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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
41

Caracterização do estado sólido de ganciclovir / Solid state characterization of ganciclovir

Roque Flores, Roxana Lili 24 July 2017 (has links)
O presente trabalho teve como objetivo o estudo do estado sólido do ganciclovir (GCV) e suas diferentes formas polimórficas. O GCV é um fármaco antiviral útil no tratamento de infecções por citomegalovírus (CMV). Embora seja um fármaco amplamente usado, poucos estudos têm sido realizados sobre seu estado sólido. Atualmente, o GCV é conhecido por apresentar quatro formas cristalinas, duas anidras (Forma I e II) e duas hidratas (III e IV). Neste trabalho, nós reportamos a solução da estrutura cristalográfica da Forma I do GCV, que foi encontrado durante o screening de cristalização do fármaco, em que nove ensaios de cristalização (GCV-1, GCV-A, GCV-B, GCV-C, GCV-D, GCV-E, GCV-F, GCV-G e GCV-H) foram realizados e os materiais resultantes foram caracterizados por Difratometria de raios X (DRX), análise térmica (DTA/TG) e Hot Stage Microscopy. De todas as cristalizações realizadas foram obtidas quatro formas sólidas, denominadas como Forma I (GCV-1, GCV-B e GCV-H), Forma III (GCV-C, GCV-D, GCV-F e GCV-G), Forma IV (GCV-A) e Forma V (GCV-E). Esta última está sendo descrita pela primeira vez na literatura e indica a presença de outra forma hidratada de GCV. As Formas I, III e IV corresponderam a forma anidra e as duas formas hidratadas do fármaco, respectivamente. Além disso, foi evidenciado por experimentos de conversão de slurry e análise térmica que o cristalizado de GCV-1 (Forma I) foi o mais estável entre os materiais obtidos, e este deu origem ao monocristal da Forma I de GCV, estrutura cristalina anidra do fármaco. Neste trabalho, pela primeira vez, a estrutura cristalina deste composto foi definida por cristalografia de raios X de monocristal. A análise estrutural mostrou que a Forma I do fármaco cristaliza no grupo espacial monoclínico P21/c e está composta por quatro moléculas de GCV na sua unidade assimétrica. Cada molécula está unida intermolecularmente por ligações de hidrogênio, que dão lugar à formação de cadeias infinitas e estas por sua vez se arranjam de maneira a formar uma estrutura tridimensional. / This presented work aims to study the solid state of ganciclovir (GCV) and its different polymorphic forms. GCV is an antiviral drug useful in the treatment of cytomegalovirus (CMV) infections. Although it is a widely-used drug, few studies have been conducted on its solid state. Currently, GCV is known to have four crystalline forms, two anhydrous (Form I and II) and two hydrates (III and IV). In this investigation, we report a successful preparation of GCV Form I and its crystallographic structure, which was found during the crystallization of the drug, in which nine crystallization tests (GCV-1, GCV-A, GCV-B, GCV- D, GCV-E, GCV-F, GCV-G and GCV-H) were performed and the resulting materials were characterized by X-ray diffractometry (XRD), thermal analysis (DTA/TG) and Hot Stage Microscopy. Of all the crystallizations performed, four solid forms were obtained, denoted as Form I (GCV-1, GCV-B and GCV- H), Form III (GCV-C, GCV-D, GCV-F and GCV-G), Form IV (GCV-A) and Form V (GCV-E). The latter is being described for the first time in the literature and indicates the presence of another hydrated form of GCV. Forms I, III and IV corresponded to the anhydrous form and the two hydrated forms of the drug, respectively. In addition, it was evident by both the slurry conversion and the thermal analysis methods that the GCV-1 crystallized (Form I) was indeed the most stable amongst the materials obtained. This gave rise to GCV Form I monocrystal, anhydrous crystalline structure of the drug. The compound was characterized by monocrystal X-ray crystallography. The structural analysis showed that Form I of the drug crystallized in the monoclinic system space group P21/c is composed of four molecules of GCV in its asymmetric unit. Each molecule is linked intermolecularly by hydrogen bonds, which give rise to the formation of infinite chains arranged in a way that form a three-dimensional structure.
42

Growth And Characterization Of Cuin1-x Gaxse2 (cigs) Thin Films For Solar Cell Structures

Candan, Idris 01 December 2009 (has links) (PDF)
Direct conversion of solar energy, which is the most powerful and unlimited one among the renewable energy sources / into the electrical energy by the photovoltaic devices, is a promising way of meeting the energy needs of future. Thin film semiconductor materials show great promise for the production of efficient, low-cost solar cell devices. Recently advanced research on thin film photovoltaics in all aspects, has attracted intense attention. Thin film semiconductors for the photovoltaic applications are deposited in large areas by different methods. In this study, deposition and characterization of CuIn1-x GaxSe2 ( CIGS ) semiconductor thin films by thermal evaporation and e-beam evaporation methods were investigated. Material properties and deposition parameters of the thin films are aimed to be optimized for solar cell applications. Structural properties of the deposited CIGS thin films were examined through X-ray diffraction and Energy Dispersive X-ray Analysis. The temperature dependent electrical conductivity, Hall effect and photoconductivity of these samples have been measured between 100 and 400 K. For the optical characterization of CIGS thin films, the transmission measurements have been carried out in the wavelength region of 325-900 nm. The changes in the structural, electrical and optical properties of samples through post-depositional annealing effect were also analyzed.
43

Si And Si(1-x)ge(x) Nanocrystals: Synthesis, Structural Characterization, And Simultaneous Observation Of Quantum Confined And Interface Related Photoluminescence

Asghar Pour Moghaddam, Nader 01 April 2010 (has links) (PDF)
In this work we have prepared Si and SI(1-X)GE(X) nanocrystals by rf magnetron cosputtering method. The eect of annealing parameters and Ge content of x on the structural and optical properties sandwiched SiO2/SiO2: Si: Ge/SiO2 nanostructures have been investigated. For characterization we have used cross-sectional high resolution electron microscope (HREM), X-ray diraction (XRD), Raman spectroscopy (RS), Fourier transform infrared (FTIR), photoluminescence (PL), and temperature dependent PL (TDPL) techniques. It was shown that Ge content of x, annealing temperature, and annealing time are important parameters aecting the structural and optical properties of the nanocrystals. We have observed a uniform SI(1-X)GE(X) nanocrystal formation upon annealing at relatively low temperatures and short annealing time. However, Ge-rich SI(1-X)GE(X) nanocrystals do not hold their compositional uniformity when annealed at high temperatures for enough long time. A segregation process leads to the separation of Ge and Si atoms from each other and formation of Si-rich core covered by a Ge-rich shell. Related to the optical properties of Si and SI(1-X)GE(X) nanocrystals, influence of annealing treatments and Ge content of x on the simultaneous observation and relative contribution of quantum confined and interface related radiative emission to PL spectra are investigated. On the other hand, temperature dependent photoluminescence (TDPL) measurements have been applied to investigate in detail the involving PL mechanisms and the competing thermally activated emission process and the thermally activated escape process of carriers into nonradiative recombination centers and/or tunneling of the excitons into the interface or to larger nanocrystals.
44

The Processing Of Mg-ti Powder For Hydrogen Storage

Cakmak, Gulhan 01 February 2011 (has links) (PDF)
A study was carried out on the selection of processing condition that would yield Mg-Ti with most favourable hydrogenation properties. Processing routes under consideration were / mechanical milling under inert atmosphere, reactive milling i.e. milling under hydrogen atmosphere, ECAP (equal channel angular pressing) and thermal plasma synthesis. Structure resulting from each of these processing routes was characterized with respect to size reduction, coherently diffracting volume and the distribution of Ti catalyst. Mechanical milling yielded a particulate structure made up of large Mg agglomerates with embedded Ti fragments with a uniform distribution. Mg agglomerates have sizes larger than 100 &micro / m which arises as a result of a balance between cold welding process and ductile fracture. Repeated folding of Mg particles entraps Ti fragments inside the Mg agglomerates resulting in a very uniform distribution. Coherently diffracting volumes measured by X-ray Rietveld analysis have small sizes ca. 26 nm which implies that the agglomerates typically comprise 1011 crystallites. Mechanical milling under hydrogen, i.e. reactive milling, led to drastic reduction in particle size. Mg and Ti convert to MgH2 and TiH2 which are milled efficiently due to their brittleness resulting in particle sizes of sub-micron range. Hydrogenation experiments carried out on Mg-10 vol % Ti milled under argon yields enthalpy and entropy values of -76.74 kJ/mol-H2 and -138.64 J/K.mol-H2 for absorption and 66.54 kJ/mol H2 and 120.12 J/K.mol H2 for desorption, respectively. For 1 bar of hydrogen pressure, this corresponds to a hydrogen release temperature of 280 &deg / C. This value is not far off the lowest desorption temperature reported for powder processed Mg based alloys. ECAP processing is a bulk process where the powders, consolidated in the first pass, have limited contact with atmosphere. This process which can be repeated many times lead to structural evolution similar to that of milling, but for efficient mixing of phases it was necessary to employ multi-pass deformation. An advantage of ECAP deformation is strain hardening of the consolidated powders which has improved milling ability. Based on this, a new route was proposed for the processing of ductile hydrogen storage alloys. This involves several passes of ECAP deformation carried out in open atmosphere and a final milling operation of short duration under inert atmosphere. The plasma processing yields Mg particles of extremely small size. Evaporation of Mg-Ti powder mixture and the subsequent condensation process yield Mg particles which are less than 100 nm. Ti particles, under the current experimental condition used, have irregular size distribution but some could be quite small, i.e. in the order of a few tens of nanometers. Of the four processing routes, it was concluded that both reactive milling and thermal plasma processing are well suited for the production of hydrogen storage alloys. Reactive milling yield particles in submicron range and plasma processing seems to be capable of yielding nanosize Mg particles which, potentially, could be decorated with even smaller Ti particles.
45

Drug Metabolites Formed by Cunninghamella Fungi : Mass Spectrometric Characterization and Production for use in Doping Control

Rydevik, Axel January 2014 (has links)
This thesis describes the in vitro production of drug metabolites using fungi of the Cunninghamella species. The metabolites were characterized with mainly liquid chromatography-mass spectrometry using ion-trap and quadrupole-time-of-flight instruments. A fungal in vitro model has several advantages e.g., it is easily up-scaled and ethical problems associated with animal-based models are avoided. The metabolism of bupivacaine and the selective androgen receptor modulators (SARMs) S1, S4 and S24 by the fungi Cunninghamella elegans and Cunninghamella blakesleeana was investigated. The detected metabolites were compared with those formed in vitro and in vivo by human and horse and most phase I metabolites formed by mammals were also formed by the fungi. The higher levels of bupivacaine metabolites in the fungal samples allowed an extensive mass spectrometric structural characterization which shows that the fungi are relevant metabolic models. Glucuronides are important drug metabolites but they are difficult to synthesize. The discovery that the fungus Cunninghamella elegans formed large amounts of glucosides led to the idea that they could be used to form glucuronides. A new concept was developed where a fungal incubate containing a SARM S1 glucoside was mixed with the free radical tetramethylpiperidinyl-1-oxy (TEMPO), sodium bromide and sodium hypochlorite which produced a glucuronide. Isolation and characterization by nuclear magnetic resonance spectroscopy proved that the new method could produce glucuronides for use as reference material. An investigation of reactive metabolite formation of the drugs paracetamol, mefenamic acid and diclofenac by the fungus Cunninghamella elegans was performed. It was demonstrated for the first time that the fungus could produce glutathione, glutathione ethyl-ester, cysteine and N-acetylcysteine conjugates that are indicative of a preceding formation of reactive intermediates. A comparison with conjugates formed by human liver microsomes showed that both models formed identical metabolites. The presented investigations prove that Cunninghamella fungi are relevant drug metabolism models. They show that the fungi to a large extent forms the same metabolites as mammals and that they can produce metabolites for use as reference material in, e.g. doping control. It was also demonstrated that the fungal model can be used in the important assessment of drug toxicity.
46

Electrical, Structural And Optical Properties Of Aggase2-xsx Thin Films Grown By Sintered Powder

Karaagac, Hakan 01 September 2010 (has links) (PDF)
In the present study, the effect of S and Se substitution on structural, electrical and optical properties of AgGa(Se2-xSx) thin films has been investigated. AgGa(Se0.5S0.5 )2 thin films were prepared by using the thermal evaporation method. X-ray diffraction (XRD) analysis has revealed that the transformation from amorphous to polycrystalline structure took place at about 450 oC. The detailed information about the stoichometry and the segregation mechanisms of the constituent elements in the structure has been obtained by performing both energy dispersive X-ray analysis (EDXA) and X-ray photoelectron spectroscopy (XPS) measurements. AgGaSe2 thin films were deposited by using both electron-beam (e-beam) and sputtering techniques. In e-beam evaporated thin films, the effect of annealing on the structural and morphological properties of the deposited films has been studied by means of XRD, XPS, scanning electron microscopy (SEM) and EDXA measurements. Structural analysis has shown that samples annealed between 300 and 600 oC were in polycrystalline structure with co-existance of Ag, Ga2Se3, GaSe, and AgGaSe2. The variation of surface morphology, chemical composition and bonding nature of constituent elements on post-annealing has been determined by EDXA and XPS analyses. AgGaSe2 thin films were also prepared by using sputtering technique. XRD measurements have shown that the mono-phase AgGaSe2 structure is formed at annealing temperature of 600 oC. The crystal-field and spin-orbit splitting levels were resolved. These levels around 2.03 and 2.30 eV were also detected from the photospectral response measurements. Thin films of Ag-Ga-S (AGS) compound were prepared by using AgGaS2 single crystalline powder and deposition of the excess silver (Ag) intralayer with double source thermal evaporation method. As a consequence of systematic optimization of thickness of Ag layer, Ag(Ga,S) with the stoichiometry of AgGa5S8 and AgGaS2 were obtained and systematic study to obtain structural, electrical and optical properties was carried out.
47

Obtenção de nanocompósitos nanotubos de carbono de parede múltipla e TiO2 e sua caracterização estrutural, óptica e de atividade fotocatalítica

Da Dalt, Silvana January 2012 (has links)
Este trabalho teve como objetivo obter nanocompósitos de nanotubos de carbono de paredes múltiplas (NTCPMs) com TiO2, e caracterizá-los quanto a sua estrutura, características ópticas e atividade fotocatalítica. Os nanocompósitos foram obtidos a partir de NTCPMs comerciais (Baytubes®), e dois diferentes TiO2: um comercial (P25) e um obtido na síntese de TiO2 tendo tetra propóxido de titânio (TTP) como precursor. Foram utilizados dois diferentes sistemas líquidos para a obtenção dos nanocompósitos NTCPM-TiO2: um, em pH ácido e outro, em pH alcalino. Os nanocompósitos obtidos a partir do TTP foram posteriormente tratados termicamente a 400 °C, 500 °C, 600 °C e 700 °C para formação de fases cristalinas de TiO2. Os nanocompósitos foram investigados quanto a sua atividade fotocatalítica, empregando-os como catalisadores na degradação do corante orgânico alaranjado de metila, em solução aquosa, sob radiação ultravioleta. Os resultados foram associados a características da estrutura dos nanocompósitos, utilizando técnicas como difração de raios X, microscopia eletrônica de varredura, microscopia eletrônica de transmissão, espectroscopia Raman e espectroscopia por infravermelho e área superficial específica. A caracterização óptica foi obtida por espectroscopia fotoluminescente e espectroscopia por refletância difusa. A análise térmica foi empregada para quantificar a presença de NTCPMs no nanocompósito empregado como catalisador. O desempenho fotocatalítico dos nanocompósitos foi correlacionado com o efeito do pH dos sistemas líquidos empregados na sua obtenção, natureza da interação (química e/ou física) entre nanotubo de carbono e TiO2, fases presentes no TiO2, energia do gap óptico e presença de defeitos estruturais no TiO2. A maior eficiência na fotocatálise foi observada nos nanocompósitos NTCPMs-TiO2 obtidos a partir do TiO2 comercial, e nos obtidos a partir do precursor TTP tratado termicamente a 500 °C, ambos em meio ácido. Estes resultados puderam ser associados às menores energias de transição e nível de defeitos no TiO2 nesses nanocompósitos, quando comparados aos demais. / This study aimed to obtain nanocomposites from multi-walled carbon nanotubes (MWCNTs) with TiO2, and characterize them according to their structure, optical properties and photocatalytic activity. The nanocomposites were obtained from commercial MWCNTs (Baytubes®) and two different types of TiO2: a commercial one (P25) and one obtained by synthesizing TiO2 with titanium tetra propoxide (TTP) as a precursor. Two different fluid systems were used for obtaining the MWCNT-TiO2 nanocomposites: one with acid pH and the other with alkaline pH. The nanocomposites obtained from TTP were subsequently heat treated at 400 °C, 500 °C, 600 °C and 700 °C to form crystalline phases of TiO2. The nanocomposites were investigated for their photocatalytic activity, employing them as catalysts in the degradation of organic methyl orange dye in an aqueous solution under ultraviolet radiation. The results were associated with the characteristics of the nanocomposites’ structure, using techniques such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, infrared spectroscopy, and specific surface area. Optical characterization was obtained by photoluminescence spectroscopy and diffuse reflectance spectroscopy. Thermal analysis was used to quantify the presence of MWCNTs in the nanocomposite employed as catalyst. The photocatalytic performance of the nanocomposites were correlated with the effect of the pH of the liquid systems employed for obtaining them, the nature of the interaction (chemical and/or physical) between the carbon nanotube and TiO2, the phases present in the TiO2, the optical energy gap and the presence of structural defects in TiO2. The highest photocatalytic efficiency was observed in the MWCNT-TiO2 nanocomposites obtained from commercial TiO2, and in those obtained from the TTP precursor heat treated at 500 °C, both in an acid medium. These results could be associated with the lower transition energy and level of defects in the TiO2 of these nanocomposites when compared to the other samples.
48

Obtenção de nanocompósitos nanotubos de carbono de parede múltipla e TiO2 e sua caracterização estrutural, óptica e de atividade fotocatalítica

Da Dalt, Silvana January 2012 (has links)
Este trabalho teve como objetivo obter nanocompósitos de nanotubos de carbono de paredes múltiplas (NTCPMs) com TiO2, e caracterizá-los quanto a sua estrutura, características ópticas e atividade fotocatalítica. Os nanocompósitos foram obtidos a partir de NTCPMs comerciais (Baytubes®), e dois diferentes TiO2: um comercial (P25) e um obtido na síntese de TiO2 tendo tetra propóxido de titânio (TTP) como precursor. Foram utilizados dois diferentes sistemas líquidos para a obtenção dos nanocompósitos NTCPM-TiO2: um, em pH ácido e outro, em pH alcalino. Os nanocompósitos obtidos a partir do TTP foram posteriormente tratados termicamente a 400 °C, 500 °C, 600 °C e 700 °C para formação de fases cristalinas de TiO2. Os nanocompósitos foram investigados quanto a sua atividade fotocatalítica, empregando-os como catalisadores na degradação do corante orgânico alaranjado de metila, em solução aquosa, sob radiação ultravioleta. Os resultados foram associados a características da estrutura dos nanocompósitos, utilizando técnicas como difração de raios X, microscopia eletrônica de varredura, microscopia eletrônica de transmissão, espectroscopia Raman e espectroscopia por infravermelho e área superficial específica. A caracterização óptica foi obtida por espectroscopia fotoluminescente e espectroscopia por refletância difusa. A análise térmica foi empregada para quantificar a presença de NTCPMs no nanocompósito empregado como catalisador. O desempenho fotocatalítico dos nanocompósitos foi correlacionado com o efeito do pH dos sistemas líquidos empregados na sua obtenção, natureza da interação (química e/ou física) entre nanotubo de carbono e TiO2, fases presentes no TiO2, energia do gap óptico e presença de defeitos estruturais no TiO2. A maior eficiência na fotocatálise foi observada nos nanocompósitos NTCPMs-TiO2 obtidos a partir do TiO2 comercial, e nos obtidos a partir do precursor TTP tratado termicamente a 500 °C, ambos em meio ácido. Estes resultados puderam ser associados às menores energias de transição e nível de defeitos no TiO2 nesses nanocompósitos, quando comparados aos demais. / This study aimed to obtain nanocomposites from multi-walled carbon nanotubes (MWCNTs) with TiO2, and characterize them according to their structure, optical properties and photocatalytic activity. The nanocomposites were obtained from commercial MWCNTs (Baytubes®) and two different types of TiO2: a commercial one (P25) and one obtained by synthesizing TiO2 with titanium tetra propoxide (TTP) as a precursor. Two different fluid systems were used for obtaining the MWCNT-TiO2 nanocomposites: one with acid pH and the other with alkaline pH. The nanocomposites obtained from TTP were subsequently heat treated at 400 °C, 500 °C, 600 °C and 700 °C to form crystalline phases of TiO2. The nanocomposites were investigated for their photocatalytic activity, employing them as catalysts in the degradation of organic methyl orange dye in an aqueous solution under ultraviolet radiation. The results were associated with the characteristics of the nanocomposites’ structure, using techniques such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, infrared spectroscopy, and specific surface area. Optical characterization was obtained by photoluminescence spectroscopy and diffuse reflectance spectroscopy. Thermal analysis was used to quantify the presence of MWCNTs in the nanocomposite employed as catalyst. The photocatalytic performance of the nanocomposites were correlated with the effect of the pH of the liquid systems employed for obtaining them, the nature of the interaction (chemical and/or physical) between the carbon nanotube and TiO2, the phases present in the TiO2, the optical energy gap and the presence of structural defects in TiO2. The highest photocatalytic efficiency was observed in the MWCNT-TiO2 nanocomposites obtained from commercial TiO2, and in those obtained from the TTP precursor heat treated at 500 °C, both in an acid medium. These results could be associated with the lower transition energy and level of defects in the TiO2 of these nanocomposites when compared to the other samples.
49

Síntese de nanopartículas de óxido de vanádio obtidas pela decomposição de peróxido / Synthesis of Vanadium Oxide Nanoparticles obtained by the decomposition of peroxide

Waldir Avansi Junior 29 September 2010 (has links)
A utilização de novas rotas de síntese de materiais nanoestruturados tem levado à obtenção de materiais apresentando novas propriedades e aplicações. O presente trabalho teve como principal objetivo realizar a síntese e a caracterização de nanopartículas de óxido de vanádio obtidas pelo método da decomposição de peróxido utilizando o tratamento hidrotermal. Por meio do controle do tempo e da temperatura de síntese, foi possível obter nanoestruturas de pentóxido de vanádio com diferentes fases cristalinas e morfologias. Os resultados de espectroscopia Raman e difração de raios X (DRX) mostraram que o tratamento hidrotermal da solução em temperaturas de até 180oC, durante 2 horas, leva à formação da fase V2O5nH2O monoclínica, apresentando uma orientação preferencial na direção 00l. A partir desta temperatura, o material obtido passou a ter a fase ortorrômbica perdendo sua orientação preferencial. Através das medidas de termogravimetria (TG) foi observado que, dependendo da condição de síntese, as amostras apresentam diferentes quantidades de moléculas de água (H2O) intercaladas em sua estrutura. Imagens de microscopia eletrônica mostraram que as nanoestruturas obtidas podem possuir a forma de fitas, fios ou bastões. Utilizando a técnica de espectroscopia de absorção de raios X (XAS), foi possível verificar a presença de íons de V4+ nas amostras de fase monoclínica, o que não foi observado naquelas que possuem estrutura ortorrômbica. Pela técnica de XAS também foi possível constatar que as amostras de estrutura ortorrômbica possuem menor grau de desordem ao redor do átomo de vanádio. O estudo do mecanismo de crescimento da nanoestrutura de V2O5nH2O mostrou que ocorre um crescimento lateral, o qual pode ser descrito pelo mecanismo denominado Coalescência Orientada ou Oriented attachment (OA). Finalmente, através da decomposição do peróxido de vanádio, foi possível obter compostos vanadatos contendo cátions de Na+ em sua estrutura. / The use of new routes for nanostructured materials synthesis has lead to materials with new properties and applications. This PhD project aimed to realize the synthesis and the characterization of vanadium pentoxide nanoparticles obtained by peroxide decomposition using the hydrothermal treatment. By controlling synthesis time and temperature it was possible to achieve vanadium pentoxide nanoparticles with different crystalline phases and orphologies. The results of Raman spectroscopy and X-ray diffraction (XRD) showed that the hydrothermal treatment of the solution at temperatures up to 180oC for two hours leads to formation of the V2O5nH2O monoclinic phase with a preferential orientation on 00l direction. From this temperature on the material obtained began to present the orthorhombic phase misleading its preferential orientation. Through thermogravimetry (TG) measurements it was seen that depending on the synthesis condition the samples contains different amounts of water molecules (H2O) interleaved in their structure. Images of transmission electron microscopy (TEM) showed that the V2O5nH2O compound could have different morphologies such as ribbons, wires and rods. From X-Ray Absorption spectroscopy (XAS) measurements, it was observed the presence of V4+ ions in the monoclinic phase samples, which was not observed on orthorhombic structure samples. Through the XAS technique was also observed that the orthorhombic structure samples have a lower degree of disorder around the vanadium atom. Regarding the growth mechanism of these nanostructures, it was possible to verify that has been a wide growth which can be explained by the mechanism denominated Oriented Attachment (OA). Finally, through vanadium peroxide decomposition vanadates compounds containing Na+ cation in its structure were carried out.
50

Estudos estruturais e bioquímicos das septinas 7 e 9 humanas / Structural and biochemical studies of human septins 7 e 9

Fernando Alessandro 07 June 2010 (has links)
As proteínas pertencentes à família das septinas foram originalmente descobertas em 1971 em decorrencia de estudos genéticos em células mutantes. Essas proteínas encontradas em fungos e animais, mas não em plantas apresentam como principais características a presença de um domínio conservado de ligação aos nucleotídeos de guanina (GTP) e a formação de filamentos homo- e hetero-oligoméricos, que são estruturas altamente organizadas. Estudos filogenéticos e moleculares em humanos identificaram 14 septinas que são divididas em 4 grupos (I, II, III e IV). Estas moléculas associam-se com membranas celulares, actina, microtúbulos do citoesqueleto e estão envolvidas em inúmeros processos que ocorrem no córtex celular e requerem organização espacial, tais como: citocinese, ciclo celular, formação de barreiras de difusão, alinhamento de fuso. Alterações na expressão das septinas estão associadas a vários tipos de tumores e a doenças de Parkinson e Alzheimer. Neste trabalho, com o objetivo de obter informações estruturais e bioquímicas das septinas 7 e 9 humanas. Este projeto é parte de um esforço conjunto coordenado pelo Prof. Dr. Richard C. Garratt e conhecido informalmente como Septimoma. As construções recombinantes SEPT 7, SEPT 7G, e SEPT 9G foram expressas em Escherichia coli e as proteínas recombinantes obtidas. As análises em eletroforese SDS-Page e em gel nativo indicam que essas proteínas foram purificadas com sucesso. A atividade GTPase e o estado oligomérico na forma dimérica foram verificados. Estudos de dicroísmo circular e fluorescência determinaram que esses recombinantes são formados por uma mistura de estruturas secundárias &alfa; e β, e também que o C e o N terminais aumentam a estabilidade das proteínas. Foram obtidos cristais da SEPT 7G e, por meio da técnica de raios-X, foi determinado um modelo tridimensional da proteína com resolução de 3,4o. / Proteins belonging to the septin family were originally discovered in 1971 through genetic studies of mutant cells. These proteins found in fungi and animals, but not in plants present, as their main characteristics, a conserved guanine nucleotide-binding domain (GTP) and they also form homo and hetero-oligomeric filaments that are highly organized structures. Phylogenetic and molecular studies in humans have identified 14 septins which are divided into 4 subfamilies (groups I, II, III and IV). These molecules associate with cell membranes, actin, cytoskeleton microtubules and they are related to a number of processes that take place in the cell cortex and that require spatial organization, such as cytokinesis, cell cycle, diffusion barrier formation and spindle alignment. Alterations in the expression of septins are associated with several types of tumors and with Parkinsons and Alzheimers diseases. In this work, with the goal of obtaining structural and biochemical information of human septins 7 and 9, the recombinants SEPT 7, SEPT 7G and SEPT 9G were expressed in E. coli. Analyses both in SDS-Page electroforesis and in native gel suggest that these proteins were purified successfully for they are soluble and homogeneous. GTpase activity has been verified in all of these recombinants, which shows that these proteins are present in native form and that additional molecules are not needed for this activity. It was possible to determine through different techniques such as molecular exclusion chromatography and SAXS that all the molecules in solution are grouped as dimeric form. Circular dichroism and fluorescence spectroscopic studies have determined both that such recombinants are formed by means of a mixture of &alfa; and β secondary structures and that the C and N-terminals increase the stability of proteins. Protein stability studies under different pH and temperature conditions show that the raise of the latter produces a greater molecular aggregation. Measurements of fluorescence emissions have indicated that the SEPT 7, SEPT 7G and SEPT 9G form structures of amyloid-like filaments found in many septins. Crystal structures of SEPT 7G have been obtained and, by means of the X-ray technique, a 3-D model of the protein has been determined with a resolution of 3.4o. It has been possible to predict, with molecular modeling studies, regions formed by loops that showed low electronic density in the GTPase crystallographic model. Therefore, it has been possible to add more structural information to this domain and to form the complete polypeptide without cuts.

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