The role of oxygen in the interaction of emeraldine base polyaniline with Cu(II) or Fe(III) ions in NMP solution

The influence of molecular oxygen in the interactions of emeraldine base form of polyaniline (EB-PANI) with Fe(III) or Cu(II) ions in 1-methyl-2-pyrrolidinone (NMP) solutions has been investigated by UV-vis-NIR, resonance Raman and electron paramagnetic resonance (EPR) spectroscopies. Through the set of spectroscopic results it was possible to rationalize the role Of O(2) and to construct a scheme of preferential routes occurring in the interaction of EB-PANI with Fe(III) or Cu(II). Solutions of 4.0 mmol L(-1) EB-PANI with 0.8, 2.0 and 20 mmol L(-1) Fe(III) or Cu(II) ions in NMP were investigated and the main observed reactions were EB-PANI oxidation to pernigraniline (PB-PANI) and EB-PANI doping process by pseudo-protonation, or by a two-step redox process. In the presence Of O(2), PB-PANI is observed in all Fe(III)/EB solutions and EB-PANI doping only occurs in solutions with high Fe(III) concentrations through pseudo-protonation. On the other hand, emeraldine salt (ES-PANI) is formed in all Fe(III)/EB solutions under N(2) atmosphere and, in this case, doping occurs both by the pseudo-protonation and two-step redox mechanisms. In all Cu(II)/EB solutions PB-PANI is formed both in the presence and absence of O(2), and only for solutions with high Cu(II) concentrations doping process occurs in a very low degree. The most important result from EPR spectra was providing evidence for redox steps. The determined Cu(II) signal areas under oxygen are higher than under N(2) and, further. the initial metal proportions (1:2:20) are maintained in these spectra, indicating that Cu(I) formed are re-oxidized by O(2) and. so, Cu(II) ions are being recycled. Consistently, for the solutions prepared under nitrogen, the corresponding areas and proportions in the spectra are much lower, confirming that a partial reduction of Cu(II) ions actually occurs. (C) 2009 Elsevier B.V. All rights reserved.

Surface-Enhanced Resonance Raman Scattering of Polyaniline on Silver and Gold Colloids

The interaction of emeraldine base (PANI-EB) with silver and gold colloids was probed by using Surface-Enhanced Resonance Raman Scattering (SERRS) at 3 different exciting radiations. Due to the great sensitivity of SERRS technique the detection limit of PANI-EB concentration was ca. 2 x 10(-7) mol L(-1) in Ag and Au colloidal suspensions. The UV-vis-NIR spectra of metal colloids in function of PANI-EB concentrations showed that gold colloids present a higher degree of aggregation than silver colloids. SERRS of PANI-EB on metal colloids allowed the study of the polymeric species formed primarily on the metallic surface. The polymer formed after the adsorption of PANI-EB on metallic nanoparticles is strongly dependent on the nature of the metal colloids. The oxidation of PANI-EB to pernigraniline occurred for silver colloids, while a doping process of PANI-EB on Au nanoparticles was evidenced through the observation of the characteristic SERRS spectrum of emeraldine salt at 1064nm.

The role of cross-linking structures to the formation of one-dimensional nano-organized polyaniline and their Raman fingerprint

In the present work. the resonance Raman. UV-vis-NIR and scanning electron microscopic (SEM) data of nanorods (about similar to 300 rim in diameter) and nanofibers (about similar to 93 nm in diameter) of PANI are presented and compared. The PANI samples were synthesized in aqueous media with dodecybenzenesulfonic acid (DBSA) and beta-naphtalenesulfonic acid (beta-NSA) as dopants, respectively. The presence of hands at 578, 1400 and 1632cm(-1) in the Raman spectra of PANI-NSA and PANI-DBSA shows that the formation of cross-linking structures is a general feature of the PANI chains prepared in micellar media. It is proposed that these structures are responsible for the one-dimensional PANI morphology formation. In addition, the Raman band at 609cm(-1) of PANI fibers is correlated with the extended PANI chain coil formation. (C) 2008 Elsevier B.V. All rights reserved.

Propriedade fotoluminescente da ZrO2: Tb+3, Eu+3, Tm+3 obtida pelo método de polimerização de complexos

Recent studies are investigating a new class of inorganic materials which arise as a promising option for high performance applications in the field of photoluminescence. Highlight for rare earth (TR +3 ) doped, which have a high luminous efficiency, long decay time and being able to emit radiation in the visible range, specific to each element. In this study, we synthesized ZrO2: Tb +3 , Eu +3 , Tm +3 nanoparticles complex polymerization method (CPM). We investigated the influences caused by the heat treatment temperature and the content of dopants in zirconia photoluminescent behavior. The particles were calcined at temperature of 400, 500 and 600 ° C for two hours and ranged in concentration of dopants 1, 2, 4 and 8 mol% TR +3 . The samples were characterized by thermal analysis, X-ray diffraction, photoluminescence of measurements and uv-visible of spectroscopies. The results of X-ray diffraction confirmed the formation of the tetragonal and cubic phases in accordance with the content of dopants. The photoluminescence spectra show emission in the region corresponding simultaneous to blue (450 nm), green (550 nm) and red (615 nm). According to the results, ZrO2 particles co-doped with rare earth ions is a promising material white emission with a potential application in the field of photoluminescence

Surface-enhanced Raman scattering and micro-Raman imaging of Langmuir-Blodgett films of rhodium phthalocyanine

Rhodium phthalocyanine (RhPc) was synthesized and ultra thin Langmuir-Blodgett (LB) films of RhPc were successfully fabricated. The LB film characterization was carried out using both UV-vis absorption spectra and Raman scattering. The Raman spectroscopy was carried out using 633 and 780 nm laser lines. LB films were deposited onto Ag nanoparticles to achieve the surface-enhanced pre-resonance Raman scattering (pre-SERRS) and surface-enhanced Raman scattering (SERS) for both laser lines, respectively, which allowed the characterization of the RhPc ultra thin films. The morphology of the LB RhPc neat film is extracted from micro-Raman imaging. (C) 2003 Elsevier B.V. All rights reserved.

Molecular architecture of thin films fabricated via physical vapor deposition and containing a poly(azo)urethane

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

Spray layer-by-layer films based on phospholipid vesicles aiming sensing application via e-tongue system

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

Molecular and morphological characterization of bis benzimidazo perylene films and surface-enhanced phenomena

Thin solid films of bis benzimidazo perylene (AzoPTCD) were fabricated using physical vapor deposition (PVD) technique. Thermal stability and integrity of the AzoPTCD PVD films during the fabrication (similar to 400 degrees C at 10(-6) Torr) were monitored by Raman scattering. Complementary thermogravimetric results showed that thermal degradation of AzoPTCD occurs at 675 degrees C. The growth of the PVD films was established through UV-vis absorption spectroscopy, and the surface morphology was surveyed by atomic force microscopy (AFM) as a function of the mass thickness. The AzoPTCD molecular organization in these PVD films was determined using the selection rules of infrared absorption spectroscopy (transmission and reflection-absorption modes). Despite the molecular packing, X-ray diffraction revealed that the PVD films are amorphous. Theoretical calculations (density functional theory, B3LYP) were used to assign the vibrational modes in the infrared and Raman spectra. Metallic nanostructures, able to sustain localized surface plasmons (LSP) were used to achieve surface-enhanced resonance Raman scattering (SERRS) and surface-enhanced fluorescence (SEF).

Inclusion complex of piroxicam with beta-cyclodextrin and incorporation in hexadecyltrimethylammonium bromide based microemulsion

The interaction of piroxicam with beta-cyclodextrin (beta-CD), hexadecyltrimethylammonium bromide-based microemulsion (ME), and ME in the presence of beta-CD aimed at the optimization of topical drug delivery was studied. UV-VIS absorption spectra at pH 5.5 were obtained with and without beta-CD and ME. The stability constant (K) values for the piroxicam/beta-CD complex in the pH range 4.5-6.0 varied from 87 to 29 M-1. The cationic microemulsion was characterized by pseudo-ternary phase diagram. The association constant (K-s) of piroxicam/ME was determined using the framework of the pseudophase model. The value of K-s obtained for piroxicam at pH 5.5 was 132 M-1. At the same pH, the value of K-s for the incorporation of piroxicam/beta-CD complex in the ME was 150 M-1. (C) 1999 Elsevier B.V. B.V. All rights reserved.

On the incorporation of the non-steroidal anti-inflammatory naproxen into cationic O/W microemulsions

Microemulsions (ME) containing hexadecyltrimethylammonium bromide (HTAB)/ethanol as surfactant, isopropylmyristate (IM) or butylstearate (BS) as oil phase and aqueous buffer were studied. Pseudo-ternary phase diagrams of the investigated systems were obtained at constant surfactant/cosurfactant molar ratio (1:5) by titration in order to characterize the proportions between the components to obtain clear systems. Oil in water microemulsions were prepared in a wide range of phase volume (phi). UV-vis absorption spectra of naproxen at pH 5.5 showed that the solubility of Np increases significantly in the presence of O/W ME in high phase volumes. For both, IM and BS microemulsions, the dynamic light scattering experiments showed that the size of the oil droplets remains constant in low values of phi, increasing abruptly in high phi values. Phase solubility study revealed that for both IM and BS microemulsions, the drug incorporation followed a straight-line profile in all range of phi. The data could be analyzed through the phase-separation model and the association constants (K) calculated varied from 27 to 90 M-1, depending on the pH and on the microemulsion oil phase. (c) 2005 Elsevier B.V. All rights reserved.

Validação de método analítico por espectrofotometria UV para sistema emulsionado lipídico contendo benznidazol

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Deposition and characterization of BiVO4 thin films and evaluation as photoanodes for methylene blue degradation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Ionizing radiation induced degradation of poly (2-methoxy-5-(2 '-ethyl-hexyloxy)-1,4-phenylene vinylene) in solution

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Electronic structure and optical properties of BaMoO4 powders

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

A new route to obtain PVDF/PANI conducting blends

Electrically conductive poly(vinylidene fluoride)(PVDF) - polyaniline blends of different composition were synthesized by chemical polymerization of aniline in a mixture of PVDF and dimethylformamide (DMF) and studied by electrical conductivity measurement, UV-Vis-NIR and FTIR spectroscopy. The samples were obtained as flexible films by pressing the powder at 180 degrees C for 5 min. The electrical conductivity showed a great dependence on the syntheses parameters. The higher value of the electrical conductivity was obtained for the oxidant/aniline molar ratio equal to 1 and p-toluenesulfonic acid-TSA/aniline ratio between 3 and 6. UV-Vis-NIR and FTIR spectra of the blend are similar to the doped PANI, indicating that the PANI is responsible for the high electrical conductivity of the blend. The electrical conductivity of blend proved to be stable as a function of temperature decreasing about one order at temperature of 100 degrees C. The route used to obtain the polymer blend showed to be a suitable alternative in order to obtain PVDF/PANI-TSA blends with high electrical conductivity. (c) 2006 Elsevier Ltd. All rights reserved.