Clinical assessment of the efficacy of low-level laser therapy on muscle pain in women with temporomandibular dysfunction, by surface electromyography

The use of low-level laser (LLL) may be an useful tool to promote reduction of muscular pain caused by TMD. Aim: This study evaluated the immediate efficacy of low-level laser therapy on women reporting pain and diagnosed with temporomandibular dysfunction (TMD). Methods: Diode laser (GaAlAs) at 790 nm wavelength (infrared spectrum) was applied as experimental treatment. Irradiations of 1.5 J/cm2 were made at 4 points of the temporomandibular joint (TMJ) and of 3 J/cm2 at 3 points in the temporal muscle. An electromyographic (EMG) evaluation of the masseter and anterior temporal was done at the following intervals: before, immediately after, 5 min and 20 min after laser application. Results: Comparison of the electrical activity at the times of measurement revealed a statistically significant difference in masseter muscles before (P=0.025) and immediately after (P=0.013) LLLT. Conclusions: Both masseter and temporal muscles showed a reduction in the measured EMG activities at all times after LLLT, and the temporal muscle showed higher EMG activity than the masseter muscle at all the evaluation times. LLLT caused significant immediate relaxation of the masseter muscles.

A graph-based framework for thermal faceprint characterization

Thermal faceprint has been paramount in the last years. Since we can handle with face recognition using images acquired in the infrared spectrum, an unique individual's signature can be obtained through the blood vessels network of the face. In this work, we propose a novel framework for thermal faceprint extraction using a collection of graph-based techniques, which were never used to this task up to date. A robust method of thermal face segmentation is also presented. The experiments, which were conducted over the UND Collection C dataset, have showed promising results. © 2011 Springer-Verlag.

Preconcentration and determination of metal ions from fuel ethanol with a new 2,2'-dipyridylamine bonded silica

A silica surface chemically modified with [3-(2,2'-dipyridylamine) propyl] groups was prepared, characterized, and evaluated for its metal ion preconcentration in fuel ethanol. To our knowledge, we are the first authors who have reported the present modification on silica gel surface. The material was characterized using infrared spectra, scanning electronic microscopy, and 13C and 29Si solid-state NMR spectra. Batch and column experiments were conducted to investigate for metal ion removal from fuel ethanol. The results showed that the Langmuir model describes the sorption equilibrium data of the metal ions in a satisfactory way. From the Langmuir isotherms, the following maximum adsorption capacities (in mmolg -1) were determined: 1.81 for Fe(III), 1.75 for Cr(III), 1.30 for Cu(II), 1.25 for Co(II), 1.15 for Pb(II), 0.95 for Ni(II), and 0.87 for Zn(II). Thermodynamic functions, the change of free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) showed that the adsorption of metal ions onto Si-Pr-DPA was feasible, spontaneous, and endothermic. The sorption-desorption of the metal ions made possible the development of a preconcentration and quantification method of metal ions in fuel ethanol. © 2012 Elsevier Inc.

Determinação de parâmetros ópticos de materiais por análise de Kramers-Kronig de espectros de infravermelho

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Craqueamento termocatalítico do óleo de buriti (Mauritia flexuosa L.), óleo de palma (Elaeis guineensis) e sabões do óleo de buriti (Mauritia flexuosa L)

O presente trabalho visa investigar o Processo de Craqueamento Termocatalítico do Óleo de Buriti (Mauritia flexuosa L.), óleo de palma (Elaeis guineensis) e sabão de óleo de buriti, considerando a transformação dos óleos vegetais e sabões via craqueamento termocatalítico em biocombustíveis, utilizando-se Na₂CO₃ (Carbonato de Sódio), CaCO₃ (Carbonato de Cálcio),CaO (óxido de cálcio) e Zeólitas Ácidas (HZSM-5) como catalisadores,as temperaturas de 420, 450 e 480 °C.O fruto de Buriti (Mauritia flexuosa L.) foi coletado e extraído óleo da polpa, em seguida este óleo foi caracterizado em relação Índice de Acidez, Índice de saponificação, Viscosidade Cinemática, Densidade , Índice de Refração e análise de CHN.Para testes preliminares foi utilizado o óleo de palma refinado e neutralizado portanto eles não foram caracterizados.O sabão de buriti foi preparado em laboratório com hidróxido de potássio e hidróxido de sódio e armazenados para pirólise térmica.Os catalisadores também foram caracterizados com relação ao infravermelho,Ressonância Magnética Nuclear de ²⁹Si e ²⁷Al, difração de raio X ,análise térmica, análise química e TPD de Amônia .No processo de craqueamento termocatalítico os produtos líquidos produzidos foram analisados quanto aos parâmetros: rendimento, índice de acidez, espectro de infravermelho, espectro de RMN e análise de CHN em seguida foram caracterizados com relação à densidade e viscosidade cinemática. No entanto, com relação ao índice de acidez dos produtos líquidos, somente os catalisadores básicos produziram craqueados com valores aceitáveis para utilização como combustível. A partir dos resultados verificou-se a eficiência dos catalisadores no qual o catalisador carbonato de sódio forneceu produtos de baixa acidez e com boas características para uso como combustível.

Síntese de hidróxidos duplos lamelares do sistema Cu, Zn, Al-CO3: propriedades morfológicas, estruturais e comportamento térmico

Hidrotalcitas são argilas aniônicas, também conhecidas como Hidróxidos Duplos Lamelares (HDLs) e possuem estrutura semelhante ao mineral brucita. Os HDLs do sistema Cu, Zn, Al-CO₃ foram sintetizados em condições que favorecem a formação de cristais pequenos e de elevada área superficial. A caracterização foi feita por difração de raios X, análise termogravimétrica, espectroscopia na região do infravermelho e microscopia eletrônica de varredura. A síntese foi feita pelo método de coprecipitação em pH variável, utilizando sulfatos de cobre e zinco, soluções de alumínio e solução de hidróxido sódio. Os difratogramas de raios X mostram que os compostos sintetizados possuem alta cristalinidade; a intensidade e a largura dos picos comprovam que os materiais se apresentam bem organizados e com empilhamento das lamelas. Os espectros de infravermelho apresentaram bandas associadas ao ânion carbonato presente na região interlamelar dos HDLs.

Síntese e caracterização do complexo de lantânio (III) e indometacina no estado sólido

In this study, the drug indomethacin, a non-steroidal anti-inflammatory indoleacetic acid derivative and the complex of indomethacin and lanthanum (III) in solid form were synthesized and characterized by Thermogravimetry (TGA), Differential Thermal Analysis (DTA), Differential Scanning Calorimetry (DSC) and powder X-ray diffractometry (XRD), infrared vibrational spectroscopy by diffuse reflectance (FTIR) and complexometric titration with EDTA. With the TG curves it was possible to determine the stoichiometry of the complex as La(Ind)3·3.5H2O where Ind is the drug indomethacin. The result of thermal analyzes provided information on the thermal stability, enthalpy of dehydration and thermal behavior of the compounds. The infrared spectrum and with the aid of theoretical calculations suggests that the indomethacin is coordinated by the carboxylate group in the bidentate mode

Generating vegetation-spectra as a basis for global monitoring of annual vegetation cycles using DOAS satellite observations

Vegetation-cycles are of general interest for many applications. Be it for harvest-predictions, global monitoring of climate-change or as input to atmospheric models.rnrnCommon Vegetation Indices use the fact that for vegetation the difference between Red and Near Infrared reflection is higher than in any other material on Earth’s surface. This gives a very high degree of confidence for vegetation-detection.rnrnThe spectrally resolving data from the GOME and SCIAMACHY satellite-instrumentsrnprovide the chance to analyse finer spectral features throughout the Red and Near Infrared spectrum using Differential Optical Absorption Spectroscopy (DOAS). Although originally developed to retrieve information on atmospheric trace gases, we use it to gain information on vegetation. Another advantage is that this method automatically corrects for changes in the atmosphere. This renders the vegetation-information easily comparable over long time-spans.rnThe first results using previously available reference spectra were encouraging, but also indicated substantial limitations of the available reflectance spectra of vegetation. This was the motivation to create new and more suitable vegetation reference spectra within this thesis.rnThe set of reference spectra obtained is unique in its extent and also with respect to its spectral resolution and the quality of the spectral calibration. For the first time, this allowed a comprehensive investigation of the high-frequency spectral structures of vegetation reflectance and of their dependence on the viewing geometry.rnrnThe results indicate that high-frequency reflectance from vegetation is very complex and highly variable. While this is an interesting finding in itself, it also complicates the application of the obtained reference spectra to the spectral analysis of satellite observations.rnrnThe new set of vegetation reference spectra created in this thesis opens new perspectives for research. Besides refined satellite analyses, these spectra might also be used for applications on other platforms such as aircraft. First promising studies have been presented in this thesis, but the full potential for the remote sensing of vegetation from satellite (or aircraft) could bernfurther exploited in future studies.

Prediction of Accurate Anharmonic Experimental Vibrational Frequencies for Water Clusters, (H2O)n, n = 2−5

Accurate anharmonic experimental vibrational frequencies for water clusters consisting of 2−5 water molecules have been predicted on the basis of comparing different methods with MP2/aug-cc-pVTZ calculated and experimental anharmonic frequencies. The combination of using HF/6-31G* scaled frequencies for intramolecular modes and anharmonic frequencies for intermolecular modes gives excellent agreement with experiment for the water dimer and trimer and are as good as the expensive anharmonic MP2 calculations. The water trimer, the cyclic Ci and S4 tetramers, and the cyclic pentamer all have unique peaks in the infrared spectrum between 500 and 800 cm-1 and between 3400 and 3700 cm-1. Under the right experimental conditions these different clusters can be uniquely identified using high-resolution IR spectroscopy.

Detección de patrones y anomalías espectrales del terreno mediante espectrometría de imagen de alta resolución : reconocimiento, optimización y evaluación multiescenario

El objeto de esta Tesis doctoral es el desarrollo de una metodologia para la deteccion automatica de anomalias a partir de datos hiperespectrales o espectrometria de imagen, y su cartografiado bajo diferentes condiciones tipologicas de superficie y terreno. La tecnologia hiperespectral o espectrometria de imagen ofrece la posibilidad potencial de caracterizar con precision el estado de los materiales que conforman las diversas superficies en base a su respuesta espectral. Este estado suele ser variable, mientras que las observaciones se producen en un numero limitado y para determinadas condiciones de iluminacion. Al aumentar el numero de bandas espectrales aumenta tambien el numero de muestras necesarias para definir espectralmente las clases en lo que se conoce como Maldicion de la Dimensionalidad o Efecto Hughes (Bellman, 1957), muestras habitualmente no disponibles y costosas de obtener, no hay mas que pensar en lo que ello implica en la Exploracion Planetaria. Bajo la definicion de anomalia en su sentido espectral como la respuesta significativamente diferente de un pixel de imagen respecto de su entorno, el objeto central abordado en la Tesis estriba primero en como reducir la dimensionalidad de la informacion en los datos hiperespectrales, discriminando la mas significativa para la deteccion de respuestas anomalas, y segundo, en establecer la relacion entre anomalias espectrales detectadas y lo que hemos denominado anomalias informacionales, es decir, anomalias que aportan algun tipo de informacion real de las superficies o materiales que las producen. En la deteccion de respuestas anomalas se asume un no conocimiento previo de los objetivos, de tal manera que los pixeles se separan automaticamente en funcion de su informacion espectral significativamente diferenciada respecto de un fondo que se estima, bien de manera global para toda la escena, bien localmente por segmentacion de la imagen. La metodologia desarrollada se ha centrado en la implicacion de la definicion estadistica del fondo espectral, proponiendo un nuevo enfoque que permite discriminar anomalias respecto fondos segmentados en diferentes grupos de longitudes de onda del espectro, explotando la potencialidad de separacion entre el espectro electromagnetico reflectivo y emisivo. Se ha estudiado la eficiencia de los principales algoritmos de deteccion de anomalias, contrastando los resultados del algoritmo RX (Reed and Xiaoli, 1990) adoptado como estandar por la comunidad cientifica, con el metodo UTD (Uniform Targets Detector), su variante RXD-UTD, metodos basados en subespacios SSRX (Subspace RX) y metodo basados en proyecciones de subespacios de imagen, como OSPRX (Orthogonal Subspace Projection RX) y PP (Projection Pursuit). Se ha desarrollado un nuevo metodo, evaluado y contrastado por los anteriores, que supone una variacion de PP y describe el fondo espectral mediante el analisis discriminante de bandas del espectro electromagnetico, separando las anomalias con el algortimo denominado Detector de Anomalias de Fondo Termico o DAFT aplicable a sensores que registran datos en el espectro emisivo. Se han evaluado los diferentes metodos de deteccion de anomalias en rangos del espectro electromagnetico del visible e infrarrojo cercano (Visible and Near Infrared-VNIR), infrarrojo de onda corta (Short Wavelenght Infrared-SWIR), infrarrojo medio (Meadle Infrared-MIR) e infrarrojo termico (Thermal Infrared-TIR). La respuesta de las superficies en las distintas longitudes de onda del espectro electromagnetico junto con su entorno, influyen en el tipo y frecuencia de las anomalias espectrales que puedan provocar. Es por ello que se han utilizado en la investigacion cubos de datos hiperepectrales procedentes de los sensores aeroportados cuya estrategia y diseno en la construccion espectrometrica de la imagen difiere. Se han evaluado conjuntos de datos de test de los sensores AHS (Airborne Hyperspectral System), HyMAP Imaging Spectrometer, CASI (Compact Airborne Spectrographic Imager), AVIRIS (Airborne Visible Infrared Imaging Spectrometer), HYDICE (Hyperspectral Digital Imagery Collection Experiment) y MASTER (MODIS/ASTER Simulator). Se han disenado experimentos sobre ambitos naturales, urbanos y semiurbanos de diferente complejidad. Se ha evaluado el comportamiento de los diferentes detectores de anomalias a traves de 23 tests correspondientes a 15 areas de estudio agrupados en 6 espacios o escenarios: Urbano - E1, Semiurbano/Industrial/Periferia Urbana - E2, Forestal - E3, Agricola - E4, Geologico/Volcanico - E5 y Otros Espacios Agua, Nubes y Sombras - E6. El tipo de sensores evaluados se caracteriza por registrar imagenes en un amplio rango de bandas, estrechas y contiguas, del espectro electromagnetico. La Tesis se ha centrado en el desarrollo de tecnicas que permiten separar y extraer automaticamente pixeles o grupos de pixeles cuya firma espectral difiere de manera discriminante de las que tiene alrededor, adoptando para ello como espacio muestral parte o el conjunto de las bandas espectrales en las que ha registrado radiancia el sensor hiperespectral. Un factor a tener en cuenta en la investigacion ha sido el propio instrumento de medida, es decir, la caracterizacion de los distintos subsistemas, sensores imagen y auxiliares, que intervienen en el proceso. Para poder emplear cuantitativamente los datos medidos ha sido necesario definir las relaciones espaciales y espectrales del sensor con la superficie observada y las potenciales anomalias y patrones objetivos de deteccion. Se ha analizado la repercusion que en la deteccion de anomalias tiene el tipo de sensor, tanto en su configuracion espectral como en las estrategias de diseno a la hora de registrar la radiacion prodecente de las superficies, siendo los dos tipos principales de sensores estudiados los barredores o escaneres de espejo giratorio (whiskbroom) y los barredores o escaneres de empuje (pushbroom). Se han definido distintos escenarios en la investigacion, lo que ha permitido abarcar una amplia variabilidad de entornos geomorfologicos y de tipos de coberturas, en ambientes mediterraneos, de latitudes medias y tropicales. En resumen, esta Tesis presenta una tecnica de deteccion de anomalias para datos hiperespectrales denominada DAFT en su variante de PP, basada en una reduccion de la dimensionalidad proyectando el fondo en un rango de longitudes de onda del espectro termico distinto de la proyeccion de las anomalias u objetivos sin firma espectral conocida. La metodologia propuesta ha sido probada con imagenes hiperespectrales reales de diferentes sensores y en diferentes escenarios o espacios, por lo tanto de diferente fondo espectral tambien, donde los resultados muestran los beneficios de la aproximacion en la deteccion de una gran variedad de objetos cuyas firmas espectrales tienen suficiente desviacion respecto del fondo. La tecnica resulta ser automatica en el sentido de que no hay necesidad de ajuste de parametros, dando resultados significativos en todos los casos. Incluso los objetos de tamano subpixel, que no pueden distinguirse a simple vista por el ojo humano en la imagen original, pueden ser detectados como anomalias. Ademas, se realiza una comparacion entre el enfoque propuesto, la popular tecnica RX y otros detectores tanto en su modalidad global como local. El metodo propuesto supera a los demas en determinados escenarios, demostrando su capacidad para reducir la proporcion de falsas alarmas. Los resultados del algoritmo automatico DAFT desarrollado, han demostrado la mejora en la definicion cualitativa de las anomalias espectrales que identifican a entidades diferentes en o bajo superficie, reemplazando para ello el modelo clasico de distribucion normal con un metodo robusto que contempla distintas alternativas desde el momento mismo de la adquisicion del dato hiperespectral. Para su consecucion ha sido necesario analizar la relacion entre parametros biofisicos, como la reflectancia y la emisividad de los materiales, y la distribucion espacial de entidades detectadas respecto de su entorno. Por ultimo, el algoritmo DAFT ha sido elegido como el mas adecuado para sensores que adquieren datos en el TIR, ya que presenta el mejor acuerdo con los datos de referencia, demostrando una gran eficacia computacional que facilita su implementacion en un sistema de cartografia que proyecte de forma automatica en un marco geografico de referencia las anomalias detectadas, lo que confirma un significativo avance hacia un sistema en lo que se denomina cartografia en tiempo real. The aim of this Thesis is to develop a specific methodology in order to be applied in automatic detection anomalies processes using hyperspectral data also called hyperspectral scenes, and to improve the classification processes. Several scenarios, areas and their relationship with surfaces and objects have been tested. The spectral characteristics of reflectance parameter and emissivity in the pattern recognition of urban materials in several hyperspectral scenes have also been tested. Spectral ranges of the visible-near infrared (VNIR), shortwave infrared (SWIR) and thermal infrared (TIR) from hyperspectral data cubes of AHS (Airborne Hyperspectral System), HyMAP Imaging Spectrometer, CASI (Compact Airborne Spectrographic Imager), AVIRIS (Airborne Visible Infrared Imaging Spectrometer), HYDICE (Hyperspectral Digital Imagery Collection Experiment) and MASTER (MODIS/ASTER Simulator) have been used in this research. It is assumed that there is not prior knowledge of the targets in anomaly detection. Thus, the pixels are automatically separated according to their spectral information, significantly differentiated with respect to a background, either globally for the full scene, or locally by the image segmentation. Several experiments on different scenarios have been designed, analyzing the behavior of the standard RX anomaly detector and different methods based on subspace, image projection and segmentation-based anomaly detection methods. Results and their consequences in unsupervised classification processes are discussed. Detection of spectral anomalies aims at extracting automatically pixels that show significant responses in relation of their surroundings. This Thesis deals with the unsupervised technique of target detection, also called anomaly detection. Since this technique assumes no prior knowledge about the target or the statistical characteristics of the data, the only available option is to look for objects that are differentiated from the background. Several methods have been developed in the last decades, allowing a better understanding of the relationships between the image dimensionality and the optimization of search procedures as well as the subpixel differentiation of the spectral mixture and its implications in anomalous responses. In other sense, image spectrometry has proven to be efficient in the characterization of materials, based on statistical methods using a specific reflection and absorption bands. Spectral configurations in the VNIR, SWIR and TIR have been successfully used for mapping materials in different urban scenarios. There has been an increasing interest in the use of high resolution data (both spatial and spectral) to detect small objects and to discriminate surfaces in areas with urban complexity. This has come to be known as target detection which can be either supervised or unsupervised. In supervised target detection, algorithms lean on prior knowledge, such as the spectral signature. The detection process for matching signatures is not straightforward due to the complications of converting data airborne sensor with material spectra in the ground. This could be further complicated by the large number of possible objects of interest, as well as uncertainty as to the reflectance or emissivity of these objects and surfaces. An important objective in this research is to establish relationships that allow linking spectral anomalies with what can be called informational anomalies and, therefore, identify information related to anomalous responses in some places rather than simply spotting differences from the background. The development in recent years of new hyperspectral sensors and techniques, widen the possibilities for applications in remote sensing of the Earth. Remote sensing systems measure and record electromagnetic disturbances that the surveyed objects induce in their surroundings, by means of different sensors mounted on airborne or space platforms. Map updating is important for management and decisions making people, because of the fast changes that usually happen in natural, urban and semi urban areas. It is necessary to optimize the methodology for obtaining the best from remote sensing techniques from hyperspectral data. The first problem with hyperspectral data is to reduce the dimensionality, keeping the maximum amount of information. Hyperspectral sensors augment considerably the amount of information, this allows us to obtain a better precision on the separation of material but at the same time it is necessary to calculate a bigger number of parameters, and the precision lowers with the increase in the number of bands. This is known as the Hughes effects (Bellman, 1957) . Hyperspectral imagery allows us to discriminate between a huge number of different materials however some land and urban covers are made up with similar material and respond similarly which produces confusion in the classification. The training and the algorithm used for mapping are also important for the final result and some properties of thermal spectrum for detecting land cover will be studied. In summary, this Thesis presents a new technique for anomaly detection in hyperspectral data called DAFT, as a PP's variant, based on dimensionality reduction by projecting anomalies or targets with unknown spectral signature to the background, in a range thermal spectrum wavelengths. The proposed methodology has been tested with hyperspectral images from different imaging spectrometers corresponding to several places or scenarios, therefore with different spectral background. The results show the benefits of the approach to the detection of a variety of targets whose spectral signatures have sufficient deviation in relation to the background. DAFT is an automated technique in the sense that there is not necessary to adjust parameters, providing significant results in all cases. Subpixel anomalies which cannot be distinguished by the human eye, on the original image, however can be detected as outliers due to the projection of the VNIR end members with a very strong thermal contrast. Furthermore, a comparison between the proposed approach and the well-known RX detector is performed at both modes, global and local. The proposed method outperforms the existents in particular scenarios, demonstrating its performance to reduce the probability of false alarms. The results of the automatic algorithm DAFT have demonstrated improvement in the qualitative definition of the spectral anomalies by replacing the classical model by the normal distribution with a robust method. For their achievement has been necessary to analyze the relationship between biophysical parameters such as reflectance and emissivity, and the spatial distribution of detected entities with respect to their environment, as for example some buried or semi-buried materials, or building covers of asbestos, cellular polycarbonate-PVC or metal composites. Finally, the DAFT method has been chosen as the most suitable for anomaly detection using imaging spectrometers that acquire them in the thermal infrared spectrum, since it presents the best results in comparison with the reference data, demonstrating great computational efficiency that facilitates its implementation in a mapping system towards, what is called, Real-Time Mapping.

Organic protomolecule assembly in igneous minerals

C—H stretching bands, νCH, in the infrared spectrum of single crystals of nominally high purity, of laboratory-grown MgO, and of natural upper mantle olivine, provide an “organic” signature that closely resembles the symmetrical and asymmetrical C—H stretching modes of aliphatic —CH2 units. The νCH bands indicate that H2O and CO2, dissolved in the matrix of these minerals, converted to form H2 and chemically reduced C, which in turn formed C—H entities, probably through segregation into defects such as dislocations. Heating causes the C—H bonds to pyrolyze and the νCH bands to disappear, but annealing at 70°C causes them to reappear within a few days or weeks. Modeling dislocations in MgO suggests that the segregation of C can lead to Cx chains, x = 4, with the terminal C atoms anchored to the MgO matrix by bonding to two O−. Allowing H2 to react with such Cx chains leads to [O2C(CH2)2CO2] or similar precipitates. It is suggested that such Cx—Hy—Oz entities represent protomolecules from which derive the short-chain carboxylic and dicarboxylic and the medium-chain fatty acids that have been solvent-extracted from crushed MgO and olivine single crystals, respectively. Thus, it appears that the hard, dense matrix of igneous minerals represents a medium in which protomolecular units can be assembled. During weathering of rocks, the protomolecular units turn into complex organic molecules. These processes may have provided stereochemically constrained organics to the early Earth that were crucial to the emergence of life.

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).

Intra-population variation and geographic correlation in Canthon humectus hidalgoensis using FTIR-ATR spectroscopy

In some cases external morphology is not sufficient to discern between populations of a species, as occurs in the dung beetle Canthon humectus hidalgoensis Bates; and much less to determine phenotypic distances between them. FTIR-ATR spectroscopy show several advantages over other identification techniques (e.g. morphological, genetic, and cuticular hydrocarbons analysis) due to the non-invasive manner of the sample preparation, the relative speed of sample analysis and the low-cost of this technology. The infrared spectrum obtained is recognized to give a unique ‘fingerprint’ because vibrational spectra are specific and unique to the molecular nature of the sample. In our study, results showed that proteins, amino acids and aromatic ethers of insect exocuticle have promising discriminative power to discern between different populations of C. h. hidalgoensis. Furthermore, the correlation between geographic distances between populations and the chemical distances obtained by proteins + amino acids + aromatic ethers was statistically significant, showing that the spectral and spatial information available of the taxa together with appropriated chemometric methods may help to a better understanding of the identity, structure, dynamics and diversity of insect populations.

Synthesis and magnetic properties of Fe-Mn-Cr multinuclear complexes with 4-amino-1,2,4-triazole and oxalate ligands

A multinuclear Fe-Mn-Cr complex with 4-amino-1,2,4-triazole (NH2trz) and oxalate (ox) ligands has been synthesized successfully. The formula of the [Fe(NH2trz)3][ClO4][MnCr(ox)3].4H2O complex has been obtained based on the metal and C, H, N contents. The presence of water molecules, metal-ligand bonding and bridge ligand in the multinuclear complex has been confirmed by its infrared spectrum. The compound crystallizes in the hexagonal system with cell parameters of a = b = 18.695 Å and c = 57.351 Å. The compound shows a gradual spin crossover for iron(II) in the [Fe(NH2trz)3]2+ with transition temperature (T1/2) of 205 K. The antiferromagnetic interaction between Cr(III) and Mn(II) ions in the [MnCr(ox)3]n n- network is observed from the Weiss constant (θ) of –2.3 K.

Efeito da salinidade da água do mar no rendimento, composição e atividades biológicas de frações polissacarídicas da Chlorophyta Caulerpa cupressoides var. flabellata

Seaweeds sulfated polysaccharides have been described as having various pharmacological activities. However, nothing is known about the influence of salinity on the structure of sulfated polysaccharides from green seaweed and pharmacological activities they perform. Therefore, the main aim of this study was to evaluate the effect of salinity of seawater on yield and composition of polysaccharides-rich fractions from green seaweed Caulerpa cupressoides var. flabellata, collected in two different salinities beaches of the coast of Rio Grande do Norte, and to verify the influence of salinity on their biological activities. We extracted four sulfated polysaccharides-rich fractions from C. cupressoides collected in Camapum beach (denominated CCM F0.3; F0.5; F1.0; F2.0), which the seawater has higher salinity, and Buzios beach (denominated CCB F0.3; F0.5; F1.0; F2.0). Different from that observed for other seaweeds, the proximate composition of C. cupressoides did not change with increased salinity. Moreover, interestingly, the C. cupresoides have high amounts of protein, greater even than other edible seaweeds. There was no significant difference (p>0.05) between the yield of polysaccharide fractions of CCM and its CCB counterparts, which indicates that salinity does not interfere with the yield of polysaccharide fractions. However, there was a significant difference in the sulfate/sugar ratio of F0.3 (p<0.05) and F0.5 (p<0.01) (CCM F0.3 and CCB F0.5 was higher than those determined for their counterparts), while the sulfate/sugar ratio the F1.0 and F2.0 did not change significantly (p>0.05) with salinity. This result suggested that the observed difference in the sulfate/sugar ratio between the fractions from CCM and CCB, is not merely a function of salinity, but probably also is related to the biological function of these biopolymers in seaweed. In addition, the salinity variation between collection sites did not influence algal monosaccharide composition, eletrophoretic mobility or the infrared spectrum of polysaccharides, demonstrating that the salinity does not change the composition of sulfated polysaccharides of C. cupressoides. There were differences in antioxidant and anticoagulant fractions between CCM and CCB. CCB F0.3 (more sulfated) had higher total antioxidant capacity that CCM F0.3, since the chelating ability the CCM F0.5 was more potent than CCB F0.5 (more sulfated). These data indicate that the activities of sulfated polysaccharides from CCM and CCB depend on the spatial patterns of sulfate groups and that it is unlikely to be merely a charge density effect. C. cupressoides polysaccharides also exhibited anticoagulant activity in the intrinsic (aPTT test) and extrinsic pathway (PT test). CCB F1.0 and CCM F1.0 showed different (p<0,001) aPTT activity, although F0.3 and F0.5 showed no difference (p>0,05) between CCM and CCB, corroborating the fact that the sulfate/sugar ratio is not a determining factor for biological activity, but rather for sulfate distribution along the sugar chain. Moreover, F0.3 and F0.5 activity in aPTT test was similar to that of clexane®, anticoagulant drug. In addition, F0.5 showed PT activity. These results suggest that salinity may have created subtle differences in the structure of sulfated polysaccharides, such as the distribution of sulfate groups, which would cause differences in biological activities between the fractions of the CCM and the CCB