Síntese e caracterização de partículas de poli(álcool vinílico) utilizadas em aplicações biomédicas: contribuição da análise fractal e entropia de Shannon

Pós-graduação em Biofísica Molecular - IBILCE

Características estruturais de géis de sílica preaparados a partir da sonohidrólise do tetraetilortosilicato com adições de álcool polivinílico

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Influência da concentração das partículas cristalinas nas propriedades dielétricas do híbrido PVAl/Cds

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Sínteses e caracterização de microesferas de poli (álcool vinilico) e sua utilização como suportes para imobilização de lipase produzida por Rhizomucor miehei e seu estudo catalítico na reação de transesterificação do óleo de soja para a produção de biodiesel via rota etílica

Pós-graduação em Microbiologia - IBILCE

Produção de nanocompósito utilizando diferentes fontes de celulose como reforço

Pós-graduação em Agronomia (Energia na Agricultura) - FCA

Immobilization of a Plant Lipase from Pachira aquatica in Alginate and Alginate/PVA Beads

This study reports the immobilization of a new lipase isolated from oleaginous seeds of Pachira aquatica, using beads of calcium alginate (Alg) and poly(vinyl alcohol) (PVA). We evaluated the morphology, number of cycles of reuse, optimum temperature, and temperature stability of both immobilization methods compared to the free enzyme. The immobilized enzymes were more stable than the free enzyme, keeping 60% of the original activity after 4 h at 50°C. The immobilized lipase was reused several times, with activity decreasing to approximately 50% after 5 cycles. Both the free and immobilized enzymes were found to be optimally active between 30 and 40°C.

Caracterização e aplicação da Blenda PEDOT : PSS/PVA na construção de eletrodos transparentes e dispositivos eletroluminescentes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Synthesis of Structured Lipids by Enzymatic Interesterification of Milkfat and Soybean Oil in a Basket-Type Stirred Tank Reactor

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

Solvent-Resistant Polymeric Sensors for Adulteration Detection in Liquid Fuels

Polymeric sensors with improved resistance to organic solvents were produced via the layer-by-layer thin film deposition followed by chemical cross-linking. According to UV-vis spectroscopy, the mass loss of polyaniline/poly(vinyl alcohol) and polyaniline/novolac-type resin based films deposited onto glass slides was less than 20% when they were submitted to successive immersions (up to 3,000 immersion cycles) into commercially available ethanol and gasoline fuel samples. Polyallylamine hydrochloride/nickel tetrasulfonated phthalocyanine films presented similar stability. The electrical responses assessed by impedance spectroscopy of films deposited onto Au-interdigitated microelectrodes were relatively unaffected after continuous or cyclic immersions into both fuels. After these studies, an array including these polymeric sensors was employed to detect adulteration in ethanol and gasoline samples. After principal component analysis, it was possible to conclude that the proposed sensor array is capable to discriminate with remarkable reproducibility ethanol samples containing different amounts of water or else gasoline samples containing different amounts of ethanol. In both examples, more than 90% of data variance was retained in the first principal component. For each type of sample, ethanol and gasoline, it was found a linear correlation between one of the principal components and the sample's composition. These findings allow one to conclude that these films present great potential for the development of reliable and low-cost sensors for fuel analysis in liquid phase.

Heteronuclear recoupling methods in solid-state NMR

This thesis is focused on the development of heteronuclear correlation methods in solid-state NMR spectroscopy, where the spatial dependence of the dipolar coupling is exploited to obtain structural and dynamical information in solids. Quantitative results on dipolar coupling constants are extracted by means of spinning sideband analysis in the indirect dimension of the two-dimensional experiments. The principles of sideband analysis were established and are currently widely used in the group of Prof. Spiess for the special case of homonuclear 1H double-quantum spectroscopy. The generalization of these principles to the heteronuclear case is presented, with special emphasis on naturally abundant 13C-1H systems. For proton spectroscopy in the solid state, line-narrowing is of particular importance, and is here achieved by very-fast sample rotation at the magic angle (MAS), with frequencies up to 35 kHz. Therefore, the heteronuclear dipolar couplings are suppressed and have to be recoupled in order to achieve an efficient excitation of the observed multiple-quantum modes. Heteronuclear recoupling is most straightforwardly accomplished by performing the known REDOR experiment, where pi-pulses are applied every half rotor period. This experiment was modified by the insertion of an additional spectroscopic dimension, such that heteronuclear multiple-quantum experiments can be carried out, which, as shown experimentally and theoretically, closely resemble homonuclear double-quantum experiments. Variants are presented which are well-suited for the recording of high-resolution 13C-1H shift correlation and spinning-sideband spectra, by means of which spatial proximities and quantitative dipolar coupling constants, respectively, of heteronuclear spin pairs can be determined. Spectral editing of 13C spectra is shown to be feasible with these techniques. Moreover, order phenomena and dynamics in columnar mesophases with 13C in natural abundance were investigated. Two further modifications of the REDOR concept allow the correlation of 13C with quadrupolar nuclei, such as 2H. The spectroscopic handling of these nuclei is challenging in that they cover large frequency ranges, and with the new experiments it is shown how the excitation problem can be tackled or circumvented altogether, respectively. As an example, one of the techniques is used for the identification of a yet unknown motional process of the H-bonded protons in the crystalline parts of poly(vinyl alcohol).

Neue Methoden zur Computersimulation von Polymersystemen auf verschiedenen Längenskalen und ihre Anwendungen

In dieser Dissertation stellen wir einen neuen Ansatz zurModellierungvon Polymersystemen vor. Es werden (von methodischer Seiteher) zweiautomatisierte Iterationschemata dazu eingeführt,Kraftfeldparametermesoskopischer Polymersysteme systematisch zu optimieren:DasSimplex-Verfahren und das Struktur-Differenzen-Verfahren. Sowerdendiejenigen Freiheitsgrade aus Polymersystemen eliminiert,die einehohe Auflösung erfordern, was die Modellierung größerersystemeermöglicht. Nach Tests an einfachen Flüssigkeiten werdenvergröberteModelle von drei prototypischen Polymeren (Polyacrylsäure,Polyvinylalkohol und Polyisopren) in unterschiedlichenUmgebungen(gutes Lösungsmittel und Schmelze) entwickelt und ihrVerhalten aufder Mesoskala ausgiebig geprüft. Die zugehörige Abbildung(vonphysikalischer Seite her) so zu gestalten, daß sie dieunverwechselbaren Charakteristiken jedes systems auf diemesoskopischeLängenskala überträgt, stellt eine entscheidende Anforderungan dieautomatisierten Verfahren dar. Unsere Studien belegen, daß mesoskopische Kraftfeldertemperatur- unddichtespezifisch sind und daher bei geändernden Bedingungennachoptimiert werden müssen. Gleichzeitig läßt sichabschätzen, beiwelchen Umgebungsbedingungen dies noch nicht notwendig wird.In allenFällen reichen effektive Paarpotentiale aus, einrealistischesmesoskopisches Modell zu konstruieren. VergröberteSimulationenwerden im Falle der Polyacrylsäure erfolgreich gegenexperimentelleLichtstreudaten getestet. Wir erzielen für Molmassen bis zu300000g/mol eine hervorragende Übereinstimmung für denhydrodynamischenRadius. Unsere Ergebnisse erklären auch Korrekturen zudessenVerhalten als Funktion der Kettenlänge ('Skalenverhalten'). Im Fallevon Polyisopren untersuchen wir sowohl statische als auchdynamischeGrößen und stellen klare Unterschiede unserer Ergebnisse zudeneneines einfachen semi-flexiblen Mesoskalenmodells fest. InderProteinforschung werden aus Datenbanken gewonnene effektivePaarwechselwirkungen dazu verwendet, die freie Energie einesneuensystems vorherzusagen. Wir belegen in einem Exkurs mittelsGittersimulationen, daß es selbst in einfachsten Fällennicht gelingt,dies auch nur qualitativ korrekt zu bewerkstelligen.

Fluorescence-encoded gold nanoparticles: library design and modulation of cellular uptake into dendritic cells.

In order to harness the unique properties of nanoparticles for novel clinical applications and to modulate their uptake into specific immune cells we designed a new library of homo- and hetero-functional fluorescence-encoded gold nanoparticles (Au-NPs) using different poly(vinyl alcohol) and poly(ethylene glycol)-based polymers for particle coating and stabilization. The encoded particles were fully characterized by UV-Vis and fluorescence spectroscopy, zeta potential and dynamic light scattering. The uptake by human monocyte derived dendritic cells in vitro was studied by confocal laser scanning microscopy and quantified by fluorescence-activated cell sorting and inductively coupled plasma atomic emission spectroscopy. We show how the chemical modification of particle surfaces, for instance by attaching fluorescent dyes, can conceal fundamental particle properties and modulate cellular uptake. In order to mask the influence of fluorescent dyes on cellular uptake while still exploiting its fluorescence for detection, we have created hetero-functionalized Au-NPs, which again show typical particle dependent cellular interactions. Our study clearly prove that the thorough characterization of nanoparticles at each modification step in the engineering process is absolutely essential and that it can be necessary to make substantial adjustments of the particles in order to obtain reliable cellular uptake data, which truly reflects particle properties.

Performance Assessment of a Polymer Electrolyte Membrane Electrochemical Reactor under Alkaline Conditions – A Case Study with the Electrooxidation of Alcohols

A novel polymer electrolyte membrane electrochemical reactor (PEMER) configuration has been employed for the direct electrooxidation of propargyl alcohol (PGA), a model primary alcohol, towards its carboxylic acid derivatives in alkaline medium. The PEMER configuration comprised of an anode and cathode based on nanoparticulate Ni and Pt electrocatalysts, respectively, supported on carbonaceous substrates. The electrooxidation of PGA was performed in 1.0 M NaOH, where a cathode based on a gas diffusion electrode was manufactured for the reduction of oxygen in alkaline conditions. The performance of a novel alkaline anion-exchange membrane based on Chitosan (CS) and Poly(vinyl) alcohol (PVA) in a 50:50 composition ratio doped with a 5 wt.% of poly (4-vinylpyridine) organic ionomer cross-linked, methyl chloride quaternary salt resin (4VP) was assessed as solid polymer electrolyte. The influence of 4VP anionic ionomer loading of 7, 12 and 20 wt.% incorporated into the electrocatalytic layers was examined by SEM and cyclic voltammetry (CV) upon the optimisation of the electroactive area, the mechanical stability and cohesion of the catalytic ink onto the carbonaceous substrate for both electrodes. The performance of the 4VP/CS:PVA membrane was compared with the commercial alkaline anion-exchange membrane FAA −a membrane generally used in direct alcohol alkaline fuel cells- in terms of polarisation plots in alkaline conditions. Furthermore, preparative electrolyses of the electrooxidation of PGA was performed under alkaline conditions of 1 M NaOH at constant current density of 20 mA cm−2 using a PEMER configuration to provide proof of the principle of the feasibility of the electrooxidation of other alcohols in alkaline media. PGA conversion to Z isomers of 3-(2-propynoxy)-2-propenoic acid (Z-PPA) was circa 0.77, with average current efficiency of 0.32. Alkaline stability of the membranes within the PEMER configuration was finally evaluated after the electrooxidation of PGA.

An experimental and finite element poroelastic creep response analysis of an intervertebral hydrogel disc model in axial compression

A hydrogel intervertebral disc (lVD) model consisting of an inner nucleus core and an outer anulus ring was manufactured from 30 and 35% by weight Poly(vinyl alcohol) hydrogel (PVA-H) concentrations and subjected to axial compression in between saturated porous endplates at 200 N for 11 h, 30 min. Repeat experiments (n = 4) on different samples (N = 2) show good reproducibility of fluid loss and axial deformation. An axisymmetric nonlinear poroelastic finite element model with variable permeability was developed using commercial finite element software to compare axial deformation and predicted fluid loss with experimental data. The FE predictions indicate differential fluid loss similar to that of biological IVDs, with the nucleus losing more water than the anulus, and there is overall good agreement between experimental and finite element predicted fluid loss. The stress distribution pattern indicates important similarities with the biological lVD that includes stress transference from the nucleus to the anulus upon sustained loading and renders it suitable as a model that can be used in future studies to better understand the role of fluid and stress in biological IVDs. (C) 2005 Springer Science + Business Media, Inc.

Desenvolvimento de bionanocompósitos: nano e microcristais de celulose com poli (álcool vinílico) e poli (ácido lático)

This work has the main objective to obtain nano and microcrystals of cellulose, extracted from the pineapple leaf fibres (PALF), as reinforcement for the manufacture of biocomposite films with polymeric matrices of Poly(vinyl alcohol) (PVA) and Poly(lactic acid) (PLA). The polymer matrices and the nano and microcrystals of cellulose were characterised by means of TGA, FTIR and DSC. The analysis was performed on the pineapple leaves to identify the macro and micronutrients. The fibers of the leaves of the pineapple were extracted in a desfibradeira mechanical. The PALF extracted were washed to remove washable impurities and subsequently treated with sodium hydroxide (NaOH) and sodium hypochlorite (NaClO) in the removal of impurities, such as fat, grease, pectates, pectin and lignin. The processed PALF fibers were hydrolysed in sulfuric acid (H2SO4) at a concentration of 13.5 %, to obtain nano and microcrystals of cellulose. In the manufacture of biocomposite films, concentrations of cellulose, 0 %, 1 %, 3 %, 6 %, 9% and 12% were used as reinforcement to the matrices of PVA and PLA. The PVA was dissolved in distilled water at 80 ± 5 oC and the PLA was dissolved in dichloromethane at room temperature. The manufacture of biocompósitos in the form of films was carried out by "casting". Tests were carried out to study the water absorption by the films and mechanical test of resistance to traction according to ASTM D638-10 with a velocity of 50 mm/min.. Chi-square statistical test was used to check for the existence of significant differences in the level of 0.05: the lengths of the PALF, lengths of the nano and microcrystals of cellulose and the procedures used for the filtration using filter syringe of 0.2 μm or filtration and centrifugation. The hydrophilicity of biocompósitos was analysed by measuring the contact angle and the thickness of biocompósitos were compared as well as the results of tests of traction. Statistical T test - Student was also applied with the significance level (0.05). In biodegradation, Sturm test of standard D5209 was used. Nano and microcrystals of cellulose with lengths ranging from 7.33 nm to 186.17 nm were found. The PVA films showed average thicknesses of 0.153 μm and PLA 0.210 μm. There is a strong linear correlation directly proportional between the traction of the films of PVA and the concentration of cellulose in the films (composite) (0,7336), while the thickness of the film was correlated in 0.1404. Nano and microcrystals of cellulose and thickness together, correlated to 0.8740. While the correlation between the cellulose content and tensile strength was weak and inversely proportional (- 0,0057) and thickness in -0.2602, totaling -0,2659 in PLA films. This can be attributed to the nano and microcrystals of cellulose not fully adsorbed to the PLA matrix. In the comparison of the results of the traction of the two polymer matrices, the nano and microcrystals have helped in reducing the traction of the films (composite) of PLA. There was still the degradation of the film of PVA, within a period of 20 days, which was not seen in the PLA film, on the other hand, the observations made in the literature, the average time to start the degradation is above 60 days. What can be said that the films are biodegradable composites, with hydrophilicity and the nano and microcrystals of cellulose, contribute positively in the improvement of the results of polymer matrices used.