Дисертації з теми "Doped POT"

Ces dernières années, le dioxyde de titane a attiré beaucoup d'attention en tant que matériau hautement stable avec une large gamme d'applications allant du pigment blanc à des applications en tant que semi-conducteur ou dispositifs photoniques de pointe. En utilisant des approches synthétiques récemment développées, la synthèse de molécules cages de type polyoxotitanate (POT, [TixOy(OR)z]) atomiquement bien définies peut être menée. Les POTs peuvent être considérés comme des modèles solubles du TiO2. Des cages dopées avec un métal M (M-POT) présentant de nouvelles propriétés peuvent être aussi préparées.Deux nouvelles cages dopées au cérium ont été synthétisées par une réaction solvothermique. Les cages [Ti28O38(OEt)38CeCl](EtOH)1,4 et [Ti8O7(OEt)21Ce](EtOH) ayant des solubilités différentes, elles vont pouvoir être séparées et caractérisées par RMN du 1H et diffraction des rayons X. Des cages POTs dopées au Fe : [Ti4(OEt)15O(FeCl)] et [FeTi14(OEt)28O14(OH)2] ont été également synthétisés.Puis après hydrolyse avec ou sans calcination, les matériaux à base de Ce ou Fe et TiO2 peuvent être obtenus. Des émulsions de ses matériaux et avec le polymère PVDC dopées au cérium ou au fer ont ensuite été déposées sur une surface de PVC. Les performances d'absorption UV et de barrière à l'eau augmentent progressivement avec l'augmentation de la quantité de matériaux déposés. Les résultats sont intéressants pour l’emploi de ces matériaux en surface d’’emballage de tablettes de médicaments, ce qui permettra d’augmenter la date de péremption de ceux-ci.La cage Eu-POT dopée avec l’Eu (III) : Ti2O(OEt)8EuIIICl(EtOH)]2 a été synthétisé, puis après hydrolyse et calcination, les propriétés de photoluminescence du matériau obtenu ont été étudiées.Enfin, un complexe AgITiIV(SC)2(HSC)(CH3CN) (SC2- = l'acide salicylique) a été préparé. Après hydrolyse et calcination, les propriétés antimicrobiennes des matériaux fabriqués ont été testé vis-à-vis avec succès du S. aureus ou de E. Colis
In recent years, titanium dioxide has attracted much attention as a highly stable material with a wide range of applications from white pigment to its applications as a semiconductor or advanced photonic devices. Using recently developed synthetic approaches, the synthesis of atomically well-defined polyoxotitanate (POT, [TixOy(OR)z]) cage molecules can be determined. POTs may be preferred as soluble models of TiO2. Cages doped with a metal M (M-POT) presenting new properties can also be prepared.Two new cages doped with cerium were synthesized by a solvothermal reaction. The cages [Ti28O38(OEt)38CeCl](EtOH)1.4 and [Ti8O7(OEt)21Ce](EtOH) having different solubilities, they will be able to be separated and characterized by 1H NMR and X-ray diffraction. The Fe-doped POTs: [Ti4(OEt)15O(FeCl)] and [FeTi14(OEt)28O14(OH)2] were also synthesized. Then after hydrolysis with or without calcination, materials based on Ce or Fe and TiO2 can be obtained. Emulsions of its materials and with the cerium-doped PVDC polymer were then deposited on a PVC surface. UV absorption and water barrier performance gradually increases with increasing amount of deposited materials. The results are interesting for the use of these materials on the packaging surface of drug tablets, which will increase their expiry date. The Eu-POT cage doped with the Eu(III): Ti2O(OEt)8EuIIICl(EtOH)]2 was also synthesized, then after hydrolysis and calcination, the photoluminescence properties of the obtained material were studied.Finally, an AgITiIV(SC)2(HSC)(CH3CN) complex (SC2- = salicylate) was prepared. After hydrolysis and calcination, the anti-microbial properties of the materials were successfully tested against S. aureus or E. Colis

L’imagerie par fluorescence (IF) et l’imagerie de résonance magnétique (IRM) comptent parmi les outils de diagnostic les plus efficaces. Dans ce contexte, des QDs possédant à la fois des propriétés fluorescentes et magnétiques sont d’un grand intérêt en tant que sondes bimodales. Dans ce travail, des QDs Ag-In-Zn-S (AIZS) et Ag-In-Ga-Zn-S (AIGZS) ont été préparés et dopés afin de développer de nouvelles sondes de sondes bimodales pour l’IF et l’IRM. Des QDs AIZS très fluorescents ont été préparés en milieu organique à l’aide de DDT et d’OAm comme ligands. Les QDs Mn:AIZS possèdent des propriétés paramagnétiques et superparamagnétiques. Les QDs AIZS et Mn:AIZS ont également été transférés en phase aqueuse à l’aide du polymère amphiphile PMAO. Par la suite, des QDs AIZS dopés Mn, Gd ou Fe ont été préparés en milieu. Des études toxicologiques et d’imagerie ont montré une bonne biocompatibilité avec les cellules KB ainsi que le fort potentiel de ces nanocristaux pour l’IF. Dans la dernière partie de ce travail, des QDs AIGZS and Mn:AIGZS QDs ont été préparés via un procédé de décomposition thermique n’utilisant qu’un seul précurseur. Ces QDs possèdent de très bonnes propriétés optiques et magnétiques. Les QDs dopés Mn ont été transférés en phase aqueuse et ont montré un fort potentiel comme agent de contraste pour l’imagerie T1 et T2
Since fluorescence imaging (FI) and magnetic resonance imaging (MRI) are among the most effective diagnostic tools, QDs with fluorescent and magnetic properties are of great interest as dual-modal probes. In this work, undoped and doped Ag-In-Zn-S (AIZS) and Ag-In-Ga-Zn-S (AIGZS) QDs were synthesized and investigated as bimodal probes for FI and MRI. Highly fluorescent AIZS QDs were prepared in organic media using DDT and OAm as capping ligands. Mn:AIZS QDs showed paramagnetic and superparamagnetic properties. AIZS and Mn:AIZS QDs were also transferred into aqueous phase using the amphiphilic PMAO polymer. Further, Mn, Gd or Fe-doped AIZS QDs were prepared in aqueous media, showed low cytotoxicity toward KB cells, and demonstrated potential as fluorescent probes for FI. Finally, AIGZS and Mn:AIGZS QDs, synthesized via a novel single precursor thermal decomposition method, showed high fluorescence and paramagnetic/superparamagnetic properties. Mn-doped aqueous transferred AIGZS QDs increased contrast in both T1-weighted and T2-weighted images with increasing in Mn loading

Els materials escintil·ladors són àmpliament utilitzats com a detectors en els sistemes de detecció de diverses aplicacions, com la imatge mèdica, la física d’alta energia, l’astrofísica i en proves no destructives (seguretat aeroportuària, control industrial, etc.). Hi ha diversos requisits importants per avaluar favorablement el rendiment d’un escintil·lador. Donat que no existeix el escintil·lador ideal, s’estan dedicant molts esforços a buscar nous escintil·ladors inorgànics amb millors propietats que els dels escintil·ladors existents. En aquesta tesi, es creixen monocristalls amb alta qualitat cristal·lina de KGd(PO3)4 tipus III dopats amb Ce3+ i Pr3+, i també nanocristalls de Pr:KGd(PO3)4 tipus III per posteriorment caracteritzar-los estructuralment i òpticament com a possibles nous materials escintil·ladors. Aquests monocristalls es creixen a partir de solucions d’alta temperatura mitjançant la tècnica Top Seeded Solution Growth-Slow Cooling (TSSG-SC) i els nanocristalls es sintetitzen mitjançant el mètode de Pechini. La caracterització estructural inclou la morfologia cristal·lina, estabilitat i expansió tèrmiques, distribució de mida de les partícules, entre altres. S’estudia amb detall l’espectroscòpia de les transicions 4f–5d, sobre les quals es basa el mecanisme d’escintil·lació. Inclou mesures d'absorció òptica, mesures de luminescència i del temps de decaiguda d’aquesta excitant amb llum de sincrotró en el rang espectral des de l'ultraviolat de buit fins l'ultraviolat (VUV-UV), mesures de radioluminescència excitant amb raigs X, entre altres. A més, es proporcionen les dades espectroscòpiques bàsiques dels monocristalls de Pr:KGd(PO3)4 tipus III per aplicacions làser en la gamma de longitud d'ona visible basades en les transicions electròniques 4f-4f. També, es determina la regió de cristal·lització primària del KYP4O12 tipus B i del KY(PO3)4 tipus IV en el sistema ternari K2O–Y2O3–P2O5, ja que són candidats interessants per actuar com a matriu per ions lantànids actius en aplicacions de centelleig.
Los materiales centelleadores son ampliamente utilizados como detectores en los sistemas de detección de diversas aplicaciones, como la imagen médica, la física de alta energía, la astrofísica y en pruebas no destructivas (seguridad aeroportuaria, control industrial, etc.). Hay varios requisitos importantes para evaluar favorablemente el rendimiento de un centelleador. Dado que no existe el centelleador ideal, se están dedicando muchos esfuerzos para buscar nuevos centelleadores inorgánicos con mejores propiedades que los de los centelleadores existentes. En esta tesis, se crecen monocristales con alta calidad cristalina de KGd(PO3)4 tipo III dopados con Ce3+ y Pr3+, y también nanocristales de Pr:KGd(PO3)4 tipo III para posteriormente caracterizarlos estructuralmente y ópticamente como posibles nuevos materiales centelleadores. Estos monocristales se crecen a partir de soluciones de alta temperatura mediante la técnica Top Seeded Solution Growth-Slow Cooling (TSSG-SC) y los nanocristales se sintetizan mediante el método de Pechini. La caracterización estructural incluye la morfología cristalina, estabilidad y expansión térmicas, distribución de tamaño de las partículas, entre otros. Se estudia con detalle la espectroscopia de las transiciones 4f-5d, sobre las que se basa el mecanismo de centelleo. Incluye medidas de absorción óptica, medidas de luminiscencia y del tiempo de decaída de ésta excitando con luz de sincrotrón en el rango espectral desde el ultravioleta de vacío hasta el ultravioleta (VUV-UV), medidas de radioluminiscencia excitando con rayos X, entre otros. Además, se proporcionan los datos espectroscópicos básicos de los monocristales de Pr:KGd(PO3)4 tipo III para aplicaciones láser en la gama de longitud de onda visible basadas en las transiciones electrónicas 4f-4f. También, se determina la región de cristalización primaria de KYP4O12 tipo B y de KY(PO3)4 tipo IV en el sistema ternario K2O-Y2O3-P2O5, ya que son candidatos interesantes para actuar como matriz para iones lantánidos activos en aplicaciones de centelleo.
Scintillators materials are widely used as detectors in the detection systems of a variety of applications, such as medical imaging, high energy physics, astrophysics and non-destructive testing (airport security, industrial control, etc.). There are several important requirements to evaluate favourably the performance of a scintillator. Since the ideal scintillator does not exist, many efforts are dedicated to find new inorganic scintillators with better properties than those of the existing scintillators. Here, Ce3+- and Pr3+-doped type III KGd(PO3)4 bulk single crystals with high crystalline quality and type III Pr:KGd(PO3)4 nanocrystals are grown and structurally and optically characterized as possible new scintillator materials. These bulk single crystals are grown from high temperature solutions by the Top Seeded Solution Growth-Slow Cooling (TSSG-SC) technique, while the nanocrystals are synthesized by the Pechini method. The structural characterization includes the crystal morphology, thermal stability, thermal expansion, particle size distribution, among others. The spectroscopy of the 4f–5d transitions, on which the scintillation mechanism is based, is studied in detail. The spectroscopic characterization includes optical absorption measurements, luminescence and decay time measurements under synchrotron vacuum ultraviolet-ultraviolet (VUV-UV) excitation, radioluminescence measurements after synchrotron X-ray irradiation, among others. In addition, the basic spectroscopic data of the type III Pr:KGd(PO3)4 crystal for lasing applications in the visible wavelength range based on the 4f–4f electronic transitions is provided. Moreover, the primary crystallization region of type B KYP4O12 and type IV KY(PO3)4 in the K2O–Y2O3–P2O5 ternary system is determined, since these are interesting candidates as hosts for active lanthanide ions in scintillation applications.

L'usage intensif de pesticides dans l'agriculture engendre une contamination sans précédent des eaux de surface et des nappes phréatiques. Les traitements classiques appliqués aux eaux usées contenant des produits organiques polluants sont basés sur la biodégradation ou sur des méthodes physiques de transfert de masse (décantation, filtration, adsorption des polluants sur du charbon actif) ou des procédés chimique tels que l'oxydation à l'ozone ou au chlore. Cependant, ces procédés demeurent inefficaces dans le cas de traitement des eaux contaminées par les polluants organiques persistants (POPs). Les procédés d'oxydation avancés sont mis en œuvre pour dégrader ou même minéraliser ces polluants. Ce travail a donc pour objectif de déterminer un protocole expérimental pour détruire efficacement les pesticides, produits chimiques largement utilisés dans l'agriculture au Maroc, tels que le monochloro-benzène, le 1,2-dichlorobenzène, l'acide 2,4,5-trichlorophénoxy-acétique, et l'imazalil en utilisant les procédés d'oxydation avancée électro-Fenton et oxydation anodique avec différentes anodes telles que BDD, Pt et DSA. Ainsi, nous avons trouvé que le taux de minéralisation par procédé électro-Fenton avec l'anode BDD était de 92%, 95%, 92% et 97%pour le monochloro-benzène, le 1,2-dichlorobenzène, l'acide 2,4,5-trichlorophénoxy-acétique, et l'imazalil, respectivement, après 4 h de traitement. Ces résultats confirment l'efficacité des procédés d'oxydation avancés électrochimiques dans le traitement des eaux polluées par des pesticides
The intensive use of pesticides in agriculture generates, nowadays, an unprecedented contamination of surface water and groundwater. Conventional treatments applied to waste water containing organic pollutants are based on biological treatments méthods or physical mass transfer methods (decantation, filtration, adsorption of the pollutants on activated carbon), chemical oxidation with ozone, chlorine, etc. However, these methods remain ineffective for the treatment of water polluted by persistent organic pollutants (POPs). Advanced oxidation processes are implemented to degrade and mineralize these pollutants. This PhD thesis work aims to establish an experimental protocol to degrade and mineralize pesticides, chemicals widely used in agriculture in Morocco, such as monochlorobenzene, 1,2-dichlorobenzene, 2,4,5-trichlorophenoxy-acetic acid , and imazalil using the electro-Fenton and anodic oxidation processes with DD Pt or DSA anodes. Thus, the rate of mineralization was 92%, 95%, 92% and 97% for the monochloro-benzene, the 1,2-dichlorobenzene, the 2,4,5-trichlorophenoxyacetic acid , and the imazalil, respectively, after 4 h treatment by electro-Fenton process. These results confirm the effectiveness of electrochemical advanced oxidation processes for treating water polluted by pesticides

S'anomenen cristalls bifuncionals aquells que posseeixen simultàniament propietats d'òptica no lineal i propietats làser. Aquest tipus de materials són molt interessants ja que, combinant aquestes dues propietats, poden auto-generar radiació làser en la regió electromagnètica del blau (≈ 450 nm) o del verd (≈ 550 nm). Els materials làser d'estat sòlid que generen radiació làser en el rang electromagnètic visible (≈ 400-800 nm) tenen actualment un paper molt important en el desenvolupament tecnològic de dispositius làser i òptics en general ja que són interessants per un gran nombre d'aplicacions com són: l'emmagatzematge òptic d'informació d'alta densitat (HDVD, per exemple), reprografia, pantalles de color, medicina, biotecnologia, comunicacions submarines, comunicacions atmosfèriques transparents, etc.
Aquest tipus de fonts làser compactes emetent en el visible poden ésser desenvolupades utilitzant un cristall bifuncional. Aquests làsers auto-dobladors de freqüència tenen associades menys pèrdues (absorció, reflexió i dispersió) que làsers dobladors de freqüència intracavitat, que significa que el disseny del ressonador és més simple i compacte. Actualment, la recerca en aquest camp està centrada en el desenvolupament de nous materials no-centrosimètrics que presentin propietats d'òptica no-lineal i que puguin allotjar ions làser actius, majoritàriament ions lantànid. Els materials d'òptica no-lineal tenen la capacitat de generar el segon harmònic de la radiació, és a dir, de doblar la seva freqüència. Si un material d'òptica no-lineal conté un ió lantànid que generi radiació làser en la regió infraroja d'aproximadament =1000 nm, podrà auto-doblar-ne la freqüència, és a dir, reduir-ne a la meitat la longitud d'ona, =500 nm, que correspon a la regió electromagnètica del blau o el verd.
El fosfat doble de potassi i gadolini de tipus III, KGd(PO3)4 (KGP), que és objecte d'aquesta tesi doctoral, és un cristall d'estructura no-centrosimètrica i per tant amb el requisit estructural necessari per a posseir propietats d'òptica no-lineal. Es va plantejar l'objectiu de sintetitzar i caracteritzar aquest cristall i a més de substituir parcial o totalment l'ió gadolini per un ió lantànid actiu en la zona de 1000 nm, com són l'iterbi i el neodimi, per tal d'aconseguir desenvolupar un nou cristall auto-doblador de freqüència.
Així doncs, l'objectiu de la present tesi doctoral va ésser l'estudi del creixement cristal.lí del KGP i del KGP dopat amb iterbi o neodimi i la seva posterior caracterització. Com que el fosfats doble de potassi i lantànid fonen incongruentment, és a dir, que es descomponen abans de fondre, és necessari utilitzar un mètode de creixement cristal.lí a partir de solució a alta temperatura per créixer cristalls. Aquest mètodes permeten créixer a una temperatura per sota la temperatura de fusió del material, i per tant evitar-ne la seva descomposició. El mètode que nosaltres em utilitzat per créixer monocristalls de KGP pur i dopat és l'anomenat top seeded solution growth-slow cooling (TSSG-SC), que permet créixer els cristalls lliures en la solució disminuint lentament la seva temperatura a partir de la temperatura se cristal.lització. Això permet obtenir cristalls volúmics amb formes cristal.logràfiques desenvolupades lliurament i determinades a partir de l'estructura cristal.lina. Després d'optimitzar el procés de creixement, hem aconseguitr sintetitzar cristalls lliures de macrodefectes i d'una mida suficient pel seu estudi i possible posterior aplicació. Posteriorment, els cristalls han estat caracteritzats estructuralment, físicament, òpticament i espectroscòpicament.
Finalment, s'han realitzat experiències de laserat amb Yb:KGP, obtenint uns resultats força encoratjadors, ja que s'ha aconseguit generar radiació làser per primer cop en aquest cristall dopat amb iterbi amb un nivell de dopatge força baix.
Com a conclusió i després dels resultats de l'estudi, podem dir que els cristalls de Yb:KGP i Nd:KGP poden ésser considerats com a candidats prometedors per a ser aplicats com a cristalls auto-dobladors de freqüència ja que s'ha provat la seva capacitat tant de generar segon harmònic com de generar radiació làser.
Bifunctional crystals are those in which the nonlinear optical process and the laser effect occur simultaneously. This kind of materials is very promising for compact solid-state laser designs operating in the visible because solid-state lasers operate mainly in the infrared. So, the nonlinear and laser properties can combine to generate blue (≈ 450 nm) or green (≈550 nm) laser radiation by self-frequency doubling. Solid-state laser sources operating in the visible spectral region (≈400-800 nm) play an important role in laser technology they are potentially interesting for numerous applications such as high-density optical data storage, reprographics, colour displays, medicine, biotechnology, submarine communications, transparent atmosphere communications, etc.
Such compact laser sources can be managed from frequency conversion by nonlinear optical processes such as frequency doubling and sum-frequency mixing by using a bifunctional crystal. Such self-frequency doubling (SFD) lasers involve fewer losses (absorption, reflection and scattering) than the intracavity frequency doubling lasers, which means that resonator designs are simpler and more compact.
Currently, efforts are focussed on the development of new noncentrosymmetric crystals with nonlinear optical properties to be used as a host for active laser ions, and mostly lanthanide ions. Nonlinear optical materials are able to double the frequency of the laser emission generated by the active ion hosted in it. Nonlinear crystals with suitable sites for lanthanide ions which emit in the infrared region around 1 m may be able to self-double the frequency, i.e. to reduce the wavelength to the half, =500 nm, which is in the blue or green spectral region.
The aim of this doctoral thesis is to synthesize and characterize the type III double phosphate of potassium and gadolinium, KGd(PO3)4 (KGP), either undoped or doped ordoped with ytterbium or neodymium, both of them emitting in the 1 m region.

The KGP crystal is noncentrosymmetric, so with the indispensable requirement to have nonlinear optical properties. We propose to use this crystal as a nonlinear host for alternatively ytterbium (Yb3+) or neodymium (Nd3+) to develop a new promising selffrequency doubling laser crystal to generate blue-green laser radiation.
As double phosphates of potassium and lanthanide melt incongruently, i.e. they decompose before melting, a high-temperature solution growth method has to be used to growth the crystals. This kind of growth methods allows growing the crystal under its melting point and so avoiding its decomposition. We use the top seeded solution growth-slow cooling (TSSG-SC) to grow the undoped and Yb- or Nd-doped KGP single crystals. This kind of growth method allows to freely growing the crystals in the solution by slowly cooling its temperature from the crystallization temperature. It allows obtaining bulk crystals with freely developed crystallographic forms determined by the crystals structure. By optimizing the growth process, we have successfully grown macrodefect-free crystals large enough for later characterizations and possible final application. The crystals have been structurally, physically, optically and spectroscopically characterized. Finally, laser operation with Yb:KGP has been proved for the first time. Although the low ion doping level in the crystal, the rather high slope efficiency obtained with this first sample is rather promising for the future.
In conclusion, single crystals of Yb:KGP and Nd:KGP can be regarded as a promising candidates to be applied as a self-frequency doubling crystals since it has been proved both the second harmonic generation ability and the laser operation.

Orientador: Aldário Chrestani Bordonalli
Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Elétrica e de Computação
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Resumo: Com a demanda por comunicação continuamente aumentando nos últimos anos, mantém-se constante a busca por aperfeiçoamento dos amplificadores ópticos a fibra. Como uma proposta de proporcionar maior largura de banda de amplificação para sistemas ópticos, este trabalho procura caracterizar o comportamento operacional de uma fibra de vidro telurito dopado com érbio e itérbio para diferentes condições iniciais de comprimento de amostra, aplicação de sinais e configuração de bombeio. As amostras, fabricadas pelo Grupo de Fibras Ópticas do IFGW/UNICAMP, foram submetidas a análises experimentais baseadas nas principais topologias de amplificadores a fibra que usam matrizes de sílica. Assim, avalia-se a potencialidade das características de amplificação do vidro telurito fabricado com dosagem de compostos inéditos, além de uma investigação da possibilidade da geração laser utilizando-se essa fibra como meio ativo em configurações com laço de realimentação. Mesmo que o ganho real do sistema não tenha sido determinado pela incerteza em relação a real potência óptica acoplada às amostras, observou-se ser possível a compensação da atenuação que o sinal que se propaga pelas amostras sofre após a aplicação de bombeio. Nesse aspecto, o vidro telurito dopado com érbio e itérbio apresentou potencial de aplicação em amplificação óptica. Uma amostra de 2 cm, comprimento muito menor que o usado em amplificadores ópticos baseados em matrizes de sílica e uma ordem de grandeza menor que os baseados em vidro telurito dopado apenas com érbio, apresentou resultados de ganho óptico on-off da ordem de 30 dB com bombeio bi-direcional de 100 mW. Em relação ao vidro telurito dopado apenas com érbio, os resultados para o ganho on-off chegaram a ser até 15 dB maiores. Além disso, as transições providas pela interação entre a matriz vítrea com o érbio e o itérbio levaram a larguras de banda de 3 dB para o espectro de ASE de até 70 nm, dependendo da configuração de bombeio
Abstract: With the recently increase in data transmission demands, the search for improved fiber amplifier physical processes, materials, and configurations is still on going. As a way to provide a wider amplification bandwidth for optical systems, this work intends to characterize the operational behavior of an erbium and ytterbium doped tellurite fiber for different sample lengths, light coupling and pump configurations. The fiber samples, manufactured by the Optical Fiber Group of the IFGW/UNICAMP, underwent experimental analyses based on the same main pump topologies as those of silica-based optical amplifiers. Thus, the potential amplification characteristics of tellurite glass doped with new compounds are evaluated, as well as an investigation of possible laser generation by using this type of fiber as gain medium within feedback loop configurations. Although real system gain was impossible to determine due to uncertainties in the actual coupled optical power, it was observed that the attenuation during signal propagation through the fiber samples could be compensated after pump application. In this context, the erbium and ytterbium doped tellurite fiber has potential for optical amplification. Samples as short as 2 cm, far shorter than the ones used in silica based amplifiers and one order of magnitude shorter than those based on Er3+ doped tellurite fiber structures, presented on-off optical gain of the order of 30 dB for bi-directional 100-mW pump. By comparing with the latter doped glass structure, the on-off gain results were as high as 15 dB greater. Furthermore, the transitions provided by the interaction between the host glass and both erbium and ytterbium have led to a 70-nm ASE bandwidth, depending on the pumping configuration
Mestrado
Telecomunicações e Telemática
Mestre em Engenharia Elétrica

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
In Brazil are located the two largest niobium reserves of the world – about 96% of the world production – and, for this reason, have been encouraged studies on its most diverse technological applications. Another aspect of prominent studies is currently the processing of ceramic materials with a microwave, which is presented as an alternative method of sintering in a muffle furnace – the use of microwave involves electromagnetic energy conversion instead of heat transfer, offering advantages when used for providing the obtainment of greater structural homogeneity of the material and a reduction of time and energy expended during processing. This work aims to perform the characterization of electrical properties of niobium pentoxide (Nb2O5) pure or doped with molybdenum (Mo) and to do an analysis of the influence of this doping when its sintering process occurs in muffle furnace or microwave. The properties characterized were the permittivity and loss tangent. Will be studied the viability of doping and/or processing the material for use as absorbent materials of electromagnetic radiation. The variation of concentrations in doping will indicate how effective, as a doping agent, molybdenum will be in the ceramic matrix, converting energy of microwave into heat energy. The results showed that the increase of doping of the niobium pentoxide with molybdenum (with 1% doping limit) combined with the sintering oven microwave increased the material conductivity values, making it more efficient in its use as absorber electromagnetic radiation
No Brasil estão localizadas as duas maiores reservas de nióbio do mundo – cerca de 96% da produção mundial –, e, por esta razão, têm sido incentivados os estudos sobre as suas mais diversas aplicações tecnológicas. Outra vertente de estudos em destaque atualmente é a do processamento de materiais cerâmicos com micro-ondas, que se apresenta como um método alternativo à sinterização em forno mufla – o uso de micro-ondas envolve conversão de energia eletromagnética, em lugar de transferência de calor, oferecendo vantagens ao ser usado por proporcionar a obtenção de uma maior homogeneidade estrutural do material e uma redução do tempo e da energia gasta durante o processamento. A proposta deste trabalho é a realização da caracterização de propriedades elétricas do pentóxido de nióbio (Nb2O5) puro ou dopado com molibdênio usando a tecnologia da metalurgia do pó e a análise da influência sobre estas dopagens quando seu processamento de sinterização se dá em forno mufla ou em forno de micro-ondas. As caracterizações feitas foram das propriedades elétricas de permissividade elétrica e tangente de perdas além de ter sido estudada a viabilidade da dopagem e/ou o tipo de processamento – na etapa de sinterização – do material para aplicação como materiais absorvedores de radiação eletromagnética. A variação das concentrações nas dopagens indicou o quão eficaz, como agente dopante, o molibdênio será na matriz cerâmica, convertendo a energia de micro-ondas em energia térmica. Os resultados mostraram que o aumento da dopagem do pentóxido de nióbio com molibdênio (com limite de dopagem de 1%) aliado à sinterização em forno de micro-ondas garantiu o aumento dos valores de condutividade do material, tornando-o mais eficiente para sua aplicação como absorvedor de radiação eletromagnética
2017-05-26

Ce travail s’inscrit dans le cadre d’une étude systématique des propriétés physico-chimiques de polyphosphates à l’argent permettant d’avancer sur de nouvelles voies pour les dispositifs tels que l’éclairage, les lasers accordables dans le visible, la radiophotoluminescence. L'objectif de ce travail vise la compréhension des mécanismes de luminescence de l’ion Ag+ dans les composés Na1-xAgxLn(PO3)4 (Ln = La et Y) dont la structure a été parfaitement déterminée. La luminescence des monocristaux provient des ions Ag+, dans des sites isolés et proches de lacunes positives (Ag2+) résultant de la photosensibilité aux UV pour les cristaux au lanthane. La luminescence des verres Na1-xAgxLa(PO3)4 (seuls vitrifiables) a été élucidée grâce à une étude après irradiation et à celle des verres Na2-xAgxZnP2O7. Elle est due aussi aux ions Ag+ dans des sites isolés
This work focuses on keeping with the general pattern of investigations of physical-chemical properties of silver-polyphosphates to find new ways for devices such as lighting, visible range laser applications and radiophotoluminescence. The goal of this study aims at understanding the processes of Ag+ luminescence in Na1-xAgxLn(PO3)4 (Ln = La et Y) compounds which structure has been completely determinated. The luminescence of the single crystals is induced by Ag+ ions in isolated sites and close to hole centers (Ag2+) resulting in UV photosensitivity for the lanthanum crystals. The photoluminescence of the Na1-xAgxLa(PO3)4 glasses (glass-forming only) has been resolved owing to UV irradiation investigations and comparison with the luminescence of Na2-xAgxZnP2O7 glass. Both are also due to Ag+ ions in isolated sites

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Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES)
Verapamil (VP) e Oxcarbazepina (OX) s?o f?rmacos de baixo ?ndice terap?utico que necessitam de rigoroso controle de qualidade em formula??es farmac?uticas, bem como de an?lises em fluidos biol?gicos para estudos farmacol?gicos de elimina??o dessas drogas. Neste sentido, o desenvolvimento de m?todos simples, r?pidos e de baixo custo ? de extrema import?ncia para quantifica??o desses f?rmacos nessas amostras. Deste modo, o presente trabalho apresenta um m?todo eletroanal?tico em fluxo para determinar VP e OX tanto em formula??es farmac?uticas, quanto em amostras de urina. A t?cnica eletroqu?mica utilizada para quantifica??o foi a Amperometria de M?ltiplos Pulsos (MPA) acoplada a um sistema de an?lise por inje??o em fluxo (FIA), utilizando o diamante dopado com boro (BDD). Foram aplicados tr?s pulsos de potencial pela MPA para determina??o do VP em meio de ?cido sulf?rico 0,1 mol L-1, sendo +1,6 V para a oxida??o e, posteriormente, +0,2 V para redu??o do produto gerado do VP e +0,1 V para a limpeza do eletrodo de BDD. Para a determina??o de OX, tamb?m foram otimizados tr?s pulsos de potencial em meio de tamp?o acetato 0,1 mol L-1 (pH 4,0), sendo + 1,7 V para a oxida??o da OX e gera??o do produto que foi reduzido em -1,1 V e -1,3 V para a limpeza do eletrodo de BDD. Em ambos os casos, apenas o sinal obtido nos pulsos de potencial de redu??o foram utilizados para quantifica??o dos f?rmacos. As faixas lineares de trabalho obtidas para quantifica??o do VP e da OX foram de 0,8 a 40,0 ?mol L-1 (R= 0,9976) e 2,0 a 80,0 ?mol L-1 (R= 0,9989), respectivamente. Os limites de detec??o foram calculados em 0,16 ?mol L-1 para VP e 0,42 ?mol L-1 para OX. Uma boa repetibilidade foi obtida para 10 an?lises consecutivas desses f?rmacos, com desvio padr?o relativo de 2,2% para VP e 0,94 % para OX. Os estudos de adi??o e recupera??o do VP e OX em amostras farmac?uticas e urina apresentaram resultados pr?ximos a 100% e o doseamento do VP foi validado pela metodologia oficial. Altas frequ?ncias anal?ticas foram alcan?adas pelo sistema FIA com 45 e 65 determina??es por hora de VP e OX, respectivamente, usando al?as de amostragem inferiores a 200 ?L e vaz?es de 3,5 mLmin-1. An?lises desses f?rmacos em amostras de urina mostraram que ? poss?vel determin?-los mesmo na presen?a de altas concentra??es de ?cido asc?rbico e ?cido ?rico. Portanto, o m?todo proposto mostrou-se como alternativa simples e r?pida para quantifica??o desses f?rmacos em formula??es farmac?uticas e urina.
Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, [2016].
Verapamil (VP) and Oxcarbazepine (OX) are drugs of narrow therapeutic index that require strict quality control in pharmaceutical formulations and analysis in biological fluids for pharmacological studies of elimination of these drugs. In this sense, the development of simple, fast and low-cost methods is very important to quantify these drugs in pharmaceutical samples. Therefore, this work presents a electroanalytical method in flow for determining VP and OX in pharmaceutical formulations and human urine samples. The electrochemical technique used for quantification was performed by multiple pulses amperometry (MPA) coupled to a flow injection analysis system (FIA), using boron-doped diamond (BDD) as working electrode. Were applied three potential pulses by MPA for the determination of VP in sulfuric acid 0.1 mol L-1: (1) +1.6 V for oxidation of VP, (2) +0.2 V for reduction of the generated product of VP in the fisrt potential pulse, (3) +0.1 V for cleaning of the BDD electrode surface. The determination of OX also was performed by MPA in three potential pulses in 0.1 mol L-1 acetate buffer (pH 4.0): (1) +1.7 V for oxidation of OX and generation of the product that it was reduced at (2) -1.1 V, and (3) -1.3 V for cleaning of the BDD electrode surface. In both cases, only the signal obtained in the reduction potential pulses were used for quantification of drugs. The linear ranges of work obtained for quantitation of VP and OX were 0.8 to 40.0 ?mol L-1 (R = 0.9976) and 2.0 to 80.0 ?mol L-1 (R = 0, 9989), respectively. The detection limits were calculated to be 0.16 ?mol L-1 for VP and 0.42 ?mol L-1 for OX. Good repeatabilities were obtained for 10 consecutives injections of these drugs, with relative standard deviation of 2.2% for VP and 0.94% for OX. The addition and recovery studies for VP and OX in pharmaceutical and urine samples were close to 100% and determination of VP was validated by the official methodology. High analytical frequencies were achieved by FIA system of 45 and 65 determinations per hour for VP and OX, respectively, using sampling handles less than 200 ?L and flow rate of 3.5 mLmin-1. The analysis of these drugs in urine showed that it is possible to determine this sample even in the presence of high concentrations of ascorbic acid and uric acid. Therefore, the present method by MPA-FIA proved to be a quick and easy alternative to quantify VP and OX in pharmaceutical formulations and urine.

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A Cotinina (CO) ? o principal metab?lito da nicotina, sendo utilizada como biomarcador para monitorar a exposi??o de um indiv?duo ao tabaco. Os m?todos comumente utilizados para a determina??o desse composto em amostras biol?gicas s?o baseados na cromatografia l?quida, os quais, em geral, s?o dispendiosos e requerem tratamentos tediosos dessas amostras. Dessa maneira, torna-se necess?rio o desenvolvimento de novos m?todos mais simples e r?pidos para determina??o da CO. Nesse contexto, o presente trabalho prop?e o uso eletrodo de diamante dopado com boro (BDD) para detec??o e caracteriza??o eletroqu?mica da CO por t?cnicas voltam?tricas, bem como sua quantifica??o em amostras de saliva por meio da amperometria de m?ltiplos pulsos (MPA) em sistema de an?lise por inje??o em fluxo (FIA). Em meio de tamp?o fosfato a 0,1 mol L-1 (pH 7) a CO apresentou dois processos eletroqu?micos, um an?dico em +1,8 V e um cat?dico em -1,2 V (vs. Ag/ AgCl), sendo o segundo dependente do primeiro e ambos de car?ter irrevers?vel. Foi verificado que o processo de transporte de massas para a oxida??o da CO ? preferencialmente difusional sobre o eletrodo de BDD e que 2 el?trons e pr?tons est?o envolvidos na rea??o eletroqu?mica. O coeficiente de difus?o calculado para a CO foi de 5,7 x 10 -2 cm2 s-1. Para determina??o da CO em saliva, MPA foi utilizada aplicando-se 4 pulsos de potencial, sendo: (1) em +1,8 V/ 400 ms potencial gerador (EG) para oxida??o da CO; (2) em -1,0 V/ 500 ms potencial para elimina??o de interferentes na amostra de saliva, (3) em -1,2 V/ 30 ms potencial coletor para reduzir e quantificar a CO gerada pelo EG; (4) em -145/ 300 ms potencial para limpeza da superf?cie do BDD. A freq??ncia anal?tica te?rica foi obtida de 24 determina??es por hora com uma vaz?o otimizada em 3,0 mL min-1 e a al?a de amostragem de 300 ?L no sistema FIA. Al?m disso, um baixo desvio padr?o relativo de 1,46% foi obtido para 10 determina??es consecutivas de CO 10 ?mol L-1. Nessas condi??es, foi obtida uma faixa linear de 0,5 a 100 ?mol L-1 (R= 0,998) com limite de detec??o calculado em 0,18 ?mol L-1 para CO. Os estudos de adi??o e recupera??o da CO em amostras de saliva foram de 96,77%, Portanto, mediante a caracteriza??o eletroqu?mica e os estudos por FIA-MPA usando eletrodo de BDD, este trabalho apresenta uma alternativa simples, r?pida e de baixo custo para monitoramento do grau de exposi??o ao tabaco pela determina??o da CO em amostras de saliva.
Disserta??o (Mestrado) ? Programa de P?s-gradua??o em Ci?ncias Farmac?uticas, Universidade Federal dos Vales do Jequitinhonha e Mucuri, [2016].
The Cotinine (CO) is the major metabolite of the nicotine an disused as a biomarker to monitor the exposure of an individual to tobacco. The methods commonly used for CO determination in biological samples are based on liquid chromatography, which generally are expensive and require tedious treatments of the samples. Thus, it becomes necessary to develop simpler and faster methods for determining CO. In this context, this paper proposes the use boron-doped diamond (BDD) film electrode for the detection and electrochemical characterization of CO by voltammetric techniques and, CO quantification in saliva samples by multiple-pulse amperometry (MPA) in analysis by flow injection (FIA) system. In phosphate buffer solution 0.1 mol L-1 (pH 7), the CO presented two electrochemical processes, one anodic at + 1.8V and one cathode at -1.2V (vs. Ag/ AgCl), with the second process dependent on the first and both irreversible process. It was found that CO electrochemical processes are controlled by diffusion and, two-protons and two-electrons are involved in the oxidation reaction. The diffusion coefficients calculated for CO was 5.7 x 10 -2 cm2 s-1. In determination of CO in saliva samples, the MPA detection was used applying four potential pulses: (1) at +1.8V/ 400ms ? generator potential pulse (EG) for oxidation of CO; (2) at-1.0V/500ms - potential for remove possible interferents, (3) at - 1.2V/30ms - collector potential pulse potential for reduction of the product generated by EG and CO quantification; (4) at-14.5V/ 300 ms- potential pulse for cleaning BDD electrode. The proposed method obtained a theoretical analytical frequency with 24 determinations per hour by FIA system in flow rate of 3.0 ml min-1 and sample loop of 300?L. Furthermore, a low relative standard deviation of 1.46% was obtained for 10 measurements of CO 10 ?mol L-1. Under these conditions, A good linear range from 0.5 to 100 ?mol L-1 (R = 0.998) was obtained with a detection limit estimated at 0.18 ?mol L-1 for CO. The addition and recovery studies of CO in saliva samples were 96.77%. Therefore, this work presents, by the first time, an electrochemical characterization of the CO and a method simple, fast and low cost for monitoring the degree of exposure to tobacco by CO determination in saliva samples using FIA-MPA technique.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES
Cloud point extraction method (CPE) was used for the determination of estrone (E1) and 17β-estradiol (E2) hormones in human urine. The combination of the electrochemical detection techniques with high-performance liquid chromatography (HPLC-EC) was used for the detection and quantification of these hormones. A boron doped diamond electrode (BDD) pretreated cathodically was used as electrode material for all electrochemical measurements. The optimized chromatographic parameters resulted in a mobile phase composition of KH2PO4 (0.01 mol L-1; pH 5.0) / ACN (72:28 V/V), flow 1.2 ml min-1. An applied potential for electrochemical detection of 1.0 V x Ag/AgCl (3.0 mol L-1) was selected from hydrodynamic voltammograms constructed for each hormone changing the potential between 0.3 V and 1.2 V x Ag/AgCl (3.0 mol L-1). Limits of detection (S/N = 3) of 500 ng mL-1 and limits of quantification of 800 ng mL-1 were obtained for both E1 and E2 hormones without any extraction process. Urine samples at pH 5.0 and 7.0 were investigated aiming the influence of pH on the efficiency of the CPE process, and the optimum results for the most current signal of the hormones was obtained at pH 7.0. Extractor solvent volumes were changed in the 0.5-2.5 mL range, and the optimum results were obtained when using 1.0 mL of Tergitol TMN-6 surfactant (10% aqueous solution). From the equation of the calibration curves obtained with and without the CPE procedure it was possible to determine the pre-concentration factor (FC) and all the other parameters involving the efficiency of CPE method. A comparison of the efficiency of CPE method with direct liquid-liquid extraction with the organic solvent CCl4 was carried out and the results showed that the CPE method was quite superior to liquid-liquid extraction. The validation of the method was carried out from intra-day recovery experiments and inter-day and evaluated the accuracy, precision and repeatability. The proposed method was applied to individual samples of urine of 1 man, 1 pregnant woman, 1 woman in fertile age, and 1woman in lactating stage. The values of the variation coefficients of the recovery percentages were lower than 15%.
Método de extração por ponto nuvem (EPN) foi usado para a determinação dos hormônios estrona (E1) e 17β-estradiol (E2) em urina humana. A combinação entre as técnicas de detecção eletroquímica e cromatografia líquida de alta eficiência (CLAE-EC) foi usada para a detecção e quantificação desses hormônios. Um eletrodo de diamante dopado com boro (DDB) pré-tratado catodicamente foi usado como material de eletrodo para todas as determinações eletroquímicas. Os parâmetros cromatográficos otimizados resultaram em uma composição de fase móvel de KH2PO4 (0,01 mol L-1; pH 5,0) / ACN (72:28 V/V) vazão de 1,2 mL min-1. Um potencial aplicado para a detecção eletroquímica de 1,0 V x Ag/AgCl (3 mol L-1) foi selecionado a partir de voltamogramas hidrodinâmicos construídos para cada hormônio variando-se o potencial entre 0,3 V e 1,2 V x Ag/AgCl (3,0 mol L-1). Limites de detecção (S/R = 3) de 500 ng mL-1 e limites de quantificação de 800 ng mL-1 foram obtidos para ambos os padrões dos hormônios E2 e E1 sem qualquer processo de extração. Amostras de urina em pH 5,0 e 7,0 foram investigadas quanto a influência do pH na eficiência do processo de extração, e o melhor resultado referente ao maior sinal de corrente dos hormônios foi obtido em pH 7,0. Os volumes de solvente extrator foram variados na faixa de 0,5-2,5 mL e o melhor resultado referente ao sinal de corrente dos hormônios foi obtido pelo uso de 1,0 mL de solução aquosa 10% do surfactante Tergitol TMN-6. A partir da equação da reta obtida das curvas analíticas, com e sem o procedimento de EPN, foi possível determinar o fator de pré-concentração (FC) e todos os demais parâmetros envolvendo a eficiência do método de EPN. Uma comparação sobre a eficiência dos métodos de EPN com extração direta líquido-líquido com o solvente orgânico CCl4 foi realizada e os resultados mostraram que método de EPN mostrou-se bastante superior a extração líquido-líquido. A validação do método foi feita a partir de ensaios de recuperação intra-dia e inter-dia, sendo avaliadas a exatidão, precisão e repetitividade. O método proposto foi aplicado em amostras individuais de urina de 1 homem, 1 mulher gestante, 1 mulher em idade fértil e 1 mulher lactante. Os valores dos coeficientes de variação das porcentagens de recuperação foram menores que 15%.

Fundação de Amparo a Pesquisa do Estado de Minas Gerais
In this work we investigated the potentiality of batch injection analysis with square-wave voltammetry (BIA-SWV) detection for simultaneous determination of Zn and naphazoline (NAF) and batch injection analysis with multiple pulse amperometric (BIA-MPA) detection for simultaneous determination of NAF and pheniramine (FEN) or NAF and chlorpheniramine (CLO). In both methods, boron-doped diamond (BDD) was used as working electrode. For the simultaneous determination of Zn and NAF by BIA-SWV, the following conditions have been optimized: supporting electrolyte: acetate buffer 0.05 mol L-1 (pH = 4.7), injection volume: 100 μL, deposition time (Zn): 5 s, deposition potential (Zn) -1.5 V, : 100 s-1, a: 60 mV, ΔEs: 6 mV. Under these conditions, the method showed linear response range between 10 and 60 μmol L-1 for Zn (r = 0.992) and between 3.0 e 21 μmol L-1 for NAF (r = 0.999), high analytical frequency (70 injections h-1) and LOD of 0.126 μmol L-1 and 0.04 μmol L-1 for Zn and NAF, respectively. In the study of repeatability (n = 20), the calculated RSD were 0.98% and 0.97% for Zn and NAF, respectively. The simultaneous determination of NAF and FEN or NAF and CLO by BIA-MPA was performed with the application of three sequential pulses in function of time to the BDD electrode using Britton-Robinson Buffer solution 0.12 mol L-1 (pH = 10.0) as supporting electrolyte. At +1.1 V/50 ms, FEN or CLO was detected (oxidation) without interference of NAF. At +1.3 V/50 ms, both compounds (FEN + NAF or CLO + NAF) were oxidized. The current of NAF can then be obtained by subtraction of the currents detected during application of both potential pulses using a correction factor. The proposed method presented good ability (RSD = 1.7 and 4.0% for FEN and NAF; 2.1% and 3.6% for CLO and NAF, respectively; n=20); high analytical frequency (110 injections h-1), linear concentration range between 16 e 100 μmol L-1 for FEN and CLO (r > 0.996) and between 2 e 15 μmol L-1 for NAF (r > 0.997). The LOD calculated were 0.367, 0.361 e 0.148 μmol L-1, for FEN, CLO and NAF, respectively. The proposed methods were used for determination of these compounds in pharmaceutical samples. The obtained results were statistically similar to that obtained by HPLC (NAF, FEN and CLO) and atomic spectroscopy (Zn).
No presente trabalho investigou-se a potencialidade do sistema de análise por injeção em batelada com detecção por voltametria de onda quadrada (BIA-SWV) para determinação simultânea de Zn e nafazolina (NAF) e do sistema análise por injeção em batelada com detecção por amperometria de múltiplos pulsos (BIA-MPA) para determinação simultânea de NAF e feniramina (FEN) ou NAF e clorfeniramina (CLO). Em ambos os métodos, diamante dopado com boro (BDD) foi usado como eletrodo de trabalho. Para determinação simultânea de Zn e NAF empregando BIA-SWV, as seguintes condições foram otimizadas: eletrólito de suporte: tampão acetato 0,05 mol L-1 (pH = 4,7), volume de injeção: 100 μL, tempo de deposição (Zn): 5 s, potencial de deposição (Zn): -1,5 V, : 100 s-1, a: 60 mV, ΔEs: 6 mV. Nestas condições, o método apresentou faixa linear de resposta entre 10 e 60 μmol L-1 para Zn (r = 0,992) e entre 3,0 e 21 μmol L-1 para NAF (r = 0,999), frequência analítica de 70 injeções h-1 e limites de detecção de 0,126 μmol L-1e 0,04 μmol L-1 para Zn e NAF, respectivamente. No estudo de repetibilidade (n = 20), os DPRs foram calculados 0,98% e 0,97% para Zn e NAF, respectivamente. A determinação simultânea de NAF e FEN ou NAF e CLO por BIA-MPA foi realizada através da aplicação de dois pulsos de potenciais em função do tempo ao eletrodo de BDD usando tampão BR 0,12 mol L-1 (pH = 10) como eletrólito suporte. Em +1,1 V/50 ms, FEN ou CLO foram oxidadas livre da interferência de NAF. Em +1,3 V/50ms, ambos os compostos (NAF + FEN ou NAF + CLO) foram oxidados. A corrente proveniente da oxidação da NAF foi obtida pela subtração entre as correntes detectadas em ambos os pulsos de potenciais com auxílio de um fator de correção (FC). O método proposto apresentou boa estabilidade (DPR = 1,7 e 3,95% para FEN e NAF; 2,1 e 3,6% para CLO e NAF, respectivamente; n=20), alta frequência analítica (110 injeções h-1), faixa linear de resposta entre 16 e 100 μmol L-1 para FEN e CLO (r > 0,996) e entre 2 e 15 μmol L-1 para NAF (r > 0,997). Os limites de detecção foram de 0,367, 0,361 e 0,148 μmol L-1 para FEN, CLO e NAF, respectivamente. Os métodos propostos foram usados na determinação destes compostos em formulações farmacêuticas. Os resultados obtidos com os métodos propostos foram estatisticamente similares aos obtidos por HPLC (NAF, FEN e CLO) ou absorção atômica (Zn).
Mestre em Química

?rea de concentra??o: Qu?mica anal?tica.
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A Teofilina (TF), Clindamicina (CM), Varfarina (VF) e Verapamil (VP) s?o f?rmacos de baixo ?ndice terap?utico que necessitam de um controle de qualidade rigoroso na elabora??o de suas formula??es. O desenvolvimento de m?todos mais simples e r?pidos para doseamento desses medicamentos ? de grande interesse no setor farmac?utico. Neste sentido, o presente trabalho apresenta uma nova metodologia para determina??o desses f?rmacos por amperometria de m?ltiplos pulsos (MPA) acoplada ao sistema de an?lise por inje??o em batelada (BIA), utilizando o eletrodo de Diamante dopado com Boro (DDB). A an?lise em BIA foi realizada em uma c?lula eletroqu?mica do tipo Wall Jet, onde as inje??es foram realizadas por meio de uma micropipeta autom?tica ou, manualmente, por uma seringa descart?vel para TF, CM e VF, mostrando a possibilidade de diminuir custo do sistema de an?lise. O comportamento eletroqu?mico da TF, CM, VF e VP foi investigado por voltametria c?clica e os eletr?litos suportes escolhidos foram o ?cido sulf?rico 0,1 mol L-1, tamp?o fosfato 0,1 mol L-1 (pH 7,0), tamp?o fosfato 0,1 mol L-1 (pH 7,0) com 10% de ?lcool et?lico e ?cido sulf?rico 0,2 mol L-1, respectivamente. Nesses eletr?litos tr?s f?rmacos apresentaram um ?nico processo de oxida??o: a TF em +1,33V, a CM em +1,18 V e a VF em +0,90 V. J? o VP apresentou tr?s processos de oxida??o entre +1,2V e +1,5V, al?m de um processo de redu??o em +0,2V depende das oxida??es. A detec??o MPA-BIA foi baseada na aplica??o de um pulso de potencial de detec??o e outro de limpeza do DDB para tr?s f?rmacos. Neste caso, os pulsos de potencial para detec??o da TF, CM e VF foram todos aplicados por 100ms em +1,5V, +1,6V e +1,2V, respectivamente. Para determina??o do VP foram utilizados tr?s pulsos de potencial, um para oxida??o do VP (gerador) em +1,6V/50ms, um para redu??o do produto gerado (coletor) e quantifica??o do VP em -0,1V/30ms, e um terceiro em +1,1V/100ms para limpeza da superf?cie do DDB. A velocidade de inje??o da MA foi otimizada em 100?L s-1, exceto para VP que foi de 47?Ls-1, e com a SD a velocidade de inje??o foi de aproximadamente 107 ?Ls-1 pra a TF, CM e VF, proporcionando uma frequ?ncia anal?tica te?rica de pelo menos 53 determina??es por hora desses f?rmacos. Um baixo desvio padr?o relativo (10 medidas) foi obtido para todos os f?rmacos, n?o ultrapassando 3,0% tanto pela inje??o autom?tica quanto pela manual. As curvas anal?ticas foram estabelecidas e uma boa faixa linear foi obtida para todos os f?rmacos com pelo menos duas ordens de concentra??o. Os coeficientes de correla??o linear para todas as regress?es foram maiores que 0,992 em todos os estudos. Os estudos de adi??o e recupera??o mostraram valores pr?ximos a 100 % para todas as amostras farmac?uticas analisadas. O m?todo proposto usando a inje??o autom?tica e manual foi devidamente validado pelo m?todo oficial para cada um dos f?rmacos avaliados. Portanto, a detec??o MPA-BIA usando o eletrodo de DDB mostrou ser uma alternativa mais simples e r?pida para determina??o da TF, CM, VF e VP em formula??es farmac?uticas, possibilitando ainda uma diminui??o do custo do sistema BIA pela substitui??o da micropipeta autom?tica por uma seringa descart?vel.
Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2016.
Theophylline (TF), Clindamycin (CM), Warfarin (VF) and Verapamil (VP) are drugs of narrow therapeutic index that require a strict quality control in the preparation of their formulations. Thus, the development of simple and rapid methods for determination of these drugs is very important in the pharmaceutical industry. In this sense, this paper presents a new methodology for determination of these drugs by multiple-pulse amperometry (MPA) coupled to batch injection analysis (BIA), using the boron-doped diamond (BDD) electrode. The analysis in BIA system was performed in an electrochemical cell (Wall Jet), where the injections were performed by automatic micropipette or manually by an disposable syringe for TF, CM and VF, showing a possibility to reduction of the analysis cost. The electrochemical behavior of the analytes was investigated by cyclic voltammetry and the support electrolytes were chosen for TF, CM, VF and VP in medium of sulfuric acid 0.1 mol L-1, phosphate buffer 0.1 mol L-1 (pH 7.0), phosphate buffer 0.1 mol L-1 (pH 7.0) with 10% ethyl alcohol and sulfuric acid 0.2 mol L-1, respectively. In these conditions, three drugs exhibited a single oxidation process: TF in +1.33V, the CM in +1.18V and the VF in +0.90V (vs Ag/AgCl). Already the VP presented three oxidation processes between +1.2V and +1.5V, besides a reduction process in +0.20 V that depends on the oxidation. The MPA-BIA detection for three drugs (TF, CM, VF) was based on the application of two potential pulses, one for detection and other for cleaning BDD electrode. In this case, the potential pulses to detection the TF, CM and VF were all applied for 100ms at +1.5V, +1.2V and +1.6 V, respectively. In determination of the VP, were used three potential pulses, one for oxidation of VP (generator potential pulse) in +1.6V/50ms, one for reducing the generated product (collector potential pulse) and performed quantification of VP in -0.1V/30ms, and a third potential pulse at +1.1V/100ms for cleaning BDD electrode. The injection speed using automatic micropipette was 100?L s-1, except for VP that was 47?Ls-1, and injection speed by insulin syringe was approximately 107?Ls-1, which provide theoretical analytical frequency of at least 53 determinations per hour of these drugs. A low standard relative deviation (10 measures) was obtained for all drugs, not extending beyond 3.0% by both injections systems. The analytical curves were established and a good linear range was obtained for all drugs with at least two orders of concentration. The linear correlation coefficients for all regressions were higher than 0.992. The addition and recovery studies show values close to 100% for all drug samples analyzed. The proposed method using automatic and manual injection was validated by official method for each analyte. Therefore, this paper presented a fast and simple method for the determination of TF, CM, VF and VP in pharmaceutical formulations using BIA-MPA detection with BBD electrode. Moreover, this work demonstrated an inexpensive method for application in routine analysis of narrow therapeutic index drugs, mainly using a manual injection in BIA system by an disposable syringe.

碩士
國立清華大學
化學系
103
Graphene quantum dots (GQDs) are nano-sized materials having unique properties like the quantum confinement effect and edge effect which has led to its emergence in fluorescence-based applications. The low toxicity, high solubility, chemically inertness, and stable luminescent properties of GQDs must be explored further for its application in sensors and bio imaging studies. A one-pot synthesis of GQDs based on the bottom-up approach has been developed in this study with citric acid and amino acids（glycine、cysteine） precursors to successfully achieve two N-doped Graphene Quantum Dots (N-GQD). In this reaction, amino acid plays dual role of donating both carbon and nitrogen atom. These as-prepared N-GQDs have a high quantum yield of 14（glycine） and 58%（cysteine） as compared to previously reported GQDs. The final product has been characterized using FT-IR, PL, TEM, UV-Vis, XPS, and AFM, which shows successful nitrogen doping as GQDs. These highly fluorescent N-GQDs have been used for faster sensing of tetracycline in honey, making this, a green method as it does not involve the use of any toxic reagent. The detection is based on the on-off mechanism and fluorescent control of N-GQDs. The sensing is primarily based on a π-π stacking interaction between N-GQD and tetracycline by quenching the fluorescence of N-GQDs. Detection of honey has been carried out using a standard addition method. A detection limit of 4 μg·L−1, recovery of 77-112%, and a relative standard deviation of 14.5% is a proof to a highly sensitive detection. Further, rapid detection of 21 commercial honey samples has been carried out, of which, four samples have been found with the presence of tetracyclin.

碩士
中原大學
應用物理研究所
93
Abstract In this thesis, we study the possibility of improvement of performance for organic photovoltaic cells by various dopants. The photovoltaic cell was primarily fabricated with conjugated polymer poly(3-octyl- thiophene) (P3OT), in conjunction with an additive based on singlewall carbon nanotubes (SWNTs), buckminsterfullerene (C60) or/and the nematic liquid-crystal E7. The samples include five constitutes: ITO/(P3OT+SWNTs)/Al, ITO/(P3OT+C60)/Al, ITO/(P3OT+E7)/Al, ITO/(P3OT+(E7+SWNTs))/Al and ITO/(P3OT+(E7+C60))/Al, and the doping concentration is chosen to be 1 wt%, 3 wt%, 5 wt% or 10 wt%. In view of photocurrent data, it is found that the samples doped with SWNTs perform poorly, likely due to the poor dispersion in the polymeric matrix. As anticipated, doping C60 can promote the photocurrent signal of the samples. The performance in photoconduction for the samples doped with E7 is the best among all samples investigated. From the experimental results of fluorescence spectra, we believe that the mechanism for the dopant E7 in the photoconducting polymer is different from that of carbon nanotubes or C60. We propose that the doapnt E7 may locally help polymeric molecules arrange more orderly and promote charge-carrier transport, leading to the higher photocurrent observed.

碩士
國立臺南大學
電機工程學系碩博士班
102
In this study, the S doped ZnO nanowires were successfully synthesized on flexible PET substrate by hydrothermal. The crystalline structure of these S doped samples were measured with SEM, EDS, XRD, PL and TEM. The doping concentration of sulfur into ZnO nanowires was 2.03 atm % in EDS. All XRD peaks of S doped ZnO shift to smaller angle. Photoluminescence spectra of S-doped ZnO nanowires show blue shift phenomenon of the green emissions compared with that of pure ZnO nanowires. By TEM EDS-Mapping analysis, we also can see that the S atomic were uniform distributed over the ZnO nanowires. In the S doped ZnO nanowires on flexible PET substrate, we combined it with device for measured the piezoelectric properties with different relative humidity (RH) and different temperature conditions. We also measured the piezoelectric properties with different relative humidity and used the 365nm UV lamp to discuss its resistance variation. In the last section, we used environmental vibration for driving our device to measure with different strain and 365nm UV lamp conditions to investigate the piezoelectric properties of it.

碩士
國立臺灣海洋大學
光電科學研究所
101
The nonlinear optical properties of lanthanum doped lead titanate (PLT) and lithium niobate (LiNbO3) were investigated using Z-scan technique with femtosecond mode-locked Ti-sapphire laser and femtosecond laser amplifier. Our laser light source was a mode-locked Ti-sapphire laser, the output pulse width was approximately 130 femtoseconds at a wavelength of 800 nm, and the repetition rate was 1 kHz. The results demonstrate self-focusing of lead lanthanum titanate (PLT) with a nonlinear refractive index, n2 of (7.08±1.26)×10-11(esu). The real part of the third-order nonlinear susceptibility χ(3) of lead lanthanum titanate (PLT) is(2.49±0.44) ×10-19(m2/V2). The results demonstrate reverse saturable absorption of lead lanthanum titanate (PLT) with a three -photon absorption coefficient, α3 of (2.05±0.54) ×10-21(cm3/W2). The fifth-order nonlinear susceptibility χ(5) ) of lead lanthanum titanate (PLT) is (1.68±2.06) ×10-36(m4/V4). The results demonstrate reverse saturable absorption of lithium niobate (LiNbO3) with a three -photon absorption coefficient, α3 of (3.92±2.05) ×10-21 (cm3/W2). The fifth-order nonlinear susceptibility χ(5) ) of lead lanthanum titanate (PLT) is (1.69±0.82) ×10-36 (m4/V4).

碩士
逢甲大學
材料與製造工程所
98
The author reported that surface treatment for PET substrates by using corona discharge and Ga and Al co-doped ZnO (GAZO) thin films deposited on as-treatment PET substrates by RF magnetron sputtering. Characterization of PET substrates after corona discharge was carrier out by contact angle and laser scanning microscopy. Experimental results showed that surfaces of PET substrates were modified corona discharge, at a power of corona discharge of 3 kW and at a transmission speed of 2 m/min, would improve surface energy above 56 mN/m. Moreover, transparent and flexible GAZO thin films were prepared by RF magnetron sputtering. Effect of substrate temperatures on crystallinity levels, microstructures, optical and electrical properties of these GAZO thin films were investigated. Experimental results also showed that deposition rates, crystallinity levels and electrical properties of GAZO thin films improved with substrate temperatures increasing. Among the GAZO thin films in this study, the films deposited on substrate temperature at 135 ℃which exhibited the best properties, namely highest crystallinity level, a resistivity of 0.372 Ω-cm, a carrier concentration of 3.03×1018 cm3 and a carrier mobility of 5.53 cm2/ Vs.

碩士
國立成功大學
機械工程學系
103
A flat plate in the deposition stage is designed to have a flexible tilt angle and thus form a variable inclination angle between the ion beam and the direction normal to a PET substrate. Five kinds of inclination angle, 0°, 15°, 30°, 45° and 60° were used to prepare the PET/aluminum-doped zinc oxide specimens in order to examine the effects of the inclination angle and the number of bending cycles on several parameters including the O2-peak intensity ratio (IRO2) from the Electron spectroscopy for chemical analysis, which is identified to be one of the controlling factors in the determinations of electrical, optical, piezoelectric and mechanical properties. The effects of inclination angle on IRO2 and the effects of IRO2 on the parameters of the volume fractions of IRZnO(002) and IRZnO(103) from XRD analyses, the composite grain size and the residual stress in the thin film are investigated systematically. Increases in the inclination angle can raise the IRO2 value; they also reduce the peak intensity, IRZnO. A rise in IRO2 can reduce the volume fraction of IRZnO(002) but raise the residual stress of thin film; it is favorable for the lowering of the composite grain size. The combination of gComposite increase and IRO2 decrease has resulted in an electrical resistivity increase and a carrier mobility decrease. An increase in the residual stress has reduced the fatigue life of bending specimen and the piezoelectric coefficient. The uses of nonzero inclination angle create favorable conditions to raise the transmittance integration over the wavelengths of visible light and the intensities of the three peaks in the photoluminescence spectrum.