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abstract: The goal of this theoretical study of infrared spectra was to ascertain to what degree molecules may be identified from their IR spectra and which spectral regions are best suited for this purpose. The frequencies considered range from the lowest frequency molecular vibrations in the far-IR, terahertz region (below ~3 THz or 100 cm-1) up to the highest frequency vibrations (~120 THz or 4000 cm-1). An emphasis was placed on the IR spectra of chemical and biological threat molecules in the interest of detection and prevention. To calculate IR spectra, the technique of normal mode analysis was applied to organic molecules ranging in size from 8 to 11,352 atoms. The IR intensities of the vibrational modes were calculated in terms of the derivative of the molecular dipole moment with respect to each normal coordinate. Three sets of molecules were studied: the organophosphorus G- and V-type nerve agents and chemically related simulants (15 molecules ranging in size from 11 to 40 atoms); 21 other small molecules ranging in size from 8 to 24 atoms; and 13 proteins ranging in size from 304 to 11,352 atoms. Spectra for the first two sets of molecules were calculated using quantum chemistry software, the last two sets using force fields. The "middle" set used both methods, allowing for comparison between them and with experimental spectra from the NIST/EPA Gas-Phase Infrared Library. The calculated spectra of proteins, for which only force field calculations are practical, reproduced the experimentally observed amide I and II bands, but they were shifted by approximately +40 cm-1 relative to experiment. Considering the entire spectrum of protein vibrations, the most promising frequency range for differentiating between proteins was approximately 600-1300 cm-1 where water has low absorption and the proteins show some differences. / Dissertation/Thesis / Ph.D. Physics 2012

BARBOZA, Felipe Moreira. Espectroscopia Raman na L-valina deuterada a baixas temperaturas. 2012. 75 f. Dissertação (Mestrado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2012. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2015-04-23T21:25:11Z No. of bitstreams: 1 2012_dis_fmbarboza.pdf: 1400454 bytes, checksum: d614be224b439b279076ca7546ca4c23 (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2015-04-29T17:45:05Z (GMT) No. of bitstreams: 1 2012_dis_fmbarboza.pdf: 1400454 bytes, checksum: d614be224b439b279076ca7546ca4c23 (MD5) / Made available in DSpace on 2015-04-29T17:45:05Z (GMT). No. of bitstreams: 1 2012_dis_fmbarboza.pdf: 1400454 bytes, checksum: d614be224b439b279076ca7546ca4c23 (MD5) Previous issue date: 2012 / Deuteration allows the identification of several species of vibrations, through the comparison of vibrational spectra of the deutered and hydrogeneted samples. In this work we base studied the vibrational properties of L-valine-d8 (99,8 % atom % D) through the Raman spectroscopy technique. At first, the assignment of all Raman active vibratonal mades of L-valine was revisited, and a comparison with a previous work was done. In particular, several bands associated to stretching of NH_3^+ and stretching of CH3, among others, which are observed in the interval 2000 – 2400 cm-1 were assigned. In the second part of the work, again using Raman spectroscopy, it was studied the vibrational modes of the crystal in the temperature range 100 – 300 K. It is known from literature that hydrogenated L-valine undergoes a phase transition at about 110 K. It also known that in deuterated crystals hydrogen bands - through Ubbehlode effect – tend to be less strange and, as a consequence, a comparative analyses between the deuterated and hydrogenated samples is very important. In a previous work on L-alanine it was observed that deutaration induces a new phase at low temperatures. In the investigation on L-valine, at least in the temperature range studied, it was not possible to note any change in the Raman spectra which could be associated to a structural phase transition. Both in the external modes region any great change is verified. As a consequence, we can infer that L-valine-d8 is stable between 100 and 300 K. A discussion about the difference behaviors at low temperatures of L-valine and L-alanine (both deuterated and hydrogenated) is also furnished in the present work. / A deuteração de uma determinada amostra permite fazer a identificação de vários tipos de vibrações, comparando-se o espectro vibracional com o de uma amostra hidrogenada. Neste trabalho estudou-se o comportamento vibracional da L-valina-d8 (99,8 átomo % D) através da técnica de espectroscopia Raman. Inicialmente revisitou-se o assinalamento de todos os modos vibracionais ativos no Raman, comparando-se com um estudo previamente realizado. Em particular foram identificadas diversas bandas associadas a vibrações do tipo estiramento do NH3+ e estiramento do CH3, entre outros, que são observadas na região entre 2000 e 2400 cm-1. Na segunda parte do trabalho foi realizado um estudo via espalhamento Raman dos modos vibracionais do cristal no intervalo de temperatura entre 100 e 300 K. Sabe-se da literatura que a L-valina hidrogenada apresenta uma transição de fase em torno de 110 K. Uma vez que nos cristais deuterados as ligações de hidrogênio via o efeito Uhbehlode tendem a ser mais fracas, uma análise comparativa entre as amostras hidrogenada e deuterada se faz necessário. Em particular, num estudo realizado na L-alanina descobriu-se que a deuteração induz a formação de uma nova fase em baixas temperaturas. No caso da L-valina, pelo menos no intervalo de temperatura investigado, não foi possível observar nenhuma mudança nos espectros Raman que pudessem ser associadas a uma transição de fase estrutural. De fato, tanto na região dos modos externos, quanto na região dos modos internos nenhuma grande modificação é verificada. Isso implica que a estrutura da L-valina-d8 é estável no intervalo de 100-300 K. Uma discussão acerca da diferença do comportamento a baixas temperaturas dos cristais de L-valina e de L-alanina nas formas hidrogenadas e deuteradas é também fornecida no presente trabalho.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-06-09T14:37:53Z No. of bitstreams: 1 leonardedonascimentorodrigues.pdf: 25854217 bytes, checksum: 453640ec8891f48fcdefadcbf1a37740 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-06-27T13:30:39Z (GMT) No. of bitstreams: 1 leonardedonascimentorodrigues.pdf: 25854217 bytes, checksum: 453640ec8891f48fcdefadcbf1a37740 (MD5) / Made available in DSpace on 2017-06-27T13:30:39Z (GMT). No. of bitstreams: 1 leonardedonascimentorodrigues.pdf: 25854217 bytes, checksum: 453640ec8891f48fcdefadcbf1a37740 (MD5) Previous issue date: 2012-08-24 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A energia é imprescindível para a economia e para o desenvolvimento do país. A iminente escassez de combustíveis fósseis e as atuais preocupações ambientais têm despertado uma nova corrida para as fontes de energia renovável. No Brasil, o uso do etanol de primeira geração é produzido por meio da fermentação do caldo de cana e o etanol de segunda geração ou etanol celulósico é produzido a partir do bagaço da cana-de-açúcar. O bagaço é normalmente queimado no próprio ambiente onde é produzido para geração de energia no processo de extração do caldo, podendo ser aproveitado para aumentar a produção de etanol celulósico. Neste trabalho, são apresentados resultados com base na utilização da espectroscopia no infravermelho por transformada de Fourier (FTIR) para caracterizar o processo de fragmentação do bagaço, visando à produção de etanol celulósico, a otimização do processo e ao entendimento teórico e experimental da espectroscopia por FTIR. A técnica de FTIR foi utilizada para caracterizar o bagaço pré-tratado de cinco variedades híbridas de cana-de-açúcar e para detectar diferenças entre essas variedades para produção de etanol. As amostras foram dividas da seguinte maneira: (a) Bagaço in natura; (b) Bagaço Extraído; (c) Celulignina; (d) Polpa celulósica. Foram caracterizadas 20 amostras. Em (a), as amostras foram apenas moídas com o objetivo de identificar as características ópticas do bagaço sem tratamento. Em (b), o bagaço foi pré-tratado com água e etanol para extração dos compostos não estruturais. Na etapa (c), o bagaço sofreu hidrólise ácida com ácido sulfúrico para romper a estrutura lignocelulósica e para remover o conteúdo de hemicelulose. Na etapa (d), o bagaço sofreu hidrólise alcalina com hidróxido de sódio para remover o maior conteúdo possível de lignina. Nas vibrações moleculares do bagaço in natura, foram obtidas bandas entre 1000 e 890 cm-1 que identificam a celulose; entre 1200 e 1000 cm-1 para hemicelulose e celulose; 1247 cm-1 para hemicelulose e lignina; entre 1430-1300 cm-1 com sobreposição para bandas de celulose, hemicelulose e lignina; entre 1610-1460 cm-1 para lignina; 1735 cm-1 para hemicelulose; entre 2920-2850 cm-1 para celulose; e entre 3800-3000 cm-1 para características de celulose cristalina. No processo de extração com água e etanol, não houve diferença. A hidrólise ácida foi efetiva na ruptura da estrutura lignocelulósica e na remoção de grande parte da hemicelulose, o que foi determinado pela diminuição ou pelo desaparecimento de algumas bandas. A hidrólise alcalina removeu parte da lignina e foi responsável pelas mudanças na estrutura lignocelulósica, comprovadas pelos deslocamentos de algumas bandas. Concluiu-se que o bagaço de cana pré-tratado com hidrólise ácida e alcalina tem ótimas condições de utilização para hidrólise enzimática e para fermentação a etanol e que as variedades de bagaço respondem de forma semelhante ao pré-tratamento. / Energy is indispensable for the economy and development of the Brazilian State. The imminent fossil fuels scarcity and current environmental concerns has attracted a new race for renewable energy sources. In Brazil, the use of first generation ethanol is produced by sugarcane juice fermentation and the second ethanol generation or cellulosic ethanol is produced from sugarcane bagasse. This residue is burned normaly in the place where is produced for energy generation in the juice extraction process, that can to be utilized for celulosic ethanol. In this context, the work present results based in use of optical Fourier transform infrared spectroscopy (FTIR) to characterize fragmentation process of sugarcane bagasse for ethanol cellulosic production and to otmize this process as well as to understand FTIR spectroscopy theory and experimentation. This technique was utilized to characterize pretreated bagass from five hybrid sugarcane varieties an to detect difference amont these varieties for ethanol production. Samples were divides as follow: (a) bagasse in nature; (b) bagasse extracted; (c) acid hidrolysis; (d) alkaline hidrolysis. 20 samples were characterized. In (a) samplas were only ground with objective to identify bagass optical characteristics no treatment. In (b) bagasse was pretreated with water and ethanol to extract non-structural compounds. In (c) bagasse suffered acid hydrolisis with sulfuric acid to disrupt bagasse lignocellulosic structure and to remove content hemicellulose and step (d) bagasse suffered hidrolisis alkaline with sodium hidroxide to remove most possible content of lignin. In molecular vibrations from in nature bagasse were obtained bands among 1000 and 890 cm-1 that identify cellulose charateristics, 1200 and 1000 cm-1 for hemicellulose and cellulose, 1247 cm-1 for hemicellulose and lignin, 1430 and 1300 cm-1 with superposition of cellulose, hemicellulose and lignin bands, among 1610 and 1460 cm-1 for lignin, 1735 cm-1 for hemicellulose, 2920 and 2850 cm-1 for cellulose and 3800 and 3000 cm-1 for crystalline cellulose characteristics. In the extraction process with water and ethanol were not observed difference. Acid hidrolysis was effective to disrupt lignocellulisic structure and to remove most part of hemicellulose, determined by decrease or disappearance of some bands. Alkaline hidrolysis removed part of lignin and was responsible by changes in the ligninocellusolic structure, provened by some bands displacements. It was concluded that pretreat sugarcane bagasse with acid and alkaline hidrolisis have great conditions of utilization to enzimatic hidrolisis and fermentation to ethanol and that bagasse varieties respond similarly to pretreatment.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23030号 / 理博第4707号 / 新制||理||1675(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 谷村 吉隆, 教授 渡邊 一也, 教授 林 重彦 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / A deuteraÃÃo de uma determinada amostra permite fazer a identificaÃÃo de vÃrios tipos de vibraÃÃes, comparando-se o espectro vibracional com o de uma amostra hidrogenada. Neste trabalho estudou-se o comportamento vibracional da L-valina-d8 (99,8 Ãtomo % D) atravÃs da tÃcnica de espectroscopia Raman. Inicialmente revisitou-se o assinalamento de todos os modos vibracionais ativos no Raman, comparando-se com um estudo previamente realizado. Em particular foram identificadas diversas bandas associadas a vibraÃÃes do tipo estiramento do NH3+ e estiramento do CH3, entre outros, que sÃo observadas na regiÃo entre 2000 e 2400 cm-1. Na segunda parte do trabalho foi realizado um estudo via espalhamento Raman dos modos vibracionais do cristal no intervalo de temperatura entre 100 e 300 K. Sabe-se da literatura que a L-valina hidrogenada apresenta uma transiÃÃo de fase em torno de 110 K. Uma vez que nos cristais deuterados as ligaÃÃes de hidrogÃnio via o efeito Uhbehlode tendem a ser mais fracas, uma anÃlise comparativa entre as amostras hidrogenada e deuterada se faz necessÃrio. Em particular, num estudo realizado na L-alanina descobriu-se que a deuteraÃÃo induz a formaÃÃo de uma nova fase em baixas temperaturas. No caso da L-valina, pelo menos no intervalo de temperatura investigado, nÃo foi possÃvel observar nenhuma mudanÃa nos espectros Raman que pudessem ser associadas a uma transiÃÃo de fase estrutural. De fato, tanto na regiÃo dos modos externos, quanto na regiÃo dos modos internos nenhuma grande modificaÃÃo à verificada. Isso implica que a estrutura da L-valina-d8 à estÃvel no intervalo de 100-300 K. Uma discussÃo acerca da diferenÃa do comportamento a baixas temperaturas dos cristais de L-valina e de L-alanina nas formas hidrogenadas e deuteradas à tambÃm fornecida no presente trabalho. / Deuteration allows the identification of several species of vibrations, through the comparison of vibrational spectra of the deutered and hydrogeneted samples. In this work we base studied the vibrational properties of L-valine-d8 (99,8 % atom % D) through the Raman spectroscopy technique. At first, the assignment of all Raman active vibratonal mades of L-valine was revisited, and a comparison with a previous work was done. In particular, several bands associated to stretching of NH_3^+ and stretching of CH3, among others, which are observed in the interval 2000 â 2400 cm-1 were assigned. In the second part of the work, again using Raman spectroscopy, it was studied the vibrational modes of the crystal in the temperature range 100 â 300 K. It is known from literature that hydrogenated L-valine undergoes a phase transition at about 110 K. It also known that in deuterated crystals hydrogen bands - through Ubbehlode effect â tend to be less strange and, as a consequence, a comparative analyses between the deuterated and hydrogenated samples is very important. In a previous work on L-alanine it was observed that deutaration induces a new phase at low temperatures. In the investigation on L-valine, at least in the temperature range studied, it was not possible to note any change in the Raman spectra which could be associated to a structural phase transition. Both in the external modes region any great change is verified. As a consequence, we can infer that L-valine-d8 is stable between 100 and 300 K. A discussion about the difference behaviors at low temperatures of L-valine and L-alanine (both deuterated and hydrogenated) is also furnished in the present work.

Starke Kopplung von Molekülen mit einem räumlich begrenzten Lichtfeld führt zur Bildung neuer polaritonischer Eigenzustände des Systems, die sowohl molekulare als auch photonische Eigenschaften erhalten und somit ein großes Potenzial für Anwendungen in der Chemie und Optoelektronik besitzen. In dieser Arbeit wird die Kopplung zwischen Oberflächenplasmonen Polaritonen (SPPs), die als das räumlich begrenzte Lichtfeld agieren, und molekularen Anregungen wie Schwingungen und polaronischen Resonanzen untersucht. Das starke Kopplungsregime zwischen einer Molekülschwingung und einem SPP wird zum ersten Mal im mittleren Infrarot unter Verwendung der Carbonylschwingung von Poly(vinylmethylketon) Polymer und Silber als Ausbreitungsmedium von SPPs demonstriert. Die neu gebildeten Hybridmoden werden durch Experimente und numerische Modellierung untersucht, wobei Messungen der abgeschwächten Totalreflexion und der thermischen Emission sowie Berechnungen mittels der Transfermatrix und der linearen Dispersionstheorie verwendet werden. Ein Anticrossing in der Dispersion der Polariton-Zweige mit einer Energieaufspaltung bis zu 15 meV, was die Hauptsignatur des starken Kopplungsregimes ist, wird beobachtet. Die starke Kopplung mit Zinkgalliumoxid, einem hochdotierten Halbleiter als Alternative zu Edelmetallen, wird auch untersucht. Experimentelle und simulierte Reflektometrie-Spektren sowie Dispersionsrelationen werden diskutiert, um Rückschlüsse auf die Eigenschaften des Systems zu ziehen. Außerdem wird ein Ansatz zur Verbesserung der Leitfähigkeit organischer Halbleiterpolymere durch starke Kopplung ihrer polaronischen Zustände an SPPs vorgestellt und Leitfähigkeitsmessungen durchgeführt. Ziel ist es, die Delokalisierung der Hybridzustände auszunutzen, um die Leitfähigkeit zu verändern. Die präsentierten Ergebnisse bieten neue Einblicke in den Nutzen der Eigenschaften der Licht-Materie-Hybridisierung, um ihr volles Potenzial für verschiedene Bereiche und Anwendungen zu erforschen. / Strong coupling of molecules with a confined light field results in the formation of new polaritonic eigenstates of the system called polaritons that inherit both molecular and photonic characteristics and thus holds strong potential for applications in chemistry and optoelectronics. In this work, coupling between propagating surface plasmon polaritons (SPPs), as confined light field, and molecular excitations, such as vibrational resonances and polaronic features, is investigated. The strong coupling regime between a molecular vibration and a propagating SPP is demonstrated for the first time in the mid-infrared spectral range using the carbonyl stretch vibration of Poly(vinyl methyl ketone) polymer and silver as metallic medium for SPPs propagation. The newly formed hybrid modes are investigated through experiments and numerical modelling, employing attenuated-total-reflection and thermal emission measurements as well as transfer-matrix and linear dispersion theory calculations. An anticrossing behavior in the dispersion of the polariton branches with an energy splitting up to 15meV, which is a key signature of the strong coupling regime, is observed. Strong coupling involving zinc gallium oxide, which is a highly doped semiconductor, as an alternative to noble metals is also investigated. Experimental and simulated reflectometry spectra as well as the dispersion relations are discussed so as to draw conclusions about the properties of the system. Furthermore, an approach to enhance the conductivity of organic semiconductor polymers by strongly coupling their polaronic states to SPPs is presented and four-point probe measurements are conducted. The goal is to exploit the delocalization of the hybrid states to alter the conductivity of the organic semiconductor. The results presented in this thesis provide new insights into the profit from the properties of light-matter hybridization in order to explore its full potential for several areas and applications.