The desire to use the tools and concepts of chemometrics when studying problems in the life sciences, especially biology and medicine, has prompted chemometricians to shift their focus away from their field‘s traditional emphasis on model predictivity and towards the more contemporary objective of optimizing information exchange via model interpretation. The complex data structures that are captured by modern advanced analytical instruments open up new possibilities for extracting information from complex data sets. This in turn imposes higher demands on the quality of data and the modeling techniques used. The introduction of the concept of orthogonal variation in the late 1990‘s led to a shift of focus within chemometrics; the information gained from analysis of orthogonal structures complements that obtained from the predictive structures that were the discipline‘s previous focus. OPLS, which was introduced in the beginning of 2000‘s, refined this view by formalizing the model structure and the separation of orthogonal variations. Orthogonal variation stems from experimental/analytical issues such as time trends, process drift, storage, sample handling, and instrumental differences, or from inherent properties of the sample such as age, gender, genetics, and environmental influence. The usefulness and versatility of OPLS has been demonstrated in over 500 citations, mainly in the fields of metabolomics and transcriptomics but also in NIR, UV and FTIR spectroscopy. In all cases, the predictive precision of OPLS is identical to that of PLS, but OPLS is superior when it comes to the interpretation of both predictive and orthogonal variation. Thus, OPLS models the same data structures but provides increased scope for interpretation, making it more suitable for contemporary applications in the life sciences. This thesis discusses four different research projects, including analyses of NIR, FTIR and NMR spectroscopic data. The discussion includes comparisons of OPLS and PLS models of complex datasets in which experimental variation conceals and confounds relevant information. The PLS and OPLS methods are discussed in detail. In addition, the thesis describes new OPLS-based methods developed to accommodate hyperspectral images for supervised modeling. Proper handling of orthogonal structures revealed the weaknesses in the analytical chains examined. In all of the studies described, the orthogonal structures were used to validate the quality of the generated models as well as gaining new knowledge. These aspects are crucial in order to enhance the information exchange from both past and future studies.

Το πρόγραμμα συντήρησης του μοναστηριακού συγκροτήματος του Αγίου Λωτ περιελάμβανε in situ επεμβάσεις συντήρησης, σωστική αποκόλληση και επανατοποθέτηση ενός από τα έξι ψηφιδωτά δάπεδα που βρίσκονταν στην Βασιλική και την ανασκαφή ενός ψηφιδωτού που είχε καταρρεύσει και κατακερματιστεί σε εκατοντάδες θραύσματα στην κλιτύ του λόφου, όπου βρίσκεται η Μονή. Η αποκόλληση του πρώτου ψηφιδωτού δαπέδου και η επακόλουθη ανακάλυψη ενός πρωιμότερου ψηφιδωτού δαπέδου κάτω από αυτό, καθώς και η εύρεση ενός ακόμα σε θραύσματα μας έδωσε την ευκαιρία να παρατηρήσουμε και να καταγράψουμε επιμελώς τις τεχνικές που χρησιμοποιήθηκαν στην κατασκευή των ψηφιδωτών. Ο χαρακτηρισμός επιλεγμένων δειγμάτων κονιαμάτων μας επέτρεψε να προσδιορίσουμε τη σύστασή τους και να ταυτοποιήσουμε το είδος των αδρανών και των προσμίξεων που εμπεριέχει. Οι τεχνικές που χρησιμοποιήθηκαν για την ανάλυση των κονιαμάτων είναι οι: η Περιθλασιμετρία κόνεως ακτίνων-Χ (XRD), η Ηλεκτρονική Μικροσκοπία Σάρωσης (SEM- EDS), η Φασματοσκοπία Απορρόφησης Υπερύθρου (FTIR) και η Οπτική Μικροσκοπία (ΟΜ). Επιπλέον, η πετρογραφική ανάλυση των ψηφίδων, που έγιναν από συνεργάτες του έργου, μας έδωσαν πληροφορίες σχετικά με την προέλευση των πρώτων υλών που χρησιμοποιήθηκαν. Μετά από αναλύσεις και λεπτομερή παρατήρηση, λάβαμε πληροφορίες σχετικά με τις πρώτες ύλες, την προετοιμασία των κονιαμάτων, την στρωματογραφία του ψηφιδωτού δαπέδου, την μέθοδο εκτέλεσης των εργασιών κατασκευής, αλλά και τον τρόπο επεξεργασίας της επιφάνειας. Οι διαφορές που παρατηρούνται στην στρωματογραφία και τη σύσταση των κονιαμάτων, όπως και στις ψηφίδες σε ψηφιδωτά που δημιουργήθηκαν σε διαφορετική χρονική περίοδο συμβάλλουν στην αρχαιολογική μελέτη και κυρίως στην κατανόηση της αρχιτεκτονικής ενότητας και μετατροπών που υπέστη κατά την διάρκεια της χρήσης του χώρου. / The conservation project at the monastic complex of Saint Lot involved the rescue lifting of one of the six mosaics which paved the basilica as well as the excavation of a second one that was found in hundreds of fragments fallen on the slope. The lifting of the first mosaic and the consequent discovery of fragments of an earlier mosaic floor underneath it, as well as the fragmentary state of the second mosaic gave us the opportunity to observe and record thoroughly the techniques employed in the construction of these mosaics. Characterization of selected mortar samples allowed the determination of their composition, identification of the aggregate and its additives. X-Ray Diffraction, Fourier transform infrared spectroscopy, Optical Microscopy and Scanning Electron Microscopy with EDS were the main techniques employed. Mineralogical analyses of tesserae samples, that was employed from other partners of the project, provided information about the provenance of the raw materials that were used. Through detailed observation and analysis, significant information on the raw material selection, preparation of mortars, bedding stratigraphy, method of execution, as well as aspects of tesserae cutting and surface finishing techniques were documented. The variation in the bedding stratigraphy, the composition of the mortars as well as the petrography of the tesserae between mosaics that were executed in different periods contribute in the study of the archaeological context and especially in understanding the succession of the renovation and modification phases of the building.

Το αντικείμενο της παρούσας μεταπτυχιακής διατριβής ειδίκευσης ήταν η μελέτη των φυσικοχημικών και μηχανικών ιδιοτήτων παθολογικά αλλοιωμένων ανθρώπινων μηνίσκων. Οι μηνίσκοι είναι ινοχόνδρινοι μηνοειδείς δίσκοι που παρεμβάλλονται μεταξύ των αρθρικών επιφανειών του μηριαίου κονδύλου και της κνημιαίας γλύνης. Αποτελούνται ως επί το πλείστον από ίνες κολλαγόνου και χονδροκύταρα. Περιέχουν ακόμα γλυκοσαμινογλυκάνες, ελλαστίνη και DNA. Συμβάλλουν καθοριστικά στη σωστή λειτουργία της άρθρωσης καθώς είναι επιφορτισμένοι με λειτουργίες, όπως η προστασία των αρθρικών επιφανειών από τη φθορά, η λίπανση και η σταθεροποίηση της άρθρωσης. Η σημαντικότερη ίσως μεταβολική νόσος των μηνίσκων είναι η χονδρασβεστίωση (chondrocalcinosis) κατά την οποία παρατηρείται ανάπτυξη ανόργανων αλάτων στην επιφάνεια ή/και στο σώμα του ιστού. Για τη μελέτη των ιδιοτήτων των παθολογικά αλλοιωμένων ανθρώπινων μηνίσκων χρησιμοποιήθηκαν τεχνικές μηχανικής και φυσικοχημικής ανάλυσης. Με Δυναμική Μηχανική Ανάλυση επιχειρήθηκε να αξιολογηθεί η επίδραση των διαφόρων τύπων παθολογικών αλλοιώσεων στις δυναμικές μηχανικές ιδιότητες των ιστών. Οι ασβεστοποιημένοι ιστοί και οι εναποθέσεις τους μελετήθηκαν με φασματοσκοπικές τεχνικές RAMAN, FT-RAMAN, FT-IR καθώς επίσης και με απεικονιστικές τεχνικές οπτικής μικροσκοπίας, σαρωτικής μικροσκοπίας ηλεκτρονίων (SEM) και μικροσκοπίας ατομικής δύναμης (AFM). Επιπλέον, για πρώτη φορά έγινε διασύγκριση της ικανότητας τριών διαφορετικών διατάξεων RAMAN (FT-RAMAN: 1064 nm, Dispersion RAMAN: 633 nm και Dispersion RAMAN: 325 nm) να εντοπίσουν την παρουσία εναποθέσεων στους ιστούς. Στην παρούσα μελέτη εξετάστηκαν 63 μηνισκικά μοσχεύματα από οστεοαρθριτικούς ασθενείς οι οποίοι υποβλήθηκαν σε ολική αρθροπλαστική γόνατος στο Περιφερειακό Πανεπιστημιακό Νοσοκομείο Πατρών. Τα μοσχεύματα αυτά εξετάστηκαν από ιστοπαθολόγο και διαγνώστηκαν οι παθολογικές αλλοιώσεις που έφερα καθένας από αυτούς. Με βάση τα ιστοπαθολογικά αποτελέσματα έγινε κατηγοριοποίηση των δοκιμίων και συσχέτιση των αποτελεσμάτων αυτών με τα αποτελέσματα των προαναφερθέντων τεχνικών. Από τα αποτελέσματα της δυναμικής μηχανικής ανάλυσης φάνηκαν μικρές αλλά όχι στατιστικά σημαντικές διαφοροποιήσεις μεταξύ ασβεστοποιημένων μηνίσκων και μηνίσκων που παρουσίαζαν μυξωματοειδή εκφυλισμό και κύστες (σύμφωνα με τα αποτελέσματα της ιστοπαθολογικής εξέτασης). Τα αποτελέσματα της περιθλασιμετρίας ακτίνων Χ των ασβεστοποιημένων ιστών έδειξαν παρουσία μείγματος τρικλινούς και μονοκλινούς διένυδρου πυροφωσφορικού ασβεστίου (CPPD) υψηλής κρυσταλλικότητας καθώς και μικροκρυσταλλικές εναποθέσεις απατιτικής σύστασης (HAP). Οι τεχνικές μικροσκοποίας (οπτική, SEM και AFM) επιβεβαίωσαν τον παραπάνω ισχυρισμό αποκαλύπτοντας το χαρακτηριστικό τρόπο ανάπτυξης κάθε τύπου εναπόθεσης. Τα αποτελέσματα της φασματοσκοπικής ανάλυσης με χρήση των τεχνικών RAMAN – FT-RAMAN – και FT-IR έδειξαν την παρουσία επίσης χαρακτηριστικών κορυφών του CPPD και του HAP. Οι εναποθέσεις από CPPD ανιχνεύθηκαν στο 82.6 % των ασβεστοποιημένων δειγμάτων (19 στα 23) ενώ από απατίτη στο 17.4% (4 στα 23) Aναφορικά με τα RAMAN, επισημαίνεται ότι ανεξάρτητα από το μήκος κύματος που χρησιμοποιήθηκε και παρά την ισχυρή μπάντα φθορισμού που επεδείκνυαν τα φάσματα, οι χαρακτηριστικές κορυφές των εναποθέσεων ήταν εμφανείς. / The aim of the present master thesis study was the physicochemical and biomechanical characterization of pathological human menisci. Menisci are semilunar shaped fibrocartilaginous tissues that lie between the femoral condyle and tibia plateau. They mainly consist of collagen fibers and chondrocytes. Additionally glycosaminoglycans, elastin and DNA are present in the tissue. Menisci play an important role in the good function of human knee joint by distributing the applied loads, contributing to the joint’s stability and lubricating the joint’s area. The most common metabolic meniscal lesion is the chondrocalcinosis where inorganic phases of calcium or sodium salts are deposited in/on the tissue. Pathologically altered human menisci were studied by mechanical and physicochemical analysis techniques. Dynamic Mechanical Analysis was used to investigate the effects of degeneration lesions on the dynamic mechanical properties of the tissue. Calcified tissues and the corresponding encrustations were studied by spectroscopic techniques such as RAMAN, FT-RAMAN, FT-IR as well as imaging techniques such as optical microscopy, scanning electron microscopy (SEM) and atomic force microscopy (AFM). Moreover, for the first time a comparison of the ability of three different RAMAN setups (FT-RAMAN: 1064 nm, Dispersion RAMAN: 633 nm and Dispersion RAMAN:325 nm) to detect calcification on the tissues was performed. The clinical sample comprised of 63 menisci with histopathologicaly confirmed alterations that were surgically extracted from osteoarthritic patients due to total knee arthroplasty in the University Hospital of Patras. Samples were classified according to the histopathological evaluation and a correlation of histopathological with mechanical or spectroscopic findings was attempted. Dynamic mechanical analysis results showed small but no statistically significant difference between the group of calcified and the group of mucoid and cystic degenerated tissues (as determined after histopathological examination) X-ray diffraction analysis of the menisci encrustations revealed highly crystallized depositions of triclinic and monoclinic Calcium Pyrophosphate Dihydrate (CPPD) and some samples with poorly crystallized apatitic depositions (HAP). Microscopic techniques (optical, SEM and AFM) confirmed the presence of CPPD and HAP and in addition revealed information regarding their growth mechanism.The results of spectroscopical analysis using RAMAN – FT-RAMAN and FT-IR showed also the characteristic peaks of the inorganic phase (CPPD or HAP) presented in/on the tissue. CPPD encrustations were detected in 82.6 % (19 of 23) of the calcified samples while apatite in 17.4 % (4 of 23). Moreover, it is notable that all RAMAN setups showed the characteristic peaks of CPPD and HAP regardless of the excitation source and the strong fluorescence band.

A conformação de dispositivos médicos implantáveis a partir de uma blenda exige o desenvolvimento de um produto com propriedades próximas do comportamento ideal, combinando propriedades térmicas e mecânicas e boa resposta tecidual. O Poli (ácido láctico-co-glicólico) (PLGA) e o Poli (isopreno) (IR) foram escolhidos como componentes da blenda com finalidade de promover boa biocompatibilidade e características mecânicas especificas. As blendas foram obtidas por dissolução dos polímeros em solvente orgânico, seguida de secagem. Para determinar a influência do teor de IR sobre as propriedades da blenda, foram realizados ensaios de espectroscopia na região de infravermelho por transformada de Fourier (FTIR), calorimetria diferencial de varredura (DSC), análise dinâmico-mecânica (DMA), microscopia óptica por luz polarizada (POM), análise de dureza, ensaio de tração e análise de viabilidade celular. A presença de IR na blenda provocou alteração na estrutura molecular semi-cristalina do PLGA, bem como influenciou o comportamento mecânico analisado a partir da curva tensão-deformação do material. A blenda se mostrou biocompativel em ambiente celular e em ensaios preliminares em animais, apresentando potencial para aplicação como biomaterial. / The conformation of an implantable medical device from a polymeric blend requires the development of a product with properties as close as possible of ideal behavior with the combination between thermal and mechanical properties and good tissue response. The poly (lactic-co-glycolic acid) (PLGA) and the poly (isoprene) (IR) were chosen as the blend components to promote good biocompatibility and specific mechanical characteristics. The blends were obtained by dissolution of polymers in organic solvent, followed by drying. In order to determine the IR content influence over the blend properties, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), polarized light optical microscopy (POM), hardness analysis, tensile test and cell viability test were carried out. The IR presence caused changes in semi-crystalline molecular structure of PLGA, as well as actuated over the mechanical response analyzed on material’s stress-strain curve. The blend showed itself biocompatible at cellular environment and at preliminary animal tests, presenting potential for application as biomaterial.

Submitted by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2016-01-06T18:54:10Z No. of bitstreams: 2 license_rdf: 22974 bytes, checksum: 99c771d9f0b9c46790009b9874d49253 (MD5) mayara_rodrigues_lessa.pdf: 2887620 bytes, checksum: 65d145401884724e28b09bbc9441aa53 (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2016-01-07T11:52:11Z (GMT) No. of bitstreams: 2 license_rdf: 22974 bytes, checksum: 99c771d9f0b9c46790009b9874d49253 (MD5) mayara_rodrigues_lessa.pdf: 2887620 bytes, checksum: 65d145401884724e28b09bbc9441aa53 (MD5) / Made available in DSpace on 2016-01-07T11:52:11Z (GMT). No. of bitstreams: 2 license_rdf: 22974 bytes, checksum: 99c771d9f0b9c46790009b9874d49253 (MD5) mayara_rodrigues_lessa.pdf: 2887620 bytes, checksum: 65d145401884724e28b09bbc9441aa53 (MD5) Previous issue date: 2014 / O caf? torrado e mo?do encontrado no mercado interno ? comercializado sob diferentes marcas, que trazem consigo uma heterogeneidade quanto ao aroma, sabor e at? o grau de torra??o. Esta diversidade de caracter?sticas est? associada a v?rios fatores, entre eles a origem dos gr?os de caf?. Considerando essas varia??es relatadas na literatura, o presente trabalho teve como objetivo realizar uma pesquisa da composi??o qu?mica e f?sico-qu?mica de caf?s comerciais em diferentes cidades da Regi?o Sudeste do Brasil. Cinquenta e oito pacotes de 250 gramas, de caf?s torrados e mo?dos acondicionados em embalagem do tipo almofada e/ou ? v?cuo foram adquiridos em diferentes cidades dos quatro Estados da Regi?o Sudeste do Brasil. Todos os produtos estavam dentro do prazo de validade e aproximadamente 58% das marcas apresentavam o selo de pureza da ABIC, enquanto 22% das marcas apresentavam o selo de qualidade da Associa??o Brasileira da Ind?stria de Caf?. As amostras foram levadas para o Laborat?rio de Tecnologia de Biomassas do Cerrado da Universidade Federal dos Vales do Jequitinhonha e Mucuri, onde foram realizadas as avalia??es de pH cujo resultado m?dio foi 5,95; acidez total titul?vel 15,03 ? 1,07(v/m)%; s?lidos sol?veis totais 1,15 ?Brix; ?ndice de colora??o com m?dia para os valores de L* de 28,87 ? 0,29, para os valores de a* de 8,99 ? 0,10 e para os valores de b* de 2,84 ? 0,21; os compostos fen?licos obtiveram uma m?dia de 4,1152 ? 0,4863 g.100g-1 e a m?dia dos flavonoides de 0,5042 ? 0,0291 g.100g-1. Os m?todos multivariados de an?lise, associados aos m?todos usando a espectroscopia na regi?o do infravermelho tem tido grandes avan?os com diversas aplica??es nas an?lises de alimentos. Com este intuito, utilizou-se a espectroscopia na regi?o do infravermelho para delinear os grupos funcionais mais representativos nas amostras de caf? analisadas com a inten??o de agrup?-las por similaridade atrav?s da estat?stica multivariada. Os resultados permitiram visualizar que poucos grupos foram formados utilizando as an?lises f?sico-qu?micas, para classificar as amostras. A An?lise das Componentes Principais foi capaz de acumular 61,98% de vari?ncia nas duas primeiras componentes e os grupos formados foram confirmados pela An?lise Hier?rquica por Agrupamento. Em rela??o aos espectros de infravermelho, as amostras foram mais agrupadas com a An?lise das Componentes Principais acumulando 41,76% da vari?ncia, os grupos das amostras foram confirmados pela An?lise Hier?rquica por Agrupamento. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2014. / ABSTRACT The roast and ground coffee found in the domestic market is sold under different brands that carry with them a heterogeneity for aroma, flavor and even the degree of roasting. This diversity of characteristics is associated with several factors, including the origin of the coffee beans. Considering these variations reported in the literature, the present study aimed to perform a search of the chemical and physico-chemical composition of commercial coffees in different cities in Southeastern Brazil. Fifty-eight packages of 250 grams of roasted and ground coffee packaged in packaging the type pad and / or vacuum were acquired in different cities of the four states of southeastern Brazil. All products were within the validity period and approximately 58% of brands had the seal of purity of ABIC, while 22% of brands had the seal of the Brazilian Association of Coffee Industry Samples were taken for Laboratory Technology Biomass of the Cerrado, Federal University of the Jequitinhonha and Mucuri, which were conducted evaluations of pH where the average yield around 5.95; titratable acidity 15.03 ? 1.07 (v / m)%; total soluble solids 1.15 ? Brix; staining index and the average for the values ??of L * was 28.87 ? 0.29 for the a * values ??was 8.99 ? 0.10 and b * values ??were 2.84 ? 0.21 ; phenolic compounds were obtained an average of 4.1152 ? 0.4863 g.100g-1 and the average of flavonoids was 0.5042 ? 0.0291 g.100g-1. The multivariate analysis methods, associated with methods using spectroscopy in the infrared region has taken great strides with several applications in food analysis. For this purpose, we used spectroscopy in the infrared region to delineate the most representative functional groups in coffee samples analyzed with the intention of grouping them by similarity using multivariate statistics. The results allowed us to visualize that few groups were formed using the physicochemical analyzes to classify the samples. The Principal Component Analysis was able to accumulate 61.98% of variance in the first two components and the groups formed were confirmed by Hierarchical Cluster Analysis. Regarding the infrared spectra of the samples were further grouped with the Principal Component Analysis accumulating 41.76% of the variance, the groups of samples were confirmed by Hierarchical Cluster Analysis.

A conformação de dispositivos médicos implantáveis a partir de uma blenda exige o desenvolvimento de um produto com propriedades próximas do comportamento ideal, combinando propriedades térmicas e mecânicas e boa resposta tecidual. O Poli (ácido láctico-co-glicólico) (PLGA) e o Poli (isopreno) (IR) foram escolhidos como componentes da blenda com finalidade de promover boa biocompatibilidade e características mecânicas especificas. As blendas foram obtidas por dissolução dos polímeros em solvente orgânico, seguida de secagem. Para determinar a influência do teor de IR sobre as propriedades da blenda, foram realizados ensaios de espectroscopia na região de infravermelho por transformada de Fourier (FTIR), calorimetria diferencial de varredura (DSC), análise dinâmico-mecânica (DMA), microscopia óptica por luz polarizada (POM), análise de dureza, ensaio de tração e análise de viabilidade celular. A presença de IR na blenda provocou alteração na estrutura molecular semi-cristalina do PLGA, bem como influenciou o comportamento mecânico analisado a partir da curva tensão-deformação do material. A blenda se mostrou biocompativel em ambiente celular e em ensaios preliminares em animais, apresentando potencial para aplicação como biomaterial. / The conformation of an implantable medical device from a polymeric blend requires the development of a product with properties as close as possible of ideal behavior with the combination between thermal and mechanical properties and good tissue response. The poly (lactic-co-glycolic acid) (PLGA) and the poly (isoprene) (IR) were chosen as the blend components to promote good biocompatibility and specific mechanical characteristics. The blends were obtained by dissolution of polymers in organic solvent, followed by drying. In order to determine the IR content influence over the blend properties, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), polarized light optical microscopy (POM), hardness analysis, tensile test and cell viability test were carried out. The IR presence caused changes in semi-crystalline molecular structure of PLGA, as well as actuated over the mechanical response analyzed on material’s stress-strain curve. The blend showed itself biocompatible at cellular environment and at preliminary animal tests, presenting potential for application as biomaterial.

O objetivo deste estudo é caracterizar a influência da relação dos componentes hidrófilos de uma resina adesiva experimental em suas propriedades intrínsecas. Para isso, foram adicionados a um sistema polimérico (BisGMA, BisEMA e TEGDMA), diferentes concentrações de HEMA totalizando quatro grupos: 0%, 15%, 30% e 50% de HEMA. As misturas foram caracterizadas quanto à cinética de polimerização através de Fourier Transformed Infrared (FTIR) em tempo real e a taxa de polimerização (RP) foi calculada através da análise de regressão não-linear; resistência coesiva à tração utilizando-se uma máquina de ensaios mecânicos com corpos de prova em forma de ampulheta com área de constrição de 1mm2; e, sorção e solubilidade baseada na normatização ISO 4049. Houve correlação entre o tempo de fotoativação e o grau de conversão para todos os grupos (r2>0.98). O grupo 0% apresentou RPMÁX elevada nos segundos iniciais de fotoativação com, no entanto, uma brusca redução. As adições de 30% e 50% de HEMA determinaram uma RPMÁX do copolímero menor que em 15% e 0%. Não houve diferença entre o grau de conversão final (60s) entre os grupos de 0, 15 e 30%, sendo 59,7%, 61,4% e 55,2% respectivamente. As adições de 30% e 50% de HEMA determinaram a redução da resistência coesiva dos polímeros (p<0,05) quando comparado aos grupos 0% e 15%. Grupos com maiores adições de HEMA apresentaram maiores graus de sorção e solubilidade (p<0,05). Maiores adições de HEMA resultaram em polímeros mais propensos à degradação. / The aim of this study was to characterize the influence of hydrophilic monomers ratios on an experimental adhesive resin properties. Four groups, with 0, 15, 30 and 50% (wt) addiction of HEMA were prepared. Comonomer blends (BisGMA, BisEMA, TEGDMA and HEMA) were analyzed with kinetics of polimerization real time FTIR and the rate of polymerization was calculated by non-linear regression analysis. Ultimate tensile strength was tested using a universal testing machine (Emic) with hour-glass shaped specimens with cross-sectional area 1mm2. Water sorption and solubility tests were based on ISO 4049. For All groups was a positive and strong correlation between light-activation time and degree of conversion (r2>0,98). Group 0% of HEMA showed higher RPMÁX in early seconds with a suddenly decrease. Additions of 30% and 50% of HEMA determined a RPMÁX lower than the comonomer blends with 15% and 0% of HEMA. There was no statistical difference of final degree of conversion of the tested groups, varying from 63% to 67% . The additions of 30% and 50% of HEMA determined reduction of ultimate tensile strength of the polymers formed (p<0,05) when compared to 0% and 15 % of HEMA. Groups with higher additions of HEMA showed higher water sorption and solubility (p<0,05). Higher additions of HEMA resulted in polymers more prone to degradation.

As células a combustível de etanol direto (DEFCs, Direct Ethanol Fuel Cells) são baseadas na eletro-oxidação do etanol à baixa temperatura e necessitam catalisadores à base de metais nobres, devido à cinética mais lenta para as reações de oxi-redução. Entre os catalisadores, a platina e as ligas de platina são os mais utilizados. Materiais para suportar os catalisadores são necessários a fim de reduzir a carga do mesmo empregada. Um dos suportes de catalisadores mais versáteis é o carvão ativado, e um dos mais utilizados tem sido o carvão mineral Vulcan. Recentemente, estudos têm sido realizados sobre a madeira como material precursor de carvão ativado, devido à sua sustentabilidade e também porque os materiais carbonosos obtidos têm excelentes propriedades finais. No presente trabalho, estudou-se a reação de eletro-oxidação do etanol, de catalisadores à base de Pt e PtSn suportados em biocarvões obtidos a partir da madeira Eucalyptus grandis. No início desse trabalho não havia relatos na literatura sobre o uso de carvões ativados obtidos a partir de madeira de Eucalyptus grandis como precursor. Foram utilizados dois métodos de ativação nos suportes, ativação física com CO2 e ativação química com ZnCl2. Os suportes de catalisadores foram caracterizados por análise textural, análise elementar, análise termogravimétrica e por espectroscopia de infravermelho. As técnicas empregadas para a caracterização dos catalisadores foram espectrometria de retroespalhamento de Rutherford (RBS), difração de raios-X (DRX), análise termogravimétrica (TGA), microscopia eletrônica de transmissão (MET), voltametria cíclica (VC) e caracterização espectroeletroquímica (ATR-FTIR in-situ). Os biocarvões apresentaram áreas superficiais maiores e tamanhos de poros menores do que o carvão Vulcan, independente do tratamento. A natureza do suporte influenciou nas características morfológicas dos eletrocatalisadores preparados. Com base nos resultados obtidos os catalisadores suportados nos suportes com ativação química apresentaram os melhores resultados de densidade de corrente para eletro-oxidação do etanol, com exceção do catalisador PtSn suportado no biocarvão ativado fisicamente (PtSn/BCAF). Pode-se dizer que os biocarvões são adequados para aplicações em células de combustível, podendo substituir o uso de suportes baseados em carvões minerais. A eletro-oxidação do etanol nos eletrocataliadores de PtSn nos carvões ativados ocorre principalmente através da produção de acetaldeído e ácido acético. / Direct ethanol fuel cells (DEFC) are based on ethanol electrooxidation at low-temperature and they require noble metal based catalysts, due to the slower kinetic of redox reactions. Among the catalysts, platinum and its alloys have been the most widely used. Catalysts support materials have been employed with the intent to reduce loading catalyst. One of the most versatile catalyst supports is activated carbon, and one of the most widely used is the Vulcan®, a mineral carbon. Currently, different studies have been conducted concerning wood as activated carbon precursor, because of its sustainability and its properties, like suitable porous texture, surface area and surface chemistry. In this work, it was studied ethanol electrooxidation reaction on Pt and PSn catalysts supported on biocarbon. Biocarbons were obtained from Eucalyptus grandis. Literature reports the use of carbon materials as catalyst support, however focused on carbon fibers and carbon nanotubes, without any precedent on the use of activated carbon obtained from Eucalyptus grandis until the start of this work. The carbon supports were obtained by physical activation using CO2, and chemical activation with ZnCl2. Catalyst support characterization boarded elemental analysis, texture analysis, thermogravimetric analysis and infrared spectroscopy. Techniques employed for the catalyst characterization were Rutherford backscattering spectrometry (RBS), X-ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), cyclic voltammetry (CV) and spectroelectrochemical characterization (ATR-FTIR in situ). Biocarbons presended the higher surface areas and smallest pore size than the Vulcan ones, independent of the treatment. The support nature influenced on the catalyst morphology. Results showed that the catalyst on the chemically activated supports presented the best current density for ethanol electro-oxidation, except for the PtSn on the physically activated biocarbon (PtSn/BCAF). Biocarbons resulted adequate for fuel cell applications and are capable of substituting the conventional supports based on mineral carbon. Ethanol electro-oxidation on PtSn catalysts takes place through the production of acetaldehyde and acetic acid reaction mechanism.

Os nitro-hidrocarbonetos policíclicos aromáticos (NPAHs – nitro-polycyclic aromatic hydrocarbons) são compostos orgânicos constituídos de dois ou mais anéis benzênicos ligados ao grupo nitro (NO2). Tais compostos são amplamente distribuídos no meio ambiente e associados a partículas atmosféricas. O objetivo do presente estudo foi identificar os grupos funcionais dos NPAHs associados ao PM1.0 por espectroscopia de infravermelho termal com transformada de Fourier (FTIR – Fourier Transform Infrared Spectroscopy), determinar a concentração de tais compostos e avaliar a sazonalidade em uma área de influência veicular na região Metropolitana de Porto Alegre (MAPA – Metropolitan Area of Porto Alegre). Além disso, estudaram-se variáveis meteorológicas e outros poluentes (NO, NO2, NOx, O3) com a finalidade de relacioná-los com os NPAHs. Partículas atmosféricas (PM1.0) foram coletadas usando filtros de PTFE (polytetrafluorethylene) no amostrador automático PM162M. Após, o espectrorradiômetro FTIR portátil, da Designs & Prototypes, modelo 102, foi utilizado para realizar medidas espectrais de transmitância e emissividade dos padrões sólidos dos NPAHs: 1-NP e 2-NF e das amostras de partículas atmosféricas. As análises por cromatografia gasosa com detecção por captura de elétrons (GC-ECD - gas chromatography with electron capture detector) foram precedidas por isolamento/derivação, sendo essas as técnicas de determinação e extração, respectivamente, de NHPAs (1-NNa, 2-NF, 3-NFl, 1-NP e 6-NChr) associados a PM1.0. Para validar o método analítico foi usado o Material de Referência Padrão – SRM 1649b – do National Institute of Standards and Technology (NIST, USA). As análises espectrais resultantes de transmitância e emissividade apresentaram bons resultados, possibilitando identificar as ligações C-N e grupo NO2, assim como alguns grupos funcionais orgânicos característicos dos padrões 1-NP e 2-NF, indicando que este método pode ser aplicado no material particulado atmosférico. Com o método empregado foi possível identificar o 1-NP em todas as amostras, enquanto que 2-NF foi identificado apenas em Canoas 1 e Sapucaia do Sul 1 e 2. As concentrações de NPAHs foram mais elevadas no inverno e Sapucaia do Sul foi o local que apresentou maiores níveis destes compostos, exceto o 6-NChr. Os NPAHs associados a PM1.0 mostraram correlações com os poluentes óxidos de nitrogênio (NO e NOx), assim como NPAHs com as variáveis meteorológicas: temperatura e velocidade do vento. Os resultados indicaram a contribuição dos veículos com motores a diesel. Isto foi confirmado pelo estudo das razões NPAHs/PAHs, 1-NP/Py, 6-NChr/Chr. / The nitro-polycyclic aromatic hydrocarbons (NPAHs) are organic compounds that consisting of two or more benzene rings linked by a nitro group (NO2). These compounds are widely distributed in the environment and are mainly found associated with atmospheric particles. The objective of this study was to identify the functional groups of NPAHs associated with PM1.0 by Fourier Transform Infrared Spectroscopy (FTIR), determine the concentration of these compounds and evaluate the seasonality in an area of vehicular influence in the Metropolitan area of Porto Alegre (MAPA). Summed to that, meteorological variables and other pollutants (NO, NO2, NOx, O3) were studied in order to relate them with the NPAHs. Atmospheric particles (PM1.0) were collected using PTFE (polytetrafluorethylene) filters in autosampler PM162M. After that, the portable spectroradiometer FTIR, model 102 of Designs & Prototypes, was used for spectral measurements of transmittance and emissivity of solid standards of NPAHs: 1-NP and 2-NF and the atmospheric particles samples. Analyses by gas chromatography with electron capture detector (GC-ECD) were preceded by isolation / derivation, those being the determination and extraction techniques, respectively, of NHPAs (1-NNa, 2-NF, 3-NFl, 1-NP and 6-NChr) associated with PM1.0. To validate the analytical method it was used the Standard Reference Material - SRM 1649b - of National Institute of Standards and Technology (NIST, USA). The spectral analysis resulting of transmittance and emissivity showed good results, allowing to identify the CN bands and NO2 group, as well as some characteristic organic functional groups of 1-NP and 2-NF standards, indicating that this method can be applied in atmospheric particulate matter. With the employed method it was possible to identify the 1-NP in all samples, while the 2-NF was identified only in Canoas 1 and Sapucaia do Sul 1 and 2. The NPAHs concentrations were higher in winter and Sapucaia do Sul was the place that had the highest levels of these compounds, except to 6-NChr. The NPAHs associated with the PM1.0 showed correlations with the nitrogen oxides (NO and NOx) pollutants, as the NPAHs with the meteorological variables: temperature and wind speed. The results indicated the contribution of vehicles with diesel engines. It was confirmed by the reasons study of NPAHs/PAHs, 1-NP/Py, 6-NChr/Chr.

Com as descobertas das inúmeras aplicações potenciais da biomassa de microalgas é necessário o desenvolvimento de ferramentas que visem auxiliar o aumento da produtividade dos cultivos. A espectrometria por infravermelho com transformada de Fourier (FTIR) é uma técnica versátil e rápida utilizada na identificação, caracterização e quantificação de diversos compostos moleculares. Sua aplicação está definida de acordo com a região espectral a ser analisada. O objetivo deste trabalho é desenvolver uma metodologia que torne possível a utilização da espectroscopia FTIR na região do infravermelho médio (MIR) para quantificar os teores de lipídeos, proteínas, carboidratos e células de Scenedesmus sp. Para tanto, a biomassa de Scenedesmus sp. foi analisada diariamente por métodos tradicionais e através do espectro FTIR. Posteriormente os dados foram correlacionados com as bandas de absorção características de cada composto. O modelo gerado para lipídeos na região entre 3000-2800 cm-1 obteve o maior coeficiente de correlação (R2) de 0,8265. Para os carboidratos, a banda de absorção que melhor representou as ligações características foi entre 1200-950cm-1, com R2=0,8023. Já para proteínas, a escolha do método tradicional não mostrou boa relação com os resultados do FTIR. Quando a concentração celular foi correlacionada com a área total foi obtido R2=0,7900. Por fim, realizaram-se experimentos para validar os modelos preditos, obtendo bons resultados para a quantificação de lipídeos e carboidratos. O FTIR mostra ser uma ferramenta eficiente para estimar os conteúdos de lipídeos e carboidratos de Scenedesmus sp. Além disso, o FTIR permite análise simultânea de múltiplos metabolitos que permitirá o monitoramento mais detalhado do cultivo em um tempo de análise muito mais curto e com alta reprodutibilidade dos resultados. / With the discoveries of the numerous potential applications of microalgal biomass, it is necessary to develop tools to help increase the productivity of cultivation. Infrared spectrometry with Fourier transform (FTIR) is a versatile and fast technique used in the identification, characterization and quantification of several molecular compounds. Its application is defined according to the spectral region to be analyzed. The objective of this work is to develop a methodology that makes possible the use of FTIR spectroscopy in the medium infrared region (MIR) to quantify lipid, protein, carbohydrate and cells contents of Scenedesmus sp. For this, the Scenedesmus sp. biomass was analyzed daily by traditional methods and through the FTIR spectrum. Subsequently the data were correlated with the absorption bands characteristic of each compound. The model generated for lipids in the region between 3000-2800 cm-1 obtained the highest coefficient of correlation (R2) of 0.8265. For carbohydrates, the absorption band that best represented the characteristic bonds was between 1200-950cm-1, with R2=0.8023. For proteins, the choice of the traditional method did not show a good relation with the FTIR results. When the cell concentration was correlated whit the total area an R2=0.7900. Finally, experiments were carried out to validate the predicted models, obtaining good results for the quantification of lipids and carbohydrates. The FTIR shows to be an efficient tool to estimate lipid and carbohydrate contents of Scenedesmus sp. In addition, the FTIR allows simultaneous analysis of multiple metabolites that will enable more detailed monitoring of the cultivation in a much shorter analysis time and with high reproducibility of the results.