Quirina Ferreira

Neural stem cell differentiation by electrical stimulation using a cross-linked PEDOT substrate: Expanding the use of biocompatible conjugated conductive polymers for neural tissue engineering.

BACKGROUND The use of conjugated polymers allows versatile interactions between cells and flexible processable materials, while providing a platform for electrical stimulation, which is particularly relevant when targeting differentiation of neural stem cells and further application for therapy or drug screening. METHODS Materials were tested for cytotoxicity following the ISO10993-5. PEDOT PSS was cross-linked. ReNcellVM neural stem cells (NSC) were seeded in laminin coated surfaces, cultured for 4 days in the presence of EGF (20 ng/mL), FGF-2 (20 ng/mL) and B27 (20 μg/mL) and differentiated over eight additional days in the absence of those factors under 100Hz pulsed DC electrical stimulation, 1V with 10 ms pulses. NSC and neuron elongation aspect ratio as well as neurite length were assessed using ImageJ. Cells were immune-stained for Tuj1 and GFAP. RESULTS F8T2, MEH-PPV, P3HT and cross-linked PEDOT PSS (x PEDOT PSS) were assessed as non-cytotoxic. L929 fibroblast population was 1.3 higher for x PEDOT PSS than for glass control, while F8T2 presents moderate proliferation. The population of neurons (Tuj1) was 1.6 times higher with longer neurites (73 vs 108 μm) for cells cultured under electrical stimulus, with cultured NSC. Such stimulus led also to longer neurons. CONCLUSIONS x PEDOT PSS was, for the first time, used to elongate human NSC through the application of pulsed current, impacting on their differentiation towards neurons and contributing to longer neurites. GENERAL SIGNIFICANCE The range of conductive conjugated polymers known as non-cytotoxic was expanded. x PEDOT PSS was introduced as a stable material, easily processed from solution, to interface with biological systems, in particular NSC, without the need of in-situ polymerization.

Long-Term Stability at High Temperatures for Birefringence in PAZO/ PAH Layer-by-Layer Films

Optical memories with long-term stability at high temperatures have long been pursued in azopolymers with photoinduced birefringence. In this study, we show that the residual birefringence in layer-by-layer (LbL) films made with poly[1-[4-(3-carboxy-4 hydroxyphenylazo)benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) alternated with poly(allylamine hydrochloride) (PAH) can be tuned by varying the extent of electrostatic interactions with film fabrication at different pHs for PAH. The dynamics of both writing and relaxation processes could be explained with a two-stage mechanism involving the orientation of the chromophores per se and the chain movement. Upon calculating the activation energies for these processes, we demonstrate semiquantitatively that reduced electrostatic interactions in films prepared at higher pH, for which PAH is less charged, are responsible for the longer stability at high temperatures. This is attributed to orientation of PAZO chromophores via cooperative aggregation, where the presence of counterions hindered relaxation.

Determination of Degree of Ionization of Poly(allylamine hydrochloride) (PAH) and Poly[1-[4-(3-carboxy-4 hydroxyphenylazo)benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) in Layer-by-Layer Films using Vacuum Photoabsorption Spectroscopy

Electrostatic and hydrophobic interactions govern most of the properties of supramolecular systems, which is the reason determining the degree of ionization of macromolecules has become crucial for many applications. In this paper, we show that high-resolution ultraviolet spectroscopy (VUV) can be used to determine the degree of ionization and its effect on the electronic excitation energies of layer-by-layer (LbL) films of poly(allylamine hydrochloride) (PAH) and poly[1-[4-(3-carboxy-4 hydroxyphenylazo)benzene sulfonamido]-1,2-ethanediyl, sodium salt] (PAZO). A full assignment of the VUV peaks of these polyelectrolytes in solution and in cast or LbL films could be made, with their pH dependence allowing us to determine the pK(a) using the Henderson-Hasselbach equation. The pK(a) for PAZO increased from ca. 6 in solution to ca. 7.3 in LbL films owing to the charge transfer from PAH. Significantly, even using solutions at a fixed pH for PAH, the amount adsorbed on the LbL films still varied with the pH of the PAZO solutions due to these molecular-level interactions. Therefore, the procedure based on a comparison of VUV spectra from solutions and films obtained under distinct conditions is useful to determine the degree of dissociation of macromolecules, in addition to permitting interrogation of interface effects in multilayer films.

Microphase separation in mixed monolayers of DPPG with a double hydrophilic block copolymer at the air-water interface: a BAM, LSCFM, and AFM study.

Phase separation and interactions in mixed monolayers of dipalmitoylphosphatidylglycerol (DPPG) with the rhodamine B end-labeled double-hydrophilic block copolymer (DHBC), poly(N,N-dimethylacrylamide)-block-poly(N,N-diethylacrylamide) (RhB-PDMA(207)-b-PDEA(177)), was studied at the air-water interface. Surface pressure versus area isotherms indicate that both components behave almost independently. Brewster angle microscopy (BAM) images show a random distribution of liquid condensed (LC) domains of DPPG in an apparent homogeneous matrix of DHBC, excluding the macroscopic phase separation. The laser scanning confocal fluorescence microscopy (LSCFM) of the rhodamine dye at the end of the PDMA chain showed how the DHBC is distributed in Langmuir-Blodgett (LB) mixed monolayers. The high spatial resolution of atomic force microscopy (AFM) combined with the LCSFM images indicates that DHBC incorporates in the expanded phase of DPPG to form mixed domains, being excluded from the condensed regions. Upon compression, nanosized LC domains of DPPG nucleate inside the mixed domains corralled in the nanopatterning of pure DHBC. The negatively charged polar group of DPPG inhibits rhodamine aggregation, while the long polymer chains promote the formation of corralled nanodomains of DPPG in two dimensions.

Villain's fractal growth of poly(1-(4-(3-carboxy-4-hydroxyphenylazo) benzenesulfonamido)-1,2-ethanediyl, sodium salt) J-aggregates onto layer-by-layer films and its effect on film absorbance spectrum

Morphology of poly(allylamine hydrochloride) and poly[1-[4-(3-carboxy-4-hydroxyphenylazo) benzenesulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) layer-by-layer (LBL) films is shown to influence the orientation of PAZO chromophores with respect to solid support surface, which in turn is related with observed red-shifts changes of the chromophore absorbance peak position relative to that of solution spectrum, as the bilayers are being deposited. For the first bilayers, an increase of red shift values is observed, while roughness and grain radius are kept practically constant; after the 5th bilayer, the red-shift values decrease, while grain sizes increase and the number of grains decreases. This behavior is consistent with adsorption of coiled PAZO molecules, treated as pseudo-particles, with the chromophores head-to-head oriented-J aggregates. These aggregates adsorb perpendicularly to the substrate surface for the first layers and, as roughness and grain radius increase, the adsorption of the J aggregate...

Synergistic effect on the efficiency of polymer light-emitting diodes upon blending of two green-emitting polymers

Light-emitting diodes based on blends of the two green-emitting polymers, poly(9,9-dioctylfluorene-alt-benzothiadiazole), F8BT, and poly(9,9-dioctylfluorene-alt-bithiophene), F8T2, show efficiencies that lie in between those of the devices based on the neat polymers (with a maximum efficiency of approximately 4 cd/A for the devices with magnesium cathodes based on F8BT), except for the blend with 5% by weight of F8T2, which is more efficient than the device based on neat F8BT (a maximum efficiency of approximately 5 cd/A is obtained). In view of the lower photoluminescence efficiency of F8T2, we attribute this improvement to the improved hole transport brought about by F8T2, though is surprising that 5% by weight, is enough to significantly improve the charge balance within the emissive layer. A detailed photophysics study was carried out for the neat polymers and their blends and no clear evidence for energy transfer between the components was found. This unanticipated devices performance improvement poi...

Improving the Efficiency of Organic Solar Cells upon Addition of Polyvinylpyridine

We report on the efficiency improvement of organic solar cells (OPVs) based on the low energy gap polyfluorene derivative, APFO-3, and the soluble C60 fullerene PCBM, upon addition of a residual amount of poly (4-vinylpyridine) (PVP). We find that the addition of 1% by weight of PVP with respect to the APFO-3 content leads to an increase of efficiency from 2.4% to 2.9%. Modifications in the phase separation details of the active layer were investigated as a possible origin of the efficiency increase. At high concentrations of PVP, the blend morphology is radically altered as observed by Atomic Force Microscopy. Although the use of low molecular weight additives is a routine method to improve OPVs efficiency, this report shows that inert polymers, in terms of optical and charge transport properties, may also improve the performance of polymer-based solar cells.

Biocellulose based materials for organic field effect transistors

Biocellulose and biocellulose composites are being investigated as substrates and as gate dielectrics for organic field effect transistors. Spin coated films of regioregular poly(3-hexylthiophene) (RR-P3HT) and thermally evaporated pentacene were used as semiconducting materials. Preliminary results on device characteristics are reported.

Layer-by-layer Assembled Films for Ocular Drug Delivery

In this paper we describe a simple and versatile method to prepare drug delivery films composed of an ocular drug used in glaucoma treatment, brimonidine, which was encapsulated in a polymer-beta cyclodextrin. The films were developed in order to allow a controlled sequential release during long periods of time. Here we show that by introducing barrier layers of graphene oxide between the drug delivery ones it is possible to delay the brimonidine release for a few days. The time interval between two dosages of drug release will be controlled by adjusting the number and/or thickness of the graphene layers.

Enhanced Efficiency of PTB7 : PC61BM Organic Solar Cells by Adding a Low Efficient Polymer Donor

Ternary blend polymer solar cells combining two electron-donor polymers, poly[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl] (PTB7) and poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (pBTTT) and [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM), as electron-acceptor, were fabricated. The power conversion efficiency of the ternary cells was enhanced by 18%, with respect to the reference binary cells, for a blend composition with 25% (wt%) of pBTTT in the polymers content. The optimized device performance was related to the blend morphology, nonrevealing pBTTT aggregates, and improved charge extraction within the device.