Characterization of the products of aniline peroxydisulfate oligo/polymerization in media with different pH by resonance Raman spectroscopy at 413.1 and 1064 nm excitation wavelengths

The pH-structure correlation of the products of aniline peroxydisulfate reaction was mainly investigated by resonance Raman spectroscopy. The reactions of aniline and ammonium peroxydisulfate were carried out in aqueous solutions of initial pH ranging from 4.9 to 13.2 and monomer/oxidant molar ratio of 4/1. For an initial pH of 4.9, the spectroscopic techniques showed that the emeraldine salt form of polyaniline (PANI-ES) is the main product, corroborating that the usual head-to-tail coupling mechanism is taking place. The resonance Raman spectra at 1064 nm exciting wavelength were useful to detect the emeraldine salt as a minor product for reactions at an initial pH of 5.3-11.5. The Raman spectra of the main product of the reaction at initial pH of 13.2 excited at 1064 and 413.1 nm showed new spectral features consistent with 1,4-Michael-type adducts of aniline monomers and 1,4-benzoquinone-monoimine unit. These compounds and their products of hydrolysis/oxidation are the predominant species for the reaction media of initial pH from 5.3 to 13.2. In order to get PANI with different nanoscale morphologies, a pH value of more than 0 or 1 was used in the aniline polymerization. The spectroscopic data obtained in this work reveal that head-to-tail coupling does not occur when aniline reacts at media pH higher than about 5. It is suggested that chemical structures of the products of aniline oxidation by an unusual mechanism are the driving force for the development of assorted morphologies. Copyright (C) 2011 John Wiley & Sons, Ltd.

(1)H NMR spectroscopy as a tool to determine accurate photoisomerization quantum yields of stilbene-like ligands coordinated to rhenium(I) polypyridyl complexes

In this work, the use of proton nuclear magnetic resonance, (1)H NMR, was fully described as a powerful tool to follow a photoreaction and to determine accurate quantum yields, so called true quantum yields (Phi(true)), when a reactant and photoproduct absorption overlap. For this, Phi(true) for the trans-cis photoisomerization process were determined for rhenium(I) polypyridyl complexes, fac-[Re(CO)(3)(NN)(trans-L)](+) (NN = 1,10-phenanthroline, phen, or 4,7-diphenyl-1,10-phenanthroline, ph(2)phen, and L = 1,2-bis(4-pyridyl) ethylene, bpe, or 4-styrylpyridine, stpy). The true values determined at 365 nm irradiation (e. g. Phi(NMR) = 0.80 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)) were much higher than those determined by absorption spectral changes (Phi(UV-Vis) = 0.39 for fac-[Re(CO)(3)(phen)(trans-bpe)](+)). Phi(NMR) are more accurate in these cases due to the distinct proton signals of trans and cis-isomers, which allow the actual determination of each component concentration under given irradiation time. Nevertheless when the photoproduct or reactant contribution at the probe wavelength is negligible, one can determine Phi(true) by regular absorption spectral changes. For instance, Phi(313) nm for free ligand photoisomerization determined both by absorption and (1)H NMR variation are equal within the experimental error (bpe: Phi(UV-Vis) = 0.27, Phi(NMR) = 0.26; stpy: Phi(UV-Vis) = 0.49, Phi(NMR) = 0.49). Moreover, (1)H NMR data combined with electronic spectra allowed molar absorptivity determination of difficult to isolate cis-complexes. (C) 2009 Elsevier B. V. All rights reserved.

Optical Characterization and Optimization of Display Components : Some Applications to Liquid-Crystal-Based and Electrochromics-Based Devices

This dissertation is focused on theoretical and experimental studies of optical properties of materials and multilayer structures composing liquid crystal displays (LCDs) and electrochromic (EC) devices. By applying spectroscopic ellipsometry, we have determined the optical constants of thin films of electrochromic tungsten oxide (WOx) and nickel oxide (NiOy), the films’ thickness and roughness. These films, which were obtained at spattering conditions possess high transmittance that is important for achieving good visibility and high contrast in an EC device. Another application of the general spectroscopic ellipsometry relates to the study of a photo-alignment layer of a mixture of azo-dyes SD-1 and SDA-2. We have found the optical constants of this mixture before and after illuminating it by polarized UV light. The results obtained confirm the diffusion model to explain the formation of the photo-induced order in azo-dye films. We have developed new techniques for fast characterization of twisted nematic LC cells in transmissive and reflective modes. Our techniques are based on the characteristics functions that we have introduced for determination of parameters of non-uniform birefringent media. These characteristic functions are found by simple procedures and can be utilised for simultaneous determination of retardation, its wavelength dispersion, and twist angle, as well as for solving associated optimization problems. Cholesteric LCD that possesses some unique properties, such as bistability and good selective scattering, however, has a disadvantage – relatively high driving voltage (tens of volts). The way we propose to reduce the driving voltage consists of applying a stack of thin (~1µm) LC layers. We have studied the ability of a layer of a surface stabilized ferroelectric liquid crystal coupled with several retardation plates for birefringent color generation. We have demonstrated that in order to accomplish good color characteristics and high brightness of the display, one or two retardation plates are sufficient.

Analysis of the four wave mixing effect (FWM) in a dispersion decreasing fiber (DDF) for a WDM system

We did a numerical investigation of the propagation of short light pulses in the region of 1.55 mu m and the conversion efficiency (CE) for the four wave mixing generation (FWM) of ordinary and dispersion decreasing fibers for use in wavelength division multiplexing (WDM) systems, Our simulations studies three different profiles, linear, hyperbolic. and constant, One conclude that for all the profiles there is decrease of the conversion efficiency with the increase in the channel separation. The hyperbolic profile present a higher efficiency of around 1000 above in magnitude compared with the others profiles at 0.2 nm of channel separation. We calculate the conversion efficiency versus the fiber length for the three profiles. The conversion efficiency for the hyperbolic profile is higher when compared to the constant and linear profiles. The other interesting point of the hyperbolic profile is that the increase of the CE in the beginning of the fiber does not show my oscillation in the CE value (log eta), which was observed for the constant and linear profiles. For all the profiles there is an increase of the conversion efficiency with the increase of the pump power. The compression factor C-i for the generated FWM signal at omega(3) was measured along the DDF's and the constant profile fibers. One can conclude that with the use of decreasing dispersion profile (DDF) fibers one can have a control of the (CE) conversion efficiency and the compression factor of the four wave mixing (FWM) generation in WDM systems. (c) 2005 Elsevier B.V. All rights reserved.

EFFECT of TYPES of NOZZLES on SPRAY DEPOSITION on TWO SOYBEAN VARIETIES IN STAGE V3

The effect of application with different nozzle types and volume rates on spray deposition in the V3 stage of two soybean cultivars was evaluated. The experiments were conducted in the Facultad de Ciencias Agronomicas of the UNESP-Botucatu/SP. The nozzles evaluated were an air induced flat fan nozzle (Al 11015 at 150 L ha(-1), Al 11002 at 200 and 250 L ha(-1)), a twin flat fan nozzle (TJ 60 11002 at 150, 200 and 250 L ha(-1)), and a cone nozzle (TX 6 at 150 L ha(-1), TX 8 at 150 L ha(-1) and TX 10 at 250 L ha(-1)). To evaluate spray deposition on the plants, a tracer (Brilliant Blue FD&C-1) was added. The experimental design was random blocks with four replications. Deposition on plants was determined by absorbancy reading in 630 nm wavelength. The data were adjusted to a calibration curve and transformed into deposited spray volume in mL. The relationship deposition per unit of dry matter was adjusted to a regression curve (Gompertz model). In cultivar CD 208, the highest deposit was for the larger volumes and for the treatment TX 8 200 L ha(-1). The most uniform treatments were all the nozzles with the volume 150 L ha(-1) and the TJ60 nozzle for 200 1, ha(-1). In cultivar CD 216, the greatest spray depositions were achieved with the treatments Al at 200 and 250 L ha(-1) and TJ 60 at 250 L ha(-1), and the most uniform treatments were the TX 6 and TJ60 nozzles for the volume150 L ha(-1).

Deriving the magnitude of niobium off-center displacement in ferroelectric niobates from infrared spectroscopy

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Development and Validation of an UV-Derivative Spectrophotometric Method for Determination of Glimepiride in Tablets

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

Development and validation of an analytical method by RP-HPLC for quantification of sibutramine hydrochloride in pharmaceutical capsules

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

Tunable visible photoluminescence of powdered silica glass

intense photoluminescence in the visible region was observed at room temperature in standard soda-lime-silica glass powder, mechanically milled in a high-energy attrition mill. The emission band maximum shows an interesting dependence on the exciting wavelength, suggesting the possibility to tune the PL emission. These findings indicate that the photoluminescence may be directly related to unsatisfied chemical bonds correlated with the high surface area. The Raman scattering and ultraviolet-visible optical reflectance measurements corroborate this assertion. Transmission electron microscopy measurements indicate that samples milled more than 10 h present the formation of nanocrystallites with about 10-20 nm. (C) 2007 Elsevier B.V. All rights reserved.

Scattering of neutral fermions by a pseudoscalar potential step in two-dimensional spacetime

The problem of scattering of neutral fermions in two-dimensional spacetime is approached with a pseudoscalar potential step in the Dirac equation. Some unexpected aspects of the solutions beyond the absence of Klein's paradox are presented. An apparent paradox concerning the uncertainty principle is solved by introducing the concept of effective Compton wavelength. Added plausibility for the existence of bound-state solutions in a pseudoscalar double-step potential found in a recent Letter is given. (C) 2003 Elsevier B.V. B.V. All rights reserved.

The peremptory influence of a uniform background for trapping neutral fermions with an inversely linear potential

The problem of neutral fermions subject to an inversely linear potential is revisited. It is shown that an infinite set of bound-state solutions can be found on the condition that the fermion is embedded in an additional uniform background potential. An apparent paradox concerning the uncertainty principle is solved by introducing the concept of effective Compton wavelength.

Bounded solutions of neutral fermions with a screened Coulomb potential

The intrinsically relativistic problem of a fermion subject to a pseudoscalar screened Coulomb plus a uniform background potential in two-dimensional space-time is mapped into a Sturm-Liouville. This mapping gives rise to an effective Morse-like potential and exact bounded solutions are found. It is shown that the uniform background potential determinates the number of bound-state solutions. The behaviour of the eigenenergies as well as of the upper and lower components of the Dirac spinor corresponding to bounded solutions is discussed in detail and some unusual results are revealed. An apparent paradox concerning the uncertainty principle is solved by recurring to the concepts of effective mass and effective Compton wavelength. (c) 2005 Elsevier B.V. All rights reserved.

Bound states of bosons and fermions in a mixed vector-scalar coupling with unequal shapes for the potentials

The Klein - Gordon and the Dirac equations with vector and scalar potentials are investigated under a more general condition, V(v) + V(s) = constant. These intrinsically relativistic and isospectral problems are solved in the case of squared hyperbolic potential functions and bound states for either particles or antiparticles are found. The eigenvalues and eigenfuntions are discussed in some detail and the effective Compton wavelength is revealed to be an important physical quantity. It is revealed that a boson is better localized than a fermion when they have the same mass and are subjected to the same potentials.

UV exposure of polymeric geomembranes

The break of polymer chemical bonds may occur due to penetration of sun short wavelengths. In sanitary landfills for instance, ultraviolet radiation affects uncovered materials and can be dangerous during the installation of the liner and before the placement of the waste. Only the ultraviolet part of the light is harmful to the geosynthetic materials, moreover, each material is sensitive to a particular wavelength. This article evaluates the effects of UV degradation and condensation in black HDPE (1.0 and 1.5 mm) and white HDPE (textured - 1.0 mm) geomembrane that were tested in laboratory during 6 months. The tests were performed using a weatherometer assembled at EESC-USP in accordance to ASTM G154. The results have shown variations in punction and tear resistance after each period of exposure.

Photopyroelectric spectroscopy of polyaniline films

Photopyroelectric spectroscopy (PPES), in the 400 < lambda < 900 nm wavelength range, was used to study thermal properties of differently doped polyaniline (PAN) films. The photopyroelectric intensity signal V-n(lambda) and its phase F-n(lambda) were independently measured, as well as the intensity V-n(f) and the phase F-n(f) (f being the chopping frequency) for a given A of the saturation part of the PPES spectrum. Equations of both the intensity and the phase of the PPES signal, taking into account the thermal and the optical characteristics of the PAN films and the pyroelectric detector, were used to fit the experimental results. From the fittings we obtained, with great accuracy, the values of thermal conductivity k and thermal diffusivity coefficient a of PAN films of different doping degrees. It was observed that, in contrast with the strong doping-dependence of the electrical conductivity, the thermal parameters of PAN films remained practically unchanged under doping. This apparent discrepancy is explained by the granular metal model of doped PAN. (C) 2000 John Wiley & Sons, Inc.