Photomechanically Induced Phase Transitions in Ferroelectric Liquid Crystals

We report optically induced phase transtions occurring in two different host ferroelectric liquid crystals; SCE13 a multicomponentmixture optimised for room temperature performance, and CE8 a single component liquid crystal. These act as host liquid crystals for a novel guest azo dye, which can be made to photoisomerise using low power density U.V. illumination, resulting in dramatic changes in sample properties. We have shown that the magnitude of spontaneous polarisation of systems can be isothermally and reversibly induced or reduced, with the consequent appearance or disappearance of optical switching hysteresis. We discuss the parameters controlling the behaviour of the systems under U.V. illumination and suggest mechansims by which the transitions may occur. © 1993, Taylor & Francis Group, LLC. All rights reserved.

Transient Reorientation of a Doped Liquid Crystal System under a Short Laser Pulse

The transient optical nonlinearity of a nematic liquid crystal doped with azo-dye DR19 is examined. The optical reorientation threshold of a 25-mu m-thick planar-aligned sample of 5CB using a 50 ns pulse duration 532 nm YAG laser pulse is observed to decrease from 800 mJ/mm(2) to 0.6 mJ/mm(2) after the addition of 1 vol% azo dopant, a reduction of three orders of magnitude. When using a laser pulse duration of 10 ns, no such effect is observed. Experimental results indicate that the azo dopant molecules undergo photoisomerization from trans-isomer to cis-isomer under exposure to light, and this conformation change reorients the 5CB molecules via intermolecular coupling between guest and host. This guest-host coupling also affects the azo photoisomerization process.

A smart ink for the assessment of low activity photocatalytic surfaces

The azo dye, basic blue 66 (BB66) is used in a photocatalyst activity indicator ink (paii) to assess the activity of low activity photocatalytic surfaces, such as commercial photocatalytic tiles and silicone contaminated self-cleaning glass. The BB66 paii is shown to respond much faster than a previously reported, resazurin (Rz) based paii, i.e. the use of a BB66 paii on low activity self-cleaning tiles was found to be >6 times faster than the Rz paii. The BB66 paii is also shown to be effective at assessing the activity of piece of commercial self-cleaning glass contaminated with a coating of silicone, on which the Rz ink, in contrast, failed to show any significant change in colour over the same time period.

Enhanced bio-decolourisation of acid orange 7 by Shewanella oneidensis through co-metabolism in a microbial fuel cell

The decolourisation of acid orange 7 (AO7) (C.I.15510) through co-metabolism in a microbial fuel cell by Shewanella oneidensis strain 14063 was investigated with respect to the kinetics of decolourisation, extent of degradation and toxicity of biotransformation products. Rapid decolourisation of AO7 (>98% within 30 h) was achieved at all tested dye concentrations with concomitant power production. The aromatic amine degradation products were recalcitrant under tested conditions. The first-order kinetic constant of decolourisation (k) decreased from 0.709 ± 0.05 h−1 to 0.05 ± 0.01 h−1 (co-substrate – pyruvate) when the dye concentration was raised from 35 mg l−1 to 350 mg l−1. The use of unrefined co-substrates such as rapeseed cake, corn-steep liquor and molasses also indicated comparable or better AO7 decolourisation kinetic constant values. The fully decolourised solutions indicated increased toxicity as the initial AO7 concentration was increased. This work highlights the possibility of using microbial fuel cells to achieve high kinetic rates of AO7 decolourisation through co-metabolism with concomitant electricity production and could potentially be utilised as the initial step of a two stage anaerobic/aerobic process for azo dye biotreatment.

A thin-layer chromatography-bioautographic method for detecting dipeptidyl peptidase IV inhibitors in plants

A thin-layer chromatography (TLC)-bioautographic method was developed with the aim to detect dipeptidyl peptidase IV (DPP IV) inhibitors from plant extracts. The basic principle of the method is that the enzyme (DPP IV) hydrolyzes substrate (Gly-Pro-p-nitroaniline) into p-nitroaniline (pNA), which diazotizes with sodium nitrite, and then reacts with N-(1-naphthyl) ethylenediamine dihydrochloride in turn to form a rose-red azo dye which provides a rose-red background on the TLC plates. The DPP IV inhibitors showed white spots on the background as they blocked enzymolysis of the substrate to produce pNA. The method was validated with respect to selectivity, sensitivity, linearity, precision, recovery, and stability after optimizing key parameters including plate type, time and temperature of incubation, concentration of substrate, enzyme and derivatization reagents, and absorption wavelength. The results showed good lineary within amounts over 0.01–0.1 μg range for the positive control, diprotin A, with the coefficient of determination (r2) = 0.9668. The limits of detection (LOD) and quantification (LOQ) were 5 and 10 ng, respectively. The recoveries ranged from 98.9% to 107.5%. The averages of the intra- and inter-plate reproducibility were in the range of 4.1–9.7% and 7.6–14.7%, respectively. Among the nine methanolic extracts of medicinal herbs screened for DPP IV inhibitors by the newly developed method, Peganum nigellastrum Bunge was found to have one white active spot, which was then isolated and identified as harmine. By spectrophotometric method, harmine hydrochloride was found to have DPP-IV inhibitory activity of 32.4% at 10 mM comparing to that of 54.8% at 50 μM for diprotin A.

New Spectrophotometric Methods for the Determination of Nimesulide

Two simple and sensitive spectrophotometric methods (A and B)in the visible region have been developed for the determination of nimesulide in bulk and in dosage forms.Method A is based on the reaction of reduced nimesulide with nitrous acid followed by its coupling with phloroglucinol to yield an yellow colored azo dye with an absorption maximum of 400 nm and method B is based on the reaction of reduced nimesulide with p-dimethylamino benzaldehyde(PDAB) to form an yellow colored chromogen wiht an absorption maximum of 415 nm.When pharmaceutical preparations (Tablets and suspension) were analysed, the results obtained by the proposed methods are in good agreement with the labelled amounts and are comparable with the results obtained by a reported method.recovery in both the method is 98-101 %.

Local gratings due to angular hole burning in a photorefractive polymer

We investigate the processes involved in writing real-time holographic gratings in a photorefractive polymer (PRP) that incorporates an azo-dye. In such systems there may be gratings due to mechanisms associated with trans–cis isomerization (angular hole burning (AHB) and/or angular redistribution), which appear in addition to those arising from the photorefractive (PR) effect. The work presented here helps to understand the interactions which may occur between these different gratings. The formation of local gratings due to mechanisms associated with photoisomerization is studied, in a new PRP based on the photoconductor poly(N-vinylcarbazole):2, 4, 7-trinitro-9-fluorenone, plasticized with N-ethylcarbazole. The polymer includes the azo-dye 4-nitro-4'-pentyloxy-azobenzene and we observe both PR and photoisomerization gratings. The gratings are shown to be both polarization-sensitive and reversible. The presence of the photoisomerization gratings (which diffract almost as strongly as the PR gratings) significantly affects the field-dependent diffractive behaviour of the composite. A measurement of the lifetime of the cis state is made (τcis = 38 s) using photoinduced dichroism. This is close to the decay time constant of the local gratings (τdecay = 42 s), and it is suggested that the local grating mechanism is AHB of the azo-dye. This is the first time (to the knowledge of the authors) that a local grating due to AHB has been demonstrated in a PRP.

Influence from the sulfonate group (RSO(3)(-)) on the conversion process and emission efficiency of poly(p-phenylene vinylene)

The discovery of an alternative route to convert poly(xylyliden tetrahydrothiophenium chloride) (PTHT) into poly(p-phenylene vinylene) (PPV) using dodecylbenzenesulfonate (DBS) has allowed the formation of ultrathin films with unprecedented control of architecture and emission properties. In this work, we show that this route may be performed with several sufonated compounds where RSO(3)(-) replaces the counter-ion (Cl(-)) of PTHT, some of which are even more efficient than DBS. Spin-coating films were produced from PTHT and azo-dye molecules, an azo-polymer and organic salts as counter-ions of PTHT. The effects of the thermal annealing step of PTHT/RSO(3)(-) films at 110 and 230 degrees C were monitored by measuring the absorption and emission spectra. The results indicate that the exchange of the counterion Cl(-) of PTHT by a linear long chain with RSO(3)(-) group is a general procedure to obtain PPV polymer at lower conversion temperature (ca. 110 degrees C) with significant increase in the emission efficiency, regardless of the chemical position and the number of sulfonate groups. With the enhanced emission caused by Congo Red and Tinopal as counter-ions, it is demonstrated that the new synthetic route is entirely generic, which may allow accurate control of conversion and emission properties. (C) 2010 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.

Discoloration process modeling by neural network

The photo-oxidation of acid orange 52 dye was performed in the presence of H2O2, utilizing UV light, aiming the discoloration process modeling and the process variable influence characterization. The discoloration process was modeled by the use of feedforward neural network. Each sample was characterized by five independent variables (dye concentration, pH, hydrogen peroxide volume, temperature and time of operation) and a dependent variable (absorbance). The neural model has also provided, through Garson Partition coefficients and the Pertubation method, the independent variable influence order determination. The results indicated that the time of operation was the predominant variable and reaction mean temperature was the lesser influent variable. The neural model obtained presented coefficients of correlation on the order 0.98, for sets of trainability, validation and testing, indicating the power of prediction of the model and its character of generalization. (c) 2007 Elsevier B.V. All rights reserved.

Estudo do equilíbrio e cinética de adsorção de um corante aniônico em quitosana

The phenomenon of adsorption is of fundamental importance for the treatment of textile effluents and removal of dyes. Chitosan is characterized as an excellent adsorbent material, not only for its adsorption capacity but also the low cost production. Equilibrium and kinetic studies were developed in this study to describe the mechanism of adsorption of the anionic azo dye Orange G in chitosan, with the isotherms obtained from the variation of the concentration of dye in the continuous phase. The kinetics of the process was analyzed based on models involving the adsorption of molecules of the dye in nonpolar and polar sites. Adsorption experiments were carried out in water and in saline media with different NaCl concentrations, both for the determination of the equilibrium time as isotherms for making kinetic curves in which the amount of dye adsorbed measured indirectly varied with time. The experiments revealed the opening of the biopolymer structure with increasing concentration of Orange G, accompanied by high pH values and change on the type of interaction between the dye and the adsorbent surface, suggesting behavior advocated by the Langmuir equation in a certain range of concentration of the adsorbate and following the Henry's Law at higher concentrations, from the increased number of sites available for adsorption. The studies conducted showed that the saline medium reduces the chitosan s adsorption capacity according to a certain concentration, the occurrence of the cooperative adsorption process steps kinetic mechanism suggested as a new alternative for the interpretation of the phenomenon

Analysis of aromatic amines in surface waters receiving wastewater from a textile industry by liquid chromatographic with electrochemical detection

A high performance liquid chromatography ( HPLC) method with electrochemical detection (ED) was developed for the determination of benzidine, 3,3-dimethylbenzidine, o-toluidine and 3,3-dichlorobenzidine in the wastewater of the textile industry. The aromatic amines were eluted on a reversed phase column Shimadzu Shimpack C-18 using acetonitrile + ammonium acetate (1 x 10(-4) mol L-1) at a ratio 46: 54 v/v as mobile phase, pumped at a flow rate of 1.0 mL min(-1). The electrochemical oxidation of the aromatic amines exhibits well-defined peaks at a potential range of +0.45 to +0.78 V on a glassy carbon electrode. Optimum working potentials for amperometric detection were from 0.70 V to +1.0 V vs. Ag/AgCl. Analytical curves for all the aromatic amines studied using the best experimental conditions present linear relationship from 1 x 10(-8) mol L-1 to 1.5 x 10(-5) mol L-1, r = 0.99965, n = 15. Detection limits of 4.5 nM (benzidine), 1.94 nM (o-toluidine), 7.69 nM (3,3-dimethylbenzidine), and 5.15 nM (3,3-dichlorobenzidine) were achieved, respectively. The detection limits were around 10 times lower than that verified for HPLC with ultra violet detection. The applicability of the method was demonstrated by the determination of benzidine in wastewater from the textile industry dealing with an azo dye processing plant.

Competition between anchoring and reversible photo-induced alignment of a nematic liquid crystal

We investigated the alignment induced on a nematic liquid crystal (LC) by a photo-aligned polymer film with azo-dye side groups. The orientation of the LC molecules can be manipulated in a reversible manner by irradiating the film with polarized light. We analyzed the competition between the orientation induced by the main chain, through rubbing of the film and that induced by the photo-aligned polymer. Anchoring strength for the different processing conditions are reported. The changes in film morphology caused by rubbing or photo-alignment could be captured by atomic force microscopy. The reversibility of the photo-induced alignment and the competition between the two anchoring mechanisms may allow recording and erasing of information in a LC display.

Bioremediation of direct dyes in simulated textile effluents by a paramorphogenic form of Aspergillus oryzae

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Photoelectrocatalytic degradation of Remazol Brilliant Orange 3R on titanium dioxide thin-film electrodes

Degradation of reactive dye Remazol Brilliant Orange 3R (RBO) has been performed using photoeletrocatalysis. A biased potential is applied across a titanium dioxide thin-film photoelectrode illuminated by UV light. It is suggested that charges photogenerated at the electrode surface give rise to chlorine generation and powerful oxidants (OH) that causes the dye solution to decolorize. Rate constants calculated from color decay versus time reveal a first-order reaction up to 5.0×10-5 mol l-1 in dye concentration. The best experimental conditions were found to be pH 6.0 and 1.0 mol l-1 NaCl when the photoelectrode was biased at +1V (versus SCE). Almost complete mineralization of the dye content (70% TOC reduction) was achieved in a 3-h period using these conditions. Effects of other electrolytes, dye concentration and applied potentials also have been investigated and are discussed. © 2003 Elsevier Science B.V. All rights reserved.