Low Molar Mass Organosiloxane Liquid Crystalline Dyes for Dye Guest Host Ferroelectric Display Devices

In low molar mass organosiloxane liquid-crystal materials the siloxane moieties micro-separate and aggregate in planes that could be regarded as an effective or virtual two-dimensional polymer backbone. We show that if a siloxane moiety is attached to a dichroic dye molecule, the micro-segregation of the siloxane moieties makes it possible to include a high concentration of the guest dye (more than 50%) in a host organosiloxane solution. This effect, combined with the temperature independent tilt angles achievable with ferroelectric organosiloxane liquid crystals, provide an ideal material for high-contrast surface-stabilised ferroelectric display devices. We present dyed ferroelectric materials with a temperature independent tilt angle greater than 42 degrees, a wide (room temperature to over 100°C) mesomorphic temperature range and a response time shorter than 500μs in the dye guest host mode.

Low molar mass organosiloxane liquid crystals for telecommunication applications

Mixtures of two proprietary low molar mass organosiloxane liquid crystals were studied in order to improve their alignment and optimize their electro-optic properties for telecommunication applications. Over a certain concentration range, mixtures exhibited an isotropic-chiral smectic A-chiral smectic C (Iso-SmA*-SmC*) phase sequence leading to exceptionally good alignment. At room temperature, the spontaneous polarization of these samples was reduced from 225 nC cm -2 in the pure SmC* liquid crystal to as low as 75 nC cm -2 in the mixture. Within this concentration range, the ferroelectric tilt angle could be varied between 35° and 15°, while the rise time decreased by 69.4%. The rise times were < 45 μs for moderate electric fields of ± 10 V μm -1 in the SmC* phase and ∼ 4 μs, independent of electric field, in the SmA* phase. At λ = 1550 nm, these mixtures exhibited very large extinction ratios of {\sim} 60 dB for binary switching in the SmC* phase and ∼ 55 dB continuous variable attenuation in the SmA* phase. © 2012 IEEE.

Phototransformation of hematoporphyrin in aqueous solution: Anomalous behavior at low oxygen concentration

The photoactivation of a photosensitizer is the initial step in photodynamic therapy (PDT) where photochemical reactions result in the production of reactive oxygen species and eventually cell death. In addition to oxidizing biomolecules, some of these photochemical reactions lead to photosensitizer degradation at a rate dependent on the oxygen concentration among other factors. We investigated photodegradation of Photogem A (R) (28 mu M), a hematoporphyrin derivative, at different oxygen concentrations (9.4 to 625.0 mu M) in aqueous solution. The degradation was monitored by fluorescence spectroscopy. The degradation rate (M/s) increases as the oxygen concentration increases when the molar ratio of oxygen to PhotogemA (R) is greater than 1. At lower oxygen concentrations (< 25 mu M) an inversion of this behavior was observed. The data do not fit a simple kinetic model of first-order dependence on oxygen concentration. This inversion of the degradation rate at low oxygen concentration has not previously been demonstrated and highlights the relationship between photosensitizer and oxygen concentrations in determining the photobleaching mechanism(s). The findings demonstrate that current models for photobleaching are insufficient to explain completely the effects at low oxygen concentration.

Influência da densidade de carga e da massa molar da poliacrilamida na reologia de sistemas microemulsionados

The knowledge of the rheological behavior of microemulsionated systems (SME) is of fundamental importance due to the diversity of industrial applications of these systems. This dissertation presents the rheological behavior of the microemulsionated system formed by RNX 95/alcohol isopropyl/p-toulen sodium sulfonate/kerosene/distilled water with the addition of polyacrylamide polymer. It was chosen three polymers of the polyacrylamide type, which differ in molar weight and charge density. It was studied the addition of these polymers in relatively small concentration 0,1% in mass and maximum concentration of 2,0%. It was made analysis of flow to determine the appearing viscosities of the SME and rheological parameters applying Bingham, Ostwald de Waale and Herschell-Buckley models. The behavior into saline environment of this system was studied for a solution of KCl 2,0%, replacing the distilled water. It was determined the behavior of microemulsions in relation with the temperature through curves of flow in temperatures of 25 to 60ºC in variations of 5ºC. After the analysis of the results the microemulsion without the addition of polymer presented a slight increase in its viscosity, but it does not mischaracterize it as a Newtonian fluid. However the additive systems when analyzed with low concentration of polymer adjusted well to the applied models, with a very close behavior of microemulsion. The higher concentration of the polymer gave the systems a behavior of plastic fluid. The results of the temperature variation point to an increase of viscosity in the systems that can be related to structural changes in the micelles formed in the own microemulsion without the addition of polymer

Optimisation of the glycerol-to-ornithine molar ratio in the feed medium for the continuous production of clavulanic acid by Streptomyces clavuligerus

Amino acids are well metabolized by Streptomyces clavuligerus during the production of clavulanic acid using glycerol as main carbon and energy source. However, only a few amino acids such as arginine and ornithine are favorable for CA biosynthesis. The aim of this work was to optimize the glycerol:ornithine molar ratio in the feed medium containing only these compounds to maximize CA production in continuous cultivation. A minimum number of experiments were performed by means of a simple two-level full-factorial central composite design to investigate the combined effect of glycerol and ornithine feeding on the CA concentration during the intermittent and continuous process in shake-flasks. Statistical analysis of the experimental data using the response surface methodology showed that a glycerol-to-ornithine molar ratio of approximately 40:1 in the feed medium resulted in the highest CA concentration when fermentation was stopped. Under these optimized conditions, in bench-scale fermentor runs, the CA concentration reached more than double the concentration obtained in shake-flasks runs. (C) 2009 Elsevier B.V. All rights reserved.

Temperature and concentration dependence of heat capacity of model aqueous solutions

Heat capacities of binary aqueous solutions of different concentrations of sucrose, glucose, fructose, citric acid, malic acid, and inorganic salts were measured with a differential scanning calorimeter in the temperature range from 5degreesC to 65degreesC. Heat capacity increased with increasing water content and increasing temperature. At low concentrations, heat capacity approached that of pure water, with a less pronounced effect of temperature, and similar abnormal behavior of pure water with a minimum around 30degreesC-40degreesC. Literature data, when available agreed relatively well with experimental values. A correction factor, based on the assumption of chemical equilibrium between liquid and gas phase in the Differential Scanning Calorimeter, was proposed to correct for the water evaporation due to temperature rise. Experimental data were fitted to predictive models. Excess molar heat capacity was calculated using the Redlich-Kister equation to represent the deviation from the additive ideal model.

Temperature and concentration dependence of density of model liquid foods

Density of binary solutions and combinations of sucrose, glucose, fructose, citric acid, malic acid, pectin, and inorganic salts were measured with an oscillating tube density meter in the temperature range from 10degrees to 60degreesC, at varying concentrations. Density can be predicted with accuracy better than 5 x 10(-5) g cm(-3) using predictive equations obtained by fitting the experimental data. Available literature values agreed well with experimental data. Relations for the excess molar volume of these solutions were derived in terms of mole fraction and temperature. A thermodynamic model for the volumetric analysis of multicomponent aqueous solutions containing electrolyte and non-electrolyte compounds was also proposed. These models can be used for prediction of density of liquid food systems, specially fruit juices and beverages, based on composition and temperature, with high accuracy and without elaborate experimental work.

Concentração, proporção molar e taxa de produção de ácidos graxos voláteis (AGV) no rúmen de bovinos alimentados com diferentes níveis de concentrado na dieta

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Interaction of the nonionic surfactant C12E8 with high molar mass poly(ethylene oxide) studied by dynamic light scattering and fluorescence quenching methods

Dynamic light scattering has been used to investigate ternary aqueous solutions of n-dodecyl octaoxyethylene glycol monoetber (C12E8) with high molar mass poly(ethylene oxide) (PEO). The measurements were made at 20 °C, always below the cloud point temperature (Tc) of the mixed solutions. The relaxation time distributions are bimodal at higher PEO and surfactant concentrations, owing to the preacute of free surfactant micelles, which coexist with the slower component, representing the polymer coil/micellar cluster comptex. As the surfactant concentration is increased, the apparent hydrodynamic radius (RH) of the coil becomes progressively larger. It is suggested that the complex structure consists of clusters of micelles sited within the polymer coil, as previously concluded for the PEO-C12E8-water system. However. C12E8 interacts less strongly than C12E8 with PEO; at low concentrations of surfactant the complex does not contribute significantly to the total scattered intensity. The perturbation of the PEO coil radius with C12E8 is also smaller than that in the C12E8 system. The addition of PEO strongly decreases the clouding temperature of the system, as previously observed for C12E8/PEO mixtures in solution Addition of PEO up to 0.2% to C12E8 (10 wt %) solutions doss not alter the aggregation number (Nagg) of the micelles probably because the surfactant monomers are equally partitioned as bound and unbound micelles. The critical micelle concentration (cmc), obtained from the I1/I3 ratio (a measure of the dependence of the vibronic band intensities on the pyrene probe environment), does not change when PEO is added, suggesting that for neutral polymer/surfactant systems the trends in Nagg and the cmc do not unambiguously reflect the strength of interaction.

Protocolo de modelagem tridimensional do primeiro pré-molar superior para o método dos elementos finitos e análise das concentrações de tensões na região cervical do esmalte

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Bone stress and strain after use of a miniplate for molar protraction and uprighting: a 3-dimensional finite element analysis

The aim of this study was to use the finite element method to evaluate the distribution of stresses and strains on the local bone tissue adjacent to the miniplate used for anchorage of orthodontic forces. Methods: A 3-dimensional model composed of a hemimandible and teeth was constructed using dental computed tomographic images, in which we assembled a miniplate with fixation screws. The uprighting and mesial movements of the mandibular second molar that was anchored with the miniplate were simulated. The miniplate was loaded with horizontal forces of 2, 5, and 15 N. A moment of 11.77 N.mm was also applied. The stress and strain distributions were analyzed, and their correlations with the bone remodeling criteria and miniplate stability were assessed. Results: When orthodontic loads were applied, peak bone strain remained within the range of bone homeostasis (100-1500 mu m strain) with a balance between bone formation and resorption. The maximum deformation was found to be 1035 mu m strain with a force of 5 N. At a force of 15 N, bone resorption was observed in the region of the screws. Conclusions: We observed more stress concentration around the screws than in the cancellous bone. The levels of stress and strain increased when the force was increased but remained within physiologic levels. The anchorage system of miniplate and screws could withstand the orthodontic forces, which did not affect the stability of the miniplate.

Purificação da dextranasacarase de L. mesenteroides FT045B, produção de dextrana de massa molar média controlada, produção de ácido ascórbico α-glicosídeo e do composto bromo-dextrana

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

Variations in Structure Explain the Viscometric Behavior of AOT Microemulsions at Low Water/AOT Molar Ratios

The viscosity of AOT/water/decane water-in-oil microemulsions exhibits a well-known maximum as a function of water/AOT molar ratio, which is usually attributed to increased attractions among nearly spherical droplets. The maximum can be removed by adding salt or by changing the oil to CCl4. Systematic small-angle X-ray scattering (SAXS) measurements have been used to monitor the structure of the microemulsion droplets in the composition regime where the maximum appears. On increasing the droplet concentration, the scattering intensity is found to scale with the inverse of the wavevector, a behavior which is consistent with cylindrical structures. The inverse wavevector scaling is not observed when the molar ratio is changed, moving the system away from the value corresponding to the viscosity maximum. It is also not present in the scattering from systems containing enough added salt to essentially eliminate the viscosity maximum. An asymptotic analysis of the SAXS data, complemented by some quantitative modeling, is consistent with cylindrical growth of droplets as their concentration is increased. Such elongated structures are familiar from related AOT systems in which the sodium counterion has been exchanged for a divalent one. However, the results of this study suggest that the formation of non-spherical aggregates at low molar ratios is an intrinsic property of AOT.

Cloride and bromide concentrations and Br-/Cl- molar ratios in pore fluids at ODP Site 134-833

Other than halite diagenesis and organic matter degradation, Cl- and Br- are considered to be conservative in marine pore fluids. Consequently, Br-/Cl- ratios should remain constant during most diagenetic reactions. Nonetheless, Br-/Cl- molar ratios decrease to 0.00127 (~18% less than seawater value) in pore fluids from Site 833 in the Aoba Basin of the New Hebrides convergent margin despite the lack of halite diagenesis and little organic matter. Sediment at this site is largely volcanic ash, which becomes hydrated with depth as it converts to clay and zeolite minerals. These hydration reactions remove sufficient water to increase the concentrations of most solutes including Cl- and Br-. The resulting concentration gradients drive diffusion, but calculations indicate that diffusion does not decrease the Br-/Cl- ratio. Some Cl- may be leached from the ash, but insufficient amounts are available to cause the observed decrease in Br-/Cl- ratio. The limited source of Cl- suggests that proportionately more Br- than Cl- is lost from the fluids to the diagenetic solids. Similar nonconservative behavior of Cl- and Br- may occur during fluid circulation at ridge crests and flanks, thereby influencing the halide distribution in the crust.

Sediment geochemistry and water trace metal concentration in Potter Cove

Recent rapid climate warming at the western Antarctic Peninsula (WAP) results in elevated glacial melting, enhanced sedimentary run-off, increased turbidity and impact of ice-scouring in shallow coastal areas. Discharge of mineral suspension from volcanic bedrock ablation and chronic physical disturbance is expected to influence sessile filter feeders such as the Antarctic soft shell clam Laternula elliptica ( King and Broderip, 1832). We investigated effects of sedimentary run-off on the accumulation of trace metals, and together with physical disturbance, the cumulative effect on oxidative stress parameters in younger and older L. elliptica from two stations in Potter Cove (King George Island, Antarctica) which are distinctly impacted by turbidity and ice-scouring. Fe, Mn, Sr, V and Zn concentrations were slightly higher in sediments of the station receiving more sediment run-off, but not enriched in bivalves of this station. The only element that increased in bivalves experimentally exposed to sediment suspension for 28 days was Mn. Concentration of the waste accumulation biomarker lipofuscin in nervous tissue was higher in L. elliptica from the "exposed" compared to the "less exposed" site, whereas protein carbonyl levels in bivalve mantle tissue were higher at the less sediment impacted site. Tissue metal content and lipofuscin in nervous tissue were generally higher in older compared to younger individuals from both field stations. We conclude that elevated sediment ablation does not per se result in higher metal accumulation in L. elliptica. Instead of direct absorbance from sediment particles, metal accumulation in gills seems to indicate uptake of compounds dissolved in the water column, whereas metals in digestive gland appear to originate from enriched planktonic or detritic food. Accumulation of cellular waste products and potentially reactive metals over lifetime presumably alters L. elliptica physiological performance with age and may contribute to higher stress susceptibility in older animals.