Self-assembly of PEGylated peptide conjugates containing a modified amyloid β-peptide fragment

The self-assembly of PEGylated peptides containing a modified sequence from the amyloid beta peptide, FEK LVFF, has been studied in aqueous solution. PEG molar masses PEG1k, PEG2k, and PEG10k were used in the conjugates. It is shown that the three FFK LVFF-PEG hybrids form fibrils comprising a FFKLVFF core and a PEG corona. The beta-sheet secondary structure of the peptide is retained in the FFK LVFF fibril core. At sufficiently high concentrations, FEK LVFF-PEG1k and FEK LVFF-PEG2k form a nema tic phase, while PEG10k-FEK LVFF exhibits a hexagonal columnar phase. Simultaneous small angle neutron scattering/shear flow experiments were performed to study the shear flow alignment of the nematic and hexagonal liquid crystal phases. On drying, PEG crystallization occurs without disruption of the FFK LVFF beta-sheet structure leading to characteristic peaks in the X-ray diffraction pattern and FTIR spectra. The stability of beta-sheet structures was also studied in blends of FFKLVFF-PEG conjugates with poly(acrylic acid) (PAA). While PEG crystallization is only observed up to 25% PAA content in the blends, the FFK LVFF beta-sheet structure is retained up to 75% PAA.

On the role of specific interactions in the diffusion of nanoparticles in aqueous polymer solutions

Understanding nanoparticle diffusion within non-Newtonian biological and synthetic fluids is essential in designing novel formulations (e.g., nanomedicines for drug delivery, shampoos, lotions, coatings, paints, etc.), but is presently poorly defined. This study reports the diffusion of thiolated and PEGylated silica nanoparticles, characterized by small-angle neutron scattering, in solutions of various water-soluble polymers such as poly(acrylic acid) (PAA), poly(Nvinylpyrrolidone) (PVP), poly(ethylene oxide) (PEO), and hydroxyethylcellulose (HEC) probed using NanoSight nanoparticle tracking analysis. Results show that the diffusivity of nanoparticles is affected by their dimensions, medium viscosity, and, in particular, the specific interactions between nanoparticles and the macromolecules in solution; strong attractive interactions such as hydrogen bonding hamper diffusion. The water-soluble polymers retarded the diffusion of thiolated particles in the order PEO > PVP > PAA > HEC whereas for PEGylated silica particles retardation followed the order PAA > PVP = HEC > PEO. In the absence of specific interactions with the medium, PEGylated nanoparticles exhibit enhanced mobility compared to their thiolated counterparts despite some increase in their dimensions.

Probing the mucoadhesive interactions between porcine gastric mucin and some water-soluble polymers

This study investigates the structural features of porcine gastric mucin (PGM) in aqueous dispersions and its interactions with water-soluble polymers (poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA), poly(ethylene oxide), and poly(ethylene glycol)) using isothermal titration calorimetry, turbidimetric titration, dynamic light scattering, and transmission electron microscopy. It is established that PAA (450 kDa) and PMAA (100 kDa) exhibit strong specific interactions with PGM causing further aggregation of its particles, while PAA (2 kDa), poly(ethylene oxide) (1 000 kDa), and poly(ethylene glycol) (10 kDa) do not show any detectable effects on mucin. Sonication of mucin dispersions prior to their mixing with PAA (450 kDa) and PMAA (100 kDa) leads to more pronounced intensity of interactions.

THE EFFECT of DENTIN PRETREATMENT on THE MICROTENSILE BOND STRENGTH of SELF-ADHESIVE RESIN CEMENTS

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

Avaliação qualitativa do efeito de agentes de limpeza na camada de lama dentinária: estudo ultra-estrutural em microscopia eletrônica de varredura

Quando qualquer instrumento abrasiona ou corta a dentina, produz na superfície uma camada de lama dentinária ou smear layer. Dependendo do agente de união indicado em Odontologia adesiva, há a necessidade ou não da remoção da camada de lama da superfície dentinária. Com a finalidade de verificar a ação de diferentes substâncias para a limpeza dentinária, utilizamos 20 dentes pré-molares superiores íntegros, mantidos em soro fisiológico, nos quais as coroas foram seccionadas ao meio no sentido mésio-distal. Com instrumento diamantado, removeu-se o esmalte da porção vestibular e da porção lingual da coroa e, com uma broca carbide cilíndrica lisa nº 56, cortou-se aproximadamente 1 mm de dentina com alta rotação sob abundante refrigeração ar/água, para produzir a camada de lama dentinária. em seguida, essa superfície foi tratada com diferentes substâncias e lavada por 30 segundos com spray ar/água. No controle, foi simplesmente utilizado o spray ar/água. Os espécimes foram montados em suportes metálicos, preparados e visualizados no MEV-DSM 950 da Zeiss, em aumentos que variaram de 100 a 5.000 vezes. Os materiais que mais removeram a camada de lama foram, em ordem crescente: 1. spray ar/água; 2. fluoreto de sódio 2%; 3. associação alternada de Dakin/Tergensol; 4. água oxigenada 3%; 5. jateamento com óxido de alumínio 50 mm; 6. flúor acidulado 1,27%; 7. ácido poliacrílico 25%; 8. ácido fosfórico 10%.

Processing of high performance composites based on peek by aqueous suspension prepregging

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

Estudo da adesão dentinária em restaurações realizadas com ionômero modificado por resina: influência de técnicas restauradoras e do preparo cavitário

Pós-graduação em Ciência Odontólogica - FOA

Avaliação da efetividade de cimentos resinosos auto-adesivos aplicados sob diferentes pré-tratamentos da dentina radicular na resistência adesiva de pinos de fibra de vidro

Pós-graduação em Ciências Odontológicas - FOAR

Rheological, mechanical, and bioadhesive behavior of hydrogels to optimize skin delivery systems

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Efeito do pré-tratamento da dentina bovina na resistência ao cisalhamento de um cimento de ionômero de vidro resina modificado

Pós-graduação em Odontologia Restauradora - ICT

Estudo das propriedades estímulo responsivas dos polímeros escovas

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

Bonding ability of paste-paste glass ionomer systems to tooth structure: in vitro studies

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Characterization and application of nanostructured films containing Au and TiO2 nanoparticles supported in bacterial cellulose

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Análise da interface adesiva entre pinos de fibra de vidro e dentina intrarradicular submetida à irrigação com diferentes agentes condicionantes

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

Visualization, manipulation and force spectroscopy of cylindrical polymer brushes

The Ph.D. thesis deals with the conformational study of individual cylindrical polymer brush molecules using atomic force microscopy (AFM). Imaging combined with single molecule manipulation has been used to unravel questions concerning conformational changes, desorption behavior and mechanical properties of individual macromolecules and supramolecular structures. In the first part of the thesis (chapter 5) molecular conformations of cylindrical polymer brushes with poly-(N-isopropylacrylamide) (PNIPAM) side chains were studied in various environmental conditions. Also micelle formation of cylindrical brush-coil blockcopolymers with polyacrylic acid side chains and polystyrene coil have been visualized. In chapter 6 the mechanical properties of single cylindrical polymer brushes with (PNIPAM) side chains were investigated. Assuming that the brushes adopt equilibrium conformation on the surface, an average persistence length of lp= (29 ± 3) nm was determined by the end-to-end distance vs. contour length analysis in terms of the wormlike chain (WLC) model. Stretching experiments suggest that an exact determination of the persistence length using force extension curves is impeded by the contribution of the side chains. Modeling the stretching of the bottle brush molecule as extension of a dual spring (side chain and main chain) explains the frequently observed very low persistence length arising from a dominant contribution of the side chain elasticity at small overall contour lengths. It has been shown that it is possible to estimate the “true” persistence length of the bottle brush molecule from the intercept of a linear extrapolation of the inverse square root of the apparent persistence length vs. the inverse contour length plot. By virtue of this procedure a “true” persistence length of 140 nm for the PNIPAM brush molecules is predicted. Chapter 7 and 8 deal with the force-extension behavior of PNIPAM cylindrical brushes studied in poor solvent conditions. The behavior is shown to be qualitatively different from that in a good solvent. Force induced globule-cylinder conformational changes are monitored using “molecule specific force spectroscopy” which is a combined AFM imaging and SMFS technique. An interesting behavior of the unfolding-folding transitions of single collapsed PNIPAM brush molecules has been observed by force spectroscopy using the so called “fly-fishing” mode. A plateau force is observed upon unfolding the collapsed molecule, which is attributed to a phase transition from a collapsed brush to a stretched conformation. Chapter 9 describes the desorption behavior of single cylindrical polyelectrolyte brushes with poly-L-lysine side chains deposited on a mica surface using the “molecule specific force spectroscopy” technique to resolve statistical discrepancies usually observed in SMFS experiments. Imaging of the brushes and inferring the persistence length from a end-to-end distance vs. contour length analysis results in an average persistence length of lp = (25 ± 5) nm assuming that the chains adopt their equilibrium conformation on the surface. Stretching experiments carried out on individual poly-L-lysine brush molecules by force spectroscopy using the “fly-fishing” mode provide a persistence length in the range of 7-23 nm in reasonable accordance with the imaging results. In chapter 10 the conformational behavior of cylindrical poly-L-lysine brush-sodium dodecyl sulfate complexes was studied using AFM imaging. Surfactant induced cylinder to helix like to globule conformational transitions were observed.