Effect of processing on the antioxidant activity of amaranth grain

Effect of processing on the antioxidant activity of amaranth grain. Amaranth has attracted increasing interest over recent decades because of its nutritional, functional and agricultural characteristics. Amaranth grain can be cooked, popped, toasted, extruded or milled for consumption. This study investigated the effect of these processes on the antioxidant activity of amaranth grain. Total phenolic content and in vitro antioxidant activity were determined according to two methods: inhibition, of lipid oxidation using the beta-carotene/linoleic acid system and the antioxidant activity index using the Rancimat (R) apparatus. The processing reduced the mean total phenolics content in amaranth grain from 31.7 to 22.0 mg of gallic acid equivalent/g of dry residue. It was observed that the ethanol extract from toasted grain was the only one that presented a lower antioxidant activity index compared with the raw grain (1.3 versus 1.7). The extrusion, toasting and popping processes did not change the capacity to inhibit amaranth lipid oxidation (55%). However, cooking increased the inhibition of lipid oxidation (79%), perhaps because of the longer time at high temperatures in this process (100 degrees C/10 min). The most common methods for processing amaranth grain caused reductions in the total phenolics content, although the antioxidant activity of popped and extruded grain, evaluated by the two methods, was similar to that of the raw grain. Both raw and processed amaranth grain presents antioxidant potential. Polyphenols, anthocyanins, flavonoids, tocopherols, vitamin C levels and Maillard reaction products may be related to the antioxidant activity of this grain.

Magnetic hysteresis loop shift in NiFe(2)O(4) nanocrystalline powder with large grain boundary fraction

Magnetic properties of nanocrystalline NiFe(2)O(4) spinel mechanically processed for 350 h have been studied using temperature dependent from both zero-field and in-field (57)Fe Mossbauer spectrometry and magnetization measurements. The hyperfine structure allows us to distinguish two main magnetic contributions: one attributed to the crystalline grain core, which has magnetic properties similar to the NiFe(2)O(4) spinel-like structure (n-NiFe(2)O(4)) and the other one due to the disordered grain boundary region, which presents topological and chemical disorder features(d-NiFe(2)O(4)). Mossbauer spectrometry determines a large fraction for the d-NiFe(2)O(4) region(62% of total area) and also suggests a speromagnet-like structure for it. Under applied magnetic field, the n-NiFe(2)O(4) spins are canted with angle dependent on the applied field magnitude. Mossbauer data also show that even under 120 kOe no magnetic saturation is observed for the two magnetic phases. In addition, the hysteresis loops, recorded for scan field of 50 kOe, are shifted in both field and magnetization axes, for temperatures below about 50 K. The hysteresis loop shifts may be due to two main contributions: the exchange bias field at the d-NiFe(2)O(4)/n-NiFe(2)O(4) interfaces and the minor loop effect caused by a high magnetic anisotropy of the d-NiFe(2)O(4) phase. It has also been shown that the spin configuration of the spin-glass like phase is modified by the consecutive field cycles, consequently the n-NiFe(2)O(4)/d-NiFe(2)O(4) magnetic interaction is also affected in this process. (C) 2010 Elsevier B.V. All rights reserved.

How grain boundaries modify the high-temperature dielectric response of ferroelectric electroceramics like BaTiO(3)?

Dielectric properties of BaTiO(3) ferroelectric ceramics were studied over wide frequency and temperature ranges. The materials showed complex dielectric behaviors, which included an anomalous increase of permittivity towards higher temperatures. Important, this property tended however to saturate to values that varied with grain-boundary density. Application of impedance spectroscopy and consideration of the series-layer model allowed a coherent discussion of these and other interesting observations from this work. In particular, analysis of the relationship existing in this model between macroscopic and microscopic dielectric properties rendered possible to account for grain vs. grain-boundary dielectric behaviors, in harmony with microstructure features, and to know the dielectric anomaly strength to be in fact expected from grain boundaries in such polycrystalline materials. (C) 2010 Elsevier Ltd. All rights reserved.

The Sphene-Centered Ocellar Texture: An Effect of Grain-Supported Flow and Melt Migration in a Hyperdense Magma Mush

The sphene-centered ocellar texture consists of leucocratic ocelli with sphene (titanite) crystals at the center, enclosed in a biotite-rich matrix. This texture has been recognized worldwide in hybrid intermediate rocks. On the basis of structural, petrological, and geochronological data from selected outcrops of the Variscan Ribadelago pluton (NW Iberian Massif), we propose that the ocelli were formed by migration and accumulation of a residual melt through a plagioclase- and biotite-dominated crystalline framework. At the late stage of crystallization, the magma acted as a hyperdense suspension and reacted to the pressure gradient caused by the regional stress field, entering the domain of grain-supported flow. Microstructures reveal that aligned crystal domains arose in the crystal framework from the shearing and compaction of the crystal mush and behaved as magmatic microshears. Relative displacement of adjacent crystal clusters along these microshears corresponded to the onset of Reynolds dilatancy that generated an expansion of the crystal mush, involving melt migration and pore aperture. The mineralogy of the ocelli, dominated by andesine and sphene, represents the composition of the migrating melt. The chemistry of this late, Ti-rich melt stems from the incongruent melting of biotite. Magmatic sphene from the ocelli yields a U-Pb age of 317 +/- 1 Ma, which represents the final crystallization of the hybridized magmatic system. Moreover, this texture offers an opportunity to better understand the rheological behavior of highly crystallized magmas.

Controls of heavy minerals and grain size in a holocene regressive barrier (Ilha Comprida, southeastern Brazil)

Ilha Comprida is a regressive barrier island located in southeastern Brazil that was formed essentially by Quaternary sandy sediments. Ilha Comprida sediments were analyzed to assess heavy mineral indices and grain size variables. The spatial variation of heavy minerals and grain size was interpreted in terms of the present barrier dynamics and the barrier`s evolution since the Middle Holocene. These analyses allowed for the identification of the main factors and processes that control the variation of heavy minerals and grain size on the barrier. Rutile and zircon (RZi) and tourmaline and hornblende (THi) are significantly sensitive to provenance and exhibit the contributions of the Ribeira de Iguape River sediments, which reach the coast next to the northeastern end of Ilha Comprida. In addition to the influence of provenance, TZi responds mainly to hydraulic sorting processes. This agrees with a sediment transport pattern characterized by a divergence of two resultant net alongshore drifts southwest of the barrier. The sediments from the Ribeira de Iguape River reach the barrier directly through the river mouth and indirectly after temporary storage in the inner shelf. The combination of grain size and heavy mineral analyses is a reliable method for determining sediment transport patterns and provenance. (C) 2010 Elsevier Ltd. All rights reserved.

Grain size and heavy minerals of the Late Quaternary eolian sediments from the Imbituba-Jaguaruna coast, Southern Brazil: Depositional controls linked to relative sea-level changes

The stratigraphic subdivision and correlation of dune deposits is difficult, especially when age datings are not available. A better understanding of the controls on texture and composition of eolian sands is necessary to interpret ancient eolian sediments. The Imbituba-Jaguaruna coastal zone (Southern Brazil, 28 degrees-29 degrees S) stands out due to its four well-preserved Late Pleistocene (eolian generation 1) to Holocene eolian units (eolian generations 2, 3, and 4). In this study, we evaluate the grain-size and heavy-mineral characteristics of the Imbituba-Jaguartma eolian units through statistical analysis of hundreds of sediment samples. Grain-size parameters and heavy-mineral content allow us to distinguish the Pleistocene from the Holocene units. The grain size displays a pattern of fining and better sorting from generation 1 (older) to 4 (younger), whereas the content of mechanically stable (dense and hard) heavy minerals decreases from eolian generation 1 to 4. The variation in grain size and heavy-mineral content records shifts in the origin and balance (input versus output) of eolian sediment supply attributable mainly to relative sea-level changes. Dunefields submitted to relative sea-level lowstand conditions (eolian generation 1) are characterized by lower accumulation rates and intense post-depositional dissection by fluvial incision. Low accumulation rates favor deflation in the eolian system, which promotes concentration of denser and stable heavy minerals (increase of ZTR index) as well as coarsening of eolian sands. Dissection involves the selective removal of finer sediments and less dense heavy minerals to the coastal source area. Under a high rate of relative sea-level rise and transgression (eolian generation 2), coastal erosion prevents deflation through high input of sediments to the coastal eolian source. This condition favors dunefield growth. Coastal erosion feeds sand from local sources to the eolian system. including sands from previous dunefields (eolian generation 1) and from drowned incised valleys. Therefore, dunefields corresponding to transgressive phases inherit the grain-size and heavy-mineral characteristics of previous dunefields, leading to selective enrichment of finer sands and lighter minerals. Eolian generations 3 and 4 developed during a regressive-progradational phase (Holocene relative sea level highstand). The high rate of sediment supply during the highstand phase prevents deflation. The lack of coastal erosion favors sediment supply from distal sources (fluvial sediments rich in unstable heavy minerals). Thus, dunefields of transgressive and highstand systems tracts may be distinguished from dunefields of the lowstand systems tract through high rates of accumulation (low deflation) in the former. The sediment source of the transgressive dunefields (high input of previously deposited coastal sands) differs from that of the highstand dunefields (high input of fluvial distal sands). Based on this case study, we propose a general framework for the relation between relative sea level, sediment supply and the texture and mineralogy of eolian sediments deposited in siliciclastic wet coastal zones similar to the Imbituba-Jaguaruna coast (C) 2009 Elsevier B.V. All rights reserved.

Fully electrochemical hyphenated flow system for preconcentration, cleanup, stripping, capillary electrophoresis with stacking and contactless conductivity detection of trace heavy metals

Successful coupling of electrochemical preconcentration (EPC) to capillary electrophoresis (CE) with contactless conductivity detection (C(4)D) is reported for the first time. The EPC-CE interface comprises a dual glassy carbon electrode (GCE) block, a spacer and an upper block with flow inlet and outlet, pseudo-reference electrode and a fitting for the CE silica column, consisting of an orifice perpendicular to the surface of a glassy carbon electrode with a bushing inside to ensure a tight press fit. The end of the capillary in contact with the GCE is slant polished, thus defining a reproducible distance from the electrode surface to the column bore. First results with EPC-CE-C(4)D are very promising, as revealed by enrichment factors of two orders of magnitude for Tl, Cu, Pb and Cd ion peak area signals. Detection limits for 10 min deposition time fall around 20 nmol L(-1) with linear calibration curves over a wide range. Besides preconcentration, easy matrix exchange between accumulation and stripping/injection favors procedures like sample cleanup and optimization of pH, ionic strength and complexing power. This was demonstrated for highly saline samples by using a low conductivity buffer for stripping/injection to improve separation and promote field-enhanced sample stacking during electromigration along the capillary. (C) 2010 Elsevier B.V. All rights reserved.

Sample stacking in CZE using dynamic thermal junctions I. Analytes with low dpK(a)/dT crossing a single thermally induced pH junction in a BGE with high dpH/dT

The possibility to compress analyte bands at the beginning of CE runs has many advantages. Analytes at low concentration can be analyzed with high signal-to-noise ratios by using the so-called sample stacking methods. Moreover, sample injections with very narrow initial band widths (small initial standard deviations) are sometimes useful, especially if high resolutions among the bands are required in the shortest run time. In the present work, a method of sample stacking is proposed and demonstrated. It is based on BGEs with high thermal sensitive pHs (high dpH/dT) and analytes with low dpK(a)/dT. High thermal sensitivity means that the working pK(a) of the BGE has a high dpK(a)/dT in modulus. For instance, Tris and Ethanolamine have dpH/dT = -0.028/degrees C and -0.029/degrees C, respectively, whereas carboxylic acids have low dpK(a)/dT values, i.e. in the -0.002/degrees C to+0.002/degrees C range. The action of cooling and heating sections along the capillary during the runs affects also the local viscosity, conductivity, and electric field strength. The effect of these variables on electrophoretic velocity and band compression is theoretically calculated using a simple model. Finally, this stacking method was demonstrated for amino acids derivatized with naphthalene-2,3-dicarboxaldehyde and fluorescamine using a temperature difference of 70 degrees C between two neighbor sections and Tris as separation buffer. In this case, the BGE has a high pH thermal coefficient whereas the carboxylic groups of the analytes have low pK(a) thermal coefficients. The application of these dynamic thermal gradients increased peak height by a factor of two (and decreased the standard deviations of peaks by a factor of two) of aspartic acid and glutamic acid derivatized with naphthalene-2,3-dicarboxaldehyde and serine derivatized with fluorescamine. The effect of thermal compression of bands was not observed when runs were accomplished using phosphate buffer at pH 7 (negative control). Phosphate has a low dpH/dT in this pH range, similar to the dK(a)/dT of analytes. It is shown that vertical bar dK(a)/dT-dpH/dT vertical bar >> 0 is one determinant factor to have significant stacking produced by dynamic thermal junctions.

Sample stacking in CZE using dynamic thermal junctions II: Analytes with high dpK(a)/dT crossing a single thermal junction in a BGE with low dpH/dT

In a previous work [M. Mandaji, et al., this issue] a sample stacking method was theoretically modeled and experimentally demonstrated for analytes with low dpK(a)/dT (analytes carrying carboxylic groups) and BGEs with high dpH/dT (high pH-temperature-coefficients). In that work, buffer pH was modulated with temperature, inducing electrophoretic mobility changes in the analytes. In the present work, the opposite conditions are studied and tested, i.e. analytes with high dpK(a)/dT and BGEs that exhibit low dpH/dT. It is well known that organic bases such as amines, imidazoles, and benzimidazoles exhibit high dpK(a)/dT. Temperature variations induce instantaneous changes on the basicity of these and other basic groups. Therefore, the electrophoretic velocity of some analytes changes abruptly when temperature variations are applied along the capillary. This is true only if BGE pH remains constant or if it changes in the opposite direction of pK(a) of the analyte. The presence of hot and cold sections along the capillary also affects local viscosity, conductivity, and electric field strength. The effect of these variables on electrophoretic velocity and band stacking efficacy was also taken into account in the theoretical model presented. Finally, this stacking method is demonstrated for lysine partially derivatized with naphthalene-2,3-dicarboxaldehyde. In this case, the amino group of the lateral chain was left underivatized and only the alpha amino group was derivatized. Therefore, the basicity of the lateral amino group, and consequently the electrophoretic mobility, was modulated with temperature while the pH of the buffer used remained unchanged.