Plasma enhanced chemical vapor deposition of titanium(IV) ethoxide-oxygen-helium mixtures

Thin films were deposited by plasma enhanced chemical vapor deposition from titanium (IV) ethoxide (TEOT)-oxygen-helium mixtures. Actinometric optical emission spectroscopy was used to obtain the relative plasma concentrations of the species H, CH, O and CO as a function of the percentage of oxygen in the feed, R(ox). The concentrations of these species rise with increasing R(ox) and tend to fall for R(ox) greater than about 45%. As revealed by a strong decline in the emission intensity of the actinometer Ar as R(ox) was increased, the electron mean energy or density (or both) decreased as greater proportions of oxygen were fed to the chamber. This must tend to reduce gas-phase fragmentation of the monomer by plasma electrons. As the TEOT flow rate was fixed, however, and since the species H and CH do not contain oxygen, the rise in their plasma concentrations with increasing R(ox) is explained only by intermediate reactions involving oxygen or oxygen-containing species. Transmission infrared (IRS) and X-ray photoelectron (XPS) spectroscopies were employed to investigate film structure and composition. The presence of CH(2), CH(3), C=C, C-O and C=O groups was revealed by IRS. In addition, the presence of C-O and C=O groups was confirmed by XPS, which also revealed titanium in the +4 valence state. The Ti content of the films, however, was found to be much less than that of the monomer material itself. (C) 2007 Elsevier B.V. All rights reserved.

Robust Bayesian analysis of heavy-tailed stochastic volatility models using scale mixtures of normal distributions

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

Evaluation of in vitro gas production of roughages and their mixtures using the curves subtraction method

The in vitro gas production of four single roughages and their paired combinations (1:1 on dry matter basis) were evaluated. Two roughage samples (100 mg) per treatment were fermented with ruminal fluid during a 48 h incubation period. Total 48 h gas volumes of fermentation dry matter (DM), neutral detergent fiber (NDF) and soluble compounds in neutral detergent (NDS) were for sugarcane = 16.8, 11.2, 6.9 mL; sugarcane + corn silage = 20.1, 12.6, 9.1 mL; sugarcane + 60-day elephantgrass = 16.5, 17.6 mL; sugarcane + 180-day elephantgrass = 13.8, 8.2, 5.9 mL; corn silage = 18.8, 16.8, 4.7 mL; corn silage + 60-day elephantgrass = 16.3, 15.4, 2.4 mL; corn silage + 180-day elephantgrass = 16.1, 11.8, 4.2 mL; 60-day elephantgrass = 16.9, 19.0 mL and 180-day elephantgrass = fermented 10.7, 12.2 mL, respectively. The NDS gas production was not possible to estimate for sugarcane + 60-day elephantgrass, 60-day elephantgrass and 180-day elephantgrass. The present data shows that the curves subtraction method can be an option to evaluate the contribution of the soluble fractions in roughages to digestion kinetics. However, this method underestimates the NDS gas contribution when roughages are low in crude protein and soluble carbohydrates. It is advisable to directly apply the two-compartmental mathematical model to the digestion curves for roughage DM, when determining the NDS gas volume and the digestion rate. This method is more straightforward and accurate when compared to the curve subtraction method. Non-structural carbohydrates combined with fiber and protein promoted a positive associative effect in sugarcane + corn silage (50:50) mixture. Therefore, it can be concluded that the soluble fraction of roughages greatly contributes to gas production. (C) 2004 Elsevier B.V. All rights reserved.

Flammability limits: A review with emphasis on ethanol for aeronautical applications and description of the experimental procedure

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

Controlled fluorination of a-C:F:H films by PECVD of ethylene-hexafluorobenzene mixtures

Highly fluorinated plasma polymers are chemically inert,acid resistant and have low friction coefficients, thereby being useful in chemical laboratories and for tribological applications. Here we report the plasma polymerization of ethylene-hexafluorobenzene mixtures by PECVD. The principal parameter of interest is the proportion of C(6)F(6) in the feed, R(F). Films were analyzed using near-normal and grazing-angle Infrared Reflection Absorption Spectroscopy (IRRAS), the latter being particularly useful for detecting modes not usually observed at near-normal incidence. The presence of CH and CF(x) (x=1 to 2) groups was thus confirmed in films deposited with R(F)>= 40%. Depending on R(F) IRRAS also revealed the presence of -CH(x) (x=1 to 3) -C=C, -C=O and phenyl rings. Deconvolution of C is spectra obtained by X-ray Photoelectron Spectroscopy (XPS) confirmed the presence of CH, CF and CF(2) groups in films deposited with R(F)>= 40%. Atomic ratios of F:C calculated from the XPS spectral data show that the degree of fluorination rises with increasing RF Some unbound fluorine is present in the films. Post-deposition reactions account for the presence of oxygen (similar to 5%) in the films. Surface energies, determined from contact angle measurements, fall with increasing R(F). (C) 2008 Elsevier B.V. All rights reserved.

Investigation on the structure of liquid N-methylformamide-dimethylsulfoxide mixtures

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

2006 GEP-ISFG collaborative exercise on mtDNA: reflections about interpretation, artefacts, and DNA mixtures

We report the results of the seventh edition of the GEP-ISFG mitochondrial DNA (mtDNA) collaborative exercise. The samples submitted to the participant laboratories were blood stains from a maternity case and Simulated forensic samples, including a case of mixture. The success rate for the blood stains was moderate (similar to 77%); even though four inexperienced laboratories concentrated about one-third of the total errors. A similar success was obtained for the analysis of mixed samples (78.8% for a hair-saliva mixture and 69.2% for a saliva-saliva Mixture). Two laboratories also dissected the haplotypes contributing to the saliva-saliva mixture. Most of the errors were due to reading problems and misinterpretation of electropherograms, demonstrating once more that the lack of a solid devised experimental approach is the main cause of error in mtDNA testing. (C) 2007 Elsevier B.V. All rights reserved.

Thermodynamic properties of liquid mixtures. II. Dimethylformamide-water

The excess enthalpy of mixing of DMF-water was measured at 25° C in the 0-1 molar fraction range. The maximum of heat is developed for a 0.33 DMF molar fraction. The excess partial molar and other excess quantities were also calculated for the DMF-water system at 25° C. The results suggest a strong interaction between DMF and water. © 1983.

NOISE GENERATED BY CAVITATION IN ORIFICE-PLATES WITH SOME GASEOUS EFFECTS.

An experimental investigation of the noise generated by cavitation in turbulent shear flows produced by confined sharp-edge orifice-plates is reported. The acoustic source strength of cavitation was determined by means of reciprocity type measurements. Experimentally determined scaling parameters are applied to a model to prototype scaling formula derived from dimensional analysis. The proposed formula is checked experimentally. Comparative photographic observations of the cavitation patterns for two different values of gas content are presented. The observed sound reduction, that occurs when supersaturated conditions exist downstream the orifice-plates, is explained by the effects of gas diffusion into the cavitation bubbles, and by simple acoustic attenuation.

Thermodynamic properties of liquid mixtures. III. Acetone-water

The excess enthalpy of mixing of acetone-water was measured at 25°C in the 0-1 molar fraction range. The minimum and the maximum in the H E (X 2) curve occurred at X 2 = 0.18 and X 2 = 0.85, respectively. The excess partial molar and other excess quantities were also calculated for the acetone-water system at 25°C. The results are interpreted in view of the influence of acetone on the structure of water. © 1983.

Ethanol tolerance of thermotolerant yeasts cultivated on mixtures of sucrose and ethanol

The final levels of ethanol (levels of ethanol produced plus that added initially to the media) reached by the thermotolerant yeasts were highest (16.5-20.3%, v/v) at 8% initial ethanol. The thermotolerant yeasts were found to have the following characteristics: constant levels of ethanol formation (10.5-12.3%, v/v), fog additions of external ethanol within the range 2-8% (v/v) of initial ethanol; constant values of product coefficients when initial ethanol was in the range of 2-6%, which increased or decreased, depending on the strain, when initial ethanol exceeded 6%; growth activity was inhibited at different levels of addition of external ethanol when final biomass and specific rate of growth were compared; significant differences among the yeast strains in the amount of external ethanol capable of reducing biomass formation by one half. In addition, the viability of the strains (early stationary phase) varied with the amount of external ethanol, the lowest viabilities occurring at concentrations of initial ethanol ranging from 4 to 7% and the highest in the range of 7 to 8% (v/v). The relative levels of trehalose (with/without 7% ethanol added initially) in the yeast strains (the stationary phase) ranged from 1.03 to 1.75, suggesting that the effect of produced ethanol on trehalose accumulation was stronger than that of external ethanol. The levels of final ethanol shown by the yeast strains were also correlated with the cellular levels of glycerol-3-phosphate dehydrogenase (increase in enzyme levels with decrease in final ethanol) for cells harvested at the stationary phase.

Interfacial concentrations of chloride and bromide and selectivity for ion exchange in vesicles prepared with dioctadecyldimethylammonium halides, lipids, and their mixtures

The local concentrations of chloride, Cl b, and bromide, Br b, in the interface of vesicles prepared with dioctadecyldimethylammonium chloride, DODAC, or bromide, DODAB, dipalmitoylphosphatidylcholine, DPPC, dimyristoylphosphatidylcholine, DMPC, and mixtures of DMPC, DPPC, and DODAC were determined by chemical trapping by analyzing product yields from spontaneous dediazoniation of vesicle-bound 2,6-dimethyl-4-hexadecylbenzenediazonium ion. The values of Cl b and Br b in DODAC and DODAB vesicles increase with vesicle size, in agreement with previous data showing that counterion dissociation decreases with vesicle size. Addition of tetramethylammonium chloride displaces bromide from the DODAB vesicular interface. The value for the selectivity constant for Br/Cl exchange at the DODAB vesicular interface obtained by chemical trapping was ∼2.0, well within values obtained for comparable amphiphiles. In vesicles of DPPC the values of Cl b were very sensitive to the nature of the cation and decreased in the order Ca 2+ > Mg 2+ > Li + > Na + > K + = Cs + = Rb + ≥ +. The effect of the cation becomes more important as temperature increases above the phase transition temperature, T m, of the lipid. The values of Cl b increased sigmoidally with the mol % of DODAC in vesicles prepared with DODAC/lipid mixtures. In sonicated vesicles prepared with DODAC and DMPC (or DPPC), the values of Cl b reach local concentrations measured for the pure amphiphile at 80 mol % DODAC. These results represent the first extensive study of local concentration of ions determined directly by chemical trapping in vesicles prepared with lipids, synthetic ampliiphiles, and their mixtures.

Evaluation of the mixtures ammonium phosphate/magnesium nitrate and palladium nitrate/magnesium nitrate as modifiers for simultaneous determination of Cd, Cr, Ni and Pb in mineral water by GFAAS

A method is described for the simultaneous determination of Cd, Cr, Ni and Pb in mineral water samples by graphite furnace atomic absorption spectrometry with a transversely heated graphite atomizer (THGA) and a longitudinal Zeeman-effect background correction system. The electrothermal behavior of analytes during pyrolysis and atomization steps was studied without modifier, in presence of 5 μg Pd and 3 μg Mg(NO3)2 and in presence of 50 μg NH4H2PO4 and 3 μg Mg(NO3)2. A volume of 20 μL of a 0.028 mol L -1 HNO3 solution containing 50 μg L-1 Ni and Pb, 10 μg L-1 Cr and 5 μg L-1 Cd was dispensed into the graphite tube at 20°C. The mixture palladium/magnesium was selected as the optimum modifier. The pyrolysis and atomization temperatures were fixed at 1000°C and 2300°C, respectively. The characteristic masses were calculated as 2.2 pg Cd, 10 pg Cr, 42 pg Ni and 66 pg Pb and the lifetime of the graphite tube was around 600 firings. Limits of detection based on integrated absorbance were 0.02 μg L-1Cd, 0.94 μg L-1 Cr, 0.45 μg L-1 Ni and 0.75 μg L-1 Pb, which exceeded the requirements of Brazilian Food Regulation that establish the maximum permissible level for Cd, Cr, Ni and Pb at 3 μg L-1, 50 μg L-1, 20 μg L-1 and 10 μg L-1, respectively. The recoveries of Cd, Cr, Ni and Pb added to mineral water samples varied within the 93-108%, 96-104%, 87-101% and 98-108% ranges, respectively. Results of analysis of standard reference materials (National Institute of Standards and Technology: 1640-Trace Elements in Natural Water; 1643d-Trace Elements in Water) were in agreement with certified values at the 95% confidence level.

Gaseous neurotransmitters and their role in anapyrexia

Mammals keep their body temperature (Tb) relatively constant even under a wide range of ambient temperature variation. However, in some particular situations it may be beneficial to increase or to decrease Tb. For instance, under hypoxic conditions, a regulated drop in Tb (anapyrexia) takes place which has been reported to be crucial for survival in a number of different species. This review highlights major advances in the research about nitric oxide (NO) and carbon monoxide (CO-where data are relatively less abundant), before focusing on the role played by these gaseous neuromediators in thermoregulation, under the conditions of euthermia and anapyrexia. Available data are consistent with the notion that both NO and CO, acting on the CNS, participate in thermoregulation, with NO decreasing Tb and CO increasing it. However further studies are required before definitive conclusions can be made as to their physiological mechanisms of action.

Effect of drying technique on some physical properties of cross-linked high amylose/pectin mixtures

Polymers mixtures as well as cross-linking reactions are approaches that have been used successfully to modulate the polymers characteristics in order to improve the control over drug release rate. High amylose and pectin are polysaccharides frequently used to prepare drug delivery systems. Since the drying technique can strongly influence the properties of such systems, the aim of this work was to characterize high amylose/pectin mixtures cross-linked with sodium trimetaphosphate and dried by different techniques-oven and lyophilization. The results showed that samples dried by lyophilization presented reduced particle size, higher porosity and higher swelling ability than the samples dried in oven. Besides, lower thermal stability and different diffraction patterns showed by the former particles should reflect the structural changes as a function of drying technique. © 2013 Informa Healthcare USA, Inc.