Control of strand registry by attachment of PEG chains to amyloid peptides influences nanostructure

The self-assembly in aqueous solution of PEG-peptide conjugates comprising a model amyloid peptide sequence FFKLVFF that contains the Ab(16–20) KLVFF motif is investigated. X-ray diffraction reveals different packing motifs dependent on PEG chain length. This is correlated to remarkable differences in self-assembled nanostructures. The control of strand registry points to a subtle interplay between aromatic stacking, electrostatic and amphiphilic interactions.

Influence of elastase on alanine-rich peptide hydrogels

The self-assembly of the alanine-rich amphiphilic peptides Lys(Ala)6Lys (KA6K) and Lys(Ala)6Glu (KA6E)with homotelechelic or heterotelechelic charged termini respectively has been investigated in aqueous solution. These peptides contain hexa-alanine sequences designed to serve as substrates for the enzyme elastase. Electrostatic repulsion of the lysine termini in KA6K prevents self-assembly, whereas in contrast KA6E is observed, through electron microscopy, to form tape-like fibrils, which based on X-ray scattering contain layers of thickness equal to the molecular length. The alanine residues enable efficient packing of the side-chains in a beta-sheet structure, as revealed by circular dichroism, FTIR and X-ray diffraction experiments. In buffer, KA6E is able to form hydrogels at sufficiently high concentration. These were used as substrates for elastase, and enzyme-induced de-gelation was observed due to the disruption of the beta-sheet fibrillar network. We propose that hydrogels of the simple designed amphiphilic peptide KA6E may serve as model substrates for elastase and this could ultimately lead to applications in biomedicine and regenerative medicine.

Self-assembling amphiphilic peptides

The self-assembly of several classes of amphiphilic peptides is reviewed, and selected applications are discussed. We discuss recent work on the self-assembly of lipopeptides, surfactant-like peptides and amyloid peptides derived from the amyloid-β peptide. The influence of environmental variables such as pH and temperature on aggregate nanostructure is discussed. Enzyme-induced remodelling due to peptide cleavage and nanostructure control through photocleavage or photo-cross-linking are also considered. Lastly, selected applications of amphiphilic peptides in biomedicine and materials science are outlined.

Tuning self-assembled nanostructures through enzymatic degradation of a peptide amphiphile

The enzymatic cleavage of a peptide amphiphile (PA) is investigated. The self-assembly of the cleaved products is distinct from that of the PA substrate. The PA C16-KKFFVLK is cleaved by α-chymotrypsin at two sites leading to products C16-KKF with FVLK and C16-KKFF with VLK. The PA C16-KKFFVLK forms nanotubes and helical ribbons at room temperature. Both PAs C16-KKF and C16-KKFF corresponding to cleavage products instead self-assemble into 5-6 nm diameter spherical micelles, while peptides FVLK and VLK do not adopt well-defined aggregate structures. The secondary structures of the PAs and peptides are examined by FTIR and circular dichroism spectroscopy and X-ray diffraction. Only C16-KKFFVLK shows substantial β-sheet secondary structure, consistent with its self-assembly into extended aggregates, based on PA layers containing hydrogen-bonded peptide headgroups. This PA also exhibits a thermoreversible transition to twisted tapes on heating.

Self-assembled arginine-capped peptide bolaamphiphile nanosheets for cell culture and controlled wettability surfaces

The spontaneous assembly of a peptide bolaamphiphile in water, namely, RFL4FR (R, arginine; F, phenylalanine; L, leucine) is investigated, along with its novel properties in surface modification and usage as substrates for cell culture. RFL4FR self-assembles into nanosheets through lateral association of the peptide backbone. The L4 sequence is located within the core of the nanosheets, whereas the R moieties are exposed to the water at the surface of the nanosheets. Kinetic assays indicate that the self-assembly is driven by a remarkable two-step process, where a nucleation phase is followed by fast growth of nanosheets with an autocatalysis process. The internal structure of the nanosheets is formed from ultrathin bolaamphiphile monolayers with a crystalline orthorhombic symmetry with cross-β organization. We show that human corneal stromal fibroblast (hCSF) cells can grow on polystyrene films coated with films dried from RFL4FR solutions. For the first time, this type of amphiphilic peptide is used as a substrate to modulate the wettability of solid surfaces for cell culture applications.

Molecular Ordering of Layer-by-Layer Polyelectrolyte Films Studied by Sum-Frequency Vibrational Spectroscopy

The molecular arrangement in organic thin films is crucial for their increasing technological applications. Here, we use vibrational spectroscopy by sum-frequency generation (SFG) to study the ordering of polyelectrolyte layers adsorbed on silica for all steps of layer-by-layer (LbL) self-assembly. In situ measurements during adsorption and rinsing showed that the adsorbed polymer has a disordered conformation and confirmed surface charge overcompensation upon polyelectrolyte adsorption by probing the interfacial electric field. In dry films, the polymer chains acquired a net orientational ordering, which was affected, however, by the adsorption of subsequent layers. Such a detailed characterization may allow the control of LbL film structure and functionality with unprecedented power.

Role of Polyelectrolyte for Layer-by-Layer Compact TiO(2) Films in Efficiency Enhanced Dye-Sensitized Solar Cells

Efficient compact TiO(2) films using different polyeleetrolytes are prepared by the layer-by-layer technique (LbL) and applied as an effective contact and blocking film in dye-sensitized solar cells (DSCs). The polyanion thermal stability plays a major role on the compact layers, which decreases back electron transfer processes and current losses at the FTO/TiO(2) interface. FESEM images show that polyelectrolytes such is sodium sullonated polystyrene (PSS) and sulfonated lignin (SE), in comparison to poly(acrylic acid) (FAA), ensure an adequate morphology for the LbL TiO(2) layer deposited before the mesoporous film, even triter the sintering step at 450 degrees C. The so treated photoanode in DSCs leads to a 30% improvement On the overall conversion efficiency. Electrochemical impedance spectroscopy (EIS) is employed to ascertain the role of die compact films with such polyelectrolytes. The significant increase in V(oc) of the solar cells with adequate polyelectrolytes in the LbL TiO(2) films shows their pivotal role in decreasing the electron recombination at the FTO surface and enhancing the electrical contact of FTO with the mesoporous TiO(2) layer.

Structural aspects, thermal behavior, and stability of a self-assembled supramolecular polymer derived from flunixin-meglumine supramolecular adducts

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Fabrication and analysis of self-assembled photonic crystals structures

This paper presents the fabrication and analysis of a three-dimensional FCC photonic crystal (PhC) based on a self-assembly synthesis of monodispersive latex spheres. Experimental optical characterization, achieved by measurements of the specular reflectance under variable angles, indicated the clear presence of a Bragg diffraction pattern. Results are further explored by theoretical calculations based on the Finite Difference Time Domain (FDTD) method to determine the full PhC band structure.

Self-assembled FePt nanocrystals with large coercivity: Reduction of the fcc-to-L1(0) ordering temperature

Herein we report the synthesis and properties of Fe55Pt45 nanoparticles, both monodisperse and self-assembled into hexagonal close-packed and cubic arrays of 4.0 +/- 0.2 nm size in an L1(0) structure, obtained by a modified polyol process. The new synthetic route improved the control over the particle composition, thereby reducing the temperature required to convert from face-centered cubic (fcc) to face-centered tetragonal (fct) phase by some 30-50 degrees C without additives. Annealing at 550 degrees C for 30 min converts the self-assembled nanoparticles into ferromagnetic nanocrystals with large coercivity, H-C = 11.1 kOe. Reducing the fcc-to-fct (L1(0)) ordering temperature avoided particle coalescence and decreased the loss in particle positional order without compromising the magnetic properties, as is generally observed when additives are used.

Novel SrTi1-xFexO3 nanocubes synthesized by microwave-assisted hydrothermal method

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Comparative analysis between experimental characterization results and numerical fdtd modeling of self-assembled photonic crystals

This paper presents a comparative analysis between the experimental characterization and the numerical simulation results for a three-dimensional FCC photonic crystal (PhC) based on a self-assembly synthesis of monodispersive latex spheres. Specifically, experimental optical characterization, by means of reflectance measurements under variable angles over the lattice plane family [1,1, 1], are compared to theoretical calculations based on the Finite Di®erence Time Domain (FDTD) method, in order to investigate the correlation between theoretical predictions and experimental data. The goal is to highlight the influence of crystal defects on the achieved performance.

Caracterização de estruturas de óxido de estanho modificado como sensores de gases

Pós-graduação em Química - IQ

Filmes de Langmuir-Blodgett de nanopartículas de prata

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Influence of the deposition parameters on the morphology and electrical conductivity of PANI/PSS self-assembled films

The influence of deposition parameters, namely polymer concentration and pH of the deposition solution, cleaning, and drying steps on the morphology and electrical characteristics of polyaniline and sulfonated polystyrene (PANI/PSS) nanostructured films deposited by the self-assembly technique is evaluated by UV-Vis spectroscopy, optical and atomic force microscopy, and electrical resistance measurements. It is found that stirring the cleaning solution during the cleaning step is crucial for obtaining homogenous films. Stirring of the cleaning solution also influences the amount of PANI adsorbed in the films. In this regard, the drying process seems to be less critical since PANI amount and film thickness are similar in films dried with N-2 flow or with an absorbent tissue. It is observed, however, that drying with N-2 flow results in rougher films. As an additional point, an assessment of the influence of the deposition method (manual versus mechanical) on the film characteristics was carried out. A significant difference on the amount of PANI and film thickness between films prepared by different human operators and by a homemade mechanical device was observed. The variability in film thickness and PANI adsorbed amount is smaller in films mechanically assembled. (c) 2007 Elsevier B.V. All rights reserved.