Determinação eletroanalítica de ácido salicílico em produto dermatológico com eletrodos de nanotubos de carbono e nanopartículas de óxido de ferro

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Tecnologias Química e Biológica, 2016.

Otimização do processo de síntese do aluminato de cobalto via método de polimerização de complexos (MPC) através do planejamento fatorial fracionado

In the ceramics industry are becoming more predominantly inorganic nature pigments. Studies in this area allow you to develop pigments with more advanced properties and qualities to be used in the industrial context. Studies on synthesis and characterization of cobalt aluminate has been widely researched, cobalt aluminate behavior at different temperatures of calcinations, highlighting especially the temperatures of 700, 800 and 900° C that served as a basis in the development of this study, using the method of polymerization of complex (CPM), economic, and this method applied in ceramic pigment synthesis. The procedure was developed from a fractional factorial design 2 (5-2) in order to optimize the process of realization of the cobalt aluminate (CoAl2O4), having as response surfaces the batch analysis data of Uv-vis spectroscopy conducted from the statistic software 7.0, for this were chosen five factors as input variables: citric acid (stoichiometric manner), puff or pyrolysis time (h), temperature (° C), and calcinations (° C/min), at levels determined for this study. By applying statistics in the process of obtaining the CoAl2O4 is possible the study of these factors and which may have greater influence in getting the synthesis. The pigments characterized TG/DSC analyses, and x-ray diffraction (XRD) and scanning electron microscope (SEM/EDS) in order to establish the structural and morphological aspects of pigment CoAl2O4, among the factors studied it were found to statically with increasing calcinations temperature 700°< 800 <900 °C, the bands of Uv-vis decrease with increasing intensity of absorbance and that with increasing time of puff or pyrolysis (h) there is an increase in bands of Uv-vis proportionally, the generated model set for the conditions proposed in this study because the coefficient of determination can explain about 99.9% of the variance (R²), response surfaces generated were satisfactory, so it s possible applicability in the ceramics industry of pigments

Membrana de alumina anódica: comportamento da microestrutura e estudo das propriedades ópticas após tratamento térmico

Thin commercial aluminum electrolytic and passed through reactions was obtained with anodic alumina membranes nanopores. These materials have applications in areas recognized electronic, biomedical, chemical and biological weapons, especially in obtaining nanostructures using these membranes as a substrate or template for processing nanowires, nanodots and nanofibers for applications noble. Previous studies showed that the membranes that have undergone heat treatment temperature to 1300° C underwent changes in morphology, crystal structure and optical properties. This aim, this thesis, a study of the heat treatment of porous anodic alumina membranes, in order to obtain and to characterize the behavior changes structures during the crystallization process of the membranes, at temperatures ranging between 300 and 1700° C. It was therefore necessary to mount a system formed by a tubular furnace resistive alumina tube and controlled environment, applying flux with special blend of Ag-87% and 13% N2, in which argon had the role of carrying out the oxygen nitrogen system and induce the closing of the pores during the densification of the membrane. The duration of heat treatment ranged from 60 to 15 minutes, at temperatures from 300 to 1700° C respectively. With the heat treatment occurred: a drastic reduction of porosity, grain growth and increased translucency of the membrane. For the characterization of the membranes were analyzed properties: Physical - thermogravimetric, X-ray diffraction, BET surface area; morphological - SEM, EDS through compositional and, optical absorbance, and transmittance in the UV-VIS, and FTIR. The results using the SEM showed that crystallization has occurred, densification and significant changes in membrane structure, as well as obtaining microtube, the BET analysis showed a decrease in specific surface area of the membranes has to 44.381 m2.g-1 to less than 1.8 m2.g-1 and in the analysis of transmittance and absorbance was found a value of 16.5% in the range of 800 nm, characteristic of the near infrared and FTIR have confirmed the molecular groups of the material. Thus, one can say that the membranes were mixed characteristics and properties which qualify for use in gas filtration system, as well as applications in the range of optical wavelength of the infra-red, and as a substrate of nanomaterials. This requires the continuation and deepening of additional study

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

Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands

A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic \[(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles.

The encapsulation of gold nanoparticles using RAFT, ATRP and miniemulsion polymerisation techniques

The investigation into the encapsulation of gold nanoparticles (AuNPs) by poly(methyl methacrylate) (PMMA) was undertaken. This was performed by three polymerisation techniques including: grafting PMMA synthesised by reversible addition-fragmentation chain transfer (RAFT) polymerisation to AuNPs, grafting PMMA synthesised by atom transfer radical polymerisation (ATRP) from the surface of functionalised AuNPs and by encapsulation of AuNPs within PMMA latexes produced through photo-initiated oil-in-water (o/w) miniemulsion polymerisation. The grafting of RAFT PMMA to AuNPs was performed by the addition of the RAFT functionalised PMMA to citrate stabilised AuNPs. This was conducted with a range of PMMA of varying molecular weight distribution (MWD) as either the dithioester or thiol end-group functionalities. The RAFT PMMA polymers were characterised by gel permeation chromatography (GPC), ultraviolet-visible (UV-vis), Fourier transform infrared-attenuated total reflectance (FTIR-ATR), Fourier transform Raman (FT-Raman) and proton nuclear magnetic resonance (1H NMR) spectroscopies. The attachment of PMMA to AuNPs showed a tendency for AuNPs to associate with the PMMA structures formed, though significant aggregation occurred. Interestingly, thiol functionalised end-group PMMA showed very little aggregation of AuNPs. The spherical polymer-AuNP structures did not vary in size with variations in PMMA MWD. The PMMA-AuNP structures were characterised using scanning electron microscopy (SEM), transition electron microscopy (TEM), energy dispersive X-ray analysis (EDAX) and UV-vis spectroscopy. The surface confined ATRP grafting of PMMA from initiator functionalised AuNPs was polymerised in both homogeneous and heterogeneous media. 11,11’- dithiobis[1-(2-bromo-2-methylpropionyloxy)undecane] (DSBr) was used as the surface-confined initiator and was synthesised in a three step procedure from mercaptoundecanol (MUD). All compounds were characterised by 1H NMR, FTIR-ATR and Raman spectroscopies. The grafting in homogeneous media resulted in amorphous PMMA with significant AuNP aggregation. Individually grafted AuNPs were difficult to separate and characterise, though SEM, TEM, EDAX and UV-vis spectroscopy was used. The heterogeneous polymerisation did not produce grafted AuNPs as characterised by SEM and EDAX. The encapsulation of AuNPs within PMMA latexes through the process of photoinitiated miniemulsion polymerisation was successfully achieved. Initially, photoinitiated miniemulsion polymerisation was conducted as a viable low temperature method of miniemulsion initiation. This proved successful producing a stable PMMA with good conversion efficiency and narrow particle size distribution (PSD). This is the first report of such a system. The photo-initiated technique was further optimised and AuNPs were included into the miniemulsion. AuNP encapsulation was very effective, producing reproducible AuNP encapsulated PMMA latexes. Again, this is the first reported case of this. The latexes were characterised by TEM, SEM, GPC, gravimetric analysis and dynamic light scattering (DLS).

Large-scale fabrication of H2(H2O)Nb2O6 and Nb2O5 hollow microspheres

Hollow micro-sized H2(H2O)Nb2O6 spheres constructed by nanocrystallites have been successfully synthesized via a bubble-template assisted hydrothermal process. In the reaction process, H2O2 acts as a bubble generator and plays a key role in the formation of the hollow structure. An in situ bubble-template mechanism has been proposed for the possible formation of the hollow structure. The spherelike assemblies of these H2(H2O)Nb2O6 nanoparticles have been transformed into their corresponding pseudohexagonal phase Nb2O5 through a moderate annealing dehydration process without destroying the hierarchical structure. Optical properties of the as-prepared hollow spheres were investigated. It is exciting that the absorption edge of the hollow Nb2O5 microspheres shifts about 18 nm to the violet compared with bulk powders in the UV/vis spectra, indicating its superior optical properties.

Investigation of electrophoretic loading and enhanced mechanical properties of hydrogels for delivery of therapeutic proteins

Hydrogels, which are three-dimensional crosslinked hydrophilic polymers, have been used and studied widely as vehicles for drug delivery due to their good biocompatibility. Traditional methods to load therapeutic proteins into hydrogels have some disadvantages. Biological activity of drugs or proteins can be compromised during polymerization process or the process of loading protein can be really timeconsuming. Therefore, different loading methods have been investigated. Based on the theory of electrophoresis, an electrochemical gradient can be used to transport proteins into hydrogels. Therefore, an electrophoretic method was used to load protein in this study. Chemically and radiation crosslinked polyacrylamide was used to set up the model to load protein electrophoretically into hydrogels. Different methods to prepare the polymers have been studied and have shown the effect of the crosslinker (bisacrylamide) concentration on the protein loading and release behaviour. The mechanism of protein release from the hydrogels was anomalous diffusion (i.e. the process was non-Fickian). The UV-Vis spectra of proteins before and after reduction show that the bioactivities of proteins after release from hydrogel were maintained. Due to the concern of cytotoxicity of residual monomer in polyacrylamide, poly(2-hydroxyethyl- methacrylate) (pHEMA) was used as the second tested material. In order to control the pore size, a polyethylene glycol (PEG) porogen was introduced to the pHEMA. The hydrogel disintegrated after immersion in water indicating that the swelling forces exceeded the strength of the material. In order to understand the cause of the disintegration, several different conditions of crosslinker concentration and preparation method were studied. However, the disintegration of the hydrogel still occurred after immersion in water principally due to osmotic forces. A hydrogel suitable for drug delivery needs to be biocompatible and also robust. Therefore, an approach to improving the mechanical properties of the porogen-containing pHEMA hydrogel by introduction of an inter-penetrating network (IPN) into the hydrogel system has been researched. A double network was formed by the introduction of further HEMA solution into the system by both electrophoresis and slow diffusion. Raman spectroscopy was used to observe the diffusion of HEMA into the hydrogel prior to further crosslinking by ã-irradiation. The protein loading and release behaviour from the hydrogel showing enhanced mechanical property was also studied. Biocompatibility is a very important factor for the biomedical application of hydrogels. Different hydrogels have been studied on both a three-dimensional HSE model and a HSE wound model for their biocompatibilities. They did not show any detrimental effect to the keratinocyte cells. From the results reported above, these hydrogels show good biocompatibility in both models. Due to the advantage of the hydrogels such as the ability to absorb and deliver protein or drugs, they have potential to be used as topical materials for wound healing or other biomedical applications.

Study of the interaction between 10-hydroxycamptothecine and DNA with the use of ethidium bromide dye as a fluorescence probe

The interaction of 10-hydroxycamptothecine (HCPT) with DNA under pseudo-physiological conditions (Tris-HCl buffer of pH 7.4), using ethidium bromide (EB) dye as a probe, was investigated with the use of spectrofluorimetry, UV-vis spectrometry and viscosity measurement. The binding constant and binding number for HCPT with DNA were evaluated as (7.1 ± 0.5) × 104 M-1 and 1.1, respectively, by multivariate curve resolution-alternating least squares (MCR-ALS). Moreover, parallel factor analysis (PARAFAC) was applied to resolve the three-way fluorescence data obtained from the interaction system, and the concentration information for the three components of the system at equilibrium was simultaneously obtained. It was found that there was a cooperative interaction between the HCPT-DNA complex and EB, which produced a ternary complex of HCPT-DNA-EB. © 2011 Elsevier B.V.

Photocatalytic hydrogen production with iron oxide under solar irradiation

As solar hydrogen is a sustainable and environmental friendly energy carrier, it is considered to take the place of fossil fuels in the near future. Solar hydrogen can be generated by splitting of water under solar light illumination. In this study, the use of nanostructured hematite thin-film electrodes in photocatalytic water splitting was investigated. Hematite (á-Fe2O3) has a narrow band-gap of 2.2 eV, which is able to utilise approximately 40% of solar radiation. However, poor photoelectrochemical performance is observed for hematite due to low electrical conductivity and a high rate of electron-hole recombination. An extensive review of useful measures taken to overcoming the disadvantages of hematite so as to enhance its performance was presented including thin-film structure, nanostructuring, doping, etc. Since semiconductoring materials which exhibit an inverse opal structure are expected to have a high surface-volume ratio, unique optical characteristics and a shorter distance for photogenerated holes to travel to the electrode/electrolyte interface, inverse opals of hematite thin films deposited on FTO glass substrate were successfully prepared by doctor blading using PMMA as a template. However, due to the poor adhesion of the films, an acidic medium (i.e., 2 M HCl) was employed to significantly enhance the adhesion of the films, which completely destroyed the inverse opal structure. Therefore, undoped, Ti and Zn-doped hematite thin films deposied on FTO glass substrate without an inverse opal structure were prepared by doctor blading and spray pyrolysis and characterised using SEM, EDX, XRD, TGA, UV-Vis spectroscopy and photoelectrochemical measurements. Regarding the doped hematite thin films prepared by doctor blading, the photoelectrochemical activity of the hematite photoelectrodes was improved by incorporation of Ti, most likely owing to the increased electrical conductivity of the films, the stabilisation of oxygen vacancies by Ti4+ ions and the increased electric field of the space charge layer. A highest photoresponse was recorded in case of 2.5 at.% Ti which seemed to be an optimal concentration. The effect of doping content, thickness, and calcination temperature on the performance of the Ti-doped photoelectrodes was investigated. Also, the photoactivity of the 2.5 at.% Ti-doped samples was examined in two different types of electrochemical cells. Zn doping did not enhance the photoactivity of the hematite thin films though Zn seemed to enhance the hole transport due to the slow hole mobility of hematite which could not be overcome by the enhancement. The poor performance was also obtained for the Ti-doped samples prepared by spray pyrolysis, which appeared to be a result of introduction of impurities from the metallic parts of the spray gun in an acidic medium. Further characterisation of the thin-film electrodes is required to explain the mechanism by which enhanced performance was obtained for Ti-doped electrodes (doctor blading) and poor photoactivity for Zn and Ti-doped samples which were synthesised by doctor blading and spray pyrolysis, respectively. Ti-doped hematite thin films will be synthesised in another way, such as dip coating so as to maintain an inverse opal structure as well as well adhesion. Also, a comparative study of the films will be carried out.

A profluorescent azaphenalene nitroxide for nitroxide-mediated polymerization

A novel nitroxide-mediated polymerization (NMP) control agent; 1,1,3,3-tetramethyl-2,3-dihydro-2-azaphenalen-2-yloxyl (TMAO), was used in the free-radical polymerization of styrene. The conversion of styrene during NMP was studied using FT-Raman spectroscopy and the effectiveness of TMAO as a NMP control agent was assessed by GPC analysis. Fidelity of the TMAO-alkoxyamine end-group on the synthesized polymers was confirmed by GPC, UV-Vis and fluorescence spectroscopic analyses. Comparison to the well known NMP control agent, TEMPO was made. TMAO showed control of molecular weight approaching that of TEMPO. Attempts to improve the properties of TMAO as an NMP control agent by synthesizing an analogue with bulkier substituents around the nitroxide did not generate the target molecule but demonstrated some of the interesting chemistry of the azaphenalene ring system

Transition from n- to p-type of spray pyrolysis deposited Cu doped ZnO thin films for NO2 sensing

The structural, optical, and gas-sensing properties of spray pyrolysis deposited Cu doped ZnO thin films were investigated. Gas response of the undoped and doped films to N02 (oxidizing) gas shows an increase and decrease in resistance, respectively, indicating p-type conduction in doped samples. The UV-Vis spectra of the films show decrease in the bandgap with increasing Cu concentration in ZnO. The observed p-type conductivity is attributed to the holes generated by incorporated Cu atoms on Zn sites in ZnO thin films. The X-ray diffraction spectra showed that samples are polycrystalline with the hexagonal wurtzite structure and increasing the concentration of Cu caused a decrease in the intensity of the dominant (002) peak. The surface morphology of films was studied by scanning electron microscopy and the presence of Cu was also confirmed by X-ray photoelectron spectroscopy. Seebeck effect measurements were utilized to confirm the p-type conduction of Cu doped ZnO thin films. Copyright © 2009 American Scientific Publishers All rights reserved.