Evaluation of grinding methods for pellets preparation aiming at the analysis of plant materials by laser induced breakdown spectrometry

It has been demonstrated that laser induced breakdown spectrometry (LIBS) can be used as an alternative method for the determination of macro (P, K. Ca, Mg) and micronutrients (B, Fe, Cu, Mn, Zn) in pellets of plant materials. However, information is required regarding the sample preparation for plant analysis by LIBS. In this work, methods involving cryogenic grinding and planetary ball milling were evaluated for leaves comminution before pellets preparation. The particle sizes were associated to chemical sample properties such as fiber and cellulose contents, as well as to pellets porosity and density. The pellets were ablated at 30 different sites by applying 25 laser pulses per site (Nd:YAG@1064 nm, 5 ns, 10 Hz, 25J cm(-2)). The plasma emission collected by lenses was directed through an optical fiber towards a high resolution echelle spectrometer equipped with an ICCD. Delay time and integration time gate were fixed at 2.0 and 4.5 mu s, respectively. Experiments carried out with pellets of sugarcane, orange tree and soy leaves showed a significant effect of the plant species for choosing the most appropriate grinding conditions. By using ball milling with agate materials, 20 min grinding for orange tree and soy, and 60 min for sugarcane leaves led to particle size distributions generally lower than 75 mu m. Cryogenic grinding yielded similar particle size distributions after 10 min for orange tree, 20 min for soy and 30 min for sugarcane leaves. There was up to 50% emission signal enhancement on LIBS measurements for most elements by improving particle size distribution and consequently the pellet porosity. (C) 2011 Elsevier B.V. All rights reserved.

k(0)-INAA for determining chemical elements in bird feathers

The k(0)-method instrumental neutron activation analysis (k(0)-INAA) was employed for determining chemical elements in bird feathers. A collection was obtained taking into account several bird species from wet ecosystems in diverse regions of Brazil. For comparison reason, feathers were actively sampled in a riparian forest from the Marins Stream, Piracicaba, Sao Paulo State, using mist nets specific for capturing birds. Biological certified reference materials were used for assessing the quality of analytical procedure. Quantification of chemical elements was performed using the k(0)-INAA Quantu Software. Sixteen chemical elements, including macro and micronutrients, and trace elements, have been quantified in feathers, in which analytical uncertainties varied from 2% to 40% depending on the chemical element mass fraction. Results indicated high mass fractions of Br (max=7.9 mgkg(-1)), Co (max= 0.47 mg kg(-1)), Cr (max =68 mg kg(-1)), Hg (max =2.79 mg kg(-1)), Sb (max= 0.20 mg kg(-1)), Se (max=1.3 mg kg(-1)) and Zn (max =192 mg kg(-1)) in bird feathers, probably associated with the degree of pollution of the areas evaluated. In order to corroborate the use of k(0)-INAA results in biomonitoring studies using avian community, different factor analysis methods were used to check chemical element source apportionment and locality clustering based on feather chemical composition. (C) 2010 Elsevier B.V. All rights reserved.

Sequential injections as an alternative to gradient exploitation for implementing differential kinetic analysis in a flow injection system

A novel flow-based strategy for implementing simultaneous determinations of different chemical species reacting with the same reagent(s) at different rates is proposed and applied to the spectrophotometric catalytic determination of iron and vanadium in Fe-V alloys. The method relies on the influence of Fe(II) and V(IV) on the rate of the iodide oxidation by Cr(VI) under acidic conditions, the Jones reducing agent is then needed Three different plugs of the sample are sequentially inserted into an acidic KI reagent carrier stream, and a confluent Cr(VI) solution is added downstream Overlap between the inserted plugs leads to a complex sample zone with several regions of maximal and minimal absorbance values. Measurements performed on these regions reveal the different degrees of reaction development and tend to be more precise Data are treated by multivariate calibration involving the PLS algorithm The proposed system is very simple and rugged Two latent variables carried out ca 95% of the analytical information and the results are in agreement with ICP-OES. (C) 2010 Elsevier B V. All rights reserved.

Branched-chain amino acids supplementation enhances exercise capacity and lipid oxidation during endurance exercise after muscle glycogen depletion

Aim. It has been demonstrated that branched-chain amino acids (BCAA) transaminase activation occurs simultaneously with exercise-induced muscle glycogen reduction, suggesting that BCAA supplementation might play an energetic role in this condition. This study aimed to test whether BCAA supplementation enhances exercise capacity and lipid oxidation in glycogen-depleted subjects. Methods. Using a double-blind cross-over design, volunteers (N.=7) were randomly assigned to either the BCAA (300 mg . kg . day (-1)) or the placebo (maltodextrine) for 3 days. On the second day, subjects were submitted to an exercise-induced glycogen depletion protocol. They then performed an exhaustive exercise test on the third day, after which time to exhaustion, respiratory exchange ratio (RER), plasma glucose, free fatty acids (HA), blood ketones and lactate were determined. BCAA supplementation promoted a greater resistance to fatigue when compared to the placebo (+17.2%). Moreover, subjects supplemented with BCAA showed reduced RER and higher plasma glucose levels during the exhaustive exercise test. Results. No significant differences appeared in FFA, blood ketones and lactate concentrations. Conclusion. In conclusion, BCAA supplementation increases resistance to fatigue and enhances lipid oxidation during exercise in glycogen-depleted subjects.

LEACHATE TREATMENT PROCESS AT A MUNICIPAL STABILIZED LANDFILL BY CATALYTIC OZONATION: AN EXPLORATORY STUDY FROM TAGUCHI ORTHOGONAL ARRAY

Catalytic ozonation has been recognized in the scientific community as an efficient technique, reaching elevated rates of recalcitrant organic material mineralization, even at the presence of scavenger species of hydroxyl free radicals. This study presents the most significant factors involving the leachate treatment stabilized by the municipal landfill of the city of Guaratingueta, State of Sao Paulo, Brazil, by using a catalytic ozonation activated by metallic ions Fe(3+), Zn(2+), Mn(2+), Ni(2+) and Cr(3+). The Taguchi L(16) orthogonal array and its associated statistical methods were also used in this study. Among the researched ions, the most notable catalysis was obtained with ferric ion, statistically significant in the reduction of COD with a confidence level of 99.5%.

Prediction of Crude Oil Properties and Chemical Composition by Means of Steady-State and Time-Resolved Fluorescence

Steady-state and time-resolved fluorescence measurements are reported for several crude oils and their saturates, aromatics, resins, and asphaltenes (SARA) fractions (saturates, aromatics and resins), isolated from maltene after pentane precipitation of the asphaltenes. There is a clear relationship between the American Petroleum Institute (API) grade of the crude oils and their fluorescence emission intensity and maxima. Dilution of the crude oil samples with cyclohexane results in a significant increase of emission intensity and a blue shift, which is a clear indication of the presence of energy-transfer processes between the emissive chromophores present in the crude oil. Both the fluorescence spectra and the mean fluorescence lifetimes of the three SARA fractions and their mixtures indicate that the aromatics and resins are the major contributors to the emission of crude oils. Total synchronous fluorescence scan (TSFS) spectral maps are preferable to steady-state fluorescence spectra for discriminating between the fractions, making TSFS maps a particularly interesting choice for the development of fluorescence-based methods for the characterization and classification of crude oils. More detailed studies, using a much wider range of excitation and emission wavelengths, are necessary to determine the utility of time-resolved fluorescence (TRF) data for this purpose. Preliminary models constructed using TSFS spectra from 21 crude oil samples show a very good correlation (R(2) > 0.88) between the calculated and measured values of API and the SARA fraction concentrations. The use of models based on a fast fluorescence measurement may thus be an alternative to tedious and time-consuming chemical analysis in refineries.

Regeneration of Activated Carbon by (Photo)-Fenton Oxidation

This work aims to study the adsorption of phenol on activated carbons (ACs) and the consecutive in situ regeneration of carbon by Fenton oxidation. Two different operations have been carried Out: (1) a batch procedure in order to investigate the influence of Fe(2+) and H(2)O(2) concentrations; (2) continuous fixed bed adsorption, followed by a batch circulation of the Fenton`s reagent through the saturated AC bed. to examine the efficiency of the real process. Two different activated carbons have been also studied: a both micro- and mesoporous AC (L27) and an only microporous One (S23). In the batch reactor the best conditions found for pollutant mineralization in the homogeneous Fenton system are not the best For AC regeneration: a continuous reduction of adsorption capacity of L27 is observed after 3 oxidations, due to the decrease of both AC weight and surface area. Higher concentration of Fe(2+) and lower concentration of H(2)O(2) (2 times the stoichiometry) lead to a 50% recovery of the initial adsorption capacity during at least four consecutive cycles for L27, while about 20% or less for S23. In the consecutive continuous adsorption/batch Fenton oxidation process, the regeneration efficiency reaches 30-40% for L27 after two cycles whatever the feed concentration and less than 10% for S23. A photo-Fenton test performed on L27 shows almost complete mineralization (contrary to ""dark"" Fenton) and further improves recovery of AC adsorption capacity although not complete (56% after two cycles).

Influence of substrate surface topography in the deposition of nanostructured diamond-like carbon films by high density plasma chemical vapor deposition

In this work, we have studied the influence of the substrate surface condition on the roughness and the structure of the nanostructured DLC films deposited by High Density Plasma Chemical Vapor Deposition. Four methods were used to modify the silicon wafers surface before starting the deposition processes of the nanostructured DLC films: micro-diamond powder dispersion, micro-graphite powder dispersion, and roughness generation by wet chemical etching and roughness generation by plasma etching. The reference wafer was only submitted to a chemical cleaning. It was possible to see that the final roughness and the sp(3) hybridization degree strongly depend on the substrate surface conditions. The surface roughness was observed by AFM and SEM and the hybridization degree of the DLC films was analyzed by Raman Spectroscopy. In these samples, the final roughness and the sp(3) hybridization quantity depend strongly on the substrate surface condition. Thus, the effects of the substrate surface on the DLC film structure were confirmed. These phenomena can be explained by the fact that the locally higher surface energy and the sharp edges may induce local defects promoting the nanostructured characteristics in the DLC films. (C) 2008 Elsevier B.V. All rights reserved.

Effect of the Partial Substitution of Soy Proteins by Highly Methyl-esterified Pectin on Chemical and Sensory Characteristics of Sausages

Pectin can be used as a natural emulsifier in food formulations. In this study, textured soybean protein (TSP), used as an emulsifier in commercial sausages, was partially replaced by a mixture containing pectin and isolated soybean proteins, which were either extruded (EXT) or not extruded (MIX), and the chemical and sensory characteristics of samples were evaluated after 60 days of storage at 4 degrees C. Responses such as oxidation measured by PV and TBARS, hardness, color, pH and sensory characteristics were compared with those of a commercial sausage (CON). The mixture containing highly methyl-esterified pectin, textured soybean proteins and isolated soybean proteins, as emulsifier agent, reduced the hardness (EXT: 21.69 +/- 0.98 and MIX: 20.17 +/- 2.76 N) and the pH (EXT: 5.46 +/- 0.03 and MIX: 5.29 +/- 0.01) of the samples and increased the concentration of peroxides (EXT: 0.10 +/- 0.01 and MIX: 0.15 +/- 0.01 meq/kg) when compared with samples formulated only with TSP (28.57 +/- 2.54 N, pH of 6.92 +/- 0.04 and PV = 0.07 +/- 0.01 meq/kg). These effects were likely caused by the anionic character of the emulsifier. However, no sensory difference was observed between the sausages containing highly methyl-esterified pectin, textured soybean proteins and isolated soybean proteins submitted to the extrusion process (EXT) and the control sausages, suggesting that the formulation proposed in this study can be a potential alternative for the further development of sausages that have functional properties or are free of artificial additives.

EFFECT OF THERMAL TREATMENT ON PHENOLIC COMPOUNDS AND FUNCTIONALITY LINKED TO TYPE 2 DIABETES AND HYPERTENSION MANAGEMENT OF PERUVIAN AND BRAZILIAN BEAN CULTIVARS (PHASEOLUS VULGARIS L.) USING IN VITRO METHODS

The effect of thermal treatment on phenolic compounds and type 2 diabetes functionality linked to alpha-glucosidase and alpha-amylase inhibition and hypertension relevant angiotensin I-converting enzyme (ACE) inhibition were investigated in selected bean (Phaseolus vulgaris L,) cultivars from Peru and Brazil using in vitro models. Thermal processing by autoclaving decreased the total phenolic content in all cultivars, whereas the 1,1-diphenyl-2-picrylhydrazyl radical scavenging activity-linked antioxidant activity increased among Peruvian cultivars, alpha-Amylase and alpha-glucosidase inhibitory activities were reduced significantly after heat treatment (73-94% and 8-52%, respectively), whereas ACE inhibitory activity was enhanced (9-15%). Specific phenolic acids such as chlorogenic and caffeic acid increased moderately following thermal treatment (2-16% and 5-35%, respectively). No correlation was found between phenolic contents and functionality associated to antidiabetes and antihypertension potential, indicating that non phenolic compounds may be involved. Thermally processed bean cultivars are interesting sources of phenolic acids linked to high antioxidant activity and show potential for hypertension prevention.

Chemical Composition and Nutritional Value of Unripe Banana Flour (Musa acuminata, var. Nanico)

Banana flour obtained from unripe banana (Musa acuminata, var. Nanico) under specific drying conditions was evaluated regarding its chemical composition and nutritional value. Results are expressed in dry weight (dw). The unripe banana flour (UBF) presented a high amount of total dietary fiber (DF) (56.24 g/100 g), which consisted of resistant starch (RS) (48.99 g/100 g), fructans (0.05 g/100 g) and DF without RS or fructans (7.2 g/100 g). The contents of available starch (AS) (27.78 g/100 g) and soluble sugars (1.81 g/100 g) were low. The main phytosterols found were campesterol (4.1 mg/100 g), stigmasterol (2.5 mg/100 g) and beta-sitosterol (6.2 mg/100 g). The total polyphenol content was 50.65 mg GAE/100 g. Antioxidant activity, by the FRAP and ORAC methods, was moderated, being 358.67 and 261.00 mu mol of Trolox equivalent/100 g, respectively. The content of Zn, Ca and Fe and mineral dialyzability were low. The procedure used to obtain UBF resulted in the recovery of undamaged starch granules and in a low-energy product (597 kJ/100 g).

Synergism between lipoxygenase-active soybean flour and ascorbic acid on rheological and sensory properties of wheat bread

BACKGROUND: The interaction between lipoxygenase-active soybean flour (LOX) and ascorbic acid (AA), on colour, rheological and sensory properties of wheat bread was studied with the aim of reducing the applied quantity of additives in bread formulations. RESULTS: The ascorbic acid (0-500 ppm) and active soybean flour (0-1%) mixture improved bread-crumb colour by lowering the yellow hue in a higher proportion than those expressed by the components alone, characterising a synergistic mechanism ((y) over cap (b) = 15.1- (1.7 x LOX) - (0.5 x AA) - (5.8 x LOX x AA), where : (y) over cap (b) represent the estimated value for the yellow hue parameter). No differences in flavour and porosity were seen between the samples. As supported by the instrumental methods, breads made with active soybean flour and ascorbic acid (LOX + AA) had whiter crumbs and were softer and springier than controls as assessed by a trained sensory panel. In summary, the combination of both active soybean flour and ascorbic acid showed synergism, promoting a greater bleaching effect than when used alone. CONCLUSION: These results suggest the potential use of active soybean flour as a synergistic ingredient in the substitution of artificial additives in bread making. Since the interaction on the bleaching response was not linear and active soybean flour showed a higher iron concentration (66.40 +/- 4.23 mu g g(-1)) than non-active soybean flour (52.30 +/- 0.40 mu g g(-1)), more studies are warranted to establish the biochemical mechanisms involved in this interaction. (c) 2007 Society of Chemical Industry.

Methods for detection of anatoxin-a(s) by liquid chromatography coupled to electrospray ionization-tandem mass spectrometry

Anatoxin-a(s) is a potent irreversible inhibitor of the enzyme acetylcholinesterase with a unique N-hydroxyguanidine methylphosphate ester chemical structure. Determination of this toxin in environmental samples is hampered by the lack of specific methods for its detection. Using the toxic strain of Anabaena lemmermani PH-160 B as positive control, the fragmentation characteristics of anatoxin-a(s) under collision-induced dissociation conditions have been investigated and new LC-MS/MS methods proposed. Recommended ion transitions for correct detection of this toxin are 253 > 58, 253 > 159, 235 > 98 and 235 > 96. Chromatographic separation is better achieved under HILIC conditions employing a ZIC-HILIC column. This method was used to confirm for the first time the production of anatoxin-a(s) by strains of Anabaena oumiana ITEP-025 and ITEP-026. Considering no standard solutions are commercially available, our results will be of significant use for the correct identification of this toxin by LC-MS/MS. (C) 2009 Elsevier Ltd. All rights reserved.

Preparation and characterization of D, L-PLA loaded 17-beta-Estradiol valerate by emulsion/evaporation methods

PLA microparticles containing 17-beta-estradiol valerate were prepared by an emulsion/evaporation method in order to sustain drug release. This system was characterized concerning particle size, particle morphology and the influence of formulation and processing parameters on drug encapsulation and in vitro drug release. The biodegradation of the microparticles was observed by tissue histological analysis. Scanning electron microscopy and particle size analysis showed that the microparticles were spherical, presenting non-aggregated homogeneous surface and had diameters in the range of 718-880 nm (inert microparticles) and 3-4 mu m (drug loaded microparticles). The encapsulation efficiency was similar to 80%. Hormone released from microparticles was sustained. An in vivo degradation experiment confirmed that microparticles are biodegradable. The preparation method was shown to be suitable, since the morphological characteristics and efficiency yield were satisfactory. Thus, the method of developed microparticles seems to be a promising system for sustained release of 17-beta-estradiol.

Bioactive Chemical Constituents and Comparative Antimicrobial Activity of Callus Culture and Adult Plant Extracts from Alternanthera tenella

Crude extracts of a callus culture (two culture media) and adult plants (two collections) from Alternanthera tenella Colla (Amaranthaceae) were evaluated for their antibacterial and antifungal activity, in order to investigate the maintenance of antimicrobial activity of the extracts obtained from plants in vivo and in vitro. The antibacterial and antifungal activity was determined against thirty strains of microorganisms including Gram-positive and Gram-negative bacteria, yeasts and dermatophytes. Ethanolic and hexanic extracts of adult plants collected during the same period of the years 1997 and 2002 [Ribeirao Preto (SP), collections 1 and 2] and obtained from plant cell callus culture in two different hormonal media (AtT43 and AtT11) inhibited the growth of bacteria, yeasts and dermatophytes with inhibition halos between 6 and 20 mm. For the crude extracts of adult plants bioassay-guided fractionation, purification, and isolation were performed by chromatographic methods, and the structures of the isolated compounds were established by analysis of chemical and spectral evidences (UV, IR, NMR and ES-MS). Steroids, saponins and flavonoids (aglycones and C-glycosides) were isolated. The minimum inhibitory concentration (MIC) of the isolated compounds varied from 50 to 500 mu g/mL.