Recentes avanços nas ciências médicas têm contribuído significativamente para que novas tecnologias de materiais e processos tecnológicos ganhem espaço. No âmbito da esterilização de materiais poliméricos termossensíveis, empregados na fabricação de ampla gama de produtos médico-hospitalares, os processos que operam sob temperaturas compatíveis com estes materiais, gás óxido de etileno e radiação ionizante, agregam desvantagens importantes envolvendo, respectivamente, aspectos de toxicidade ocupacional, ambiental e ao paciente, bem como alterações intrínsecas aos mesmos. O processo inovador e potencialmente compatível por gás plasma representa promissora alternativa, onde o agente letal agrega entidades altamente reativas provenientes de gás ionizado por aplicação de descarga elétrica e originalmente desprovido de atividade microbicida. O presente trabalho teve por objetivo proceder a estudos que permitam conhecimento da eficácia esterilizante de processos empregando plasma de O2 puro e sua mistura com H2O2 em produtos médico-hospitalares de natureza polimérica, configuração tubular, longa extensão e calibre reduzido. Os lumens desses materiais foram preenchidos com suportes vítreos (lamínulas de 8 x 18mm) intencionalmente contaminados com biocargas restritas de Bacillus subtilis var. niger ATCC 9372, que atuaram como biosensores, constituindo os monitores biológicos. Esses dispositivos foram submetidos a ciclos por plasma sob distintas combinações de parâmetros envolvendo distintos sistemas (RIE e ICP), potências de rádio-freqüência e tempos de exposição sub-letais. Após os ciclos esterilizantes, os monitores biológicos foram abertos e submetidos à análise microbiológica para a enumeração de possíveis esporos sobreviventes, usando o método do número mais provável (NMP), possibilitando o cálculo dos valores D (principal parâmetro de resistência de uma população microbiana). Adicionalmente, foram objeto de investigação polímeros distintos utilizados na confecção de produtos médico-hospitalares, a fim de esclarecer a influência do plasma sobre as características intrínsecas desses materiais. Foram selecionados o poli (cloreto de vinila) - PVC, polietileno de alta densidade (HDPE), polipropileno (PP), poliuretano (PUR) e policarbonato (PC). As amostras foram expostas em ambos sistemas de plasma (RIE e ICP) usando gás O2 puro e sua mistura gasosa O2/H2O2, potências de RF de 150W e 300W e tempo de exposição de 30 min. As amostras foram submetidas a espectroscopia fotoacústica no infravermelho, microscopia eletrônica de varredura, microanálise e perfilometria a fim de avaliar possíveis danos aos polímeros expostos, assim como citotoxicidade in vitro para esclarecer sobre a biocompatibilidade dos mesmos. Os resultados demonstraram que a eficácia esterilizante do plasma foi dependente do calibre dos monitores biológicos e das potências de RF aplicadas. Os menores valores D foram obtidos para os monitores biológicos de maior calibre (7mm) e potências de 150W/300W em ambos sistemas RIE e ICP, respectivamente. A mistura gasosa O2/H2O2 apresentou maior efeito microbicida quando comparada ao O2 puro em ambos sistemas de plasma. Paralelamente, a exposição ao plasma levou à modificação em nível superficial (oxidação e aumento da rugosidade) para todos os polímeros expostos. Foi observado efeito mais agressivo quando usando plasma gerado em sistema ICP usando mistura gasosa O2/H2O2. Os dados sugerem que a massa interna ou bulk de todos as amostras não foi afetada, assim como as alterações observadas não promoveram modificação na biocompatibilidade dos polímeros estudados. / The sterilization of heat sensitive materials like medical devices made of polymers has been under intense investigation regarding new technologies and sterilization agents, as far as mechanical problems and innocuity of currency processes such as ionizing radiation and ethylene oxide gas, respectively, are concerned. Plasma sterilization of medical devices is emerging as an attractive substitute to conventional sterilization technologies, once is recognized as an atoxic and low-temperature process. It uses different gases that are activated by an electrical discharge, generating reactive species which promote lethal effect on microorganisms. In this work, it was performed experimental studies to evaluate the sterilization effectiveness of pure O2 and O2/H2O2 mixture gas plasma against a standard load of 103 Bacillus subtilis var. niger ATCC 9372 spores inoculated on 8 x 18mm glass carriers placed inside and in central position of PVC catheters 64cm long with internal diameters of 7mm and 1mm. These assemblages simulated the challenge of medical devices as biological monitors. The gas plasma sterilization efficiency was studied as a function of plasma systems (RIE and ICP), radio frequency powers and sub-lethal exposition times. After sterilization, the biological monitors were disassembled and the survivors were growth in trypticase soy broth using the most probable number (MPN) technique. Hence, it was possible to calculate the time D required to decrease a given population by a factor of 10 (90% reduction). On the other hand, there was a need to evaluate the safety of plasma sterilization in terms of polymer damage. Materials used in this study were: polyvinylchloride (PVC), high density polyethylene (HDPE), polypropylene (PP), polyurethane (PUR) and polycarbonate (PC). Samples were exposed to pure O2 and O2/H2O2 plasma sterilization using both plasma systems (RIE and ICP), radio frequency powers of 150W/300W and exposition time of 30 minutes. Fourier transform infrared photoacoustic spectroscopy (FT-IR/PAS), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and profilometry, which are surface and bulk characterization techniques, were used to study plasma sterilization polymers compatibility, as well as \"in vitro\" citotoxicity to acess the biocompatibility of exposed polymers. The results demonstrated that plasma antimicrobial activity depended on the inside catheters diameter and radio frequency powers. The smallest D values were obtained when using biological monitors of 7mm of internal diameter and 150W/300W of RF powers, in, respectively, RIE/ICP systems. The mixture O2/H2O2 exhibited higher microbicidal efficacy than pure O2 in both plasma systems. In addition, both plasma systems led to near-surface layers modification, with the increase of roughness and surface oxidation of all the polymers studied. ICP system and O2/H2O2 mixture were more effective to induce the surface modifications observed. The bulk of all polymers showed not to be affected by all plasma conditions used and the surface alterations did not affected the biocompatibility of all the polymers studied.

A ocorrência de monofluoroacetato de sódio (MFA-Na) em plantas foi registrada, pela primeira vez, em Dichapetalum cymosum. Posteriormente, esta substância tóxica foi encontrada em outras espécies de plantas, como Palicourea marcgravii, causadora de morte súbita. Amorimia rigida, que é bastante conhecida e frequente no Nordeste do Brasil, está entre as plantas tóxicas, que também causam morte súbita em bovinos, com quadro clínico semelhante ao decorrente da ingestão de plantas que contém fluoroacetato de sódio e ao apresentado por animais intoxicados experimentalmente com este tóxico. À A. rigida são imputadas significativas perdas econômicas, motivo pelo qual o objetivo do presente estudo foi identificar a substância tóxica nela presente e também estabelecer bioindicadores de efeito, quando da intoxicação por esta planta. No estudo por cromatografia em camada delgada de celulose - tendo como fase móvel solução de etanol/hidróxido de amônio/piridina/água (95:3:1:1, v/v/v/v) e como agente derivatizante o azul do Nilo - do extrato aquoso obtido da planta seca e moída, foi detectada a presença de MFA-Na. O fracionamento do extrato hidroalcoólico de A. rigida em coluna XAD-2 forneceu 4 frações: H2O 100% (F1), H2O:MeOH 80/20 (F2), H2O:MeOH 40/60 (F3) e MeOH 100% (F4) das quais, como indicado pelo monitoramento por CCDC, apenas a fração F1 continha o MFA-Na. Essa fração foi submetida à cromatografia em camada delgada preparativa, para isolamento do princípio ativo o qual, em estudo por espectrometria de infravermelho e em comparação com padrão de MFA-Na, comprovou a presença de mistura de mono, di e trifluoroacetato nas folhas desta planta. No estudo bioquímico, animais intoxicados com o padrão de MFA-Na e com o extrato de A. rigida apresentaram alterações nos níveis séricos de cálcio e citrato, sendo estas moléculas consideradas bioindicadoras de efeito a exposição ao MFA-Na. / The first occurrence of sodium monofluoroacetate in plants was reported in Dichapetalum cymosum. Further, this toxic substance was found in other plant species, as Palicourea marcgravii, which causes \"sudden death\". Amorimia rigida, which is well known and frequent in northeastern Brazil, it is among the poisonous plants that have identical lethal effects in cattle to that caused by the ingestion of plants containing sodium fluoroacetate. These intoxication signs are the same that ones presented by experimentally poisoned animals with this toxic. Significant economic losses can be imputed to A. rigida, therefore our aim was to identify its toxic compound and also to establish its biomarkers of effect. The study by cellulose thin layer chromatography using as mobile phase solution of ethanol /ammonium hydroxide/pyridine/water (95:3:1:1, v/v/v/v) and Nile blue as the derivatizing agent - of the aqueous extract of milled dried plant showed the presence of MFA-Na. The fractionation of the hydroalcoholic extract of A. rigida by XAD-2 column chromatography gave four fractions: 100% H2O (F1), H2O: MeOH 80/20 (F2) H2O: MeOH 40/60 (F3) and 100% MeOH (F4); only F1 fraction contained MFA-Na, according to CCDC monitoring. This fraction was subjected to preparative thin layer chromatography, in order to isolate the toxic principle which, in a study by infrared spectroscopy and by comparison with standard MFA-Na, confirmed being a mixture of mono-, di and trifluoroacetate. In the biochemical study, animals intoxicated by MFA-Na and by A. rigida extract showed serum calcium/citrate imbalances; such alterations may be considered biomarkers of MFA-Na exposure effect.

É notório o fato de que o interesse pela detecção de vida fora da Terra tenha aumentado no mundo científico. A existência de possíveis traçadores biológicos na atmosfera terrestre, a presença de material vivo ou de material orgânico decomposto em superfícies e no mar aumentam as possibilidades de sucesso das pesquisas. A vida na Terra é encontrada em todas as partes, e o planeta está saturado de suas manifestações. O objetivo da presente tese é o desenvolvimento de uma metodologia que ofereça ideias para a detecção de bioassinaturas fora da Terra, particularmente em exoplanetas. Em termos de biologia molecular, a principal assinatura de vida é o DNA (ácido desoxirribonucleico), que organiza e sedia o código genético de todos os seres vivos. Outras moléculas que denunciam a presença de vida são a clorofila, carotenoides, fragmentos de DNA, moléculas orgânicas, etc. Na tentativa de se encontrar bioassinaturas na atmosfera de exoplanetas, um requisito deve ser atendido: a identificação de bandas características que permitam a detecção de um sinal que esteja associado a uma biomolécula complexa, preferencialmente na região do infravermelho, vista em meio aos picos de gases atmosféricos. Sendo assim, uma série de análises espectrais foram realizadas para amostras de DNA/células do micro-organismo extremófilo Halobacterium salinarum, com a finalidade de serem comparadas ao espectro infravermelho, obtido de forma direta da atmosfera terrestre. A pesquisa por marcadores específicos foi realizada a fim de determinar os picos que permitam a detecção desses componentes singulares quando suspensos em gases atmosféricos. Os resultados da pesquisa mostram que a atmosfera terrestre está contaminada com moléculas complexas. Existem 37 absorções em comum quando se compara o espectro da atmosfera terrestre com os espectros de células ou DNA (por exemplo 966, 936, 924, 886 e 866 cm-1). Entre elas, os picos centrados em aproximadamente 1018, 996, 900 e 840 cm-1, denunciam a presença de estruturas biogênicas ligadas à presença de ácidos nucleicos (riboses e grupos fosfatos). Investigou-se, também, a possibilidade de certas assinaturas biológicas serem mascaradas pela presença de gases quando observadas remotamente. A conclusão é que as bandas de gases como o SO2 (1136 cm-1), O3 (1042 e 1124 cm-1) e C2H6 (826 cm-1), podem tornar a detecções de algumas bioassinaturas uma tarefa árdua e até mesmo impossível. Outras perguntas de pesquisa ligadas à determinação da quantidade mínima de material biológico capaz de oferecer um sinal que possa ser identificado e atribuído a um material biológico específico, assim como a possibilidade de determinação de uma banda de absorção apta a servir como fator de calibração foram abordadas. Conclui-se que há possibilidades de se detectar alguma característica biológica mesmo após diluições cobrindo 5 ordens de magnitude (variação de 760 a 0.076 ng/µl). A banda centrada em 893 cm-1 pode ser utilizada para futuras calibrações, pois responde linearmente com a variação da quantidade de material biológico. O resultado da pesquisa mostrou que existem bandas moleculares em comum entre a atmosfera e o material biológico, sendo atribuídas a potenciais marcadores moleculares que, possivelmente, poderão ser detectados de forma remota em futuras missões espaciais. / It is notorious that interest in detecting life beyond Earth has increased in the scientific world. The existence of possible biological markers the terrestrial atmosphere, the presence of living material or organic material decomposed on surfaces and at the sea increase the chances of success of the research. Life on Earth is everywhere and the planet is saturated with its manifestations. The objective of this thesis is the development of a methodology that offers ideas for the detection of bioassinatures outside the Earth, particularly in exoplanets. In terms of molecular biology, the main signature of life is DNA (desoxyribonucleic acid), which organizes and hosts the genetic code all of the living things. Other molecules that denounce the presence of life are chlorophyll, carotenoids, DNA fragments, organic molecules, etc. In an attempt to find bioassinatures in the atmosphere of exoplanets, a requirement must be met: the identification of characteristic bands that allow the detection of a signal associated with a complex biomolecule, preferably in the infrared region, seen in the middle of the peaks of gases atmospheric conditions. Thus, a series of spectral analyzes were performed for DNA samples/cells of the extremophilic microorganism Halobacterium salinarum, to be compared to the infrared spectrum obtained directly from the Earths atmosphere. The search for specific markers was performed in order to determine the peaks that allow the detection of these singular components when suspended in atmospheric gases. The results of the research show that the Earths atmosphere is contaminated with complex molecules. There is a total of 37 common absorptions found in the spectrum of the Earths atmosphere and in Cells or DNA spectra (for example 966, 936, 924, 886 and 866 cm-1). Among them, the peaks centered at approximately 1018, 996, 900 and 840 cm-1, denote the presence of biogenic structures linked to the presence of nucleic acids (riboses and phosphate groups). It was also investigated the possibility of certain biological signatures being masked by the presence of gases when observed remotely. The conclusion is that gas bands such as SO2 (1136 cm-1), O3 (1042 and 1124 cm-1) and C2H6 (826 cm-1) can make the detection of some bioassinatures a difficult task. Other research questions related to the determination of the minimum quantity of biological material can providing a signal capable of being identified and assigned to a specific biological material, as well as the possibility of determining an absorption that could a serving as a calibration factor were addressed . It is concluded that it is possible to detect a same biological characteristic after dilutions covering 5 orders of magnitude (ranging from 760 to 0.076 ng/µl). The band centered at 893 cm-1 can be used for future calibrations because it responds linearly with the variation of the amount of biological material. The research results showed that there are molecular bands in common between the atmosphere and biological material and are attributed to potential molecular markers that may possibly be detected remotely in future space missions.

In the anthropological analysis of burned bone, the presence of a white heat line aids in determining a bone’s physical condition prior to burning, distinguishing between those burned fleshed or wet versus dry. However, while the relationship between this thermal signature and a bone’s physical condition has been studied, there is a lack of research concerning the chemical composition of white heat lines. The present study assessed the composition of white heat lines that form on burned bone using Fourier transform infrared spectroscopy (FTIR) with the potassium bromide (KBr) pellet method. The present study examined the effects of soft tissue and the retention of bone’s organic material, including naturally-occurring grease and water, on the development and appearance of a white heat line. Experimental remains consisted of isolated long bones from white-tailed deer (Odocoileus virginianus), elk (Cervus canadensis), sheep (Ovis aries), and pig (Sus scrofa) in five physical conditions – fleshed (fresh bones with adhering soft tissue), very wet (recently defleshed bone, greasy), partially wet (defleshed, slight grease retention), dry (defleshed, naturally degreased), and soaked (formerly dry bone immersed in water). These bones were burned over a wood fire made within a 55-gallon drum. After a visual analysis to evaluate white heat line formation, chemical composition was analyzed by determining spectral peak heights of the carbonate (CO3) ν3 (1415 cm-1), phosphate (PO4) ν3 (1035 cm-1), and amide I (1660 cm-1) vibrational bands. These thermal signatures appear to form superficially, measuring approximately 1.5 mm in depth. Results indicate that white heat lines that formed on fleshed bone contain an increased amount of CO3, PO4, and amide I in comparison to their unburned controls, while those that formed on very wet bone contain decreased amounts instead. These findings further our knowledge of how fire modifies physical remains and the effect that bone’s physical condition prior to burning has on the development of a white heat line and the resulting compositional changes. In order to build upon the results gained from the present study, continuing research is needed to investigate compositional differences between white heat lines that form on fleshed versus very wet bone and to assess bone’s fat content as a possible contributing factor. Additional FTIR research is needed to assess the other vibrational bands of CO3, PO4, and amide that are present in bone.

Children who struggle to learn math are often identified by their poor performance on common math learning activities, such as number line estimations. While such behavioral assessments are useful in the classroom, naturalistic neuroimaging of children engaged in real-world math learning activities has the potential to identify concurrent behavioral and neurological correlates to poor math performance. Such correlates may help pinpoint effective teaching strategies for atypical learners, and may highlight instructional methods that elicit typical neurological response patterns to such activities. For example, multisensory stimulation that contains information about number enhances infants' and preschool children's behavioral performance on many numerical tasks and has been shown to elicit neural activation in areas related to number processing and decision-making. Thus, when applied to math teaching tools, multisensory stimulation may provide a platform through which both behavioral and neural math-related processes may be enhanced. Common approaches to neuroimaging of math processing lack ecological validity and are often not analogous to real-world learning activities. However, because of its liberal tolerance of movement, near-infrared spectroscopy (NIRS) provides an ideal platform for such studies. Here, NIRS is used to provide the first concurrent examination of neurological and behavioral data from number line estimation performance within children and adults. Moreover, in an effort to observe the behavioral and neurological benefits to number line estimations that may arise from multisensory stimulation, differential feedback (i.e., visual, auditory, or audiovisual) about estimation performance is provided throughout a portion of the task. Results suggest behavioral and neural performance is enhanced by feedback. Moreover, significant effects of age suggest young children show greater neurological response to feedback, and increase in task difficulty resulted in decreased behavioral performance and increased neurological activation associated with mathematical processing. Thus, typical math learners effectively recruit areas of the brain known to process number when math activities become increasingly difficult. Data inform understanding typical behavioral and neural responses to real-world math learning tasks, and may prove useful in triangulating signatures of atypical math learning. Moreover, results demonstrate the utility of NIRS as a platform to provide simultaneous neurological and behavioral data during naturalistic math learning activities.

Electrolytic cells convert chemical energy directly into electrical energy cleanly and efficiently. An integral component of a fuel cell and an electrolytic cell is the electrolyte, a material that conducts ions. Liquid electrolytes can be aqueous as in the phosphoric acid and alkaline fuel cells, or molten, as in the molten carbonate fuel cells. A solid electrolyte is preferable because it allows sturdier, more efficient and corrosion resistant systems to be built. The main objective of this work is to develop a solid electrolyte for hydrogen production by electrolysis of hydrogen sulfide. Barium Hydrogen Phosphate, Barium Dihydrogen Phosphate, Cesium Hydrogen Carbonate, and Ammonium Iodide received brief attention but Cesium Hydrogen Sulfate was the primary candidate considered. Initial investigation has verified that Cesium Hydrogen Sulfate undergoes an impressive first-order phase transition at approximately 140°C at which the proton conductivity increases by almost four orders of magnitude. An electrochemical cell was designed and developed by Erik Todd for the production of hydrogen. Hydrogen sulfide can electrolyzed into hydrogen and sulfur in an electrochemical cell. Sulfur is in a low viscosity molten state at a temperature of 150°C. A cell with cesium hydrogen sulfate electrolyte canoperate at this temperature where liquid sulfur and gaseous hydrogen can move out of the cell as they are formed. Consequently, the electrolyte must possess a high conductivity at this temperature to facilitate the migration of hydrogen ions to the negative electrode through the electrolyte. Cesium Hydrogen Sulfate is known to act as an insulator at room temperature and a protonic conductor at 140°C. Hence it comes as an obvious choice as an electrolyte in a hydrogen sulfide electrochemical cell. The structural and chemical properties of Cesium Hydrogen Sulfate were investigated. • The CsHSO4 electrolyte was prepared by the reaction of cesium carbonate and cesium sulfate with sulfuric acid respectively. • A punch, die and base were designed and fabricated to 0.5" and 2.0" diameter pellets for that purpose. • X-ray diffraction was performed on the 0.5" diameter pellets to identify and characterize the polycrystalline phases of the solid acid electrolyte. • Differential Scanning Calorimetry was performed so as to ascertain the phase transition temperature. • The temperature at which the phase transition occurs was further confirmed by impedance measurements. A test setup was built in order to perform impedance measurements. An experiment to measure the impedance of a 0.5" diameter pellet of silver iodide was performed in order to test the validity of the setup. • An infrared analysis was performed on the prepared sample CsHSO4 in order to identify the bond environment of the electrolyte. • Differential scanning calorimetry was performed with Barium Hydrogen Phosphate, Barium Dihydrogen Phosphate, Cesium Hydrogen Carbonate and Ammonium Iodide to identify their phase transition temperatures. • A successful electrolysis of steam experiment was carried out using the CsHSO4 electrolyte to evaluate its performance. • Finally, the CsHSO4 electrolyte was tested in the hydrogen sulfide electrochemical cell for the production of hydrogen and sulfur.

The closed shell structures of certain all-carbon fragments originally observed in mass spectroscopy experiments leads to the enhanced stability of these species, known as fullerenes, which have excited sufficient interest amongst chemists and physicists over the last decade to warrant the award of the 1996 Nobel Prize for Chemistry to their discoverers. ¶ Studies of the stability, symmetry, and consequent remarkable properties of fullerenes began in earnest in 1991 with the development of a technique enabling the production and purification of macroscopic quantities of material. The best known and most widely studied fullerene is the truncated icosahedral C[subscript 60] molecule, which forms the basis of the present work. ¶ One important property of C[subscript 60] is that it forms salts with sufficiently electropositive species, such as the alkali metals. The resulting salts contain C[subscript 60] anions and are known as fullerides. Certain of these salts display metallic behaviour, and some superconduct at temperatures as high as 33 K. ¶ Three aspects of fulleride research are addressed in this work. These are: i) the preparation, crystal structure determination and superconductivity characterization of several new fullerides, particularly those including ammonia as an additional intercalant; ii) the electronic structure of the C[superscript n-, subscript 60] (n = 1 - 6) anions, as probed by solution-phase near infrared absorption spectroscopy; and iii) the molecular dynamics of a number of fullerides, superconducting and non-superconducting, by inelastic neutron scattering. ¶ This work has grown out of an Honours project also concerning C[subscript 60], the combined duration of the two studies covering essentially the entire history of this widely and competitively studied field.

<p>The European Union Water Framework Directive (WFD), with initiatives to manage surface water resources, has increased the need for fast and inexpensive methods for monitoring conditions in streams. The objective of this thesis is to assess the potential of near-infrared spectroscopy (NIRS) of epilithic material to become such method. NIRS, which is a technique that is commonly used in industry for process monitoring and quality control of products, registers the chemical properties of organic material on a molecular level. Epilithic material, i.e. the layer of dead and alive material that covers stone surfaces in streams, is continuously influenced by the stream water that flows over it, and it has the potential to integrate chemical and biological conditions over time. The temporal integration is a significant factor, since conditions in streams can change within hours or days. The thesis consists of two published papers. In the first paper a new sampler for epilithic material, the Stone Brusher, was described and the performance evaluated. The Stone Brusher is designed to take qualitative or semi-quantitative samples of epilithic material from stones at 7–50 cm water depth. The epilithic material is dislodged from the stone surface with a rotating brush enclosed in a chamber, and the material is drawn up directly into the sample bottle with an air-cylinder. The operator takes a sample quickly and without putting hands into the water. The sampler is made of plastic, stainless steel and aluminium and weighs 3.1 kg. It is designed to meet the demand for standardized sampling for research and environmental monitoring and to improve working conditions for sampling personnel. The equipment allows sampling from surfaces of bedrock and large stones that cannot be lifted from the bottom. Using data of near-infrared spectroscopy and diatom analyses, this new sampler was evaluated in comparison to the toothbrush method, a primitive method which is the current standard in EU. The results indicate that the Stone Brusher reduces sampling variability compared with the toothbrush method.</p><p>In the second paper, the Stone Brusher was used to collect epilithic material from 65 sites (42 uncontaminated and 23 contaminated) from streams in the widespread mining area called the Skellefte-district in Västerbotten, northern Sweden, in order to test the hypothesis that impact on the epilithic material caused by emissions from mining and mining-related industries can be detected using NIRS. The epilithic material was filtered onto glass fibre filters, measured by NIRS, and the results were modelled using Principal Component Analysis (PCA). The NIRS approach was evaluated by comparing it with the results of chemical and diatom analyses of the same samples. Based on PCA, the NIRS data distinguished contaminated from uncontaminated sites and performed slightly better than chemical analyses and clearly better than diatom analyses. Of the streams designated a priori as contaminated, 74 % were identified as contaminated by NIRS, 65 % by chemical analysis and 26 % by diatom analysis. Unlike chemical analyses of water or of epilithic material samples, NIRS data reflect biological impacts in the streams. Given that, and the simplicity of NIRS-analyses, further studies to assess the use of NIRS of epilithic material are justified. NIRS has the potential to become a fast method for screening in regions where large numbers of streams occur to find impacted streams or as a routine method for temporal monitoring in selected streams for early detection of environmental impact, similar to process monitoring in industry.</p>

Résumé : Ce travail avait pour but de contribuer à la détermination précise des paramètres de raies du disulfure de carbone en vue d'applications atmosphériques. Il s'agissait de déterminer théoriquement et expérimentalement les coefficients d'élargissement collisionnel de raies de la bande gamma 3 du disulfure de carbone perturbé par l'air atmosphérique ainsi que leur dépendance en température. Pour cela, nous avons déterminé les coefficients d'élargissement collisionnel du disulfure de carbone perturbé par l'azote, l'oxygène et enfin par l'argon, principaux composants de l'air atmosphérique, aussi bien que leur dépendance en température. En outre, nous avons déterminé théoriquement et expérimentalement les coefficients d'auto élargissement collisionnel de raies de la bande gamma 3 - gamma 1 du disulfure de carbone, à température ambiante. La dépendance vibrationnelle des largeurs collisionnelles étant négligeable, les résultats sont valables quel que soit le niveau supérieur de la transition. Enfin, nous avons déterminé les intensités absolues de quelques raies de la bande gamma 3 - gamma 1 du disulfure de carbone qui nous ont permis de mettre en exergue une des applications atmosphériques des paramètres de raie mesurés en laboratoire. Pour la partie expérimentale, un spectromètre diode-laser haute résolution (5x10-4cm-1) a été utilisé pour enregistrer les différents spectres. De ces derniers, nous avons déterminé les différents paramètres de raie d'absorption en ajustant aux profils expérimentaux des modèles de profils théoriques. Du point de vue théorique, les différents coefficients d'élargissement collisionnel ont été calculés sur base du formalisme semi-classique d'Anderson-Tsao-Curnutte amélioré par J. Bonamy et D. Robert, moyennant quelques modifications pour accorder les valeurs à celles mesurées en laboratoire. Ceci a permis de valider les différents potentiels d'interaction pour les différents systèmes moléculaires considérés. Abstract The purpose of this thesis was to contribute to the accurate determination of line parameters of carbon disulfide for atmospheric applications. We have determined experimentally as well as theoretically the collisional broadening coefficients of lines in the gamma 3 band of carbon disulfide perturbed by the atmospheric air and their temperature dependence. To this end, we determined collisional broadening coefficients, as well as their temperature dependence, of carbon disulfide diluted in nitrogen, oxygen and argon; the main components of the atmospheric air. In addition, we determined the self broadening coefficients of lines in the gamma 3 - gamma 1 band of carbon disulfide at room temperature. As the vibrational dependence of collisional widths is negligible, our results are valid whatever the higher level of transition. Finally, we determined the absolute intensities of a few lines in the gamma 3 - gamma 1 band of carbon disulfide, which have enabled us to highlight one of the atmospheric applications of line parameters measured in the laboratory. For the experimental part, a high resolution diode-laser spectrometer (5x10-4cm-1) was used to record the different spectra. Of these, we determined the parameters of absorption line by adjusting theoretical lineshape models to experimental profiles. From a theoretical point of view, different collisional broadening coefficients were calculated on the basis of semi classical formalism of Anderson-Tsao-Curnutte improved by J. Bonamy and D. Robert, with some modifications to make the calculated values more consistent with those measured. This enabled us to validate the different potentials of interactions for the different molecular systems considered.

The work presented in this thesis has striven toward improving the capability to study proteins using infrared (IR) spectroscopy. This includes development of new and improved experimental and theoretical methods to selectively observe and simulate protein vibrations. A new experimental method of utilising adenylate kinase and apyrase as helper enzymes to alter the nucleotide composition and to perform isotope exchange in IR samples was developed. This method enhances the capability of IR spectroscopy by enabling increased duration of measurement time, making experiments more repeatable and allowing investigation of partial reactions and selected frequencies otherwise difficult to observe. The helper enzyme mediated isotope exchange allowed selective observation of the vibrations of the catalytically important phosphate group in a nucleotide dependent protein such as the sarcoplasmic reticulum Ca2+-ATPase. This important and representative member of P-type ATPases was further investigated in a different study, where a pathway for the protons countertransported in the Ca2+-ATPase reaction cycle was proposed based on theoretical considerations. The transport mechanism was suggested to involve separate pathways for the ions and the protons. Simulation of the IR amide I band of proteins enables and supports structure-spectra correlations. The characteristic stacking of beta-sheets observed in amyloid structures was shown to induce a band shift in IR spectra based on simulations of the amide I band. The challenge of simulating protein spectra in aqueous medium was also addressed in a novel approach where optimisation of simulated spectra of a large set of protein structures to their corresponding experimental spectra was performed. Thereby, parameters describing the most important effects on the amide I band for proteins could be determined. The protein spectra predicted using the optimised parameters were found to be well in agreement with experiment. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 5: Manuscript.</p>