Development, optimization and validation of gas chromatographic fingerprinting of Brazilian commercial gasoline for quality control

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Gotas suspensas: uma proposta para amostragem e análise de gases traços da atmosfera

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

Organic acid profile of commercial sour cassava starch

A presença de ácidos orgânicos no polvilho azedo, além de contribuir com aspectos como sabor e aroma, tem, conforme a literatura indica, correlação com a propriedade de expansão, que é um fator determinante no uso alimentício. Amostras de polvilho azedo foram coletadas nas Regiões Sul e Sudeste diretamente nas empresas ou no comércio. Foram preparadas para análise em cromatografia líquida de alta eficiência (CLAE), sendo que o cromatógrafo estava equipado com coluna Biorad Aminex HPX-87H para análise de ácidos orgânicos e detector refratométrico. As condições de análise envolveram o emprego da fase móvel ácido sulfúrico 0,005M, fluxo de 0,6 ml/min e temperatura da coluna de 60oC. Os ácidos quantificados foram lático (0,036 a 0,813 g/100g), acético (0 a 0,068 g/100g), propiônico (0 a 0,013 g/100g) e butírico (0 a 0,057 g/100g), presentes na fermentação natural. Os resultados revelaram grande variação entre as amostras, com diferenças mesmo dentro das Regiões. Algumas amostras apresentaram quantidades elevadas de ácidos, especialmente do ácido lático, mas nestas amostras os ácidos propiônico e butírico não foram detectados. A ausência do ácido butírico não era esperada, uma vez que esse ácido está diretamente relacionado com o aroma característico do polvilho azedo. O fato pode sugerir que a obtenção de algumas das amostras estudadas pode ter ocorrido sem o processo fermentativo natural.

Synthesis and sintering of PZT ceramics

Lead zirconate powder, with Zr/Ti ratio of 50/50 was prepared by polymeric precursor method and doped with 3, 5 and 7 mol% of Sr+2 Or Ba+2, as well as by 0.2 to 5 mol% of Nb+5. The powder was calcined at 750 degrees C by 4 hours and milled during 1.5 h in isopropilic alcohol. Powders were characterized by surface area measurements (BET method), by infrared spectroscopy and by X-ray diffraction to characterize the crystal structure. Isostatically pressed samples were sintered in a dilatometer furnace by using a constant heating rate of 10 degrees C/min from ambient to 1200 degrees C. Synthetic air and air with water vapor were used as atmospheres. Both Sr+2 and Ba+2 substitute Pb+2 and favor the formation of rhombohedral phase. Otherwise, Nb+5 substitute preferentially Zr+4 favoring tetragonal phase. The concentration of dopants and the atmosphere influence the densification and the microstructure of the PZT, which alters the dielectric and piezoelectric properties of the ceramics.

Colorimetric determination of formaldehyde in air using a hanging drop of chromotropic acid

A simple and sensitive method to determine parts per billion (ppb) of atmospheric formaldehyde in situ, using chromotropic acid, is described. A colorimetric sensor, coupled to a droplet of 15.5 muL chromotropic acid, was constructed and used to sample and quantify formaldehyde. The sensor was set up with two optical fibers, a right emitting diode (LED) and two photodiodes. The reference and transmitted light were measured by a photodetection arrangement that converts the signals into units of absorbance. Air was sampled around the chromotropic acid droplet. A purple product was formed and measured after the sampling terminated (typically 7 min). The response is proportional to the sampling period, analyte concentration and sample flow rate. The detection limit is similar to2 ppb and can be improved by using longer sampling times and/or a sampling flow rate higher than that used in this work, 200 mL min(-1). The present technique affords a simple, inexpensive near real-time measurement with very little reagent consumption. The method is selective and highly sensitive. This sensor could be used either for outdoor or indoor atmospheres.

Supercritical fluid extraction from fennel (Foeniculum vulgare): global yield, composition and kinetic data

Supercritical fluid extraction (SFE) from solids has proven to be technically feasible for almost any system; nonetheless, its economical viability has been proven for a restricted number of systems. A common practice is to compare the cost of manufacturing of vegetable extracts by a variety of techniques without deeply considering the huge differences in composition and functional properties among the various types of extracts obtained; under this circumstance, the cost of manufacturing do not favor SFE. Additionally, the influence of external parameters such as the agronomic conditions and the SFE system geometry are not considered. In the present work, these factors were studied for the system fennel seeds + CO2. The effects of the harvesting season and the degree of maturation on the global yields for the system fennel seeds + CO2 were analyzed at 300 bar and 40 degrees C. The effects of the pressure on the global yields were determined for the temperatures of 30 and 40 degrees C. Kinetics experiments were done for various ratios of bed height to bed diameter. Fennel extracts were also obtained by hydrodistillation and low-pressure solvent extraction. The chemical composition of the fennel extracts were determined by gas chromatography. The SFE maximum global yield (12.5%, dry basis) was obtained with dry harvested fennel seeds. Anethole and fenchone were the major constituents of the extract; the following fat acids palmitic (C16H32O2), palmitoleic stearic (C18H36O2), oleic (C18H34O2), linoleic (C18H32O2) and linolenic (C18H30O2) were also detected in the extracts. A relation between amounts of feed and solvent, bed height and diameter, and solvent flow rate was proposed. The models of Sovova, Goto et al. and Tan and Lion were capable of describing the mass transfer kinetics. (c) 2005 Elsevier B.V. All rights reserved.

Production of low methoxyl pectin using immobilized pectin methylesterase silica from acerola (Malpighia glabra L.)

The aim of this work was to develop an efficient reactor for the production of low methoxyl pectin, using pectinmethylesterase (PME, EC 3.1.1.11) from acerola immobilized on silica. The immobilized enzyme was used in up to 50 successive bioconversion runs at 50 degrees C with an efficiency loss of less than 20%. The fixed-bed reactor (6.0 x 1.5 cm) was prepared using PME immobilized in glutaraldehyde-activated silica operated at 50 degrees C with an optimum flow rate of 10 mL h(-1). The bioconversion yield was shown to strongly depend on the nature of the enzymatic preparation. An efficiency of 44% was achieved when concentrated PME was used, compared with only 30% with purified PME, both after an 8-h run. The process described could provide the basis for the development of a commercial-scale process. (c) 2006 Society of Chemical Industry.

Comparison of metallic and ceramic tubes as atomization cells for tin determination by TS-FF-AAS

This work describes the development of an analytical procedure for on-line tin determination using thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS). Two tubes were evaluated as atomization cells: a metallic tube (Ni-Cr, principal components composition: 73.95% Ni and 16.05% Cr) and a ceramic tube (99.8% Al2O3). The use of air as the carrier was made by employing a Rheodyne valve to inject the samples, allowing an analytical frequency of 90 h(-1) and avoiding sample dispersion. The carrier flow rate (air), sample volume injected, and acid concentration (HCl) were evaluated for the optimization of the TS-FF-AAS system. The sensitivity for 50 mL of analytical solution with TS-FF-AAS was 2 and 5 times higher (to metallic and ceramic tube, respectively) than using an acetylene-nitrous oxide flame with pneumatic aspiration (requiring a sample volume of approximately 20 times higher.

Use of sugar cane bagasse as solid phase extractor for cadmium determination by FAAS

The present paper describes the use of sugar cane bagasse as solid phase extractor for cadmium determination after complexation of the analyte with ammonium diethyldithiophosphate (ADDP) and sorption of the Cd-DDP complexes on the solid support. The concomitants were separated using a flow injection analysis (FIA) system coupled to flame atomic absorption spectrometry (FAAS) for determination. The main parameters such as ADDP concentration, acid medium, flow rate, reaction coil length, and reaction time were investigated.The results obtained with HNO3 showed good accuracy and precision. The enhancement factor was 20.5 times for a 120-second preconcentration time, and the analytical frequency was 25 determinations per hour. The calibration curve was linear over the concentration range of 1-40 mu g L-1 Cd with a LOD of 0.697 mu g L-1 Cd and a relative standard deviation of 0.96% after 12 successive measurements of 30 mu g L-1 Cd.The proposed method was evaluated for the FIA-FAAS analysis of certified reference materials (tomato leaves, spinach leaves, and bovine liver) and Cd-spiked foods (shrimp, sardine, tuna, chicken liver and bovine liver). Good recoveries (80.0-97.1%) for the Cd-spiked samples and certified reference materials were obtained. The results of bagasse-packed minicolumns were compared with Si-C,8 packed minicolumns. The F-test was applied between Si-C-18/Bagasse minicolumns, Si-C-18/certified values, and bagasse/certified values. It was found that the results were in agreement with the certified values at a 95% confidence level.

Sintering of ZnO doped SnO2

Dense SnO2 ceramics were obtained by doping with ZnO concentrations varies from 0.5 to 5.0 mel. The obtained powder was isostaticaly pressed to 210MPa in cylindrical shape and sintered from ambient to 1.500 degrees C using constant heating rate of 10 degrees C/min. Densities above 97% were obtained depending on the ZnO doping concentration. A maximum density was reached with the addition of 2 mol%. It can be concluded from shrinkage data and the observed microstructure obtained by SEM that the solid solution limit for ZnO in SnO2 is about 1.0 mol%. Above this concentration the formation of a second ceramic phase is observed.

Measurements of ambient ozone using indigo blue-coated filters

Ozone monitoring techniques utilize expensive instruments that are often large and heavy. These instruments are not easy to handle in the field, and their size also limits some sampling schemes, principally for indoor ozone determination. We have developed a lightweight, inexpensive, and sensitive method that offers flexibility to undertake measurements of ambient ozone in many environments, both indoor and outdoor. The method is based on the reaction of ozone with indigo blue dye. The indigo molecule contains 1 carbon double bond (C = C) that reacts with ozone and results in nearly colorless reaction products. During sample collection, 2 cellulose filters coated with 40 mu L of 1.0 x 10(-3) M indigo blue were used. The determinations were done spectrophotometrically at 250 and 600 nm. The analytical parameters studied were sampling time and flow rate. Analytical curves were constructed with concentrations ranging from 37 to 123 parts per billion by volume (ppbv) of standard ozone, at 0.4 L/min and 15 min sampling time. The detection limits achieved were 6 and 9 ppbv, respectively, at 250 and 600 nm. Considering interferences, measurements made at 250 nm gave more reliable and specific values for ozone.

Modeling and simulation of cephalosporin C production in a fed-batch tower-type bioreactor

Immobilized cell utilization in tower-type bioreactor is one of the main alternatives being studied to improve the industrial bioprocess. Other alternatives for the production of beta -lactam antibiotics, such as a cephalosporin C fed-batch p recess in an aerated stirred-tank bioreactor with free cells of Cepha-losporium acremonium or a tower-type bioreactor with immobilized cells of this fungus, have proven to be more efficient than the batch profess. In the fed-batch process, it is possible to minimize the catabolite repression exerted by the rapidly utilization of carbon sources (such as glucose) in the synthesis of antibiotics by utilizing a suitable flow rate of supplementary medium. In this study, several runs for cephalosporin C production, each lasting 200 h, were conducted in a fed-batch tower-type bioreactor using different hydrolyzed sucrose concentrations, For this study's model, modifications were introduced to take into account the influence of supplementary medium flow rate. The balance equations considered the effect of oxygen limitation inside the bioparticles. In the Monod-type rate equations, eel concentrations, substrate concentrations, and dissolved oxygen were included as reactants affecting the bioreaction rate. The set of differential equations was solved by the numerical method, and the values of the parameters were estimated by the classic nonlinear regression method following Marquardt's procedure with a 95% confidence interval. The simulation results showed that the proposed model fit well with the experimental data,and based on the experimental data and the mathematical model an optimal mass flow rate to maximize the bioprocess productivity could be proposed.

Dielectric spectroscopy on Bi3Zn2Sb3O14 ceramic: an approach based on the complex impedance

The dielectric properties and loss of Bi1.5ZnSb1.5O7 a poor-semiconducting ceramic were investigated by impedance spectroscopy, in the frequency range from 5 Hz to 13 MHz. Electric measurements were performed from 100 to 700 degreesC. Pyrochlore type phase was synthesized by the polymeric precursor method. Dense ceramic with 97% of the theoretical density was prepared by sintering via constant heating rate. The dielectric permittivity dependence as a function of frequency and temperature showed a strong dispersion at frequency lower than 10 kHz. The losses (tan delta) exhibit slight dependence with the frequency at low temperatures presenting a strong increase at temperatures higher than 400 degreesC. A decrease of the loss magnitude occurs with increasing frequency. Relaxation times were extracted using the dielectric functions Z(omega) and M(omega). The plots of the relaxation times tau(Z'), and tau(M) as a function of temperature follow the Arrhenius law, where a single slope is observed with activation energy values equal to 1.38 and 1.37 eV, respectively. (C) 2003 Elsevier Ltd. All rights reserved.

Uroflow studies in children: Correlation with age, weight and body surface area.

Peak flow rate data (Q(max)) are important for diagnosis of lower urinary tract obstruction. However, the lack of uroflowmetry studies in children, makes their interpretation difficult. With this aim, we studied 167 boys classified in four groups according to their age (G1 : n = 48, 6-7 years; G2 : n = 43, 8-9 years; G3 : n = 37, 10-11 years; G4: n = 39, 12-14 years). We studied in all children, weight, height, body surface area, peak flow rate (Q(max) and the correspondant urinary volume (Vol). Means and standard deviations of Q(max) (ml/sec) were : 15 +/- 5 (G1), 15 +/- 5 (G2), 17 +/- 5 (G3) and 22 +/- 7 (G4) respectively. Corresponding urinary volumes (Vol) (mean standard deviation - in ml) were : G1 = 123 +/- 75; G2 = 122 +/- 79; G3 = 158 +/- 96 and G4 = 162 +/- 101. We found a significant correlation (p < 0,01) between Q(max) and Vol in groups G2, G3 and G4; and between Q(max) and height in groups G1 and G4.The authors demonstrated a positive correlation between maximum flow and voided volume, and an increase of Q(max) with age.

EFFECT OF ASCORBIC-ACID DEFICIENCY ON THE GROWTH, GILL FILAMENT LESIONS AND BEHAVIOR OF PACU FRY (PIARACTUS-MESOPOTAMICUS HOLMBERG, 1887)

The effect of ascorbic acid deficiency was determined in Piaractus mesopotamicus Holmberg, 1887, fish (pacu) under laboratory conditions. A total of 120 fish with an average body weight of 8.64 +/- 1.62 g and measuring 6.15 +/- 0.33 cm in length at the beginning of the experiment were fed diets containing 0, 50, 100 or 200 mg palmitate-coated ascorbic acid/kg dry ration for a period of 24 weeks with measurements every 4 weeks. The experiment was conducted in 20 fiber-cement aquaria of 81-liter capacity. Each aquarium was supplied with dechlorinated water at a flow rate of 1 l/min. Water temperature was measured daily and pH, dissolved oxygen, alkalinity and water conductivity were determined weekly. A fully randomized experimental design was utilized, with 5 replicates of each treatment and 6 fish per aquarium. Ascorbic acid-supplemented fish presented significantly increased growth when compared to unsupplemented fish. Furthermore, unsupplemented fish presented a higher incidence of hyperplasia, hypertrophy and dysplasia of the bone cartilage of gill filaments. The gill lamellae of unsupplemented fish had twisted cartilage and an inflammatory infiltrate at the ends. Anorexia and increased handling stress were also observed in fish fed the unsupplemented diet. The present study suggests that 50 mg ascorbic acid/kg dry ration is sufficient to improve development of pacu fingerlings but the optimum level under aquarium conditions, determined by regression analysis, is 139 mg ascorbic acid/kg dry ration.