Preferential location of prilocaine and etidocaine in phospholipid bilayers: A molecular dynamics study

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

Kinetics of interface state-limited hole injection in alpha-naphthylphenylbiphenyl diamine (alpha-NPD) thin layers

Injection-limited operation is identified in thin-film, alpha-NPD-based diodes. A detailed model for the impedance of the injection process is provided which considers the kinetics of filling/releasing of interface states as the key factor behind the injection mechanism. The injection model is able to simultaneously account for the steady-state, current-voltage (J-V) characteristics and impedance response. and is based on the sequential injection of holes mediated by energetically distributed surface states at the metal-organic interface. The model takes into account the vacuum level offset caused by the interface dipole, along with the partial shift of the interface level distribution with bias voltage. This approach connects the low-frequency (similar to 1 Hz) capacitance spectra, which exhibits a transition between positive to negative values, to the change in the occupancy of interface states with voltage. Simulations based on the model allow to derive the density of interface states effectively intervening in the carrier injection (similar to 5 x 10(12) cm(-2)), which exhibit a Gaussian-like distribution. A kinetically determined hole barrier is calculated at levels located similar to 0.4 eV below the contact work function. (C) 2008 Elsevier B.V. All rights reserved.

Magnetic field effects on the conductivity of organic bipolar and unipolar devices at room temperature

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

Effect of the doping medium on blends of polyurethane and polyaniline

Flexible and free-standing films from blends of polyurethane, based on castor oil, and polyaniline were obtained with various compositions by casting. Significant increase on conductivity followed by a considerable decrease on doping time was obtained by doping the films in N,N-dimethylformamide (DMF) solution with p-toluene sulphonic acid (TSA) or HCl instead of the conventional doping in aqueous solution. This doping efficiency is proposed to be due to an improved swelling of the blend structure caused by the solvent. The electrical conductivity increases significantly upon polyaniline content increase reaching 10(-2) S/cm for a polyaniline content of about 10% (w/w).

Polyaniline mixed LB films exposed to X-rays

X-ray irradiation is shown to affect electronic properties of polyaniline (PANi) in composite Langmuir-Blodgett (LB) films of PANi and cadmium stearate, in a similar way to acid doping. The time it takes for the shift in the UV-vis spectra, characteristic of PANi doping, increases linearly with the film thickness, thus indicating a surface-controlled process. The humidity of the environment under which the films are irradiated is also of extreme importance. No shin is observed under vacuum or under dry atmospheres of N-2, O-2 and Ar. For humid environments the time for the shift decreases with increasing relative humidity.

Study of charge transport in blends of natural rubber and poly(o-methoxyaniline) based on a resistor network statistical model

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

The use of Langmuir-Blodgett films of a perylene derivative and polypyrrole in the detection of trace levels of Cu2+ ions

Langmuir films of a tetracarboxylic perylene derivative and polypyrrole display condensed surface pressure isotherms that are shifted when Cu2+ ions are added to the ultrapure water subphase. These films were transferred onto interdigitated gold electrodes leading to Y-type Langmuir-Blodgett (LB) films. The electrodes modified with 5-layer LB films were immersed into a flask with ultrapure water and water containing Cu2+ ions at concentrations ranging from mM to muM. Impedance measurements indicated a distinct electrical response for the two types of films. Although the materials chosen have no specificity for ionic metals, they can be combined for detecting trace levels of Cu2+, which may be exploited in water quality monitoring. (C) 2004 Elsevier B.V. All rights reserved.

Electroactive layer-by-layer films of iron tetrasulfonated phthalocyanine

Electroactive films of iron tetrasulfonated phthalocyanine (FeTsPc) were assembled via the electrostatic layer-by-layer technique (LBL), in which FeTsPc layers were alternated with the polycationic poly(allylamine hydrochloride) (PAN). The multilayer formation was monitored via UV-Vis spectroscopy by measuring the increase in the Q Band of FeTsPc at 676 nm. Film thickness was estimated by profilometry as ca. 10 Angstrom per bilayer. Fourier transform infrared and UV-Vis absorption spectroscopy suggested specific interactions between FeTsPc and PAR Cyclic voltammograms showed reproducible pairs of oxidation-reduction peaks at 0.92 mV and 0.70 mV, respectively, for a 50-bilayer PAH/FeTsPc film at 50 mV/s (vs Ag/AgNO3).

Photoconductivity excitation spectrum for stretch-oriented PPV

We have obtained the photoconductivity (PC) excitation spectrum for a stretch-oriented poly(paraphenylene vinylene) film over a wide spectral range (up to 5 eV). The measurements were performed in the surface cell configuration with the electric field parallel or perpendicular to the stretch direction. Although the sample had a stretch ratio of similar to 4, the dark conductivity and the steady-state photoconductivity were both about 40 and 20 times higher with the electric field parallel to the average chain direction, respectively. However, the shape of the PC excitation spectrum was independent of field direction and did not show a significant rise in the ultraviolet, as is usually observed for measurements in the photodiode configuration. The implications of these results to the charge photogeneration mechanism in conjugated polymers are discussed.

Soliton clusters inducing insulator-to-metal transition in polyacetylene: a Su-Schrieffer-Heeger model study

The Su-Schrieffer-Heeger (SSH) Hamiltonian has been one of most used models to study the electronic structure of polyacetylene (PA) chains. It has been reported in the literature that in the SSH framework a disordered soliton distribution can not produce a metallic regime. However, in this work (using the same SSH model and parameters) we show that this is possible. The necessary conditions for true metals (non-vanishing density of states and extended wavefunctions around the Fermi level) are obtained for soliton concentration higher than 6% through soliton segregation (clustering). These results are consistent with recent experimental data supporting disorder as an essential mechanism behind the high conductivity of conducting polymers. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Layer-by-layer hybrid films of polyaniline and vanadium oxide

Supramolecular structures of polyaniline (PANI) and vanadium oxide (V2O5) have been assembled via the electrostatic layer-by-layer (LBL) technique. The films were characterized by vibrational analyses which indicated that the interactions between the two components lead to different properties in the films when compared to sol-gel films. of the neat compounds. In particular, using surface enhanced Raman scattering we were able to probe LBL film properties that depend on which material comprises the topmost layer.

Weak ferromagnetism in poly(3-methylthiophene)(PMTh)

Ferromagnetic behaviour at 300 K has been observed from SQUID experiments in ClO4- doped PMTh, the samples were prepared electrochemically at 25 degreesC in acetonitrile with 0.1M LiClO4 and then partially reduced. Atomic absorption analysis discards magnetic particles contamination. Hysteresis curves were observed for pressed pellets in ail range of temperatures (300K-2K). The remanence at 300 K and pressed at 250 bar was around 8.06x10(-4) emu/g with coercitivity of 130 Oe. The influence of water content in the solvent during the sample synthesis and the pressure is shown. We discuss a model that explains our data in terms of the anisotropic superexchange Dziatoshinski-Moriya interaction giving rise to weak ferromagnetism.

Excitation spectrum for ultrafast photogeneration of charged solitons in polyacetylene

Ultrafast photoinduced absorption by IRAV modes is used to detect charged solitons in oriented polyacetylene. We find that soliton pairs are photogenerated within our time resolution of similar to250 fs with similar to100% quantum efficiency (phi(ch)). The excitation spectrum of phi(ch) shows an onset at 1.0 eV, with a weak photon energy dependence up to 4.7 eV. These results agree with the ultrafast soliton formation predicted by Su and Schrieffer and with the SSH threshold of 2E(g)/pi for soliton pair production.

Conductive composites of natural rubber and carbon black for pressure sensors

Composites of natural rubber and carbon black have attracted great interest due to their technological applications. In this work natural rubber (NR) and carbon black (CB) were compounded, aiming the development of composites with good mechanical properties, processability and electrical conductivity for use as pressure sensors. The electrical conductivity changes from 10(-11) to 10(-2) S.cm(-1) depending on the percentage of CB in the composite. It was also observed that the conductivity varies reversibly and linearly with the applied pressure. The latter demonstrates that this material can be used as pressure sensors.

Morphology of poly(vinylidene fluoride) and poly(o-metoxyaniline) blends

Blends of poly(o-methoxyaniline) - POMA - and poly(vinylidene fluoride) - PVDF - of various compositions were prepared from organic solvent solutions. Flexible, free-standing and stretchable films were obtained by casting, which were characterized by conductivity measurements, electron microscopy and differential scanning calorimetry. As expected, the blends conductivity increases with increasing contents of the conducting polymer. The onset of the conductivity at low contents of conducting polymer indicates a low percolation threshold for the blends. Despite the presence of the conductive host, the blends displayed the crystalline spherulitic morphology and the beta-phase characteristic of pure PVDF. This morphology appears to be destroyed, however, if the film is stretched by zone-drawing.