An exactly soluble multiatom-multiphoton coupling model

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

Effect of temperature on the interaction between the nonionic surfactant C(12)E(5) and poly(ethylene oxide) investigated by dynamic light scattering and fluorescence methods

The interaction between the nonionic surfactant C(12)E(5) and a high molar mass (M = 5.94 x 10(5)) poly(ethylene oxide) (PEG) in aqueous solution has been examined as a function of temperature by dynamic light scattering and fluorescence methods over a broad concentration range. Clusters of small surfactant micelles form within the PEO coil, leading to its extension. The hydrodynamic radius of the complex increases strongly with temperature as well as with the concentrations of surfactant and polymer. At high concentrations of the surfactant, the coil/micellar cluster complex coexists with free C(12)E(5) micelles in the solution. Fluorescence quenching measurements show a moderate micellar growth from 155 to 203 monomers in PEO-free solutions of C(12)E(5) over a wide concentration range (0.02-2.5%) at 8 degrees C. Below 0.25% C(12)E(5), the average aggregation number (N) of the micelles is smaller in the presence of PEO than in its absence. However, N increases with increasing surfactant concentration up to a plateau value of about 270 at about 1.2% (ca. 30 mM) C(12)E(5). At high surfactant concentrations, N is larger in the presence of polymer than in its absence, a finding which is connected to a significant lowering of the clouding temperature due to the PEO at these compositions. Similar results of increasing aggregation number followed by a plateau were also found at a fixed concentration of surfactant (2.5%) and varied PEO.

Planar and UV written channel optical waveguides prepared with siloxane poly(oxyethylene)-zirconia organic-inorganic hybrids. Structure and optical properties

Organic-inorganic hybrids were prepared using ureapropyltriethoxysilane, methacryloxypropyltrimethoxysilane and acrylic acid modified zirconium(IV) n-propoxide precursors and were characterized by small angle X-ray scattering, X-ray diffraction and photoluminescence spectroscopy. The results indicate an effective interaction between the zirconium-based nanoparticles and the siliceous nanodomains that induces changes in the hybrids' emission features. Planar waveguides were obtained by spin-coating of the prepared sols on sodalime and silica substrates. Refractive index, thickness, number of propagating modes, and attenuation coefficient were measured at 543.5, 632.8 and 1550 nm by the prism coupling technique. The synergism between the two hybrid precursors resulted in monomode planar waveguides with low losses in the infrared ( from 0.6-1.1 dB cm(-1)) which also support a number of propagating modes in the visible ( losses from 0.4-1.5 dB cm(-1)). Channel waveguides were also obtained by UV photopatterning using amplitude or phase masks and propagating modes were observed at 1550 nm.

Langmuir and langmuir-blodgett films of polyfluorenes and their use in polymer light-emitting diodes

The Langmuir and Langmuir-Blodgett (LB) film properties of two polyfluorene derivatives, namely poly(2,7-9,9'-dihexylfluorene-dyil) (PDHF) and poly(9,9 dihexylfluorene-dyil-vynilene-alt-1,4-phenylene-vyninele) (PDHF-PV), are reported. Surface pressure (Pi-A) and surface potential (Delta V-A) isotherms indicated that PDHF-PV forms true monolayers at the air/water interface, but PDHF does not. LB films could be transferred onto various types of substrate for both PDHF and PDHF-PV. Only the LB films from PDHF-PV could withstand deposition of a layer of evaporated metal to form a light-emitting diode (PLED), which had typical rectifying characteristics and emitted blue light. It is inferred that the ability of the polymer to form true monomolecular layers at the air/water interface seems to be associated with the viability of the LB films in PLEDs.

Electroactive LbL films of metallic phthalocyanines and poly(O-methoxyaniline) for sensing

Multilayered nanostructured films have been widely investigated for electrochemical applications as modified electrodes, including the layer-by-layer (LbL) films where properties such as thickness and film architecture can be controlled at the molecular level. In this study, we investigate the electrochemical features of LbL films of poly (o-methoxyaniline; POMA) and tetrasulfonated phthalocyanines containing nickel (NiTsPc) or copper (CuTsPc). The films displayed well-defined electroactivity, with redox pairs at 156 and 347 mV vs SCE, characteristic of POMA, which allowed their use as modified electrodes for detecting dopamine and ascorbic acid at concentrations as low as 10(-5) M.

Cathodic stripping voltammetric determination of ceftazidime with reactive accumulation at a poly-L-lysine modified hanging mercury drop electrode

Ceftazidime is hydrolysed only slowly at pH 10 at room temperature. This is indicated by a small cathodic stripping voltammetric peak obtained at pH 10 at a hanging mercury drop electrode at about -0.6 V which corresponds to the reduction of the hydrolysis product. This peak is enhanced more than tenfold by the addition of poly-L-lysine (PLL) to the electrolyte solution. The optimum accumulation potential is between 0 and -0.1 V: the size of the peak decreases steadily, however, as the accumulation potential is moved to more negative potentials and is about one-sixth the size for accumulation at -0.4 V. Existing knowledge of the organic chemistry of cephalosporins indicates that the accumulation must involve an aminolysis reaction of the unprotonated PLL with the beta-lactam ring of the ceftazidime. The limit of detection (3 sigma) in standard solutions was calculated to be 1 x 10(-10) mol l(-1). The detection limit in buffer solution containing 1% of urine was calculated to be 5 x 10(-9) mol l(-1), i.e. 5 x 10(-6) mol l(-1) in the urine. (C) 1999 Elsevier B.V. B.V. AU rights reserved.

Oil-soluble dyes for marking Spodoptera frugiperda (Lepidoptera : Noctuidae)

Although various biological aspects of Spodoptera frugiperda (J.E. Smith) (Lepidoptera: Noctuidae) have been examined, adult movement and dispersal of this insect pest is not well understood. Release-recapture techniques by using marked insects is a useful approach for dispersal studies; however, the marking technique should not significantly affect insect biology or behavior. Therefore, the effect of different concentrations of oil-soluble dyes (Solvent Blue 35 [C.I. 61554], Sudan Red 7B [C.I. 26050], Sudan Black B [26150], Sudan Orange G [C.I. 11920], and Sudan I 103624 [C.I. 12055]) on development, mortality, and fecundity of S. frugiperda was evaluated. Dyes were added to artificial diet used to feed larvae. Larval and pupal development and mortality, adult longevity, and female fecundity were evaluated. High concentrations (400 and 600 ppm) of all dyes led to longer larval and pupal stages. Adult life span and number of eggs were not affected by the dyes. Sudan Red 7B marked both adults and eggs very well. Solvent Blue 35 marked both adults and eggs, but the blue-marked eggs could not be distinguished from some bluish eggs laid by nonlabeled females. Adults and eggs were not adequately marked by the Sudan Black B, Sudan Orange G, and Sudan I 103624 (a yellow dye).

Structural modelling of Eu3+-based siloxane-poly( oxyethylene) nanohybrids

The modelling of the local structure of sol-gel derived Eu3+-based organic/inorganic hybrids is reported, based on Small-Angle X-ray Scattering (SAXS), photoluminescence and mid-infrared spectroscopy. The hybrid matrix of these organically modified silicates, classed as di-ureasils and termed U(2000) and U(600), is formed by poly( oxyethylene) (POE) chains of variable length grafted to siloxane domains by means of urea cross-linkages. Europium triflate, Eu(CF3SO3)(3), was incorporated in the two di-ureasil matrices with compositions 400 greater than or equal ton greater than or equal to 10, n is the molar ratio of ether oxygens per Eu3+. The SAXS data for undoped hybrids (n=infinity) show the presence of a well-defined peak attributed to the existence of a liquid-like spatial correlation of siloxane rich domains embedded in the polymer matrix and located at the ends of the organic segments. The obtained siloxane particle gyration radius Rg(1) is around 5 Angstrom (error within 10%), whereas the interparticle distance d is 25 +/-2 Angstrom and 40 +/-2 Angstrom, for U(600) and U(2000), respectively. For the Eu3+-based nanocomposites the formation of a two-level hierarchical local structure is discerned. The primary level is constituted by strongly spatially correlated siloxane particles of gyration radius Rg(1) (4-6 and 3-8 Angstrom, errors within 5%, for U(600())n Eu(CF3SO3)(3), 200 greater than or equal ton greater than or equal to 40, and U(2000)(n)Eu(CF3SO3)(3), 400 greater than or equal ton greater than or equal to 40, respectively) forming large clusters of gyration radius Rg(2) (approximate to 75 +/- 10 Angstrom). The local coordination of Eu3+ in both di-ureasil series is described combining the SAXS, photoluminescence and mid-infrared results. In the di-ureasils containing long polymer chains, U(2000)(n)Eu(CF3SO3)(3), the cations interact exclusively with the carbonyl oxygens atoms of the urea bridges at the siloxane-POE interface. In the hybrids containing shorter chains, U(600)(n)Eu(CF3SO3)(3) with n ranging from 200 to 60, the Eu3+ ions interact solely with the ether-type oxygens of the polymer chains. Nevertheless, in this latter family of hybrids a distinct Eu3+ local site environment involving the urea cross-linkages is detected when the europium content is increased up to n=40.

Dynamic viscosity of binary and ternary mixtures containing poly(ethylene glycol), potassium phosphate, and water

Dynamic viscosity of binary mixtures of poly(ethylene glycol) molar mass 1500 da + water, potassium phosphate + water, and ternary mixtures of poly(ethylene glycol) molar mass 1500 da + potassium phosphate + water were determined at 303.15 K Binary and ternary mixture viscosities showed a direct logarithm-type relation with the increase of poly(ethylene glycol) and potassium phosphate contents. The models used for viscosity correlation gave a good fit to the experimental data.

Dynamic scale theory for characterizing surface morphology of layer-by-layer films of poly(o-methoxyaniline)

The dynamic scale theory and fractal concepts are employed in the characterization of surface morphological properties of layer-by-layer (LBL) films from poly(o-methoxyaniline) (POMA) alternated with poly(vinyl sulfonic acid) (PVS). The fractal dimensions are found to depend on the procedures to fabricate the POMA/PVS multilayers, particularly with regard to the drying procedures. LBL films obtained via drying in ambient air show a more homogeneous surface, compared to films dried under vacuum or a flow of nitrogen, due to a uniform rearrangement of polymer molecules during solvent evaporation.

Phase transition in poly(vinylidene fluoride) investigated with micro-Raman spectroscopy

The phase transition from the non-polar a-phase to the polar beta-phase of poly(vinylidene fluoride) (PVDF) has been investigated using micro-Raman spectroscopy, which is advantageous because it is a nondestructive technique. Films of alpha-PVDF were subjected to stretching under controlled rates at 80 degrees C, while the transition to P-PVDF was monitored by the decrease in the Raman band at 794 cm(-1) characteristic of the a-phase, along with the concomitant increase in the 839 cm-1 band characteristic of the P-phase. The alpha ->beta transition in our PVDF samples could be achieved even for the sample stretched to twice (2 X -stretched) the initial length and it did not depend on the stretching rate in the range between 2.0 and 7.0 mm/min. These conclusions were corroborated by differential scanning calorimetry (DSC) and X-ray diffraction experiments for PVDF samples processed under the same conditions as in the Raman scattering measurements. Poling with negative corona discharge was found to affect the a-PVDF morphology, improving the Raman bands related to this crystalline phase. This effect is minimized for films stretched to higher ratios. Significantly, corona-induced effects could not be observed with the other experimental techniques, i.e., X-ray diffraction and infrared spectroscopy.

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.