenge, as observed in some insects. AMPs are amphipathic molecules, usually cationic and formed by 9 to 100 residues. The study of these peptides, besides allowing the discovery of new molecules that exert their mode of action alternatively from the conventional antibiotics, permits a wider understanding of the immunological system from different groups of animals, as well as the origin of their mechanisms in the evolutionary history. The harvestman Acutisoma longipes was used in this work as na experimental model for the characterization of AMPs from its haemolymph, taking into account that there are no records of using representatives of the Opiliones order in such kind of study. Firstly, it was demonstrated the occurrence of several fractions, obtained from the haemolymph purification, that presented anti-M. luteus activity, consisted by peptides that are apparently constitutive. One of these fractions was pure and presented a 2.1 kDa peptide which had its primary structure, composed by 18 residues, completely elucidated by de novo and N-terminal sequencing (SGYLPGKEYVYKYKGKVF). This linear peptide was named longipin. The synthetic peptide presented antimicrobial activity against Escherichia coli and Micrococcus luteus bacteria and Candida albicans and C. tropicalis yeasts, in addition to the absence of hemolytic activity at the highest concentration used (100mM). It was shown that longipin preferentially binds to large unilamellar vesicles (LUVs), constituted by anionic phospholipds (POPG), that mimics the membrane surface of microbe cells. The peptide biding to LUVs composed, in 1:1 molar ratio, by POPG and POPC (zwitterionic) causes dye leakage (carboxyfluorescein) from their inside. This peptide in solution or in the presence of POPC solely containing mimic system is mostly unstructured. However, upon its binding to POPG:POPC 1:1, it adopts b and intermolecular aggregates amyloid-like fibrils structures.

Neste trabalho, foram estudadas estratégias para caracterização de bebidas à base de soja (BBS), por meio de análises por espectroscopia no infravermelho médio com transformada de Fourier com acessório de reflexão total atenuada (FTIR-ATR). Foram utilizadas 20 amostras comerciais de BBS, de 7 diferentes sabores e 3 diferentes marcas. Os teores estudados nas BBS foram glicídios totais, glicídios redutores, glicídios não redutores, e proteínas totais. Os modelos de regressão multivariada foram construídos por mínimos quadrados parciais (PLS), empregando como seleção de variáveis os métodos de mínimos quadrados parciais por intervalo (iPLS) e mínimos quadrados parciais por sinergismo de intervalos (siPLS). As seleções de variáveis por siPLS apresentaram os melhores resultados para os modelos construídos. Entre as propriedades avaliadas, a de glicídios totais apresentou modelos com erros de calibração e previsão (RMSECV e RMSEP) baixos, e coeficientes de determinação (R2cv e R2prev) próximos de um. Para proteínas totais, os modelos apresentaram resultados promissores, pois também tiveram erros de calibração e previsão (RMSECV e RMSEP) baixos, e coeficientes de determinação (R2cv e R2prev) próximos de um, considerando-se que as amostras reais e não apresentavam uma variabilidade de concentração de proteínas ideal. Para as propriedades de glicídios redutores e glicídios não redutores, não foram obtidos bons resultados para os modelos de regressão. Desta forma, a metodologia proposta apresenta potencial em análises de rotinas para determinação simultânea de glicídios totais e proteínas, atendendo aos requisitos referente às informações nutricionais na rotulagem das BBS, somando-se às vantagens da espectroscopia no infravermelho, tais como rapidez na análise, elevada frequência analítica, pequena quantidade de amostra necessária, baixo custo, não ser destrutiva e ser ambientalmente amigável. / In this work, strategies were studied for the characterization of soy-based beverages (SBB), by means of Fourier transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR). Twenty commercial samples of SBB were used, of 7 different flavors and 7 different brands. The contents studied in SBB were total sugar, reducing sugar, non-reducing sugars, and total proteins. The multivariate regression models were constructed by partial least squares (PLS), with evaluation of the methods by interval partial least squares (iPLS) and by sinergy interval partial least squares (siPLS), for selection of variables. The selections of variables per siPLS presented the best results for the constructed models. Among the evaluated properties, the total sugar content presented models with low calibration and prediction errors (RMSECV and RMSEP), and determination coefficients (R2cv and R2prev) close to one. For total proteins, the models presented promising results, as they also had low calibration and prediction errors (RMSECV and RMSEP), and determination coefficients (R2cv and R2prev) close to one, considering that the actual samples did not present an ideal protein concentration variability. For the properties of reducing sugars and non-reducing sugars, good results were not obtained for the regression models. In this way, the proposed methodology presents potential in routine analysis for simultaneous determination of total glycogen and protein, taking into account the requirements referring to the nutritional information in the SBB labeling, adding to the advantages of the infrared spectroscopy, such as speed in the analysis, high analytical frequency, small amount of sample required, low cost, non destructive and environmentally friendly.

Independent control of the surface and bulk properties is advantageous for many applications such as adhesives, release coatings, and antimicrobial films. Traditional methods for achieving independent control typically require multiple processing steps such as wet-on-wet or wet-on-dry coating methods. Independent control over the surface properties can achieved in a single step utilizing the temporal and spatial control inherent to photopolymerization. Specifically, a co-photopolymerization of monomers with different reactivities in the presence of a light gradient is capable of producing a polymer film with a surface chemistry that differs from the bulk chemistry. The light gradient, produced via the concentration of photoinitiator in the formulation, results in a reaction gradient through the film with the higher rates of reaction occurring in the high light intensity regions of the film. The preferentially reacting monomer adds at a greater rate in the high light intensity regions resulting in non-uniform consumption yielding a concentration gradient. Consequently, diffusion of the preferentially reacting monomer from the bulk to the surface of the film and a counter-diffusion of the other monomer from the surface to the bulk of the film occurs from the non-uniform monomer consumption thus producing a film with a concentration gradient through the depth of the film with the preferentially reacting monomer enriching the high light intensity regions. A variety of kinetic differences capable of producing a stratified film will be presented including inherent monomer reactivity, number of functional groups per monomer, oxygen inhibition, thiol-ene chemistry, and Norrish type two initiation. Additionally, parameters that control the degree of stratification, such as methods of varying polymerization rate and the light gradient, will be examined. Changes in surface properties (such as contact angle, surface hardness, adhesion) and bulk properties (such as mechanical properties measured by dynamic mechanical analysis and polymer swelling) are studied as a function of stratification. Finally, a mathematical model which describes and predicts the production of stratified films via photopolymerization is presented. Photopolymerization allows for a facile, single step method of generating stratified films with controllable surface chemistries.

Ce travail de thèse est consacré à la caractérisation physique de la surface de Mars et à l'étude des facteurs dynamiques la modifiant. Deux aspects sont étudiés. Le premier concerne les propriétés thermo-physiques qui sont un moyen de contraindre les actions que les forces érosives et sédimentaires cumulées sur les temps géologiques ont joué à la surface de Mars. Le second est l'hydratation de la surface de Mars qui est une donnée importante du système climatique martien en tant que réservoir d'eau.Afin de caractériser ces deux propriétés physiques de la surface de Mars, nous avons combiné l'approche orbitale permettant une couverture globale, l'approche in situ qui fournit une interprétation locale robuste et l'utilisation d'outils de simulation des processus physiques. Les données des instruments OMEGA, un spectro-imageur à bord de Mars Express en orbite autour de Mars depuis 2004, et le capteur de température de surface de l'instrument REMS, embarqué à bord de Curiosity et en opération dans le cratère Gale depuis 2012 ont été analysées en détail. Les mesures de température de surface de ces deux instruments ont été inversées pour caractériser les propriétés thermo-physiques de la surface au moyen d'un modèle climatique. Nous présentons la première carte globale de l'inertie thermique de la surface de Mars calculées à partir des données OMEGA et nous mettons en évidence de manière inédite des comportements thermiques spécifiques d'assemblages hétérogènes à la surface de Mars ou de processus physiques négligés.Les informations relatives à l'hydratation de la surface ont pu être extraites des données OMEGA grâce à la prise en compte de mesures en laboratoire et ont été interprétées de concert avec les résultats de plusieurs missions autour ou à la surface de Mars et des simulations climatiques du cycle de l'eau afin de reconstruire l'histoire de cette hydratation. Nous trouvons que l'hydratation est stable tout au long de l'année martienne et qu'elle augmente avec la latitude de manière asymétrique entre les deux hémisphères. La distribution spatiale de l'hydratation coincide avec les zones en contact régulier avec des dépôts de givre, qui apparaît ainsi être à l'origine du processus responsable de l'implémentation de l'eau dans le régolite martien. / This thesis work is devoted to the physical characterization of the Martian surface and to the study of dynamic processes modifying it. Two aspects are addressed. The first concerns the thermo-physical properties which are a mean to putting constraints on to the erosive and sedimentary actions summed over the geologic history. The second is the hydration of the Martian surface which plays, as a planetary reservoir of water, an important role on the Martian climate.In order to characterize these two physical parameters of the Martian surface, we have combined the orbital view which allows a global coverage with in situ measurements, which provides a robust local interpretation, and we have used tools allowing numerical simulations of physical processes. Data from OMEGA, an imaging spectrometer onboard Mars Express orbiting Mars since 2004, and from the ground temperature sensor of the REMS instrument onboard Curiosity have been analyzed in details. Surface temperature measurements from these two instruments have been inverted using a climate model for characterizing the thermo-physical properties of the Martian surface. We present the first global map of the Martian surface thermal inertia constructed from OMEGA data and we directly highlight for the first time some thermal behavior caused by heterogeneous mixtures or neglected physical processes at the surface of Mars.Information regarding the hydration of the Martian surface have been extracted from OMEGA data using a large set of laboratory experiments. This information has been interpreted together with scientific results from multiple mission orbiting or at the surface of Mars and with numerical simulations of the Martian water cycle in order to reconstruct the history of this hydration. We find that the hydration remains stable throughout the whole Martian year and that it increases with latitude with an asymetry between the two hemispheres. The spatial distribution of the hydration fits areas that are in regular contact with water frost, which therefore seems to be involved in the process of water implementation in the Martian regolith.