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The thesis contains two major parts. The first part deals with structural investigations on different coordination compounds performed by using infrared absorption and FT-Raman spectroscopy in combination with density functional theory calculations. In the first section of this part the starting materials Ph2P-N(H)SiMe3 and Ph3P=NSiMe3 and their corresponding [(MeSi)2NZnPh2P-NSiMe3]2 and Li(o-C6H4PPh2NSiMe3)]2·Et2O complexes have been investigated in order to determine the influence of the metal coordination on the P–N bond length. In the next section the vibrational spectra of four hexacoordinated silicon(IV) and germanium(IV) complexes with three symmetrical bidentate oxalato(2-) ligands have been elucidated. Kinetic investigations of the hydrolysis of two of them, one with silicon and another one with germanium, have been carried out at room temperature and at different pH values and it was observed that the hydrolysis reaction occurs only for the silicon compound, the fastest reaction taking place at acidic pH. In the last section of this part, the geometric configurations of some hexacoordinated silicon(IV) complexes with three unsymmetrical bidentate hydroximato(2-) ligands have been determined. The second part of the thesis contains vibrational investigations of some biologically active molecules performed by means of Raman spectroscopy together with theoretical simulations. The SER spectra of these molecules at different pH values have also been analysed and the adsorption behaviour on the metal surface as well as the influence of the pH on the molecule-substrate interaction have been established. / Die vorliegende Arbeit besteht aus zwei Teilen. Der erste Teil beschäftigt sich mit strukturelle Untersuchungen einiger Koordinationsverbindungen mittels IR- und Raman-Spektroskopie in Kombination mit quantenchemischen Rechnungen basierend auf der Dichtefunktionaltheorie. In ersten Kapitel dieses Teils wurden die Edukten Ph2P-N(H)SiMe3 (1a) und Ph3P=NSiMe3 (1b) und ihren entsprechenden Metallkomplexen [(Me3Si)2NZnPh2PNSiMe3]2 (2a) und [Li(o-C6H4PPh2NSiMe3)]2·EtO (2b) untersucht, um so den Einfluss der Koordination zu einem Metallzentrum auf die P-N-Bindungslänge festzustellen. In nächsten Kapitel wurden die IR- und Raman-Spektren einiger neuer hexakoordinierten Silizium(IV)- und Germanium(IV)-Komplexe mit drei symmetrischen zweizähnigen Oxalato(2-)-Liganden untersucht. Zudem wurden noch kinetische Untersuchungen der Hydrolyse zweier Silizium- bzw. Germanium-Komplexe durchgeführt und es konnte festgestellt werden, dass die Hydrolysereaktion nur im Fall des Siliziumkomplexes auftritt. Die Geschwindigkeitskonstanten wurden bei Raumtemperatur für unterschiedliche pH-Werte bestimmt. Somit konnte gezeigt werden, dass die Reaktion am schnellsten im Säuren abläuft. In letzten Kapitel wurde die Konformation einiger hexakoordinierter Silizium(IV)-Komplexe mit drei antisymmetrischen zweizähnigen Liganden vom Hydroximato(2-)-Typ aufgeklärt. Im zweiten Teil der vorliegenden Arbeit wurden Raman-Spektroskopie in Kombination mit theoretischen Berechnungen zur Schwingungscharakterisierung einiger biologisch aktiver Moleküle angewandt. Die SER-Spektren für unterschiedliche pH-Werte wurden untersucht, um die Adsorptionsverhalten auf der Silberoberfläche zu beschreiben.

Tese (doutorado)—Universidade de Brasília, Instituto de Química, 2004. / Submitted by Tania Milca Carvalho Malheiros (tania@bce.unb.br) on 2009-08-05T12:17:37Z No. of bitstreams: 1 Tese_Tereza_Cristina_Monteiro_Pastore.pdf: 2003113 bytes, checksum: 0064369caee82816989a349b288663a6 (MD5) / Rejected by Tania Milca Carvalho Malheiros(tania@bce.unb.br), reason: on 2009-08-05T12:23:30Z (GMT) / Submitted by Tania Milca Carvalho Malheiros (tania@bce.unb.br) on 2009-08-05T12:25:14Z No. of bitstreams: 1 Tese_Tereza_Cristina_Monteiro_Pastore.pdf: 2003113 bytes, checksum: 0064369caee82816989a349b288663a6 (MD5) / Approved for entry into archive by Guimaraes Jacqueline(jacqueline.guimaraes@bce.unb.br) on 2009-08-06T15:36:20Z (GMT) No. of bitstreams: 1 Tese_Tereza_Cristina_Monteiro_Pastore.pdf: 2003113 bytes, checksum: 0064369caee82816989a349b288663a6 (MD5) / Made available in DSpace on 2009-08-06T15:36:20Z (GMT). No. of bitstreams: 1 Tese_Tereza_Cristina_Monteiro_Pastore.pdf: 2003113 bytes, checksum: 0064369caee82816989a349b288663a6 (MD5) Previous issue date: 2004 / Duas técnicas espectroscópicas de refletância foram usadas para monitorar as modificações causadas por 200 h de irradiação ultravioleta (UV) sobre a superfície das madeiras tropicais: angelim vermelho (Dinizia excelsa Ducke), jatobá (Hymenaea courbaril L. var. courbaril), garapeira (Apuleia molaris Spruce ex Benth) e marupá (Simarouba amara Aubl.). As variações de cor foram mensuradas por espectrocolorimetria (segundo o sistema CIE-L*a*b*) e as modificações estruturais dos componentes principais da madeira – celulose, holocelulose e lignina – foram detectadas por espectrometria de reflectância difusa no infravermelho com transformada de Fourier (DRIFT). Na região do visível, por meio do resultado da diferença entre os espectros Kubelka Munk (KM) da madeira (não-irradiadairradiada), pode-se observar em todas as espécies investigadas o aparecimento de banda forte próxima a 410 nm. Além desta banda, as madeiras de cor escura apresentaram absorções adicionais em outros comprimentos de onda. Pelos parâmetros CIE-L*a*b*, verificou-se que o jatobá deslocou a cor para o vermelho e as outras três espécies para o amarelo. O marupá foi a espécie que sofreu a maior variação de cor e o angelim vermelho foi o menos afetado. Os espectros de diferença KM (DRIFT) mostraram que as bandas associadas à lignina (1600 cm-1 e 1508 cm-1) diminuíram em intensidade, enquanto que a banda associada ao grupo carbonílico (1736 cm-1) aumentou de intensidade com o tratamento UV. Os resultados sugerem que os extrativos interferem no processo de fotodegradação, aumentando a tendência ao amarelecimento e contribuindo com o aumento de intensidade da banda do grupo carbonila. Na região do IR, verificou-se que a celulose também foi degradada pela radiação UV. A holocelulose apresentou tendência muito grande a formar compostos carbonílicos nãoconjugados e a celulose mostrou variação na intensidade da absorção. As quatro madeiras tropicais estudadas não puderam ser classificadas taxonomicamente via DRIFT, adotando-se os critérios de espécies de clima temperado. As duas técnicas de refletância correlacionaramsesignificativamente, indicando que a radiação UV formou produtos cromóforos resultantes da fotodecomposição da lignina, que continham o grupo carbonílico não-conjugado. A presença dos extrativos da madeira pode ser detectada pela espectroscopia FT-Raman, porém esta técnica não se mostrou adequada para monitorar a fotodecomposição. _________________________________________________________________________________________ ABSTRACT / Two reflectance spectroscopic techniques were used to monitor modifications caused by 200 h of ultraviolet (UV) irradiation on the surface of tropical hardwoods species: angelim vermelho (Dinizia excelsa Ducke), jatobá (Hymenaea courbaril L. var. courbaril), garapeira (Apuleia molaris Spruce ex Benth), and marupá (Simarouba amara Aubl.). Colour variations have been evaluated by spectrocolorimetry (according to the CIE-L*a*b* system). Chemical changes of the wood main components – cellulose, lignin and holocellulose – have been detected by Diffuse Reflectance Fourier Transform (DRIFT) spectroscopy in the infrared. The Kubelka Munk (KM) difference spectra (non-irradiated-irradiated) in the visible region, from the woods have shown that all investigated species developped a strong absorption band near 410 nm. Besides this band, darker woods showed addicional absorptions at other wavelengths. The CIE-L*a*b* parameters (∆L, ∆a, and ∆b) have shown that jatobá shifted its color to reddish while the other three species have a tendency to become yellowish. Marupá was the species that suffered major color changes and angelim vermelho was the least affected. In the IR region, the KM difference spectra have shown that bands associated to lignin (1600 and 1508 cm-1) decreased in intensity, while those associated to carbonyl group (1736 cm-1) have increased under UV exposure. The results suggest that the extractives interfere in the photodegradation process, increasing the tendency to yellowing and contributing to the increase of carbonyl band intensity. In the IR region, it was observed that cellulose was also degradeted by UV radiation. Holocellulose presented a very high tendency to produce nonconjugated carbonyl groups, while cellulose showed variation only in the absorption intensity. The four tropical wood species studied did not match the taxonomic classification by DRIFT, adopting the rules developted for temperated wood species. The two reflectance techniques were significantly correlated, indicating that the UV radiation has formed cromophores products resulting of lignin hotodecomposition and that these products contain nonconjugated carbonyl group. The presence of wood extractives was detected by FT-Raman spectroscopy, although this technique has not shown to be appropriated to monitor the photodegradation process.

Stuttgart, Univ., Diss., 2003.

No / There is developing interest in the analytical use of human hair from archaeological contexts in key research areas such as DNA, trace elemental and isotopic analyses. Other human tissues, especially bone, that have been used for trace element, isotopic and DNA analyses have had extensive study concerning their diagenesis, but this has not been done for hair. Consideration must be given to the complex interaction of hair with its buried environment, thereby laying a firm basis for the use of hair in future research. Since human hair is known to survive under a diverse range of environmental conditions, a pilot study has investigated the basic processes of hair degradation, using samples from different climatic zones and burial types. Variation in the degree of preservation of archaeological hair was characterized by light microscopy, electron microscopy, and FT-Raman spectroscopy, relating morphological change of the surface and internal structure of hair to its biochemical integrity. The results demonstrate a breakdown of cortical cell boundaries and disruption of the cuticular layering, coupled with infiltration of material from the burial matrix that suggests a progressive loss of cohesion that is in part due to microbiological activity. Medullated hair is shown to be more susceptible to physical breakdown by providing two routes for microbial and environmental attack. At the molecular level the proteinaceous component undergoes alteration, and the S-S cystine linkages, responsible for the strength and resilience of hair in living individuals, are lost.

No / Cocrystal monohydrate of nitrofurantoin (NF) with melamine (MELA) has been studied as NF is an antibacterial drug used for the treatment of urinary tract infections. The structure of nitrofurantoin-melamine-monohydrate (NF-MELA-H2O) is characterized by FT-IR and FT-Raman spectroscopy. The energies and vibrational frequencies of the optimized structures calculated using quantum chemical calculations. Supported by normal coordinate analyses and potential energy distributions (PEDs), the complete vibrational assignments recommended for the observed fundamentals of cocrystal hydrate. With the aim of inclusion of all the H-bond interactions, dimer of NF-MELA-H2O has been studied as only two molecules of cocrystal hydrate are present in the unit cell. By the study of dimeric model consistent assignment of the FT-IR and FT-Raman spectrum obtained. H-bonds are of essential importance in an extensive range of molecular sciences. The vibrational analyses depict existence of H-bonding (O-H⋯N) between water O-H and pyridyl N atom of MELA in both monomer and dimer. To probe the strength and nature of H-bonding in monomer and dimer, topological parameters such as electron density (ρBCP), Laplacian of electron density (∇2ρBCP), total electron energy density (HBCP) and H-bond energy (EHB) at bond critical points (BCP) are evaluated by quantum theory of atoms in molecules (QTAIM). Natural bond orbitals (NBOs) analyses are carried out to study especially the intra and intermolecular H-bonding and their second order stabilization energy (E(2)). The value of HOMO-LUMO energy band gap for NF-MELA-H2O (monomer and dimer both) is less than NF, showing more chemical reactivity for NF-MELA-H2O. Chemical reactivity has been described with the assistance of electronic descriptors. Global electrophilicity index (ω = 7.3992 eV) shows that NF-MELA-H2O behaves as a strong electrophile than NF. The local reactivity descriptors analyses such as Fukui functions, local softnesses and electrophilicity indices performed to determine the reactive sites within NF-MELA-H2O. In MEP map of NF-MELA (monomer and dimer) electronegative regions are about NO2 and C=O group of NF, although the electropositive regions are around NH2, N-H group and H2O molecule. Molar refractivity (MR) value of NF-MELA-H2O (monomer and dimer) lies within the range set by Lipinski's modified rules. This study could set as an example to study the H-bond interactions in pharmaceutical cocrystals.

No

LIMA, Kellen Cristina Vilhena. Qualidade de gasolinas automotivas através de Espectroscopia Vibracional FT-Raman, combinada com correlação 2D generalizada. 2005. 305 f. Tese (Doutorado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2005. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2015-05-25T22:26:07Z No. of bitstreams: 1 2005_tese_kcvlima.pdf: 10475763 bytes, checksum: e618c6deda94d946c15be6e420912ad1 (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2015-05-27T18:52:53Z (GMT) No. of bitstreams: 1 2005_tese_kcvlima.pdf: 10475763 bytes, checksum: e618c6deda94d946c15be6e420912ad1 (MD5) / Made available in DSpace on 2015-05-27T18:52:53Z (GMT). No. of bitstreams: 1 2005_tese_kcvlima.pdf: 10475763 bytes, checksum: e618c6deda94d946c15be6e420912ad1 (MD5) Previous issue date: 2005 / It is reported the use of Generalized Two-Dimensional FT-Raman Correlation Spectroscopy (2DCOS-FT-Raman) method to monitor the quality of automotive gasoline in the gas stations. It is presented a procedure to identify the adulteration of automotive gasoline by the illicit addition of ethanol, methanol, aromatic and paraphinic compounds through the analysis of the Raman spectra obtained for different compositions of adulterants added to gasoline “A” type and to gasoline “A” type plus ethanol samples. It is discussed the data preconditioning step, the application of 2DCOS method, and the calibration curves that correlates the integrated intensities of the Raman bands of a given adulterant with its percentage in a given gasoline sample. It shown the protocol for using the 2DCOS-FT-Raman method to verify the adulteration in a given gasoline sample compared with a specific standard. This work emphasizes the flexibility and viability of using this method to have a specific standard for each gasoline distribution firm and also for each new gasoline derived from the refinery. / Relata a utilização da espectroscopia FT-Raman combinada com Correlação 2D Generalizada como método alternativo para a realização do controle de qualidade de Gasolinas automotivas diretamente nos postos de combustível. Apresenta os procedimentos para identificar a adulteração da Gasolina automotiva pela adição irregular de Etanol, Metanol e compostos aromáticos e parafínicos, através da análise dos espectros Raman obtidos para os diferentes adulterantes separadamente, misturados à Gasolina A e misturados à Gasolina A e ao Etanol. Descreve os procedimentos de pré-tratamento sobre os espectros Raman, a aplicação do método de Correlação 2D Generalizada aos sistemas estudados e a determinação das curvas de calibração que relacionam as intensidades integradas das bandas Raman com o teor de adulterante na Gasolina. Apresenta a praticidade de aplicação do método, que possibilita verificar a adulteração da Gasolina automotiva através da comparação entre o espectro Raman da amostra cuja conformidade se deseja verificar com o espectro da amostra padrão. Enfatiza a flexibilidade e a viabilidade de se ter um padrão específico para cada distribuidora, ou até mesmo para cada nova produção de Gasolina da refinaria.

[pt] A determinação de componentes da gasolina, e a contribuição destes na qualidade e desempenho final, tem levado há um grande número de estudos que possam criar rotinas para o monitoramento deste combustível. O objetivo deste trabalho é identificar e quantificar os principais grupos de compostos que compõem a gasolina comercial distribuída em parte da região sudeste, através de análise multivariada de dados de espectroscopia FT-Raman, através de regressão por Mínimos Quadrados Parciais (PLS - Partial Least Squares) e utilizando à análise dos componentes principais (PCA). Foram utilizadas 120 amostras aleatórias, do laboratório de combustíveis da PUC-Rio no período de janeiro a junho de 2004, as quais fazem parte do programa de controle de combustível. Todas as amostras foram submetidas à análise por cromatografia gasosa (CG) e espectroscopia FT-Raman no mesmo dia. Foram coletados todos os espectros FTRaman, e foram determinados a concentração dos principais grupos componentes da composição das gasolinas comerciais pelo método PONA/PEONA para parafinas(P), olefinas(O), naftênicos(N), aromáticos(A) e etanol(E). Os dados obtidos foram tratados por PLS/PCA de modo a se obter uma correlação de cada região específica dos espectros FT-Raman com os resultados obtidos por CG através dos métodos PONA/PEONA. / [en] The determination of the gasoline components, and the contribution of these in the quality and final performance, had in the past a great number of studies that can create routines for the monitoramento of this fuel. The objective of this work is to identify and to quantify the main groups of composites that compose the distributed commercial gasoline in part of the Southeastern region, through multivaried analysis of data of FT-Raman spectroscopy, through regression for Squared Minimums Partial (PLS - Partial Least Squares) using for the analysis of the main components (PCA), 120 random samples of the fuel laboratory of PUC-Rio in the period of January the June of 2004, which is part of the program of fuel control. All the samples had been submitted to the analysis for gaseous chromatography (GC) and FT-Raman spectroscopy in the same day. The FTRaman spectra had been all collected, and had been determined the concentration of the main component groups of the composition of the commercial gasolinas for method PONA/PEONA for paraffin(P), olefin(O), naphthene(N), aromatic(A) and ethanol(E). The experimental data had been treated by PLS/PCA in order to get a correlation of each specific region of the FT-Raman spectra with the results giving for GC through methods PONA/PEONA.

Estudos têm mostrado que a dentina pode ser modificada pelo laser pulsado de CO2 tornando-a um substrato mais ácido-resistente. Este estudo in vitro se propôs a estabelecer parâmetros seguros e efetivos de um laser pulsado de CO2 com comprimento de onda 10,6 ?m e avaliou seu efeito sobre a morfologia superficial e a composição química, assim como sobre a redução da desmineralização da dentina radicular. Noventa e cinco superfícies radiculares humanas obtidas de quarenta e oito terceiros molares foram aleatoriamente divididas em 5 grupos (n=15 para o grupo de controle e n=20 para os grupos irradiados com laser): G1 - Nenhum tratamento (controle), G2 - 2,5 J/cm2, G3 - 4,0 J/cm2, G4 - 5,0 J/cm2 e G5 - 6,0 J/cm2. A temperatura intrapulpar foi mensurada por meio de análise termográfica com termômetro de radiação infravermelha, as modificações químicas, por meio de espectroscopia FT-Raman e as alterações morfológicas por meio de microscopia eletrônica de varredura. Após o tratamento da superfície, os espécimes foram submetidos a 7 dias de ciclagem de pH, permanecendo diariamente em soluções desmineralizadora e remineralizadora por 3 h e 21 h, respectivamente. Após o desafio ácido, os espécimes foram seccionados e a perda mineral foi determinada por meio do teste de microdureza Knoop (5 g, 5 seg) em profundidades pré-determinadas em relação à superfície de dentina radicular (20 ?m - 275 ?m). Para todos os grupos irradiados, as mudanças de temperatura intrapulpar mostraram-se abaixo de 0,9°C. A espectroscopia FT-Raman não evidenciou alterações químicas entre os espécimes não-irradiados e os irradiados com laser de CO2. Entretanto a análise em microscópio eletrônico de varredura indicou que as densidades de energia a partir de 4,0 J/cm2 foram suficientes para induzir mudanças morfológicas na dentina radicular. Adicionalmente, para as densidades de energia iguais ou superiores a 4,0 J/cm2, foram observados efeitos de redução da desmineralização da dentina radicular induzidos pela irradiação laser. Pode-se concluir que densidades de energia em torno de 4,0 a 6,0 J/cm2 podem ser aplicadas à dentina radicular, a fim de promover mudanças morfológicas e reduzir a reatividade ácida da mesma, sem comprometer a vitalidade pulpar. / Studies have shown that dentin can be modified by pulsed CO2 laser to form a more acid-resistant substrate. This in vitro research aimed to establish safe parameters of a pulsed study 10.6 ?m CO2 laser and evaluate its effect on chemical and morphological features in dentinal surface, as well as on the reduction of root dentin demineralization. Ninety five human root surfaces obtained from forty eight third molars were randomly divided in 5 groups (n=15 for control group and n=20 for laser groups): G1 - No treatment (control), G2 -2.5 J/cm2, G3 - 4.0 J/cm2, G4 - 5.0 J/cm2 and G5 - 6.0 J/cm2. Intrapulpal temperature was evaluated during dentin irradiation by an infrared thermometer, chemical modifications by FT-Raman spectroscopy, and morphological modifications by SEM. After the surface treatment, the specimens were submitted to a 7 days pH-cycling model, consisted of the daily immersion in demineralizing and remineralizing solutions for 3 h and 21 h, respectively. After the acid challenge, the specimens were sectioned and the mineral loss was determined by means of cross-sectional Knoop microhardness (5 g, 5 sec) at different depths from the dentin root surface (20 ?m - 275 ?m). For all irradiated groups, intrapulpal temperature changes were below 0.9°C. FT-Raman spectroscopy did not show chemical changes in the irradiated specimens. However, scanning electron microscopy images indicated that fluences as low as 4.0 J/cm2 were sufficient to induce morphological changes in root dentin. Additionally, for fluences reaching or exceeding 4.0 J/cm2, laser-induced inhibitory effects on root dentin demineralization were observed. It was thus concluded that the laser energy density in the range of 4.0 to 6.0 J/cm2 could be applied to dental root dentin in order to produce morphological changes and reduce the acid reactivity of dentin without compromising the pulp vitality.