Tungsten permanent chemical modifier with co-injection of Pd(NO3)(2)+Mg(NO3)(2) for direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry

A tungsten carbide coating on the integrated platform of a transversely heated graphite atomizer (THGA((R))) used together with Pd(NO3)(2) + Mg(NO3)(2) as modifier is proposed for the direct determination of lead in vinegar by graphite furnace atomic absorption spectrometry. The optimized heating program (temperature, ramp time, hold time) of atomizer involved drying stage (110 degrees C, 5 s, 30 s; 130 degrees C, 5 s, 30 s), pyrolysis stage (1000 degrees C, 15 s, 30 s), atomization stage (1800 degrees C, 0 s, 5 s) and clean-out stage (2450 degrees C, I s, 3 s). For 10 mu L of vinegar delivered into the atomizer and calibration using working standard solutions (2.5-20.0 mu g L-1 Pb) in 0.2% (v/v) HNO3, analytical curve with good linear correlation (r = 0.9992) was established. The characteristic mass was 40 pg Pb and the lifetime of the tube was around 730 firings. The limit of detection (LOD) was 0.4 mu g L-1 and the relative standard deviations (n = 12) were typically <8% for a sample containing 25 pg L-1 Pb. Accuracy of the proposed method was checked after direct analysis of 23 vinegar samples. A paired t-test showed that results were in agreement at 95% confidence level with those obtained for acid-digested vinegar samples. The Pb levels varied from 2.8 to 32.4 pg L-1. Accuracy was also checked by means of addition/recovery tests and recovered values varied from 90% to 110%. Additionally, two certified reference materials were analyzed and results were in agreement with certified values at a 95% confidence level. (C) 2006 Elsevier Ltd. All rights reserved.

Temperature dependence of photoinduced birefringence in polystyrene doped with Disperse Red-1

A theoretical model on the basis of the free-volume concept is presented explaining the temperature dependence of photoinduced birefringence in polystyrene films that contain Disperse Red-1. Birefringence increases with temperature up to 180 K as the free volume for isomerization increases, and then decreases as thermally activated processes dominate. The fast process of birefringence decay has a time constant that increases with temperature at low temperatures, due to the change kin photoisomerization.

Physiological and genomic variations in rice cells recovered from direct immersion and storage in liquid nitrogen

The use of cryoprotectants and slow cooling rates are routine procedures for the cryopreservation of plant cell lines. However, our results with rice (Oryza sativa L,, ev. Taipei 309) show that calli can be cryopreserved by direct immersion and stored in liquid nitrogen without any cryoprotection, the efficiency of recovery using this method, as well as a conventional method was generally increased with a previous abscisic acid (ABA) treatment. Following cryopreservation, calli demonstrated some differences with respect to unfrozen calli of the same lines, Thus, resistance to freezing stress (- 20 degrees C for 2 h) increased significantly in all lines tested, irrespective of their pre-incubation with ABA, Calli that had been directly stored in liquid nitrogen also demonstrated a higher competence for genetic transformation than their unfrozen counterparts, as indicated by the transient gene expression levels obtained after particle bombardment, These differences might lead to further biotechnological applications, A genetic analysis of amplified DNA polymorphisms was performed with three independent lines that had been subjected to four combinations of ABA treatment and direct immersion in liquid nitrogen, At the loci screened with the randomly amplified polymorphic DNA (RAPD) markers tested, the genetic variations among lines and among calli of the same line appear to bd more related to tissue-culture-induced somaclonal variation than to cryoselection.

Mechanisms behind blue, green, and red photoluminescence emissions in CaWO4 and CaMoO4 powders

A combined experimental and theoretical study was conducted to analyze the photoluminescence (PL) properties of ordered and disordered CaWO4 (CW) and CaMoO4 (CM) powders. Two mechanisms were found to be responsible for photoluminescence emission in CW and CM powders. The first one, in the disordered powders, was caused by oxygen complex vacancies [MO3 center dot V-O(x)], [MO3 center dot V-O(center dot)] and [MO3 center dot V-O(center dot center dot)], where M=W or Mo, which leads to additional levels in the band gap. The second mechanism, in ordered powders, was caused by an intrinsic slight distortion of the [WO4] or [MoO4] tetrahedral in the short range. (c) 2007 American Institute of Physics.

Direct and simultaneous determination of As, Cu, and Pb in Brazilian sugar cane spirits by graphite furnace AAS using Tungsten permanent modifier with Co-injection of Pd/Mg(NO3)(2)

A method was developed using the multi-element graphite furnace atomic absorption spectrometry technique for the direct and simultaneous determination of As, Cu, and Pb in Brazilian sugar cane spirit (cachaqa) samples. Also employed was the end-capped transversely heated graphite atomizer (THGA) with platforms pre-treated with W permanent modifier and co-injection of Pd/Mg(NO3)(2). Pyrolysis and atomization temperature curves were established in a cachaqa medium (1+1; v/v) containing 0.2% (v/v) HNO3 and spiked with 20 mu g L-1 As and Pb and 200 mu g L-1 Cu. The effect of the concentration of major elements usually present in cachaqa matrices (Ca, Mg, Na, and K) and ethanol on the absorbance of As, Cu, and Pb was investigated. Analytical working solutions of As, Cu, and Pb were prepared in 10% (v/v) ethanol plus 5.0 mg L-1 Ca, Mg, Na, and K. Acidified to 0.2% (v/v) HNO3, these solutions were suitable to build calibration curves by matrix matching. The proposed method was applied to the simultaneous determination of As, Cu, and Pb in commercial sugar cane spirits. The characteristic mass for the simultaneous determination was 16 pg As, 119 pg Cu, and 28 pg Pb. The pretreated tube lifetime was about 450 firings. The limit of detection (LOD) was 0.6 mu g L-1 As, 9.2 mu g L-1 Cu, and 0.3 pig L-1 Pb. The found concentrations varied from 0.81 to 4.28 mu g L-1 As, 0.28 to 3.82 mg L-1 Cu and 0.82 to 518 mu g L-1 Pb. The recoveries of the spiked samples varied from 94-112% (As), 97-111% (Cu), and 95-101% (Pb). The relative standard deviation (n=12) was 6.9%, 7.4%, and 7.7% for As, Cu, and Pb, respectively, present in a sample at 0.87 mu g L-1, 0.81 mg L-1, and 38.9 mu g L-1 concentrations.

Evaluation of Bi as internal standard to minimize matrix effects on the direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry using Ru permanent modifier with co-injection of Pd/Mg(NO3)(2)

Bismuth was evaluated as an internal standard for the direct determination of Pb in vinegar by graphite furnace atomic absorption spectrometry using Ru as a permanent modifier with co-injection of Pd/Mg(NO3)(2). The correlation coefficient of the graph plotted from the non-nalized absorbance signals of Bi versus Pb was r=0.989. Matrix effects were evaluated by analyzing the slope ratios between the analytical curve, and analytical curves obtained from Pb additions in red and white wine vinegar obtained from reference solutions prepared in 0.2% (v/v) HNO3, samples. The calculated ratios were around 1.04 and 1.02 for analytical curves established applying an internal standard and 1.3 and 1.5 for analvtical curves without. Analytical curves in the 2.5-15 pg L-1 Pb concentration interval were established using the ratio Pb absorbance to Bi absorbance versus analvte concentration, and typical linear correlations of r=0.999 were obtained. The proposed method was applied for direct determination of Pb in 18 commercial vinegar samples and the Pb concentration varied from 2.6 to 31 pg L-1. Results were in agreement at a 95% confidence level (paired t-test) with those obtained for digested samples. Recoveries of Pb added to vinegars varied from 96 to 108% with and from 72 to 86% without an internal standard. Two water standard reference materials diluted in vinegar sample were also analyzed and results were in agreement with certified values at a 95% confidence level. The characteristic mass was 40 pg Pb and the useful lifetime of the tube was around 1600 firings. The limit of detection was 0.3 mu g L-1 and the relative standard deviation was <= 3.8% and <= 8.3% (n = 12) for a sample containing, 10 mu L-1 Pb with and without internal standard, respectively. (C) 2007 Elsevier B.V. All rights reserved.

Direct determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by simultaneous GFAAS using integrated platforms pretreated with W-Rh permanent modifier together with Pd plus Mg modifier

A method is proposed for the simultaneous determination of Al, As, Cu, Fe, Mn, and Ni in fuel ethanol by electrothermal atomic absorption spectrometry (ETAAS) using W-Rh permanent modifier together with Pd(NO3)(2) + Mg(NO3)(2) conventional modifier. The integrated platform of a transversely heated graphite atomizer (THGA) was treated with tungsten, followed by rhodium, forming a deposit containing 250 mug W + 200 mug Rh. A 500-muL, volume of fuel ethanol was diluted with 500 muL, of 0.14 mol L-1 HNO3 in an autosampler cup of the spectrometer. Then, 20 muL, of the diluted ethanol was introduced into the pretreated graphite platform followed by the introduction of 5 mug Pd(NO3)(2) + 3 mug Mg(NO3)(2). The injection of this modifier was required to improve arsenic and iron recoveries in fuel ethanol. Calibrations were carried out using multi-element reference solutions prepared in diluted ethanol (1 + 1, v/v) acidified to 0. 14 mol L-1 HNO3. The pyrolysis and atomization temperatures of the heating program were 1200degreesC and 2200degreesC, respectively, which were obtained with multielement reference solutions in acidic diluted ethanol (1 + 1, v/v; 0. 14 mol L-1 HNO3). The characteristic masses for the simultaneous determination in ethanol fuel were 78 pg Al, 33 pg As, 10 pg Cu, 14 pg Fe, 7 pg Mn, and 24 pg Ni. The lifetime of the pretreated tube was about 700 firings. The detection limits (D.L.) were 1.9 mug L-1 Al, 2.9 mug L-1 As, 0.57 mug L-1.Cu, 1.3 mug L-1 Fe, 0.40 mug L-1 Mn, and 1.3 mug L-1 Ni. The relative standard deviations (n = 12) were 4%, 4%, 3%, 1.5%, 1.2%, and 2.2% for Al, As, Cu, Fe, Mn, and Ni, respectively. The recoveries of Al, As, Cu, Fe, Mn, and Ni added to the fuel ethanol samples varied from 81% to 95%, 80% to 98%, 97% to 109%, 85% to 107%, 98% to 106% and 97% to 103%, respectively. Accuracy was checked for the Al, As, Cu, Fe, Mn, and Ni determination in 10 samples purchased at a local gas station in Araraquara-SP City, Brazil. A paired t-test showed that at the 95% confidence level the results were in agreement with those obtained by single-element ETAAS.

INFLUENCE OF DIABETES-MELLITUS ON THE GLUTATHIONE REDOX SYSTEM OF HUMAN RED-BLOOD-CELLS

Several components of the erythrocyte-dependent glutathione redox system (reduced glutathione, GSH; oxidized glutathione, GSSG; glutathione peroxidase, GSH-Px; glutathione reductase, GSH-Red) were determined in patients with types I and II diabetes mellitus (DM). All groups studied were male subjects: G1, 20 young healthy individuals (aged 23.7 +/- 4.2 years); G2, 15 young insulin-treated type I DM patients; G3, 20 older insulin-treated type II DM patients; 04, 21 older oral hypoglycemic agent-treated type II DM patients; G5, 28 aged healthy individuals (aged 68.9 +/- 11.5 years). There were no differences between G1 and G2, G3 or G4 regarding erythrocyte GSH, GSSG, and GSH-Red (without FAD) levels. GSH-Px activity was significantly lower in G2 when compared to G1 (15.2 +/- 4.9 vs 20.6 +/- 6.6 IU/g Hb). The GSH-Red and GSH-Px activities and GSH levels were significantly higher in 03 (4.6 +/- 1.7 IU/g Hb, 20.2 +/- 8.7 IU/g Hb and 3.5 +/- 1.3-mu-M/g Hb) and G4 (5.0 +/- 2.2 IU/g Hb, 16.9 +/- 6.1 IU/g Hb and 5.0 +/- 2.3-mu-M/g Hb) when compared to G5 (3.4 +/- 0.9 IU/g Hb, 12.0 +/- 3.6 IU/g Hb and 2.3 +/- 0.9-mu-M/g Hb). The findings suggest that treatment of DM can stimulate the redox activity of red blood cells in aged subjects.

Cellular and tissue effects induced by photogemA (R) and red LED in photodynamic therapy

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

Soil-lime reactions: the behaviour of a Brazilian red soil.

A red tropical soil was selected, with the main purpose of investigating how it reacted with calcitic and dolomitic limes, and which products are formed. Under normal (23-28oC) or slightly accelerated (40o and 60oC) conditions there is a rapid and substantial interaction between lime (calcitic or dolomitic) and the soil. The reactions take place in two steps, one before 7 g lime/100 g soil, and the other after 8 g lime/100 g of soil, either for calcitic or dolomitic lime. A morphologically discrete reaction product (tri-calcium aluminate hexahydrate) was found in the study, and in spite of the difference in morphology the product is shown to be the same by XRD for all compositions and T.-J.M.H.

Cumulative effects of vinasse on the characteristics of red-yellow latosols under cerrado vegetation

Vinasse, a liquor effluent from the alcohol and sugar making industry, was applied annually for twelve years to medium-textured red-yellow latosols under cerrado vegetation sensu stricto, to study the environmental impacts on the biotic and abiotic factors. Four plots were established of which two acted as control and the other two received annual doses of vinasse. The studies were begun in 1980 when the first annual dose of 20 L m-2 year-1 was added to the soil without removing the top scrub layer. Theses doses were added to the soil until 1983, but in 1984 the doses were increased to 50 L m-2 year-1 and used until 1991. Soil samples were taken at a depth of 15 cm every three months from 1987 to 1991. Twenty seven environmental variables in the vinasse-treated and untreated plots were studied. These factors consisted of different enzymatic activities, a number of filamentous fungi, bacteria, actinomycetes and other micro-organisms, nutrients and some micro-climatic factors. The results obtained were statistically analyzed using the Tukey test, Pearson correlation and variance test methods with replicates and three factors. Matrices were determined using the correlation coefficient method and were compared with those of earlier published studies in the same area. The comparison of the results helped characterize changes in the environmental factors studied and in the correlation between them, after using annual cumulative doses of vinasse. Positive effects were observed only for the first six years of this application but vinasse had negative effects after the seventh year. It is concluded that medium-textured red-yellow latosols cannot be treated with vinasse for proloned periods.

Effects of temperature, irradiance and photoperiod on growth and pigment content in some freshwater red algae in culture

The responses of relative growth rate (% day-1) and pigment content (chlorophyll a, phycocyanin and phycoerythrin) to temperature, irradiance and photoperiod were analyzed in culture in seven freshwater red algae: Audouinella hermannii (Roth) Duby, Audouinella pygmaea (Kützing) Weber-van Bosse, Batrachospermum ambiguum Montagne, Batrachospermum delicatulum (Skuja) Necchi et Entwisle, 'Chantransia' stages of B. delicatulum and Batrachospermum macrosporum Montagne and Compsopogon coeruleus (C. Agardh) Montagne. Experimental conditions included temperatures of 10, 15, 20 and 25°C and low and high irradiances (65 and 300 μmol photons m-2 s-1, respectively). Long and short day lengths (16:8 and 8:16 LD cycles) were also applied at the two irradiances. Growth effects of temperature and irradiance were evident in most algae tested, and there were significant interactions among treatments. Most freshwater red algae had the best growth under low irradiance, confirming the preference of freshwater red algae for low light regimens. In general there was highest growth rate in long days and low irradiance. Growth optima in relation to temperature were species-specific and also varied between low and high irradiances for the same alga. The most significant differences in pigment content were related to temperature, whereas few significant differences could be attributed to variation in irradiance and photoperiod or interactions among the three parameters. The responses were species-specific and also differed for pigments in distinct temperatures, irradiances and photoperiods in the same alga. Phycocyanin was generally more concentrated than phycoerythrin and phycobiliproteins were more concentrated than chlorophyll a. The highest total pigment contents were found in two species typical of shaded habitats: A. hermannii and C. coeruleus. The expected inverse relationship of pigment with irradiance was observed only in C. coeruleus. In general, the most favorable conditions for growth were not coincident with those with highest pigment contents.

Avaliação dos produtos de degradação oxidativa da Hb S em eritrócitos de doentes falcêmicos

Analysis of the products of oxidative degradation of Hb S was made by methahemoglobin measurement and a count of red blood cells with Heinz bodies. Free radicals originating from oxidation cause extensive injury to erythrocytes, decreasing their useful survival period especially in Hb S carriers. The Superoxide ion (O 2) is the most responsible for the oxidation process of Hb forming membrane-bound haemachromes which afterwards evolve to Heinz bodies, damaging the membrane and provoking erythrocytes hemolysis. The results from this work showed that the SS genotype is more susceptible to the action of the free radicals than the S/Tal genotype. The β genotype has a lower oxidative susceptibility than the SS because it has only one β s mutation. The results allowed us to conclude that: a) the simple presence of Hb S, independent of its genotype and its concentration, is sufficient to produce methaemoglobin from this Hb; b) there is not a direct relationship between methaetnoglobin concentration and the Heinz bodies count; c) the intensity of Heinz bodies in the sickled erythrocytes seems to be independent of the Hb Fetal concentration; d) The genotype SS is more susceptible to Hb oxidation with the release of products of oxidative degradation; e) methaemoglobin formation in blood of people with Hb AA and Hb AS, assessed over 24, 48, 72 and 163 hourly-periods, showed greater oxidative intensity in the Hb AS compared with Hb AA.

Photoacclimation in three species of freshwater red algae

Three freshwater Rhodophyta species (Audouinella eugenea, A. hermannii and Compsopogon coeruleus) were tested as to their responses (photosynthesis, growth and pigment concentration) to two irradiances (low light, LL, 65 μmol m -2 s-1 and high light, HL, 300 μmol m-2 s-1) and two periods (short time, ST, 4 d, and long time, LT, 28 d). Higher growth rates were consistently observed at LL but significant differences were observed only for A. hermannii. Higher values of photoinhibition at LL were found for the three species, which is consistent with the dynamic photoinhibition as a reversible photoprotective mechanism against high irradiance. Light-induced decreases of effective quantum yield (EQY) were observed in the three species consisting of pronounced decreases from LL to HL. Rapid increases of non-photochemical quenching (NPQ) were observed mainly at LL, indicating energy dissipation by reaction centers. Results revealed distinct photoacclimation strategies to deal with high irradiances: the two Audouinella species had only characteristics of shade-adapted algae: acclimation by changes of size of photosy stem units (PSU) under LT and by PSU number under ST; higher values of the photoinhibition parameter (β) and NPQ, and lower values of EQY at LL; higher recovery capacity of potential quantum yield (PQY) at LL and under ST; highly significant positive correlation of electron transport rate (ETR) with NPQ. In addition, C. coeruleus mixed some characteristics of sun-adapted algae: acclimation by changes of PSU number under LT and by PSU size under ST; higher recovery capacity of EQY than the other two species; weak or no correlation of ETR with NPQ. Thus, these characteristics indicate that C. coeruleus cope with high irradiances more efficiently than the Audouinella species.