L'investigation du système BaBiO3-BaRuO3 a permis de mettre en évidence trois nouvelles phases qui cristallisent dans trois différents polytypes de la perovskite. L'interprétation des propriétés magnétiques de ces phases, ainsi que des considérations cristallochimiques, montrent qu'il s'établit un phénomène de transfert de charge entre le ruthénium et le bismuth selon le schéma réactionnel: 2 Ru4+ + Bi5+->2 Ru5+ + Bi3+. L'activité catalytique de ces composés pour la réduction de NO a été étudiée. Cinq nouveaux composés ont ete isoles dans le système Ba(Sr)-Ru-O. Leurs structures sont caractérisées par des groupements [Ru3O12] ou [Ru2O9], formant des systèmes de basse dimensionnalité (clusters, système 2D). Des modèles structuraux ont été développés et ont permis d'établir des filiations structurales avec des structures type telles que K2NiF4, la perovskite 2H et Sr4PtO6. Les propriétés magnétiques ont été étudiées et pour certaines phases, interpretées en termes d'entités isolées selon un modèle d'Heisenberg.

Dans une première partie, nous mesurons l'affinité de l'interaction entre [Ru(pby)2dppz]2+ et l'ADN en utilisant la luminescence induite lors de la complexation. Nous étudions l'évolution de l'affinité lorsque la force ionique de la solution augmente. Dans une deuxième partie, nous modifions les extrémités d'un double brin d'ADN en y greffant des fluorophores. De la mesure de transfert d'énergie non-radiative entre ces fluorophores, nous étudions l'évolution de la longueur du complexe. Nous effectuons un dosage d'un double brin de 15 paires de bases d'ADN par le complexe ruthéné. Nous nous servons de la luminescence induite par l'intercalation du groupement dppz. Cependant, l'incrément de luminescence par groupement intercalé n'est pas connu, et nous ne pouvons pas le mesurer en saturant le brin d'ADN. Nous utilisons alors une technique mise au point par Nishida [Method for Measuring the Binding of Small Molecules to Proteins from Binding-Induced Alterations of Physical-Chemical Properties], dans laquelle deux titrations de deux solutions d'ADN de deux concentrations différentes sont effectuées. En utilisant le fait que, lorsque deux solutions d'ADN complexé par le composé ruthéné, possèdent la même luminescence par paire de base , le taux de complexation de ces deux solutions doit être le même, nous pouvons alors déterminer, sans hypothèse supplémentaire, le taux de complexation de l'ADN. De l'évolution de ce taux en fonction avec la concentration de ligand, nous déduisons son affinité pour l'ADN. Nous étudions maintenant le changement de longueur d'un double brin d'ADN de 15 paires de bases, modifié à ses deux extrémités par deux fluorophores : Alexa488 et Alexa568. Lorsque Alexa 488 est porté dans un état excité, il peut se désexciter en transférant de l'énergie de manière non-radiative à Alexa568, qui se désexcite alors en émettant des photons de plus faibles énergie que ceux émis par Alexa488. L'efficacité de ce transfert d'énergie peut être quantifié à partir de la mesure des intensités émises à basse et haute énergie. Elle dépend a priori de l'efficacité couplage (et en conséquence de la distance) entre les deux fluorophores. Nous effectuons des mesures de temps de vie des états excités de chacun des fluorophores. Nous avons observé que l'addition de ligand a pour conséquence une forte inhibition quenching des fluorophores. De l'analyse de l'évolution du temps de vie du fluorophore donneur d'une part et de celui du fluorophore accepteur d'autre part, nous déduisons l'évolution de l'efficacité du transfert d'énergie en fonction de la concentration de ligand. Nous confrontons les résultats obtenus par chacune de ces analyses, et en déduisons finalement, en nous servant de l'analyse de l'équilibre effectuée dans la première partie, l'évolution de la longueur de la chaîne en fonction du taux de complexation

Made available in DSpace on 2014-12-17T14:08:36Z (GMT). No. of bitstreams: 1 NisarRO.pdf: 2584049 bytes, checksum: f18a00826204d450659ba7d3316e358e (MD5) Previous issue date: 2009-05-08 / Among the many types of noise observed in seismic land acquisition there is one produced by surface waves called Ground Roll that is a particular type of Rayleigh wave which characteristics are high amplitude, low frequency and low velocity (generating a cone with high dip). Ground roll contaminates the relevant signals and can mask the relevant information, carried by waves scattered in deeper regions of the geological layers. In this thesis, we will present a method that attenuates the ground roll. The technique consists in to decompose the seismogram in a basis of curvelet functions that are localized in time, in frequency, and also, incorporate an angular orientation. These characteristics allow to construct a curvelet filter that takes in consideration the localization of denoise in scales, times and angles in the seismogram. The method was tested with real data and the results were very good / Dentre os diversos tipos de ru?dos existentes nos dados s?smicos terrestres est? o Ru?do de Rolamento Superficial tamb?m conhecido como ground roll que ? um tipo particular de ondas de Rayleigh com amplitude forte, freq??ncia baixa e velocidade baixa que gera um cone de grande mergulho no sismograma. O ru?do de rolamento superficial contamina os sinais relevantes e pode mascarar a informa??o desejada, trazidas por ondas espalhadas em regi?es mais profundas das camadas geol?gicas. Nesta disserta??o ser? apresentada uma ferramenta que atenua o ru?do de rolamento superficial baseada na transformada curvelet. A t?cnica consiste em decompor o sismograma em uma base de fun??es curvelets as quais s?o localizadas no tempo e na freq??ncia, al?m de incorporarem uma orienta??o angular. Tais caracter?sticas permitem a constru??o de um filtro curvelet que leva em considera??o a localiza??o do ru?do em escalas, limiares de corte dos coeficientes curvelets e dos ?ngulos no sismograma. O m?todo foi testado com dados reais e os resultados obtidos foram muito bons

Made available in DSpace on 2014-12-17T14:08:44Z (GMT). No. of bitstreams: 1 DanielE_DISSERT.pdf: 1217613 bytes, checksum: edb565b9e30a0c09780fcf4efd4a52dc (MD5) Previous issue date: 2011-04-05 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / In the Hydrocarbon exploration activities, the great enigma is the location of the deposits. Great efforts are undertaken in an attempt to better identify them, locate them and at the same time, enhance cost-effectiveness relationship of extraction of oil. Seismic methods are the most widely used because they are indirect, i.e., probing the subsurface layers without invading them. Seismogram is the representation of the Earth s interior and its structures through a conveniently disposed arrangement of the data obtained by seismic reflection. A major problem in this representation is the intensity and variety of present noise in the seismogram, as the surface bearing noise that contaminates the relevant signals, and may mask the desired information, brought by waves scattered in deeper regions of the geological layers. It was developed a tool to suppress these noises based on wavelet transform 1D and 2D. The Java language program makes the separation of seismic images considering the directions (horizontal, vertical, mixed or local) and bands of wavelengths that form these images, using the Daubechies Wavelets, Auto-resolution and Tensor Product of wavelet bases. Besides, it was developed the option in a single image, using the tensor product of two-dimensional wavelets or one-wavelet tensor product by identities. In the latter case, we have the wavelet decomposition in a two dimensional signal in a single direction. This decomposition has allowed to lengthen a certain direction the two-dimensional Wavelets, correcting the effects of scales by applying Auto-resolutions. In other words, it has been improved the treatment of a seismic image using 1D wavelet and 2D wavelet at different stages of Auto-resolution. It was also implemented improvements in the display of images associated with breakdowns in each Auto-resolution, facilitating the choices of images with the signals of interest for image reconstruction without noise. The program was tested with real data and the results were good / Na atividade explorat?ria de hidrocarbonetos a grande inc?gnita ? a localiza??o das jazidas. Grandes esfor?os s?o empreendidos na tentativa de melhor identific?-las, localiz?-las e, ao mesmo tempo, otimizar a rela??o custo-benef?cio da extra??o de Petr?leo. Os m?todos s?smicos s?o os mais utilizados pelo fato de serem indiretos, isto ?, sondam as camadas de subsuperf?cie sem invadi-las. O sismograma ? a representa??o do interior da Terra e de suas estruturas atrav?s de um arranjo convenientemente disposto dos dados obtidos por meio da s?smica de reflex?o. Um grande problema nessa representa??o ? a intensidade e variedade de ru?dos presentes no sismograma, como o ru?do de rolamento superficial que contamina os sinais relevantes e pode mascarar as informa??es desejadas, trazidas por ondas espalhadas em regi?es mais profundas das camadas geol?gicas. Desenvolvemos uma ferramenta para suprimir estes ru?dos que usa transformadas Wavelets 1D e 2D. O programa, em linguagem Java, faz a separa??o das imagens S?smicas considerando as dire??es (horizontal, vertical e mistas ou locais) e faixas de comprimentos de ondas que formam essas imagens, usando Wavelets de Daubechies, Autoresolu??o que duplica o comprimento das ondas e Produto Tensorial das bases de Wavelets. Desenvolvemos a op??o, em uma mesma imagem, de usar o produto tensorial de Wavelets de dimens?o 2 ou produto tensorial de Wavelets de dimens?o 1 pelas identidades. Neste ?ltimo caso, temos a Decomposi??o em Wavelets de um sinal bidimensional em uma ?nica dire??o. Esta decomposi??o permite alongar numa determinada dire??o as Wavelets bidimensionais, corrigindo efeitos de escalas ao aplicarmos Autoresolu??es. Em outras palavras, aperfei?oamos o tratamento de uma imagem s?smica, usandoWavelet 1D eWavelet 2D em etapas diferentes de Autoresolu??es. Tamb?m implementamos melhorias na visualiza??o das imagens associadas ?s decomposi??es em cada Autoresolu??o, facilitando as escolhas das imagens com os sinais de interesse para reconstru??o da imagem sem os ru?dos. O programa foi testado com dados reais e os resultados obtidos foram de boa qualidade

The alluring order in which complex biological networks exist in nature stimulated the interest of chemists to replicate such systems synthetically. With such examples as the deoxyribonucleic acid (DNA) double helix and the phospholipid bilayers, the influence of forces within these networks are solely credited for their excellent stability. The synthetically ordered chemical networks are also held together by interactions within them with little or no external force as seen in the natural systems. This spontaneous and reversible association of molecules or ions to form larger, more complex entities according to the intrinsic information contained in the molecules themselves is known as self-assembly. The self-assembly process is pre-eminent to the formation of ordered structures emerging spontaneously from the precursors in which, the overall structure of the final assemblies is controlled by the symmetry of each of the building blocks. The highly ordered and thermodynamically stable scaffolds are formed via non-covalent interactions including hydrophobic interaction, π-stacking, dipole-dipole interaction, ion-dipole interaction, hydrogen bonding, Van der Waals forces, solvophobic interaction and reversible metal-ligand coordination. These non-covalent interactions are termed as supramolecular interactions. Among several of these self-assembly protocols, the directional metal-ligand coordination strategy has evolved to be a well-established process for the preparation of supramolecular ensembles with pre-defined shapes, cavities and functionalities in a “one-pot” synthesis. Coordination-driven self-assembly strategy is governed by the combination of electron-deficient metal centres and electron-rich organic ligands. The outcome of the final supramolecular architecture is determined by the choice of the pre-designed metal acceptor building blocks as well as the flexibility and steric demands of the ancillary organic ligands. Accurate stoichiometry of each of the building blocks is also a very important factor in coordination-driven self-assembly; although serendipity sometimes happen which is quite unexpected. A large number of these self-assembled supramolecular networks have found useful applications in optoelectronics, material chemistry, adsorption, drug delivery, catalysis, host-guest chemistry, photo- and electro-chemical sensing as well as prospective chemotherapeutics. Transition metals are widely desired as electron-deficient building blocks in supramolecular chemistry. They readily accept lone pair of electrons from electron-rich building blocks. The functional properties of these metals have also been considered during the pre-design of these electron acceptors such that the functional property of each metal can be induced in the final architecture. Pd(II) and Pt(II) metals are highly desirable electron acceptors in supramolecular self-assembly because of their rigid square-planar nature. Nonetheless, Ru(II) and Fe(II) have also been explored as electron acceptors based on their octahedral geometry. Electron-rich building blocks have lone pairs of electrons on their donor sites (nitrogen, oxygen or sulphur) which effortlessly donate electrons to electron-deficient building blocks. The pyridyl appended ligands have been mostly used as the electron-rich building blocks in the construction of supramolecular architectures because of their predictable coordination modes and the symmetrical nature. However, imidazole appended ligands holds a distinctive spot in supramolecular chemistry because of its rotational flexibility and unpredictable binding modes which may lead to uncommon architectures not obtainable with pyridyl appended ligands. Thus, imidazole-based supramolecular architectures are less explored because the outcome of the final architecture cannot be pre-determined during the design. Ruthenium p-cymene complexes have spurred much interest in the last two decades because they possess extremely stable octahedral geometry and has been extensively used in the construction of 2D and 3D supramolecular architectures. The recent search for viable alternatives to platinum drugs in cancer chemotherapy discovered ruthenium as an excellent alternative to platinum because of its low toxicity when compared to platinum. The robustness of the arene head on interaction with biomolecules and the accumulation of large molecular weight compounds specifically in cancer cells rather than in healthy cells also improved the activity of ruthenium supramolecular architectures in cancer therapy. This recent outcome has propelled significant research channelled towards synthesizing better ruthenium-based chemotherapeutics. Additionally, the presence of two different metals in a single self-assembled architecture may also impart an increased activity when compared to the individual activity of each metal. Thus, the heterometallic supramolecular architectures can open a new kind of chemotherapeutics which may give a distinct mechanistic pathway different from those reported in literature. Chapter 1 of this thesis describes the coordination-driven self-assembly strategy with specific emphasis on ruthenium p-cymene self-assembled architectures and their applications. A brief introduction on cancer and cancer therapy is discussed. The use of mononuclear and dinuclear metal-based chemotherapeutics is included while the use of heterometallic complexes as anticancer agents was also highlighted. Chapter 2 showcases the self-assembly of a series of 2D and 3D ruthenium(II) p-cymene architectures constructed from bidentate and tridentate rigid imidazole-based ligands and dinuclear ruthenium(II) building units. The influence of the rotational flexibility of the imidazole ligands on the final architecture was probed. In spite of the likelihood of the formation of different conformational isomeric architectures (syn and anti) and/or polymeric products due to free rotation on the donor sites of the imidazole ligands, the exclusive formation of a single conformational isomer (anti) as the only product turned out to be a noteworthy observation. This indicates that the coordination mode and flexibility of imidazole ligand can control and determine the geometry, topology and conformations of the final molecular architectures. Scheme 1: Self-assembly of 2D macrocycles [2 - 7](OTf)4 employing dinuclear ruthenium(II) building units [1a - 1c](OTf)2 and bidentate rigid imidazole ligands L1 - L2 in methanol at room temperature. Furthermore, the unexpected formation of a tetranuclear cationic macrocycle [8](OTf)4 was reported in the 2 + 3 self-assembly reaction of triazine-based tridentate imidazole ligand L3 and dinuclear ruthenium(II) building unit [1a](OTf)4 over the expected hexanuclear prismatic cage [8a](OTf)6 which is quite surprising. Scheme 2: Schematic representation of the formation of an unexpected tetranuclear macrocycle [8](OTf)4 over the expected hexanuclear prismatic cage [8a](OTf)6. Chapter 3 reports the synthesis of eight octanuclear cages via the coordination-driven self-assembly of two tetradentate pyridyl-based organic ligands and four dinuclear p-cymene Ru(II) acceptor clips. These octanuclear cages were explored in vitro as potential anticancer agents against human lung adenocarcinoma A549 and human cervical cancer HeLa cell lines. Four of the cages with polyaromatic spacers in their Ru(II) acceptor clip unit showed very low micromolar IC50 values and also possess higher anticancer activity than cisplatin against the tested cancer cell lines. The four dinuclear p-cymene Ru(II) acceptor clips A3 in OC-3 and OC-7 revealed some kind of synergy which is evident in their IC50 values against the tested cancer cell lines. In addition, OC-3 and OC-7 trigger both early and late apoptotic phases while OC-4 and OC-8 trigger majorly late apoptotic phase in the cancer cell lines tested. The mechanistic pathway by which cell death is progressing is through the generation of reactive oxygen species (ROS) which is of significant amount in OC-4 and OC-8. Scheme 3: Self-assembly of the discrete octanuclear cages (OC-1 - OC-8) in methanol at room temperature and the schematic illustration of the apoptosis mechanistic pathway. Chapter 4 describes the use of “metalloligands” as electron-rich building blocks and the subsequent use of the metalloligand for “one-pot” self-assembly reactions in the presence of electron-deficient metal acceptor building blocks. The pyridyl donors are the most preferred in metalloligands because of their predictable directionality in self-assembly. The introduction of a second metal into the ligand component of the self-assembled architecture is to bestow additional functionality as well as to construct elegantly designed discrete heterobimetallic supramolecular architectures. Four discrete Ru(II)-Pt(II) hexanuclear trigonal prismatic cages were synthesized employing a tritopic platinum(II) metalloligand and four p-cymene ruthenium(II) clips via coordination-driven self-assembly. The formation of these cages were confirmed by well-known spectroscopic techniques and their structural features was elucidated by geometry optimization. In vitro anticancer studies of these heterometallic cages failed because of solubility challenges in the culture media presumably due to their high molecular weights and many alkyl groups. Scheme 4: Energy minimized structures of the heterometallic trigonal prismatic cages 3a (left) and 3b (right). Hydrogen atoms have been removed for the sake of clarity [Ru: green, Pt: pink, O: red, N: blue, P: orange, C: grey]. Chapter 5 discusses the synthesis of two bidentate platinum(II) metalloligands as well as the self-assembly of six new heterometallic rectangles obtained from four Ru2(OOꓵOO)2(p-cymene)2Cl2 pillars and two bidentate pyridyl-based platinum(II) metalloligands. The Ru4Pt2 and Ru4Pt4 rectangles were structurally characterized and supported by geometry optimisation. Additionally, two Ru4Pt2 and two Ru4Pt4 rectangles were examined for their anticancer properties in eight human cancer cell lines with the aim of checking if the platinum metal centres in the metalloligands can enhance the anticancer activity of the rectangles. The results showed that these heterometallic rectangles are cytotoxic against the cancer cell lines tested but the incorporation of platinum(II) metal(s) into the metalloligand did not further enhance the cytotoxicity in the rectangles tested as hypothesized. The mechanism of cell death is via the generation of reactive oxygen species (ROS) and two Ru4Pt4 rectangles activates both early and late apoptosis. Cell cycle analysis showed that one of the Ru4Pt4 rectangles is a moderate inhibitor of cell cycle progression at the sub G1 phase similar to cisplatin while nuclear condensation and cell blebbing in the cells was also observed in the presence of the two Ru4Pt4 rectangles tested. The overall activity of the heterometallarectangles against the cancer cell lines tested was increased when they exist as a single entity thus reiterating the importance of heterobimetallic supramolecular architectures in cancer therapy. Scheme 5: Schematic diagram of the discrete Ru4Pt4 heterometallic rectangles and illustration of the cell death pathway. The results of the investigation reported in this thesis contribute to the rapidly developing field of organometallic ruthenium(II) self-assembled anticancer chemotherapeutics with specific evidences of the mechanistic pathway of cell death. This results can further guide the design and development of better chemotherapeutics for future use.

Made available in DSpace on 2014-12-17T15:36:39Z (GMT). No. of bitstreams: 1 MarcosRRS_TESE_2red.pdf: 2914202 bytes, checksum: 607aa226333ce661d0e57d380f43b9e9 (MD5) Previous issue date: 2012-08-07 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The acoustic ecology concept involve the relation between the live organisms and their sound environment and is applied in the present work to study the context in which the humpback whale (Megaptera novaeangliae) singing behavior, known as the most complex display in the nature, occurred in the northeastern Brazilian coast, outside the core area of Abrolhos Bank, between 2005 and 2010.I analyze the singer male occurrence , their spatial distribution and probable relations with oceanographic features, such as depth, tide regimen and moon phases. I also describe the acoustic structure and temporal variation of the singing behavior, based on song frequency and time measurements outside the Abrolhos Bank, and further compare the song complexity, registered in the same period, between Abrolhos Bank (16?- 19? S, 37?- 39? W) and the adjacent North Coast, herein considered from Itacar? (14? S, 38? W) to Aracaju (11? S, 37? W). Additionally, I look for describe and analyze anthropogenic noise sources in the marine environment of the study area, produced by the oil industry as well as by the whale watching operation, relating their frequencies to the acoustic niche utilized by the humpbacks. The results indicated a great plasticity in the singing behavior, evidenced by the occurrence of singer males in diverse social structures, from solitary individuals to other groups, even containing females and calves, as well as by the diversity which compound the song, when compared between two regions inside the same breeding area, which present distinct oceanographic characteristics. The singer male distribution may be related with the continental shelf extent along the study area. The anthropogenic noise presented frequency range, amplitude and sound intensity in potential to interfere acoustically in the singing behavior of the species, may resulting in disturbance during the breeding season in the Brazilian coast. Implications about the obtained results in the humpback whale mating system are discussed. In this way, I pretend to contribute with the acoustic ecology subject and provide information to subsidize humpback whale conservation / O conceito de ecologia ac?stica envolve a rela??o entre os organismos vivos e o seu ambiente sonoro e ? aplicado no presente trabalho para estudar o contexto no qual ocorreu o comportamento de canto da baleia jubarte (Megaptera novaeangliae), considerado o mais complexo comportamento reprodutivo (display) da natureza, na costa nordeste do Brasil, fora da concentra??o reprodutiva do Banco de Abrolhos, entre os anos de 2005 e 2010. Analiso a ocorr?ncia de machos cantores em diferentes estruturas de grupo, sua distribui??o espacial e prov?veis rela??es com fatores oceanogr?ficos, como profundidade, regime de mar?s e fases da lua. Tamb?m descrevo a estrutura ac?stica e a varia??o temporal do comportamento de canto, baseado em medi??es de frequ?ncia e tempo dos cantos, fora do Banco de Abrolhos, al?m de comparar a complexidade do canto, registrada no mesmo per?odo de estudo, entre o Banco de Abrolhos (16?- 19? S, 37?- 39? W), e a Costa Norte adjacente, aqui considerada desde Itacar? (14? S, 38? W) a Aracaj? (11? S, 37? W). Ainda busco descrever e analisar as fontes de ru?dos antropog?nicos no ambiente marinho da ?rea de estudo, produzidos pela atividade de explora??o de petroleo e g?s e tamb?m pelo turismo de observa??o de baleias, relacionando-os com o nicho ac?stico utilizado pela jubarte. Os resultados indicaram uma grande plasticidade no comportamento de canto, evidenciado pela ocorr?ncia dos cantores em diversas estruturas sociais, de indiv?duos solit?rios a grupos contendo outros animais, inclusive f?meas com filhotes, bem como pela diversidade que comp?e o canto da esp?cie, quando comparado entre duas regi?es dentro da mesma ?rea de reprodu??o, como o Banco de Abrolhos e a Costa Norte, que apresenta caracter?sticas oceanogr?ficas distintas. A distribui??o dos machos cantores parece estar relacionada com a extens?o da plataforma continental na ?rea de estudo. Os ru?dos antropog?nicos produzidos demonstraram uma faixa de frequ?ncias, amplitude sonora e intensidade capazes de interferir acusticamente no comportamento de canto da esp?cie, podendo resultar em dist?rbios durante o per?odo de reprodu??o da esp?cie na costa brasileira. Implica??es sobre os resultados obtidos na teoria do sistema de acasamento da esp?cie s?o discutidas. Dessa forma, pretendo contribuir com o tema da ecologia acustica e gerar informa??es que subsidiem a conserva??o da baleia jubarte

Made available in DSpace on 2014-12-17T15:36:59Z (GMT). No. of bitstreams: 1 DalilaTLM_DISSERT.pdf: 2036255 bytes, checksum: ed8754e17f7a4951187f5fb000aa8918 (MD5) Previous issue date: 2010-04-26 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The wide distribution along the Brazilian coast of specie Sotalia guianensis has been growing interest in searchers on the ecology of this species, addition to commercial interests by whalewatching. This work described the accoustic repertory of S. guianensis and their behavior associated and found if underwater noises affect this repertorie in Pipa-RN. It were analyzed 18:49h of recordings maked between april and june/2009. It were found 3258 whistles, 289 calls, 873 clicks and no gargle. The frequencies range of guiana dolphins was 1 a 48kHz and may be related to system response recorder and population s regionalization. The frequencies overlaps the noise made by motorboats, schooners and water bomb. The behavior travelling ocurred siletly in 72,58% and socialization presented no sound (56,4%) and presence of sound (43,6%). This great absence of sound may be relacioned to saving energy, probably because in this behaviors they can use physical and visual contacts. The foraging presented highest records of all class noise with 46,84% clicks, 33,84% whistles and 9,02% calls. All this sounds occurred differently in each behavior (travelling: x2 = 134,35 df = 3 p = 0,0001; foraging: x2 = 19,83 df = 3 p= 0,00018 and socialization x2 = 60,35 df = 3 p = 0,0001). It was possible to determine that underwater noise cause changes in the repertorie and does a considerable increase in whistle s number and reduce clicks. Also occurs changes in some whistles (FI: t=2,42, p=0,015; FF: t= -2,22, p=0,025), calls (FMI: t= -3,13, p=0,001; FMA: t= -3,49, p=0,0005; FD: t= -2,21, p=0,027; D: t=2,89, p=0,004) and clicks parameters (D: t= -3,85, p=0,0001; I: t= -5,32, p=0,0001) during presence of noise. These changes may be a strategy of these animals to win this sound barrier. We can not say which noise has more impact, ix however the water bomb seems to affect more the clicks and the motorboats seems to affect the others sounds. Little is know about auditive sensibility of this specie, but daily exposure to this noise may cause damage and this specie appears to have residence. The specie conservation is necessary because the population already seems to suffer damage as decrease in length of stay, number of individuals entering the inlet and the apparent diminution in the foragind during vessels presence and control standards and ambiental education can help. So, we can advance in knowledge about the ecology of this specie especially when it come to bioacoustics and their behaviors associated and reveals some of the impacts that the noise have brought to this population / A ampla distribui??o na costa brasileira da esp?cie Sotalia guianensis tem feito crescer o interesse pelos pesquisadores sobre a ecologia dessa esp?cie, al?m de interesses comerciais atrav?s do turismo de observa??o. Esse trabalho descreveu o repert?rio ac?stico S. guianensis e suas associa??es comportamentais e ainda, verificou se ru?dos subaqu?ticos de motores afetam o padr?o desse repert?rio, na regi?o de Pipa/RN. Foram analisadas 18:49h de grava??es realizadas entre os meses de abril e junho de 2009. Foram encontrados 3258 assobios, 289 gritos, 873 sequ?ncias de estalos e nenhum registro de gargarejo. A faixa de frequ?ncia dos botos variaram de 1 a 48kHz, que pode estar relacionada com a taxa de amostragem de 96kHz e com a regionaliza??o das popula??es. Essa faixa se sobrep?e as faixas utilizadas pelos ru?dos produzidos por lanchas, escunas e uma bomba d ?gua. Nas associa??es comportamentos e ac?stica, o estado de deslocamento ocorreu em 72,58% com aus?ncia de som e a socializa??o apresentou aus?ncia (56,4%) e presen?a de sons (43,6%). Essa aus?ncia de som pode estar relacionada com a economia de energia, visto que nesses comportamentos muitos eventos envolvem contatos f?sicos e visuais. A alimenta??o apresentou os maiores registros de todas as classes sonoras, com 46,84% de estalos, 33,84% de assobios e 9,02% de gritos. Todos os sons ocorreram com diferen?as significativas dentro de cada estado comportamental (deslocamento: x2 = 134,35 df = 3 p = 0,0001; alimenta??o: x2 = 19,83 df = 3 p= 0,00018 e socializa??o x2 = 60,35 df = 3 p = 0,0001). Com rela??o aos ru?dos, foi poss?vel verificar que esses sons causam modifica??es na vocaliza??o, com aumento consider?vel no n?mero de assobios e redu??o dos estalos. Ocorre, tamb?m vii altera??es de alguns par?metros dos assobios (FI: t=2,42, p=0,015; FF: t= - 2,22, p=0,025), gritos (FMI: t= -3,13, p=0,001; FMA: t= -3,49, p=0,0005; FD: t= -2,21, p=0,027; D: t=2,89, p=0,004) e estalos (D: t= -3,85, p=0,0001; I: t= -5,32, p=0,0001) durante a presen?a desses sons. Essas modifica??es podem ser uma estrat?gia que essa popula??o est? desenvolvendo para vencer a barreira dos ru?dos. N?o se pode afirmar qual dos tr?s ru?dos analisados causa maior impacto, entretanto a bomba d ?gua parece afetar mais os estalos, aumentando os valores de seus par?metros e a lancha parece afetar mais as outras classes sonoras. Pouco se sabe sobre a sensibilidade auditiva dessa esp?cie, mas exposi??es di?rias aos ru?dos podem trazer danos e essa esp?cie aparenta ter resid?ncia. Medidas para mitiga??o, como normas de controle das embarca??es e educa??o ambiental s?o necess?rias para a conserva??o da esp?cie, visto que a popula??o j? aparenta sofrer com danos como diminui??o do tempo de perman?ncia e n?mero de indiv?duos que entram na enseada, al?m da aparente diminui??o da alimenta??o durante a presen?a de embarca??es. Dessa forma, avan?a-se no conhecimento sobre a ecologia dessa esp?cie, principalmente quando se trata de bioac?stica e suas associa??es comportamentais, al?m de revelar alguns dos impactos que os ru?dos tem trazido para essa popula??o

Current fossil fuels (Coal and Petroleum) based economy is not sustainable in the long run because of its dwindling resources, and increasing concerns of climate change due to excessive carbon dioxide (CO2) emission. To mitigate CO2 emission and climate change, scientists across the world have been looking for clean and sustainable energy sources. Among them hydrogen gas (H2) could be more promising because it is the most clean fuel and can be produced from cheap source (water) which is renewable and abundant. Nevertheless, the bottleneck for hydrogen economy is lying in the cost of hydrogen production from water. Still there are no any efficient systems developed which can deliver hydrogen from water in economically viable way. Meanwhile, recent research on old molecule ammonia-borane (H3N•BH3, AB) as hydrogen source has increased the hope towards the hydrogen economy, however, catalytic recycling (or efficient regeneration) of AB from the dehydrogenated product polyborazylene (PB or BNHx) is the biggest hurdle which prevents use of AB as practical hydrogen storage material. Therefore, it is imperative to understand the dehydrogenation pathways of ammonia-borane (or related amine-boranes) which lead to polymeric or oligomeric product(s). On the other hand, methane (CH4) is abundant (mostly untamed) but cleaner fuel than its higher hydrocarbon analogs. To develop highly efficient catalytic systems to transform CH4 into methanol (gas to liquid) is of paramount importance in the field of catalysis and it could revolutionize the petrochemical industry. Therefore, to activate CH4, it is crucial to understand its binding interaction with metal center of a molecular catalyst under homogenous condition. However, these interactions are too weak and hence σ–methane complexes are very elusive. In this context, σ-H2 and σ-borane complexes bear some similarities in σ-bond coordination (and four coordinated boranes are isoelectronic with methane) could be considered as good models to study σ-methane complexes. Studying the H−H and B−H bond activation in H2 and amine-boranes, respectively, would provide fundamental insights into methane activation and its subsequent functionalization. Moreover, the proposed methanol economy by Nobel laureate George Olah seems more promising because methanol can be produced from CH4 (CO2 as well). This in turn will gradually reduce the amount of two powerful greenhouse gases from the earth’s atmosphere. Thus, efficient and economic production of methanol from CH4 and CO2 is one of most challenging problems of today in the field of catalysis and regarded as the holy grails. Furthermore, very recently formic acid (HCOOH) is envisaged as a promising reversible hydrogen storage material because it releases H2 and CO2 in the presence of a suitable and efficient catalyst or vice versa under ambient conditions. Objective of the research work: Taking the account of the above facts, the research work in this thesis is mostly confined to utilize electrophilic Ru(II)-complexes for activation of small molecules such as ammonia-borane (H3N•BH3) [and related amine-borane (Me2HN•BH3)], hydrogen (H2), methane (CH4), formic acid (HCOOH) and carbon dioxide (CO2) and investigation of their mechanistic pathways using NMR spectroscopy under homogeneous conditions. Though these molecules are small, they have huge impacts on chemical industries (energy sector and chemical synthesis: drugs/natural products) and environment [CO2 and CH4 are potent green house gases] as well. However, they are relatively inert molecules, especially CH4 and CO2, and impose very tough challenges to activate and functionalize them into useful products under ambient conditions. The partial oxidation of the strong C−H bond in CH4 for its transformation into methanol under relatively mild condition using an organometallic catalyst is considered as a holy grail in the field of catalysis which is mentioned earlier. More importantly, to develop better and highly efficient homogeneous catalytic systems for the activation of these molecules, it is imperative to understand the mechanistic pathways using well defined homogeneous metal complexes. Thus, an understanding of the interaction of these inert molecules with metal center is obligatory. In this context, discovery of a σ-complex of H2 gave remarkable insights into H−H bond activation pathways and its implications in catalytic hydrogenation reactions. Subsequently, σ-borane complexes of amine-boranes were discovered and found to be relatively more stable because of stronger M−H−B interaction and hence act as good models to study the M−H−C interaction of elusive σ-methane complex. On the other hand, HCOOH, a promising hydrogen storage material and its efficient catalytic dehydrogenation/decarboxylation and CO2 hydrogenation back to HCOOH using well defined homogeneous catalysts could lead to a sustainable energy cycle. Therefore, it is quite significant to understand the mechanistic pathways of formic acid dehydrogenation/decarboxylation and carbon dioxide reduction to formic acid for the development of next generation efficient catalysts. Chapter highlights: Keeping all these in view, we carried out thorough studies on the activation of these small molecules by electrophilic Ru(II)-complexes. This thesis provides useful insights and perspective on the detailed investigation of mechanistic pathways for the activation of small molecules such as H3N•BH3 [and Me2HN•BH3], H2, CH4, HCOOH and CO2 using electrophilic Ru(II)-complexes under homogeneous conditions using NMR spectroscopy. In Chapter 1 we provide brief overview of small molecule activation using organometallic complexes. This chapter presents pertinent and latest results from literature on the significance of small molecule activation. Although there are several small molecules which need our attention, however, we have focused mainly on H3N•BH3 [and Me2HN•BH3], H2, CH4, HCOOH and CO2. In Chapter 2, we present detailed investigation of mechanistic pathways of B−H bond activation of H3N•BH3 and Me2HN•BH3 using electrophilic [RuCl(dppe)2][OTf] complex using NMR spectroscopy as a model for methane activation. In these reactions, using variable temperature (VT) 1H, 31P{1H} and 11B NMR spectroscopy we detected several intermediates en route to the final products at room temperature including a σ-borane complex. On the basis of elaborative studies using NMR spectroscopy, we have established the complete mechanistic pathways for dehydrogenation of H3N•BH3/Me2HN•BH3 and formation of B−H bond activated/cleaved products along with several Ru-hydride and Ru-(dihydrogen) complexes. Keeping the B−H bond activation of amine-boranes in view as a model for methane activation, we attempted to activate methane using [RuCl(dppe)2][OTf] complex. In addition, [Ru(OTf)(dppe)2][OTf] complex having better electrophilicity than [RuCl(dppe)2][OTf], was synthesized and characterized. The [Ru(OTf)(dppe)2][OTf] complex has highly labile triflate bound to Ru-metal and therefore its reactivity studies toward H2 and CH4 were carried out where H2 activation was successfully achieved, however, no any spectroscopic evidence was found for C−H bond activation of CH4. The Chapter 3 describes the synthesis and characterization of several Ru-Me complexes such as trans-[Ru(Me)Cl(dppe)2], [Ru(Me)(dppe)2][OTf], trans-[Ru(Me)(L)(dppe)2][OTf] (L = CH3CN, tBuNC, tBuCN, H2) with an aim to trap corresponding σ-methane intermediate at low temperature. However, interestingly, we observed spontaneous but gradual methane elimination and orthometalation of [Ru(Me)(dppe)2][OTf] complex at room temperature. We thoroughly investigated mechanistic details of methane elimination and orthometalation of [Ru(Me)(dppe)2][OTf] using VT NMR spectroscopy, NOESY and DFT calculations. Furthermore, H2 activation was confirmed unambiguously by [Ru(Me)(dppe)2][OTf] and Ru-orthometalated complexes using NMR spectroscopy under ambient conditions. An effort was also made to activate methane using Ruorthometalated complex in pressurized condition of methane in a pressure stable NMR tube. Moreover, preliminary studies on protonation reaction of [Ru(Me)(dppe)2][OTf] using VT NMR spectroscopy to trap σ-methane at low temperature was carried out which provided us some useful information on dynamics between proton and Ru-Me species. The Chapter 4 provides useful insights into the mechanistic pathways of dehydrogenation/decarboxylation of formic acid using [RuCl(dppe)2][OTf]. Catalytic dehydrogenation of HCOOH using [RuCl(dppe)2][OTf] was observed in presence of Hunig base (proton sponge). In addition, a complex [Ru(CF3COO)(dppe)2][OTf] was synthesized and characterized using NMR spectroscopy, and found to readily dehydrogenate HCOOH. Moreover, preliminary results on transfer hydrogenation of CO2 into formamide using [RuCl(dppe)2][OTf] as a precatalyst and tert-butyl amine-borane (tBuH2N•BH3) as secondary hydrogen source was confirmed using 13C NMR spectroscopy. The mechanisms were proposed for HCOOH dehydrogenation and transfer hydrogenation of CO2 based on our NMR spectroscopic studies. Furthermore, a few test reactions of transfer hydrogenation of selected alkenes such as cyclooctene, acrylonitrile, 1-hexene using [RuCl(dppe)2][OTf] as pre-catalyst and tert-butyl amine-borane (tBuH2N•BH3) as secondary hydrogen source showed quantitative conversion to hydrogenated products.

Poly-N-isopropylacrylamide (PNIPAM) gels grafted to redox-active metal monomers undergo sudden expansion-contraction activity in response to change in environmental conditions, such as temperature, pH, ion concentration, and oxidation states of the metal. The relevance of these conditions to biological systems has garnered attention for PNIPAM-based polymer as potential biomedical materials. Candidate transition metal monomers containing ruthenium and nickel cores were designed and synthesized for copolymerization with NIPAM and cross-linker methylene-bis-acrylamide in order to attain metallopolymer microspheres with a high percentage of metal incorporation. Synthesis of 4-vinyl-4'-methyl-2,2'-bipyridine (vmbpy) was optimized from literature procedures for usage in the metal-containing monomers. Metal-containing monomers were then synthesized, purified, and characterized using electrospray ionization mass spectrometry (ESI-MS), proton nuclear magnetic resonance ( 1 H-NMR), X-ray diffraction, Ultraviolet-Visible light (UV-Vis) spectroscopy, and spectrofluorometry. While the Ru complex was pure and exhibited interesting photochemical properties, lability of the ligands on the Ni monomers resulted in complication of their synthesis. Polymer microspheres of poly(NIPAM-co-vmbpy), the cross-linked copolymer constructed from NIPAM and vmbpy monomers, were synthesized from modified emulsion polymerization procedures. Experimental setup parameters and conditions—such as the methods of injection of initiator and stirring, the time duration for incubating the emulsion, and the initiation temperature—were varied to assess their influences on the material properties of the final product. The polymers were tested for size and morphological uniformity by dynamic light scattering (DLS) and scanning electron microscopy (SEM). While varying the method of initiator injection had no measurable effect on the product, strong mechanical stirring and incubation of the polymer emulsion for 15-25 minutes at 71 °C procured similar polymer products. Consistent properties ensured the polymers' suitability for further material development. Preliminary morphological and spectroscopic characterization was conducted of metallopolymers made from Ru and Ni grafted to PNIPAM. Metallopolymers containing polypyridyl Ru cores exhibited desirable spectroscopic properties and spherical morphology.

Die in den letzten Jahrzehnten aufgenommenen Satellitenbilder zur Erdbeobachtung bieten eine ideale Grundlage für eine genaue Langzeitüberwachung und Kartierung der Erdoberfläche und Atmosphäre. Unterschiedliche Sensoreigenschaften verhindern jedoch oft eine synergetische Nutzung. Daher besteht ein dringender Bedarf heterogene Multisensordaten zu kombinieren und als geometrisch und spektral harmonisierte Zeitreihen nutzbar zu machen. Diese Dissertation liefert einen vorwiegend methodischen Beitrag und stellt zwei neu entwickelte Open-Source-Algorithmen zur Sensorfusion vor, die gründlich evaluiert, getestet und validiert werden. AROSICS, ein neuer Algorithmus zur Co-Registrierung und geometrischen Harmonisierung von Multisensor-Daten, ermöglicht eine robuste und automatische Erkennung und Korrektur von Lageverschiebungen und richtet die Daten an einem gemeinsamen Koordinatengitter aus. Der zweite Algorithmus, SpecHomo, wurde entwickelt, um unterschiedliche spektrale Sensorcharakteristika zu vereinheitlichen. Auf Basis von materialspezifischen Regressoren für verschiedene Landbedeckungsklassen ermöglicht er nicht nur höhere Transformationsgenauigkeiten, sondern auch die Abschätzung einseitig fehlender Spektralbänder. Darauf aufbauend wurde in einer dritten Studie untersucht, inwieweit sich die Abschätzung von Brandschäden aus Landsat mittels synthetischer Red-Edge-Bänder und der Verwendung dichter Zeitreihen, ermöglicht durch Sensorfusion, verbessern lässt. Die Ergebnisse zeigen die Effektivität der entwickelten Algorithmen zur Verringerung von Inkonsistenzen bei Multisensor- und Multitemporaldaten sowie den Mehrwert einer geometrischen und spektralen Harmonisierung für nachfolgende Produkte. Synthetische Red-Edge-Bänder erwiesen sich als wertvoll bei der Abschätzung vegetationsbezogener Parameter wie z. B. Brandschweregraden. Zudem zeigt die Arbeit das große Potenzial zur genaueren Überwachung und Kartierung von sich schnell entwickelnden Umweltprozessen, das sich aus einer Sensorfusion ergibt. / Earth observation satellite data acquired in recent years and decades provide an ideal data basis for accurate long-term monitoring and mapping of the Earth's surface and atmosphere. However, the vast diversity of different sensor characteristics often prevents synergetic use. Hence, there is an urgent need to combine heterogeneous multi-sensor data to generate geometrically and spectrally harmonized time series of analysis-ready satellite data. This dissertation provides a mainly methodical contribution by presenting two newly developed, open-source algorithms for sensor fusion, which are both thoroughly evaluated as well as tested and validated in practical applications. AROSICS, a novel algorithm for multi-sensor image co-registration and geometric harmonization, provides a robust and automated detection and correction of positional shifts and aligns the data to a common coordinate grid. The second algorithm, SpecHomo, was developed to unify differing spectral sensor characteristics. It relies on separate material-specific regressors for different land cover classes enabling higher transformation accuracies and the estimation of unilaterally missing spectral bands. Based on these algorithms, a third study investigated the added value of synthesized red edge bands and the use of dense time series, enabled by sensor fusion, for the estimation of burn severity and mapping of fire damage from Landsat. The results illustrate the effectiveness of the developed algorithms to reduce multi-sensor, multi-temporal data inconsistencies and demonstrate the added value of geometric and spectral harmonization for subsequent products. Synthesized red edge information has proven valuable when retrieving vegetation-related parameters such as burn severity. Moreover, using sensor fusion for combining multi-sensor time series was shown to offer great potential for more accurate monitoring and mapping of quickly evolving environmental processes.