Modelos para dispersão Raman em polímeros conjugados

Raman dispersion refers to the dependence of the position of Raman bands on the energy of the exciting radiation. In this work, the three main models currently used to explain this phenomenon (Conjugated Length Model, Amplitude Mode Model and Effective Conjugation Coordinate Model) are discussed. Raman dispersion is a consequence of pi electron delocalization, but each model describes in a different way how pi electron delocalization affects the position of Raman bands. Here the features, qualities and problems of the three models are highlighted.

Estudo dos espectros vibracionais de poliacetilenos substituídos

Neste trabalho foram sintetizados a poli-2-etinilpiridina (P2EP), poli-4etinilpiridina (P4EP), o iodeto de poli(2-N-t-butilpiridiniumilacetileno) (P2EPtBu) e a poli-β-etinilnaftaleno (Pβ:EN), os quais são poliacetilenos substituídos. Estes polímeros, juntamente com o cloreto de poli(2-piridínio-2-piridilacetileno) (P2EPH), foram caracterizados por espectroscopia vibracional no infravermelho e Raman. Estes polímeros apresentaram variação na posição das bandas Raman com a energia da radiação excitante - chamada dispersão Raman ou fotosseletividade - da ordem de 10 cm-1, bem inferior ao apresentado pelo poliacetileno (cerca de 60 cm-1). Este deslocamento foi interpretado utilizando-se dois dos modelos existentes para descrever este fenômeno: o Modelo de Modo de Amplitude (AMM) e o Modelo de Coordenada de Conjugação Efetiva (ECCM), os quais fornecem informações sobre a estrutura polimérica e sobre seus níveis eletrônicos. Utilizando-se o AMM foi possível obter informações sobre os níveis eletrônicos excitados de mesma simetria que o estado eletrônico fundamental. Por outro lado, o ECCM, com a ajuda de cálculos DFT, mostrou diferenças na extensão da conjugação e no grau de dimerização entre o P2EP na forma cis e trans e indicou que este polímero apresentava, predominantemente, a estrutura cis, fato este confirmado pelos espectros no infravermelho. A dopagem com I2 provocou efeitos diferentes na estrutura dos polímeros. Os espectros no infravermelho dos polímeros dopados indicaram que o P2EP e o P2EPH apresentaram aumento na quantidade de segmentos cis enquanto o P2EPtBu apresentou diminuição na quantidade desses segmentos. Os espectros Raman dos polímeros dopados confirmaram os dados dos espectros no infravermelho. Esta diferença foi interpretada como sendo devida à diferença no volume do substituinte, pois grupos volumosos favorecem o isômero trans-cisóide onde a distância entre os substituintes é maior. A dopagem também levou a um aumento na condutividade dos polímeros, porém os valores de condutividade obtidos foram bem inferiores que os apresentados pelo poliacetileno dopado (10-5 a 10-7 contra 102 S cm-1, tipicamente).

Controlo de reacções de polimerização em miniemulsão através de técnicas de espectroscopia NIR e Raman

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Classification Of Frankfurters By Ft-raman Spectroscopy And Chemometric Methods.

Frankfurters are widely consumed all over the world, and the production requires a wide range of meat and non-meat ingredients. Due to these characteristics, frankfurters are products that can be easily adulterated with lower value meats, and the presence of undeclared species. Adulterations are often still difficult to detect, due the fact that the adulterant components are usually very similar to the authentic product. In this work, FT-Raman spectroscopy was employed as a rapid technique for assessing the quality of frankfurters. Based on information provided by the Raman spectra, a multivariate classification model was developed to identify the frankfurter type. The aim was to study three types of frankfurters (chicken, turkey and mixed meat) according to their Raman spectra, based on the fatty vibrational bands. Classification model was built using partial least square discriminant analysis (PLS-DA) and the performance model was evaluated in terms of sensitivity, specificity, accuracy, efficiency and Matthews's correlation coefficient. The PLS-DA models give sensitivity and specificity values on the test set in the ranges of 88%-100%, showing good performance of the classification models. The work shows the Raman spectroscopy with chemometric tools can be used as an analytical tool in quality control of frankfurters.

Detection Of Explosives On The Surface Of Banknotes By Raman Hyperspectral Imaging And Independent Component Analysis.

The aim of this study was to develop a methodology using Raman hyperspectral imaging and chemometric methods for identification of pre- and post-blast explosive residues on banknote surfaces. The explosives studied were of military, commercial and propellant uses. After the acquisition of the hyperspectral imaging, independent component analysis (ICA) was applied to extract the pure spectra and the distribution of the corresponding image constituents. The performance of the methodology was evaluated by the explained variance and the lack of fit of the models, by comparing the ICA recovered spectra with the reference spectra using correlation coefficients and by the presence of rotational ambiguity in the ICA solutions. The methodology was applied to forensic samples to solve an automated teller machine explosion case. Independent component analysis proved to be a suitable method of resolving curves, achieving equivalent performance with the multivariate curve resolution with alternating least squares (MCR-ALS) method. At low concentrations, MCR-ALS presents some limitations, as it did not provide the correct solution. The detection limit of the methodology presented in this study was 50μgcm(-2).

Estudo por espectroscopia micro-Raman dos mecanismos de separação de fase em vidros fosfatos de metais de transição

Glass-ceramics are prepared by controlled separation of crystal phases in glasses, leading to uniform and dense grain structures. On the other hand, chemical leaching of soluble crystal phases yields porous glass-ceramics with important applications. Here, glass/ceramic interfaces of niobo-, vanado- and titano-phosphate glasses were studied by micro-Raman spectroscopy, whose spatial resolution revealed the multiphase structures. Phase-separation mechanisms were also determined by this technique, revealing that interface composition remained unchanged as the crystallization front advanced for niobo- and vanadophosphate glasses (interface-controlled crystallization). For titanophosphate glasses, phase composition changed continuously with time up to the equilibrium composition, indicating a spinodal-type phase separation.

Emprego da fluorescência de raios X por dispersão de energia para o mapeamento de troncos de árvores em Campinas, São Paulo

Dendrochemistry is based on the determination of elements retained in tree rings, which can be useful to characterize environmental occurrences. This work shows elemental mappings obtained by EDXRF of the cross section of a tree stem. The tree is originated from a polluted area in Campinas, São Paulo. Some profiles, as the sulfur one, show variations that can be attributed to external contributions, whereas the silicon one can be inferred to a protection defense natural mechanism. Besides being simultaneous and multielementar, the main advantages here are its performance through a non-destructive sample treatment and the ease of operation of XRF equipments.

Desenvolvimento de um algoritmo para identificação e correção de spikes em espectroscopia Raman de imagem

Raman imaging spectroscopy is a highly useful analytical tool that provides spatial and spectral information on a sample. However, CCD detectors used in dispersive instruments present the drawback of being sensitive to cosmic rays, giving rise to spikes in Raman spectra. Spikes influence variance structures and must be removed prior to the use of multivariate techniques. A new algorithm for correction of spikes in Raman imaging was developed using an approach based on comparison of nearest neighbor pixels. The algorithm showed characteristics including simplicity, rapidity, selectivity and high quality in spike removal from hyperspectral images.

Dispersão de sementes de Vismia cayennensis (Jacq.) Pers. (Guttiferae) por morcegos na região de Manaus, Amazonas

We studied the feeding behavior of bats and their role in the seed dispersal of Vismia cayennensis in Manaus region, Amazonas State, northern Brazil. The characteristics of the plant and its fruits fit the chiropterocory syndrome. Five species of phyllostomid bats fed on Vismia fruits: Sturnira lilium, Sturnira tildae, Artibeus concolor, Carollia perspicillata and Rhinophylla pumilio. Apparently there is a relationship between flock foraging behavior and fruit availability in early night. The feeding behavior was similar for all bat species, varying with the presentation mode of the fruits. Seed germination tests and the distributional patterns of the plants indicate that bats are the dispersers of V. cayennensis.

Origem e dispersão dos Tupiguarani: o que diz a morfologia craniana?

A origem e a dispersão dos povos Tupiguarani têm sido intensamente debatidas entre arqueólogos e linguistas nas últimas cinco décadas. Em resumo, pode-se dizer que a ideia de que esses povos, que ocuparam grande parte do território brasileiro e parte da Bolívia, do Paraguai, do Uruguai e da Argentina, tiveram sua etnogênese na Amazônia e dali partiram para o leste e para o sul, por volta de 2.500 anos antes do presente, é bastante aceita entre os especialistas, embora uma dispersão no sentido oposto, isto é, do sul para o norte, com origem na bacia do Tietê-Paraná, não seja completamente descartada. Entre os arqueólogos que consideram a Amazônia como berço desses povos, alguns acreditam que esse surgimento se deu na Amazônia central. Outros acreditam que a etnogênese Tupiguarani ocorreu no sudoeste da Amazônia, onde hoje se concentra a maior diversidade linguística do tronco Tupi. Neste trabalho, a morfologia de 19 crânios associados à cerâmica Tupiguarani ou etnograficamente classificados como tais foram comparados a várias séries cranianas pré-históricas e etnográficas brasileiras por meio de estatísticas multivariadas. Duas técnicas multivariadas foram empregadas: Análise de Componentes Principais, aplicada sobre os centróides de cada série, e Distâncias de Mahalanobis, aplicadas aos dados individuais. Os resultados obtidos sugerem uma origem amazônica para os povos Tupiguarani, sobretudo pela forte associação encontrada entre crânios Tupi e Guarani do sudeste e do sul brasileiro e dos Tupi do norte do Brasil, com os espécimes provenientes da ilha de Marajó incluídos no estudo.

Synthesis of Fe/Ti oxides from a single source alkoxide precursor under inert atmosphere

The heterometal alkoxide [FeCl{Ti2(OPr i)9}] (1) was employed as a single source precursor for the preparation of Fe/Ti oxides under inert atmosphere. Three different synthetic procedures were adopted in the processing of 1, either employing aqueous HNO3 or HCl solutions, or in the absence of mineral acids. Products were characterised by powder X-ray diffractometry, scanning electron microscopy combined with energy dispersive X-ray spectroscopy (SEM/EDS) and Raman, electron paramagnetic resonance (EPR) and Mössbauer spectroscopies. Oxide products contained titanium(IV) and either iron(III) or iron(II), depending on reaction conditions and thermal treatment temperatures. An interesting iron(III)→iron(II) reduction was observed at 1000 ºC in the HNO3-containing system, leading to the detection of ilmenite (FeTiO3). SEM/EDS studies revealed a highly heterogeneous metal distribution in all products, possibly related to the presence of a significant content of carbon and of structural defects (oxygen vacancies) in the solids.

Aplicação de espectroscopias raman e infravermelho na identificação e quantificação de plastificantes em filmes comerciais de PVC esticável

This paper reports the use of Raman and infrared techniques for the qualitative and quantitative analysis of plasticizers in polyvinylchloride (PVC) commercial films. FT-Raman marker bands were indentified for di-2-ethyl-hexyl adipate (DEHA) and di-2-ethyl-hexyl phthalate (DEHP), allowing for the rapid identification of these species in the commercial film. Quantitative analysis by FT-IR resulted in plasticizers concentrations ranging from 11 to 27% (w/w). Considering the little sample preparation and the low cost of the techniques, FT-IR and FT-Raman are viable techniques for a first assessment of plasticizers in commercial samples.

Electrochemical and photocatalytic reactions of polycyclic aromatic hydrocarbons investigated by raman spectroscopy

This paper presents the study of photochemical behavior of polycyclic aromatic hydrocarbons (PAHs), potential pollutants in secondary reactions in aerosols, through Raman spectroscopy compared with its electrochemical behavior. The PAHs studied include pyrene, anthracene, phenanthrene and fluorene. These were adsorbed onto TiO2 and irradiated with ultraviolet light (254 nm). Their electrochemical oxidation was studied by in situ Surface-enhanced Raman Scattering (SERS) and led to the formation of carbonyl-containing products. Oxidized intermediates bearing the C=O group were also formed during photodegradation. The joint analysis of the photodegradation data with those produced by electrochemical means - using spectroscopic techniques for the identification and characterization of the products - revealed the formation of identical products for anthracene, but not for pyrene. A reasonable explanation for this difference in results is that photochemical and electrochemical oxidation reactions proceed via different mechanisms. While photocatalytic degradation over TiO2 is initiated by hydroxyl radicals, electrochemical oxidation is initiated by the direct electron transfer from adsorbed PAH to the electrode, generating PAH cation radicals that undergo subsequent reactions.

Análise de pinturas rupestres do Abrigo do Janelão (Minas Gerais) por microscopia raman

Rock art paintings from Abrigo do Janelão (Minas Gerais, Brazil) were non-destructively investigated by Raman Microscopy, aiming at the identification of materials used, their interaction and degradation. This technique is particularly tailored for heterogeneous samples and allows unequivocal identification of the substances present in the investigated sample. Pigments, were identified together with products of microbiological degradation; no binders were detected. White pigment was identified as calcite (CaCO3), whereas charcoal was used as black, goethite (α-FeOOH) as yellow and hematite (α-Fe2O3) as red. Whewellite (CaC2O4.H2O) and weddelite (CaC2O4.2H2O) were detected and their origin was assigned to degradation products from microbiological activity.

Um exemplo de aplicação da Microscopia Raman na autenticação de obras de arte

In the present work, Raman Microscopy was employed in the characterization of the pigments used in a drawing assigned to Tarsila do Amaral, one of the most important Brazilian artists. The work (colored pencil on paper), supposedly produced in the 1920 decade, is of a very simple composition, where blue, green and brown were the colors used. Prussian Blue was found as the blue pigment, whereas green was a mixture of copper phthalocyanine and a yellow dye, probably a diarylide; the brown pigment was a carbonaceous compound. Prussian Blue was replaced by phthalocyanine as pigment since the end of the 1930's and the possibility that it could have been used as pigment in the 1920's can be ruled out.