Com o crescimento populacional e aumento das atividades humanas, grandes quantidades de poluentes são despejadas diariamente no meio ambiente. Nos ecosssistemas aquáticos, organismos são expostos por longos períodos à baixas concentrações de contaminantes. Assim estudos que focam em novas metodologias que sejam rápidas e não invasivas, são necessários para a avaliação de efeitos subletais. Um exemplo é a espectroscopia no infravermelho com transformada de Fourier (FTIR). Esta técnica é capaz de detectar alterações macromoleculares em amostras biológicas de forma rápida e não destrutiva, sendo uma ferramenta atrativa para análises ecotoxicológicas. Assim, o objetivo deste estudo foi verificar a aplicabilidade do FTIR como metodologia alternativa, utilizando perfis de composição macromoleculares como indicadores de efeitos subletais, em organismos expostos a elementos-traço. Para tal, ostrácodes (Chlamydoteca sp.) foram expostos aos elementos Cu, Cd, Hg e Mn. As alterações em perfis biomoleculares foram avaliadas em ostrácodes expostos por 48h ao Mn. Os resultados revelaram uma correlação negativa entre concentração de exposição e proporção de ácidos graxos saturados e insaturados com relação à proteína em organismos expostos ao Mn e a mesma correlação foi observada para o conteúdo de ácidos nucléicos. Isto sugere que os organismos tiveram seu metabolismo lipídico e sua capacidade de produção de proteína celular alterados devido à exposição ao Mn. Ademais, foram realizados testes crônicos (9 dias) com ostrácodes expostos ao Cu, Cd, Hg e Mn. Foi observada a diminuição de lipídios saturados e insaturados em relação à proteína em organismos expostos ao Cd, sugerindo o uso de reservas lipídicas devido ao estresse fisiológico. Ostrácodes expostos ao Cu, tiveram o aumento dos ácidos nucléicos, no qual o DNA pode ter sido o componente dominante. Alterações significativas relacionadas ao conteúdo de carbonato de cálcio foram reveladas nos organismos expostos ao Cd e ao Cu, o que sugere mudanças na composição da carapaça e possível alteração na capacidade de muda e crescimento dos organismos. Portanto, este estudo permite concluir que a espectroscopia de FTIR é capaz de detectar indícios de efeitos subletais em organismos expostos a contaminantes e que as alterações de composição macromolecular são uma ferramenta complementar promissora para futuras avaliações ecotoxicológicas. / With population growth and increases in human activities, large amounts of pollutants are released daily into the environment. In aquatic ecosystems organisms are exposed for long periods at low concentrations of contaminants. Therefore, studies that focus on fast and non-invasive new methodologies are necessary for the assessment of sublethal effects in organisms. An example is the Fourier Transform Infrared Spectroscopy (FTIR). This technique can detect macromolecular changes of biological samples in a fast, inexpensive and non-destructive way, all of which lend to the attractiveness of this methodology for ecotoxicological analyzes. Thus, the aim of this study was to verify the applicability of FTIR as an alternative methodology, using the composition of macromolecular profiles as an indicator of sublethal effects in organisms exposed to trace elements. For this, ostracods (Chlamydoteca sp.) were exposed to the elements Cu, Cd, Hg and Mn. Changes in biomolecular profiles were evaluated in ostracods exposed for 48h to Mn. The results showed a negative correlation between the concentration of exposure and the proportion of saturated and unsaturated fatty acids for protein in organisms exposed to Mn and the same correlation was observed for the content of nucleic acids. This suggests that the organisms had their lipid metabolism and their cellular protein production capacity altered due to Mn exposure. In addition, four chronic tests (9 days) were performed on ostracods exposed to the trace elements Cu, Cd, Hg and Mn. A decrease in saturated and unsaturated lipids in relation to the protein was observed in organisms exposed to Cd, suggesting that the use of lipid reserves was due to the physiological stress. Ostracods exposed to Cu had an increase in nucleic acids, in which DNA may have been the dominant component. Significant changes related to the calcium carbonate content were revealed in the organisms exposed to Cd and Cu, which suggests changes in carapace composition and the possible alteration in the organism capacity of molting and growth. Therefore, this study concludes that FTIR spectroscopy can detect indications of sublethal effects in organisms exposed to contaminants and that changes in macromolecular composition are a promising complementary tool for future ecotoxicological assessments.

Os eletrocatalisadores PtRh/C foram preparados nas seguintes proporções atômicas: (100,0), (0,100), (90,10), (70,30) e (50,50). Os métodos empregados nas sínteses foram redução via borohidreto de sódio e redução por álcool. Os sais metálicos empregados foram H2PtCl6.6H2O e (RhNO3)3 e o suporte de carbono utilizado foi carbon Vulcan XC72, a composição metálica em massa foi de 20%; e o suporte, 80%. Os eletrocatalisadores foram caracterizados por técnicas físico-químicas, espectroeletroquímica e por experimento em célula a combustível, cujo emprego se deu por uma célula unitária direta a álcool com membrana alcalina. Os eletrodos de trabalho foram preparados pela técnica de camada fina porosa. A técnica de difração de raios X permitiu verificar ligas metálicas, fases segregadas e calcular a porcentagem de ligas metálicas, bem como constatar os tipos de fases cristalinas. A técnica de espectroscopia no infravermelho permitiu verificar que a oxidação eletroquímica do etanol se dá pelo mecanismo indireto de oxidação, ou seja, para todos materiais estudados houve a produção de espécies intermediárias, em que PtRh(70:30)/C sintetizado pelo médodo de redução via borohidreto de sódio produziu grandes quantidades de CO2 e C2H4O. Rh/C mostrou-se ativo eletroquimicamente para ambos os métodos de síntese empregados. A técnica de microscopia eletrônica de transmissão permitiu calcular o tamanho médio e a área superficial média dos eletrocatalisadores. As técnicas eletroquímicas permitiram verificar a estabilidade, potencial onset e pares redox dos sistemas considerados. / PtRh/C were prepared by the following atomic proportions: (100,0), (0,100), (90,10), (70,30) and (50,50). The methods employed in the synthesis of these materials were reduction by sodium borohydride and reduction by alcohol. The metal salts used were H2PtCl6.6H2O and (RhNO3)3, the support used was Carbon black XC72 and the bulk metal composition was 20% and 80% of support. The electrocatalysts were characterized by Energy Dispersive X-ray spectroscopy, X-ray diffraction and Transmission electron microscopy. The ethanol electrochemical oxidation mechanism was investigated by in situ Fourier Transform Infrared Spectroscopy couple to an Attenuated Total Reflection technique. The electrocatalytic activity were evaluated by Cyclic Voltammetry, Linear Sweep Voltammetry and Chronoamperometry techniques. The Fuel Cells tests were made in a single direct alcohol fuel cell with alkaline membrane. The working electrodes were prepared by a thin porous coating technique. X-ray diffraction allowed us to verify metallic alloys, segregate phases and to calculate the percentage of metallic alloys. It was else possible to identify crystallographic phases. Infrared Spectroscopy allowed us to verify that the electrochemical oxidation of ethanol was carried out by an incomplete mechanism. PtRh(70:30)/C prepared by sodium borohydride produced large amounts of carbon dioxide and acetaldehyde. Rh/C showed electrocatalytic activity when compared with other materials studied.

Hydroxyl terminated polybutadiene (HTPB) based polyurethanes (PUs) are low modulus materials and degrade easily at low temperature. Polycarbodiimide (PCDI) and polysiloxane (PSi) are reactive-type fillers when formed by carbodimidzation and sol-gel process, respectively. During the combustion, PCDI and PSi give off non-toxic, non-corrosive volatile gases, and finally form carbonaceous and siliceous chars. In this study, modified PUs were prepared by incorporating PCDI or PSi into PUs to give high carbon, nitrogen and silicon materials. These modified PUs are kinds of organic-inorganic hybrids with higher modulus and higher thermal stability than HTPB-based PUs. In addition, new silicone based insulation materials were prepared by mixing two silicone rubber materials LSR-2670 and RTV-627 from GE Silicones, in order to improve the heat insulation and to reduce the ablation rate. These inhibitors can keep the rocket motor from the high temperature ablation for a long time, especially castable silicone based heat insulations for the case of the ramjet engines. The mechanical properties at room temperature and the thermal stability of these modified PUs and silicone rubbers were investigated using a tensile tester and a thermogravimetric analyzer (TGA). ATR/FTIR (Attenuated total reflectance / Fourier transform infrared) technique is applied to monitor the synthesis process of PCDI and to examine the change of surface chemistry of insulator before and after thermal degradation via TGA. TGA coupled with FTIR (TGA/FTIR) was used to analyze the kinetics and the mechanism of thermal degradation under nitrogen and/or air. The Friedman and Kissinger methods of analysis were used for calculating the activation energy of degradation from dynamic TGA. The modified PUs (HIPTD-40%Psi¤ÎHIPTD-30%PMPS-PSi) with average activation energy of 88 and 112 kcal/mole (0.5¡Õ£\¡Õ0.9, under N2) and the modified silicone rubber (LR-5%HTB) with activation energy of 46.2~67.0 kcal/mole (0.1¡Õ£\¡Õ0.9, under N2) and 34.0~59.1 kcal/mole (0.1¡Õ£\¡Õ0.9, under air).The maximum degradation temperature (Tmax) and char yield (CY) of thermal degradation were estimated from a series of experiments with heating rates of 1, 3, 5, 10, 20, 30, 40 and 50 ¢J/min, under nitrogen or air. It is apparent that the maximum degradation temperature is dependent on heating rate. By assuming the heating rate for the insulator used in a rocket operating environment is about 5000¢J/min, Tmax calculated for the modified PUs (HIPTD-40%PSi and HIPTD-30%PMPS-PSi under N2) are found as 538 and 562¢J and for the modified silicone rubber (LR-5%HTB under N2 and air) are found as 576 and 562¢J, respectively. CY calculated for the modified silicone rubber (LR-5%HTB under N2 and air) is found as 71.5% and 66.2%. The morphology of modified PUs and silicone rubbers before and after thermal degradation via TGA was observed by optical and scanning electron microscope (SEM).

In this dissertation, the results of detailed investigation of the seven unique art objects are presented. The presented results show that complex apllying of the instrumental analytical methods of OM, FTIR, SEM/EDX, XRD, μXRD and µRS is accurate and efficient way to identify composition of works of art and archaeological finds of glass, pigments or describe their technology. IR spectroscopy has been successfully applied to determine pigments and some pigment mixtures in painting‘s ground, paint layers, and destruction products in archaeological glass. The SEM/EDX analysis successfully can be used in determining the main elements of the paint samples at different cross-section points perform a qualitative analysis of the pigments (cinnabar, lead white, chalk, smalt et. al. ), in some cases, to discuss the features of the production of pigments. The SEM/EDX provided a possibility to examine three archaeological glass beads. According to the elemental composition, microstructure, and the specific features in different areas of the glass was defined nature of the destruction of glass. XRD and μXRD analysis successfully can be used in determining the crystalline phases in the paint and archaeological glass samples. Identify following pigments and their mixtures: calcite CaCO3, carbon, lead tin yellow type I Pb2SnO4, lead tin yellow type II PbSn03, hydrocerussite 2PbCO3 ∙ Pb (OH)2, cerussite PbCO3, Egyptian blue CaCuSi4O10, gypsum CaSO4 ∙ 2H2O, anhydrite CaSO4, huntite Mg3Ca(CO3)4... [to full text] / Septynių unikalių, didelę istorinę ir meninę vertę turinčių objektų – trijų XVII ir XVIII a. paveikslų, Senovės Egipto sarkofago bei trijų archeologinių stiklo karolių iš Kernavės-Kriveikiškių kapinyno – tyrimams sėkmingai pritaikyti OM, FTIR, SEM/EDX, XRD, μXRD ir µRS analizės metodai. Konstatuota, kad taikant kompleksinius tyrimus galima tiksliai ir efektyviai identifikuoti kūrinių medžiagas, charakterizuoti jų sandarą, apibūdinti technologijas. IR spektroskopija sėkmingai panaudota identifikuojant tapybos grunto ir dažų sluoksnių neorganinius tapybos pigmentus ir jų mišinius bei stiklo korozijos produktus. Parodyta, kad IR spektroskopija gali būti sėkmingai panaudota identifikuojant istorines restauravimo medžiagas. SEM/EDX analizės metodu nustatyta tapybos elementinė sudėtis, identifikuoti cinoberio, švino baltojo, kreidos, smaltos, suriko ir kt. pigmentai. SEM/EDX analizės metodu ištirti trys archeologiniai stiklo karoliai. Pagal elementinės sudėties skirtumus ir specifinius mikrostruktūros bruožus nustatytas stiklo destrukcijos pobūdis. XRD ir μXRD analizės metodais sėkmingai identifikuoti šie pigmentai ir/ar jų mišiniai: kalcitas CaCO3, anglis, I tipo Pb–Sn geltonasis Pb2SnO4, II tipo Pb–Sn geltonasis PbSn03, hidrocerusitas 2PbCO3∙Pb(OH)2, cerusitas PbCO3, Egipto mėlynasis CaCuSi4O10, gipsas CaSO4∙2H2O, anhidritas CaSO4, huntitas Mg3Ca(CO3)4, dolomitas CaMg(CO3)2. Pirmą kartą μRS metodu identifikuotas II tipo švino alavo geltonasis pigmentas, archeologiniam stiklui... [toliau žr. visą tekstą]

Septynių unikalių, didelę istorinę ir meninę vertę turinčių objektų – trijų XVII ir XVIII a. paveikslų, Senovės Egipto sarkofago bei trijų archeologinių stiklo karolių iš Kernavės-Kriveikiškių kapinyno – tyrimams sėkmingai pritaikyti OM, FTIR, SEM/EDX, XRD, μXRD ir µRS analizės metodai. Konstatuota, kad taikant kompleksinius tyrimus galima tiksliai ir efektyviai identifikuoti kūrinių medžiagas, charakterizuoti jų sandarą, apibūdinti technologijas. IR spektroskopija sėkmingai panaudota identifikuojant tapybos grunto ir dažų sluoksnių neorganinius tapybos pigmentus ir jų mišinius bei stiklo korozijos produktus. Parodyta, kad IR spektroskopija gali būti sėkmingai panaudota identifikuojant istorines restauravimo medžiagas. SEM/EDX analizės metodu nustatyta tapybos elementinė sudėtis, identifikuoti cinoberio, švino baltojo, kreidos, smaltos, suriko ir kt. pigmentai. SEM/EDX analizės metodu ištirti trys archeologiniai stiklo karoliai. Pagal elementinės sudėties skirtumus ir specifinius mikrostruktūros bruožus nustatytas stiklo destrukcijos pobūdis. XRD ir μXRD analizės metodais sėkmingai identifikuoti šie pigmentai ir/ar jų mišiniai: kalcitas CaCO3, anglis, I tipo Pb–Sn geltonasis Pb2SnO4, II tipo Pb–Sn geltonasis PbSn03, hidrocerusitas 2PbCO3∙Pb(OH)2, cerusitas PbCO3, Egipto mėlynasis CaCuSi4O10, gipsas CaSO4∙2H2O, anhidritas CaSO4, huntitas Mg3Ca(CO3)4, dolomitas CaMg(CO3)2. Pirmą kartą μRS metodu identifikuotas II tipo švino alavo geltonasis pigmentas, archeologiniam stiklui... [toliau žr. visą tekstą] / In this dissertation, the results of detailed investigation of the seven unique art objects are presented. The presented results show that complex apllying of the instrumental analytical methods of OM, FTIR, SEM/EDX, XRD, μXRD and µRS is accurate and efficient way to identify composition of works of art and archaeological finds of glass, pigments or describe their technology. IR spectroscopy has been successfully applied to determine pigments and some pigment mixtures in painting‘s ground, paint layers, and destruction products in archaeological glass. The SEM/EDX analysis successfully can be used in determining the main elements of the paint samples at different cross-section points perform a qualitative analysis of the pigments (cinnabar, lead white, chalk, smalt et. al. ), in some cases, to discuss the features of the production of pigments. The SEM/EDX provided a possibility to examine three archaeological glass beads. According to the elemental composition, microstructure, and the specific features in different areas of the glass was defined nature of the destruction of glass. XRD and μXRD analysis successfully can be used in determining the crystalline phases in the paint and archaeological glass samples. Identify following pigments and their mixtures: calcite CaCO3, carbon, lead tin yellow type I Pb2SnO4, lead tin yellow type II PbSn03, hydrocerussite 2PbCO3 ∙ Pb (OH)2, cerussite PbCO3, Egyptian blue CaCuSi4O10, gypsum CaSO4 ∙ 2H2O, anhydrite CaSO4, huntite Mg... [to full text]

When microalgae are exposed to changing environmental conditions, e.g., light-dark cycles or oscillations in nutrient availability (CO2, nitrogen, phosphate or silicate) they respond with metabolic changes in the carbon allocation pattern. Short time regulations in the time range of few seconds to minutes can be mirrored best by mass spectroscopy based metabolomics. However, these snap shots do not reflect the alterations in the carbon flow to the cellular macromolecules like protein, carbohydrate or lipid. In this review it is shown how the combination of FTIR spectroscopy and Chla-in-vivo-fluorescence based electron transport rates can reveal changes in the metabolic flux rates of carbon during a shift of the environmental conditions. The review will demonstrate in which time range FTIR spectroscopy can deliver significant information and how FTIR spectroscopy data can synergistically support metabolome analysis by mass-spectroscopy.

The solvent-solute interface of a biomolecule is a dynamic but yet highly structured domain that links a chemically diverse solute surface to the chemically homogeneous bulk aqueous phase. The role of the resulting intermediate domain, i.e. the "hydration shell", in regulating DNA structure and recognition has been addressed here by time-resolved infrared spectroscopy. A highly reproducible automated hydration pulse regime was established and implemented for attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy to monitor the structural response of DNA to an incremental growth of its hydration shell on its intrinsic time scale of seconds. The transition from the crystallographically defined BI to the BII substate of B-DNA was found to be driven by the increase of water disorder upon growth of the hydration shell, derived from the water OH-stretching absorption frequency and band width changes. 2D correlation analysis was used to identify different water clusters from the temporal behaviour of their water OH stretching frequencies. The results show that BII-stabilizing structural constraints are exerted by strong water-DNA H-bonds in the grooves of B-DNA and are relieved when the groove-bound water merges into a contiguous hydration shell with the less H-bonded PO2- -solvation sphere at ~14 water molecules per DNA phosphate. The H-bond imbalance at the disjunct hydration sites is split symmetrically around the average H-bond strength of bulk water. Thus, merging into a contiguous hydration shell proceeds at little enthalpic cost and homogeneous connectivity to the outer bulk-like H-bond network, such that alteration in the network distant from the DNA can regulate the BI-BII transition in a cooperative manner. The water connectivity is disrupted by DNA-binding peptides. Remarkably, the data show that the replacement of hydration shell water upon ligand biding is crucial in conferring substate specific recognition by peptides that have little intrinsic structural preference. The antibacterial peptide indolicidin secreted from bovine neutrophils dehydrates the non-PO2--bound hydration sites, thereby rendering the unstructured peptide highly specific for the BI state with vibrational signature almost identical to the bacterial minor groove binder netropsin. The proposed dominant role of hydration shell water for DNA conformation was challenged by studying the competing effect of structured water in the coordination-shell of the lanthanide Eu3+ on water structure in the DNA hydration shell. Whereas no effect is seen at low hydration, a hydrogen-like phase is formed at a stoichiometric ratio of Eu3+ :DNA:H2O of 1:10:140, characterized by a strong increase of the molar volume of hydration water. This novel phase appears attractive for lanthanide and possibly actine separation approaches based on biomolecular coordination.

O objetivo deste estudo foi avaliar, in vitro, o efeito das soluções irrigadoras quitosana a 0,2%; hipoclorito de sódio a 1% e EDTA a 17% na superfície dentinária e na interface de união da dentina/material obturador resinoso. Sessenta fragmentos de dentina, obtidos de 10 caninos superiores humanos, com 4 mm2 de área foram distribuídos em quatro grupos (n=15) de acordo com o tratamento: G1 NaOCl + EDTA + NaOCl, G2 NaOCl + Quitosana + NaOCl, G3 Quitosana + Quitosana + Quitosana, G4 Quitosana + EDTA + Quitosana. As amostras foram imersas por 6 minutos na primeira solução irrigadora (Tempo 1), 3 minutos na segunda (Tempo 2) e 1 minuto na terceira (Tempo 3), simulando o tratamento endodôntico. Foi analisada a composição orgânica e inorgânica das amostras por meio da Espectroscopia Infravermelha por Transformada de Fourier (FTIR) após cada etapa de irrigação. Para segunda fase, 24 caninos superiores humanos, divididos em 4 grupos (n=6), tiveram suas coroas cortadas e as raízes instrumentadas mecanicamente com instrumentos K3 até o instrumento 60.04, irrigadaos com NaOCl a 1% e Quitosana a 0,2% durante o preparo e EDTA a 17% e Quitosana a 0,2% como irrigação final. As amostras foram cortados longitudinalmente para análise do número e do perímetro dos túbulos expostos nos diferentes tempos e a rugosidade da superfície antes (baseline) e após cada fase do tratamento, além da penetração do cimento endodôntico, e avaliação da interface material obturador/dentina, após a obturação (Tempo 3), por meio de microscopia confocal a laser. Os dados foram analisados pela ANOVA e pós-teste de Tukey (p<0,05). Por meio do FTIR, constatou-se que o G4 apresentou maiores valores de matéria orgânica quando comparado aos outros grupos (p<0,05), e foram observados maiores valores para o T3 quando comparado ao T0. Quanto aos valores de matéria inorgânica, o G1 apresentou valores superiores (p<0,05) aos G2 e G3. Não houve diferença quando comparado os tempos para o conteúdo inorgânico (p>0,05). O terço apical apresentou maior valores de conteúdo inorgânico quando comparado aos demais (p<0,05). Por meio do confocal, observou-se que apenas o G3 apresentou maiores valores de perímetro dos túbulos com diferença em relação ao G1,(p<0,05), que o T2 apresentou valores semelhantes ao T1 (p>0,05), e não houve diferença entre os terços radiculares. Na análise da contagem dos túbulos dentinários, observa-se que o G4 apresentou maiores valores, semelhantes ao G3 (p>0,05). O T2 apresentou os maiores valores e o T0 os menores (p<0,05), e o terço cervical apresentou maiores valores em relação aos demais (p<0,05). Na análise da rugosidade, não houve diferença entre os grupos, e nem entre os terços radiculares (p>0,05), sendo que o T0 apresentou maiores valores, com diferença em relação ao T1 e T2 (p<0,05). Na análise da interface material obturador/dentina, não houve diferença entre os grupos, e o terço apical apresentou menor extensão de tags formados (p<0,05). A Quitosana como solução irrigadora produziu efeitos favoráveis na dentina radicular sem afetar a interação do substrato com o cimento endodôntico. / The aim of this study was to evaluate, in vitro, the influence of irrigation solutions, used during instrumentation of root canals - chitosan at 0.2%; 1% sodium hypochlorite and 17% EDTA - on dentin, by means of Fourier Transform Infrared Spectroscopy (FTIR) and laser confocal microscopy. Sixty dentin fragments, obtained from 10 human canines, with 4 mm2 area were distributed in four groups (n = 15) according to the treatment: G1 NaOCl + EDTA + NaOCl, G2 NaOCl + Chitosan + NaOCl, G3 Chitosan + Chitosan + Chitosan, G4 Chitosan + EDTA + Chitosan. The samples were immersed for 6 minutes in the first irrigation solution (Time 1), 3 minutes in the second (Time 2) and 1 minute in the third (Time 3), simulating the endodontic treatment. The organic and inorganic composition of the samples were analyzed by Fourier Transform Infrared Spectroscopy (FTIR) after each irrigation step. In a second phase, 24 teeth were divided into 4 groups (n = 6), cut longitudinally to analyze the number and perimeter of the exposed tubules at different times, the surface roughness before and after each treatment phase. The penetration of the endodontic sealer, and evaluation of the dentin interface, after the obturation (Time 3), by laser confocal microscopy. Data were analyzed by ANOVA and Tukey post hoc test (p<0.05). Using FTIR, G4 presented higher values of organic content when compared to the others groups (p <0.05), and higher values were observed for T3 when compared to T0. There was no difference when comparing the times for the inorganic content (p> 0.05). The apical third had higher values of inorganic content when compared to the others (p <0.05). With the aid of the confocal analysis, it was observed that only G3 presented higher values of tubule perimeter with difference in relation to the G1, (p <0.05), that T2 presented values similar to T1 (p> 0.05), And there was no difference between the root thirds. In the analysis of the dentinal tubule count, it was observed that G4 presented higher values, similar to G3 (p> 0.05). The T2 presented the highest values and T0 the lowest (p <0.05), and the cervical third had higher values compared with the others (p <0.05). Regarding the analysis of roughness, there was no difference between the groups, nor between the root thirds (p> 0.05), and the T0 presenting higher values compared with T1 and T2 (p <0.05). In the analysis of the dentin interface, there was no difference between the groups, and the apical third had a smaller extension of the formed tags (p <0.05). Chitosan produced less chemical changes in root dentin when compared to the other solutions.

Les particules de suie émises par les moteurs d'avion influencent le climat en absorbant/diffusant la lumière solaire. Elles agissent aussi comme noyaux glaciogènes dans l’atmosphère en participant à la formation des traînées de condensation et des cirrus artificiels, ce qui augmente la nébulosité et affecte l'équilibre radiatif de l'atmosphère. Dans les zones aéroportuaires, elles contribuent à la dégradation de la qualité de l’air et peuvent affecter la santé humaine. Connaître leurs propriétés physico-chimiques est donc primordial pour évaluer leurs impacts environnementaux, sanitaires et agir pour leur réglementation. Nous avons caractérisé les propriétés physiques et chimiques de suies émises par un turboréacteur SaM146-1S17 alimenté avec du kérosène JET A-1 et fonctionnant à différents régimes, dont le régime de croisière. Des informations précises sur leur morphologie, leur (nano)structure, leur composition/spéciation chimique ont été obtenues par microscopie électronique à transmission (TEM), spectroscopie infra-rouge (FTIR), spectroscopie d'absorption des rayons X (NEXAFS) et photoémission X (XPS). Ces techniques ont également permis de caractériser des suies de laboratoire produites par un générateur commercial (miniCAST, Jing Ltd.) et de montrer qu’il permet de générer de bons analogues des suies aéronautiques. La production de quantités importantes de ces analogues aux propriétés physico-chimiques contrôlées offre de nouvelles perspectives quant à l’étude en laboratoire de la réactivité des suies aéronautiques vis-à-vis des environnements atmosphériques et biologiques, permettant d’améliorer notre compréhension de leurs impacts environnementaux et sanitaires. / Soot particles emitted from aircraft engines influence climate by absorbing and scattering sunlight. They also act as ice condensation nuclei in the atmosphere by participating to the formation of condensation trails and artificial cirrus clouds that increase the cloudiness and affects the radiative balance of the Earth’s atmosphere. In airport areas, they contribute to the degradation of air quality and can affect human health. Knowing their physical and chemical properties is therefore of prime importance to assess their environmental and health impacts as well as acting for their regulation. We have characterized physical and chemical properties of soot emitted by a SaM146-1S17 turbofan engine fueled with kerosene JET A-1 and operated at different regimes, including the cruise regime. Accurate information about their morphology, (nano)structure, chemical composition/speciation have been obtained by transmission electron microscopy (TEM), infrared spectroscopy (FTIR), Near-Edge X-ray Absorption Fine Structure (NEXAFS) and X-Ray Photoelectron Spectroscopy (XPS). These techniques have also been used to characterize laboratory soot produced by a commercial generator (miniCAST, Jing Ltd.) and to show that it can generate relevant analogues of aeronautic soot. The production of large amounts of these analogues with controlled physico-chemical properties offers new prospects for laboratory studies of aeronautic soot’s reactivity with respect to atmospheric and biological environments aiming at improving our understanding of their environmental and health impacts.

Esta dissertação de mestrado aborda dois estudos que foram desenvolvidos utilizando a técnica de microscopia FTIR (micro-FTIR): a reatividade do grafeno funcionalizado e a eletroquímica in-situ com micro-FTIR para avaliação de reações redox. A reatividade e a distribuição de cargas em materiais 2D, mais especificamente em folhas individuais de grafeno, têm sido alvo de muita investigação na última década. No entanto, ainda não é conhecido como elas se apresentam em grafeno com grandes áreas, uma vez que a maioria dos estudos utilizam áreas muito pequenas (~&mu;m2). Neste estudo, investigou-se experimentalmente como um eletrodo formado por uma única folha de grafeno se comporta quando sua estrutura é alterada por funcionalização covalente. Utilizando microespectroscopia na região do infravermelho, avaliou-se a funcionalização de grafeno com unidades de ácido benzoico no grafeno ancorados eletroquimicamente. O mapeamento químico mostrou que a distribuição espacial dessas unidades não ocorre uniformemente, ao invés disso, existem pontos específicos de ancoramento. Por fim, observou-se que a funcionalização ocorre mais intensamente na borda da folha de grafeno, alterando as propriedades óticas e eletroquímicas deste material, reduzindo o ganho ótico proporcionado pelos plásmons e aumentando a resistência de transferência heterogênea de elétrons. Para o segundo capítulo dessa dissertação, aplicou-se a microespectroscopia FTIR multiplex ao estudo da mudança química de um eletrodo de ouro modificado com azul da prússia (AP). Para isso, observou-se que uma etapa limitante era a confecção de um porta-amostra que reduzisse a camada de eletrólito ao mínimo de forma que a água não mais absorvesse a radiação de forma majoritária. Logo, foi possível o estudo vibracional de vários pontos da superfície do eletrodo, observando-se a influência do potencial aplicado, onde tem-se uma grande dependência dos sinais referentes ao estiramento C&equiv;N do AP com a condição de potencial imprimida no eletrodo. / This Masters dissertation approaches two studies developed using the FTIR microspectroscopy technique (micro-FTIR): the activity of graphene functionalized and the in-situ electrochemistry with micro-FTIR for the evaluation of redox reactions. Reactivity and charge distribution in 2D materials, especially in single graphene sheets, have been the focus of extensive investigation during the last decade. However, there is still no knowledge on how large-area graphene behaves, since most of the studies utilize too small areas (~&mu;m2). In this study, we aim to investigate experimentally how an electrode composed of only one single sheet of graphene behaves when its structure is changed by covalent functionalization. Using infrared microspectroscopy, the electrochemically induced covalent functionalization of graphene with benzoic acid unities was evaluated. The chemical mapping showed that the spatial distribution of these unities does not occur uniformly, instead, there are specific anchoring points. Lastly, it was observed that the functionalization occurs more intensely on the edges of the graphene sheet and that the covalent, affecting its optical and electrochemical properties, reducing the optical gain provided by the plasmons and increasing the resistance of heterogeneous electron transfer. In the second chapter of this dissertation, multiplex FTIR microspectroscopy was applied to the study of the chemical changes of a gold electrode modified with Prussian blue (PB). It was observed that the limiting step for this type of analysis was the building of a sample holder that reduces the electrolyte layer to the minimum in a way that water did not absorb the radiation in majority. Therefore, a vibrational study of several points of the electrode surface was possible evaluating the influence of the applied potential, where there is a dependence of the signals related to the C&equiv;N stretching mode from PB on the potential condition applied to the electrode.