Towards near-infrared photoactivation of anticancer metal complexes.

171 p.

Fabricación y caracterización de películas delgadas de óxidos transparentes con aplicaciones ópticas.

Los óxidos transparentes conductores (TCO′ s) son materiales compuestos conformados por oxígeno y un metal, que presentan una combinación única de alta estabilidad química, alta concentración electrónica y alta transparencia óptica. Por esta razón, el procesamiento de TCO′ s en película delgada va orientado hacia aplicaciones específicas tales como ventanas ópticas en celdas solares, sensores de gases, electrodos en dispositivos de pantallas planas, ventanas inteligentes. En este proyecto se trabajó en la síntesis experimental de dos TCO′ s relevantes tanto en investigación fundamental como en aplicaciones tecnológicas: el óxido de indio (In2O3) y el óxido de estaño (SnO2). Ambos TCO′ s se depositaron por la técnica de erosión iónica reactiva por corriente directa (DC). Para el análisis de las películas se utilizaron varias técnicas de caracterización: difracción de rayos X, espectroscopia UV-Visible, resistividad eléctrica, efecto Hall, así como microscopías electrónica de barrido y de fuerza atómica. Se fabricó también una bicapa de In2O3/SnO2, la cual se caracterizó además con espectroscopia de fotoemisión de rayos X (XPS).En esta tesis se reporta por primera vez la síntesis y caracterización de esta bicapa, la cual abre una línea de investigación en el área de interfaces. Asimismo, se desarrolló e implementó un procedimiento, basado en los modelos ópticos, tal que permite obtener parámetros que se utilizan para evaluar a cualquier película delgada TCO como potencial metamaterial. Las propiedades de las muestras se analizaron en función de la temperatura aplicada post-depósito: temperatura ambiente (TA), 100oC, 200oC, 300oC, bajo una atmósfera de argón o argón-oxígeno. Los resultados confirman que las películas presentan un crecimiento de tipo poli cristalino. Además, la calidad cristalina tiende a incrementarse como función del incremento de la temperatura. El In2O3 creció con estructura cúbica bcc (a=10.11 ˚A, ICDD #71-2195). A partir de 200C, se detectaron trazas de la fase romboédrica (a=5.490 ˚A, c=14.520 ˚A, ICDD #73-1809). Asimismo, el SnO2 creció con estructura tetragonal (a = 4.737 ˚A, c = 3.186 ˚A, ICDD #88-0287). Las películas de In2O3 poseen una transparencia promedio del 90 % en una ventana de 500 nm a 1100 nm. El borde de absorción se recorre al azul como función de la temperatura, de Eg=3.3 eV a Eg=3.7 eV por el efecto Burstein-Moss. Por otra parte, la bicapa presentó una interfaz claramente definida, sin difusión de especies metálicas. Al incrementarse la temperatura, de TA a 400oC, se detectaron dos fases de óxido de estaño: SnO2 y SnO, en un porcentaje atómico de ≈70 %:30 %, respectivamente. Se concluye que los parámetros y valores obtenidos de las películas como son el texturizado y espesor homogéneo, alta transparencia, crecimiento preferencial, ancho prohibido y resistividad eléctrica, son comparables a los que se requieren del In2O3 y SnO2 en película delgada para aplicaciones optoelectrónicas.

Síntese de pigmento cerâmico ferrita de cobalto utilizando planejamento experimental

Synthetic inorganic pigments are the most widely used in ceramic applications because they have excellent chemical and thermal stability and also, in general, a lower toxicity to man and to the environment. In the present work, the ceramic black pigment CoFe2O4 was synthesized by the polymerization Complex method (MPC) in order to form a material with good chemical homogeneity. Aiming to optimize the process of getting the pigment through the MPC was used a fractional factorial design 2(5-2), with resolution III. The factors studied in mathematical models were: citric acid concentration, the pyrolysis time, temperature, time and rate of calcination. The response surfaces using the software statistica 7.0. The powders were characterized by thermal analysis (TG/DSC), x-ray diffraction (XRD), scanning electron microscopy (SEM) and spectroscopy in the UV-visible. Based on the results, there was the formation of phase cobalt ferrite (CoFe2O4) with spinel structure. The color of the pigments obtained showed dark shades, from black to gray. The model chosen was appropriate since proved to be adjusted and predictive. Planning also showed that all factors were significant, with a confidence level of 95%

Preparação e caracterização de catalisadores à base de titânio suportado em MCM-41 para produção de compostos oxigenados através da pirólise catalítica do capim elefante

In recent years, the area of advanced materials has been considerably, especially when it comes to materials for industrial use, such as is the case with structured porosity of catalysts suitable for catalytic processes. The use of catalysts combined with the fast pyrolysis process is an alternative to the oxygenate production of high added value, because, in addition to increasing the yield and quality of products, allows you to manipulate the selectivity to a product of interest, and therefore allows greater control over the characteristics of the final product. Based on these arguments, in this work were prepared titanium catalysts supported on MCM-41 for use in catalytic pyrolysis of biomass, called elephant grass. The reactions of pyrolysis of biomass were performed in a micro pyrolyzer, Py-5200, coupled to GC / MS, the company CDS Corporation, headquartered in the United States. The catalysts Ti-MCM-41 in different molar ratios were characterized by XRD, TG / DTG, FT-IR, SEM, XRF, UV-visible adsorption of nitrogen and the distribution of particle diameter and specific surface area measurement by the BET method. From the catalytic tests it was observed that the catalysts synthesized showed good results for the pyrolysis reaction.The main products were obtained a higher yield of aldehydes, ketones and furan. It was observed that the best reactivity is a direct function of the ratio Si/Ti, nature and concentration of the active species on mesoporous supports. Among the catalysts Ti-MCM-41 (molar ratio Si / Ti = 25 and 50), the ratio Si / Ti = 25 (400 ° C and 600 ° C) favored the cracking of oxygenates such as acids , aldehydes, ketones, furans and esters. Already the sample ratio Si / Ti = 50 had the highest yield of aromatic oxygenates

Propriedade fotoluminescente da ZrO2: Tb+3, Eu+3, Tm+3 obtida pelo método de polimerização de complexos

Recent studies are investigating a new class of inorganic materials which arise as a promising option for high performance applications in the field of photoluminescence. Highlight for rare earth (TR +3 ) doped, which have a high luminous efficiency, long decay time and being able to emit radiation in the visible range, specific to each element. In this study, we synthesized ZrO2: Tb +3 , Eu +3 , Tm +3 nanoparticles complex polymerization method (CPM). We investigated the influences caused by the heat treatment temperature and the content of dopants in zirconia photoluminescent behavior. The particles were calcined at temperature of 400, 500 and 600 ° C for two hours and ranged in concentration of dopants 1, 2, 4 and 8 mol% TR +3 . The samples were characterized by thermal analysis, X-ray diffraction, photoluminescence of measurements and uv-visible of spectroscopies. The results of X-ray diffraction confirmed the formation of the tetragonal and cubic phases in accordance with the content of dopants. The photoluminescence spectra show emission in the region corresponding simultaneous to blue (450 nm), green (550 nm) and red (615 nm). According to the results, ZrO2 particles co-doped with rare earth ions is a promising material white emission with a potential application in the field of photoluminescence

Transport in the blood of an anti-tumor water-soluble rutheniun cyclopentadienyl complex: a fluorescence study on albumin binding

Dissertação de mestrado, Qualidade em Análises, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2014

Photocurrents in P3MeT Schottky barrier diodes

The photocurrent action spectrum of a Schottky diode formed from electrodeposited poly(3-methylthiophene) is shown to follow closely the UV-visible absorption spectrum. At low forward bias, the peak photocurrent asymptotes to the expected square-root dependence on total potential, V-t, across the depletion region. At high reverse bias the superlinear dependence of the photocurrent on V-t suggests that internal photoemission from the rectifying aluminium electrode may be the dominant process.

Obtenção de álcool alílico (PROP-2-EN-1-OL) a partir da glicerina derivada do biodiesel de óleo de mamona

In this work, biodiesel was produced from castor oil that was a byproduct glycerin. The molar ratio between oil and alcohol, as well as the use of (KOH) catalyst to provide the chemical reaction is based on literature. The best results were obtained using 1 mol of castor oil (260g) to 3 moles of methyl alcohol (138g), using 1.0% KOH as catalyst at a temperature of 260 ° C and shaken at 120 rpm. The oil used was commercially available, the process involves the reaction of transesterification of a vegetable oil with methyl alcohol. The product of this reaction is an ester, biodiesel being the main product and the glycerin by-product which has undergone treatment for use as raw material for the production of allyl alcohol. The great advantage of the use of glycerin to obtain allyl alcohol is that its use eliminates the large amount of waste of the biodiesel and various forms of insult to the environment. The reactions for the formation of allyl alcohol was conducted from formic acid and glycerin in a ratio 1/1, at a temperature of 260oC in a heater blanket, being sprayed by a spiral condenser for a period of 2 hours and the product obtained contains mostly the allylic alcohol .. The monitoring of reactions was performed by UV-Visible Spectrophotometer: FTIR Fourier transform, the analysis showed that these changes occur spectrometer indicating the formation of the product allylic alcohol (prop-2-en-1-ol) in the presence of water, This alcohol was appointed Alcohol GL. The absorption bands confirms that the reaction was observed in (υ C = C) 1470 -1600 cm -1 and (υ CO), 3610-3670 attributed to C = C groups and OH respectively. The thermal analysis was carried out in a thermogravimetric analyzer SDT Q600, where the mass and temperature are displayed against time, that allows checking the approximate rate of heating. The innovative methodology developed in the laboratory (LABTAM, UFRN), was able to treat the glycerine produced by transesterification of castor oil and used as raw material for production of allyl alcohol, with a yield of 80%, of alcohol, the same is of great importance in the manufacture of polymers, pharmaceuticals, organic compounds, herbicides, pesticides and other chemicals

Tunnig optical A-Sic/A-Si active filters by UV bias light in the visible and infrared spectral ranges

Visible range to telecom band spectral translation is accomplished using an amorphous SiC pi'n/pin wavelength selector under appropriate front and back optical light bias. Results show that background intensity works as selectors in the infrared region, shifting the sensor sensitivity. Low intensities select the near-infrared range while high intensities select the visible part according to its wavelength. Here, the optical gain is very high in the infrared/red range, decreases in the green range, stays close to one in the blue region and strongly decreases in the near-UV range. The transfer characteristics effects due to changes in steady state light intensity and wavelength backgrounds are presented. The relationship between the optical inputs and the output signal is established. A capacitive optoelectronic model is presented and tested using the experimental results. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Performance characteristics of UV and visible spectrophotometry methods for quantitative determination norfloxacin in tablets

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Thermal analysis and validation of UV and visible spectrophotometric methods for the determination of new antibiotic tigecycline in pharmaceutical product

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Loading effect in copper(II) oxide cluster-surface-modified titanium(IV) oxide on visible- and UV-light activities

Cu(acac)2 is chemisorbed on TiO2 particles [P-25 (anatase/rutile = 4/1 w/w), Degussa] via coordination by surface Ti–OH groups without elimination of the acac ligand. Post-heating of the Cu(acac)2-adsorbed TiO2 at 773 K yields molecular scale copper(II) oxide clusters on the surface (CuO/TiO2). The copper loading amount (Γ/Cu ions nm–2) is controlled in a wide range by the Cu(acac)2 concentration and the chemisorption–calcination cycle number. Valence band (VB) X-ray photoelectron and photoluminescence spectroscopy indicated that the VB maximum of TiO2 rises up with increasing Γ, while vacant midgap levels are generated. The surface modification gives rise to visible-light activity and concomitant significant increase in UV-light activity for the degradation of 2-naphthol and p-cresol. Prolonging irradiation time leads to the decomposition to CO2, which increases in proportion to irradiation time. The photocatalytic activity strongly depends on the loading, Γ, with an optimum value of Γ for the photocatalytic activity. Electrochemical measurements suggest that the surface CuO clusters promote the reduction of adsorbed O2. First principles density functional theory simulations clearly show that, at Γ < 1, unoccupied Cu 3d levels are generated in the midgap region, and at Γ > 1, the VB maximum rises and the unoccupied Cu 3d levels move to the conduction band minimum of TiO2. These results suggest that visible-light excitation of CuO/TiO2 causes the bulk-to-surface interfacial electron transfer at low coverage and the surface-to-bulk interfacial electron transfer at high coverage. We conclude that the surface CuO clusters enhance the separation of photogenerated charge carriers by the interfacial electron transfer and the subsequent reduction of adsorbed O2 to achieve the compatibility of high levels of visible and UV-light activities.

UV and visible photoconductivity of undoped diamond films: morphology and related electrical transport phenomena

UV and visible photoconductivity and electrical features of undoped diamond thin films grown by microwave plasma-assisted chemical vapour deposition (MP-CVD) on silicon and copper substrates are studied. The results are correlated with morphology properties analysed by atomic force microscopy (AFM) and micro-Raman. The photoconductivity presents several bands from 1.8 to 3.8 eV that are dependent on the substrate used to grow the samples in spite of some common bands observed. The J-V curve tin DC) in samples grown on Si has a rectifier behaviour (Schottky emission) in opposition to the samples grown on Cu that have no rectification (SCLC conduction). With these results we can conclude that diamond based optoelectronic devices behaviour is controlled by two kinds of structural defects localized in microcrystal and in its boundaries. A general structure model for the optoelectronic behaviour is discussed. (C) 2000 Elsevier Science S.A. All rights reserved.

UV and visible photoconductivity of undoped diamond films: morphology and related electrical transport phenomena

UV and visible photoconductivity and electrical features of undoped diamond thin films grown by microwave plasma-assisted chemical vapour deposition (MP-CVD) on silicon and copper substrates are studied. The results are correlated with morphology properties analysed by atomic force microscopy (AFM) and micro-Raman. The photoconductivity presents several bands from 1.8 to 3.8 eV that are dependent on the substrate used to grow the samples in spite of some common bands observed. The J-V curve tin DC) in samples grown on Si has a rectifier behaviour (Schottky emission) in opposition to the samples grown on Cu that have no rectification (SCLC conduction). With these results we can conclude that diamond based optoelectronic devices behaviour is controlled by two kinds of structural defects localized in microcrystal and in its boundaries. A general structure model for the optoelectronic behaviour is discussed. (C) 2000 Elsevier Science S.A. All rights reserved.