Geochronological data from the Faxinal coal succession, southern Parana Basin, Brazil: A preliminary approach combining radiometric U-Pb dating and palynostratigraphy

A radiometric zircon age of 285.4 +/- 8.6 Ma (IDTIMS U-Pb) is reported from a tonstein layer interbedded with coal seams in the Faxinal coalfield, Rio Grande do Sul, Brazil. Calibration of palynostratigraphic data with the absolute age shows that the coal depositional interval in the southern Parana Basin is constrained to the Sakmarian. Consequently, the basal Gondwana sequence in the southern part of the basin should lie at the Carboniferous-Permian boundary, not within the Sakmarian as previously considered. The new results are significant for correlations between the Parana Basin and the Argentinian Paganzo Basin (302 +/- 6 Ma and 288 +/- 7 Ma) and with the Karoo Basin, specifically with the top of the Dwyka Tillite (302 +/- 3 Ma and 299.2 +/- 3.2 Ma) and the lowermost Ecca Group (288 +/- 3 Ma and 289.6 +/- 3.8 Ma). The evidence signifies widespread latest Carboniferous volcanic activity in western Gondwana. (C) 2007 Elsevier Ltd. All rights reserved.

Neoproterozoic glacial dynamics revealed by provenance of diamictites of the Bebedouro Formation, Sao Francisco Craton, Central Eastern Brazil

One of the main questions on Neoproterozoic geology regards the extent and dynamics of the glacial systems that are recorded in all continents. We present evidence for short transport distances and localized sediment sources for the Bebedouro Formation, which records Neoproterozoic glaciomarine sedimentation in the central-eastern Sao Francisco Craton (SFC), Brazil. New data are presented on clast composition, based on point counting in thin section and SHRIMP dating of pebbles and detrital zircon. Cluster analysis of clast compositional data revealed a pronounced spatial variability of clast composition on diamictite indicating the presence of individual glaciers or ice streams feeding the basin. Detrital zircon ages reveal distinct populations of Archean and Palaeoproterozoic age. The youngest detrital zircon dated at 874 +/- 9 Ma constrains the maximum depositional age of these diamictites. We interpret the provenance of the glacial diamictites to be restricted to sources inside the SFC, suggesting deposition in an environment similar to ice streams from modern, high latitude glaciers.

U-Pb-Hf-trace element systematics and geochronology of zircon from a granulite-facies metamorphosed mafic-ultramafic layered complex in Central Brazil

Zircon recrystallization is a common process during high-grade metamorphism and promotes partial or complete resetting of the original isotopic and chemical characteristics of the mineral and thus complicates U-Pb geochronological interpretation. In Central Brazil, this complexity may be illustrated by three composite mafic-ultramafic intrusions metamorphosed under amphibolite-to-granulite conditions. Their ages of emplacement and metamorphic ages have been a matter of controversy for the last thirty years. The Serra da Malacacheta and Barro Alto complexes make up the southernmost of these layered bodies and four samples from distinct rock types were investigated in order to verify the consequences of metamorphic alteration of zircon for U-Pb dating. Cathodoluminescent imaging reveals internal features which are typical of concomitant dissolution-reprecipitation processes, such as convolute zoning and inward-moving recrystallization fronts, even in samples in which partially preserved igneous textures are observed. Due to this extensive alteration, LA-ICPMS U-Pb isotopic analysis yielded inconclusive data. However, in situ Hf isotopic and trace-element analyses help to clarify the real meaning of the geochronological data. Low Lu/Hf (<0.004) and homogeneous (176)Hf/(177)Hf(t) values imply that the zircon populations within individual samples have crystallized in a single episode, despite the observed variations in age values. Trace element signatures of zircon grains from garnet-bearing samples reveal that they were unreactive to the development of the peak metamorphism mineral assemblage and, thus, the main chemical feature in such grains is attributed to a coupled dissolution-reprecipitation process. However, in the Cafelandia amphibolite an additional alteration process is identified, probably related to the influx of late-stage fluids. Combined isotopic and geochemical investigation on zircon grains allowed the distinction of two magmatic events. The first corresponds to the crystallization of the Serra da Malacacheta Complex and characterizes a juvenile magmatism at similar to 1.3 Ga. The younger episode, recognized in the Barro Alto Complex, is dated at ca. 800 Ma and is represented by mafic and ultramafic rocks showing intense contamination with continental crust, implying that the emplacement took place, most likely, in a continental back-arc setting. Altered zircon domains as well as titanite grains date the metamorphic event at ca. 760-750 Ma. (C) 2011 Elsevier B.V. All rights reserved.

Closing the Clymene ocean and bending a Brasiliano belt: Evidence for the Cambrian formation of Gondwana, southeast Amazon craton

We report new paleomagnetic and geochronological data from Ediacaran rift-drift carbonates in the Paraguai belt at the southern end of the suture zone between the Amazon craton and the Sao Francisco and Rio de Plata cratons, South America. Early thrusting resulted in remagnetization ca. 528 +/- 36 Ma or later; the mean age is established by (40)Ar/(39)Ar encapsulation dating of mixed authigenic and detrital illite from remagnetized carbonates from the unmetamorphosed fold-thrust belt. This remagnetization overlaps with a 525 Ma Gondwana reference pole. Metamorphic illite from the slate belt yields (40)Ar/(39)Ar ages of 496-484 Ma, the timing of peak regional metamorphism. Oroclinal bending of the Paraguai belt was caused by a 90 degrees clockwise rotation of the east-west limb after ca. 528 Ma, probably reflecting the irregular margin of the southeast Amazon craton. The age of the Paraguai belt overlaps with that of the Pampean orogeny farther south along the western margin of the Rio de Plata craton, suggesting a coeval closure for the Clymene ocean separating the Amazon craton from the Sao Francisco and Rio de Plata cratons.

U-Pb zircon and (40)Ar-(39)Ar K-feldspar dating of syn-sedimentary volcanism of the Neoproterozoic Marica Formation: constraining the age of foreland basin inception and inversion in the Camaqua Basin of southern Brazil

New U-Pb zircon and (40)Ar-(39)Ar K-feldspar data are presented for syn-sedimentary volcanogenic rocks from the Neoproterozoic Marica Formation, located in the southern Brazilian shield. Seven (of nine) U-Pb sensitive high-resolution ion microprobe analyses of zircons from pyroclastic cobbles yield an age of 630.2 +/- 3.4 Ma (2 sigma), interpreted as the age of syn-sedimentary volcanism, and thus of the deposition itself. This result indicates that the Marica Formation was deposited during the main collisional phase (640-620 Ma) of the Brasiliano II orogenic system, probably as a forebulge or back-bulge, craton-derived foreland succession. Thus, this unit is possibly correlative of younger portions of the Porongos, Brusque, Passo Feio, Abapa (Itaiacoca) and Lavalleja (Fuente del Puma) metamorphic complexes. Well-defined, step-heating (40)Ar-(39)Ar K-feldspar plateau ages obtained from volcanogenic beds and pyroclastic cobbles of the lower and upper successions of the Marica Formation yielded 507.3 +/- 1.8 Ma and 506.7 +/- 1.4 Ma (2 sigma), respectively. These data are interpreted to reflect total isotopic resetting during deep burial and thermal effects related to magmatic events. Late Middle Cambrian cooling below ca. 200 degrees C, probably related to uplift, is tentatively associated with intraplate effects of the Rio Doce and/or Pampean orogenies (Brasiliano III system). In the southern Brazilian shield, these intraplate stresses are possibly related to the dominantly extensional opening of a rift or a pull-apart basin, where sedimentary rocks of the Camaqua Group (Santa Barbara and Guaritas Formations) accumulated.

Development and Validation of a Mice liar Electrokinetic Chromatography Method for Quantitative Determination of Butenolides in Piper malacophyllum (C. Presl) C. DC.

Introduction - A large number of natural and synthetic compounds having butenolides as a core unit have been described and many of them display a wide range of biological activities. Butenolides from P. malacophyllum have presented potential antifungal activities but no specific, fast, and precise method has been developed for their determination. Objective - To develop a methodology based on micellar electrokinetic chromatography to determine butenolides in Piper species. Methodology - The extracts were analysed in an uncoated fused-silica capillaries and for the micellar system 20 mmol/L SDS, 20% (v/v) acetonitrile (ACN) and 10 mmol/L STB aqueous buffer at pH 9.2 were used. The method was validated for precision, linearity, limit of detection (LOD) and limit of quantitation (LOQ) and the standard deviations were determined from the standard errors estimated by the regression line. Results - A micellar electrokinetic chromatography (MEKC) method for determination of butenolides in extracts gave full resolution for 1 and 2. The analytical curve in the range 10.0-50.0 mu g/mL (r(2) = 0.999) provided LOD and LOQ for 1 and 2 of 2.1/6.3 and 1.1/3.5 mu g/mL, respectively. The RSD for migration times were 0.12 and 1.0% for peak area ratios with 100.0 +/- 1.4% of recovery. Conclusions - A novel high-performance MEKC method developed for the analysis of butenolides 1 and 2 in leaf extracts of P. malacophyllum allowed their quantitative determined within an analysis time shorter than 5 min and the results indicated CE to be a feasible analytical technique for the quantitative determination of butenolides in Piper extracts. Copyright (C) 2010 John Wiley & Sons, Ltd.

Flow injection amperometric determination of hydrogen peroxide in household commercial products with a ruthenium oxide hexacyanoferrate modified electrode

Hydrogen peroxide was determined in oral antiseptic and bleach samples using a flow-injection system with amperometric detection. A glassy carbon electrode modified by electrochemical deposition of ruthenium oxide hexacyanoferrate was used as working electrode and a homemade Ag/AgCl (saturated KCl) electrode and a platinum wire were used as reference and counter electrodes, respectively. The electrocatalytic reduction process allowed the determination of hydrogen peroxide at 0.0 V. A linear relationship between the cathodic peak current and concentration of hydrogen peroxide was obtained in the range 10-5000 mu mol L(-1) with detection and quantification limits of 1.7 (S/N = 3) and 5.9 (S/N = 10) mu mol L(-1), respectively. The repeatability of the method was evaluated using a 500 mu mol L(-1) hydrogen peroxide solution, the value obtained being 1.6% (n = 14). A sampling rate of 112 samples h(-1) was achieved at optimised conditions. The method was employed for the quantification of hydrogen peroxide in two commercial samples and the results were in agreement with those obtained by using a recommended procedure.

The reduction of Cu(II)/neocuproine complexes by some polyphenols: Total polyphenols determination in wine samples

A new method is presented for spectrophotometric determination of total polyphenols content in wine. The procedure is a modified CUPRAC method based on the reduction of Cu(II), in hydroethanolic medium (pH 7.0) in the presence of neocuproine (2,9-dimethyl-1,10-phenanthroline), by polyphenols, yielding a Cu(I) complexes with maximum absorption peak at 450 nm. The absorbance values are linear (r = 0.998, n = 6) with tannic acid concentrations from 0.4 to 3.6 mu mol L(-1). The limit of detection obtained was 0.41 mu mol L(-1) and relative standard deviation 1.2% (1 mu mol L(-1); n = 8). Recoveries between 80% and 110% (mean value of 95%) were calculated for total polyphenols determination in 14 commercials and 2 synthetic wine samples (with and without sulphite). The proposed procedure is about 1.5 more sensitive than the official Folin-Ciocalteu method. The sensitivities of both methods were compared by the analytical responses of several polyphenols tested in each method. (C) 2010 Elsevier Ltd. All rights reserved.

Electroanalytical determination of promethazine hydrochloride in pharmaceutical formulations on highly boron-doped diamond electrodes using square-wave adsorptive voltammetry

The electrochemical oxidation of promethazine hydrochloride was made on highly boron-doped diamond electrodes. Cyclic voltammetry experiments showed that the oxidation mechanisms involved the formation of an adsorbed product that is more readily oxidized, producing a new peak with lower potential values whose intensity can be increased by applying the accumulation potential for given times. The parameters were optimized and the highest current intensities were obtained by applying +0.78 V for 30 seconds. The square-wave adsorptive voltammetry results obtained in BR buffer showed two well-defined peaks, dependent on the pH and on the voltammetric parameters. The best responses were obtained at pH 4.0, frequency of 50 s(-1), step of 2 mV, and amplitude of 50 mV. Under these conditions, linear responses were obtained for concentrations from 5.96 x 10(-7) to 4.76 x 10(-6) mol L-1, and calculated detection limits of 2.66 x 10(-8) mol L-1 (8.51 mu g L-1) for peak 1 and of 4.61 x 10(-8) mol L-1 (14.77 mu g L-1) for peak 2. The precision and accuracy were evaluated by repeatability and reproducibility experiments, which yielded values of less than 5.00% for both voltammetric peaks. ne applicability of this procedure was tested on commercial formulations of promethazine hydrochloride by observing the stability, specificity, recovery and precision of the procedure in complex samples. All results obtained were compared to recommended procedure by British Pharmacopeia. The voltammetric results indicate that the proposed procedure is stable and sensitive, with good reproducibility even when the accumulation steps involve short times. It is therefore very suitable for the development of the electroanalytical procedure, providing adequate sensitivity and a reliable method.

Ethanol oxidation reactions using SnO(2)@Pt/C as an electrocatalyst

This paper presents a study on the ethanol oxidation reaction using SnO(2)@Pt/C core-shell structures as electrocatalysts. All the materials used, including Pt/C and PtSn/C E-tek, were 20% (w/w) metal on carbon. The formation of core-shell nanoparticles (SnO(2)@Pt/C) was measured by UV-vis spectrophotometry. X-ray diffraction measurements showed Pt (shell) diffraction patterns without influence from the SnO(2) core and without any shift in 2 theta values for Pt. The diameters of the core-shell particle structures, measured using high-resolution transmission electron microscopy images, were in the range of 3-16 nm. The electrochemical profile for SnO(2)@Pt/C in an acidic medium (H(2)SO(4) at a concentration of 0.5 mol L(-1)) was almost the same as the typical electrochemical behavior for Pt in an acidic medium. Furthermore, the onset potential for the ethanol oxidation reaction using SnO(2)@Pt/C was almost the same as that for PtSn/C E-tek (0.23 V versus the reversible hydrogen electrode). However, the mass current peak densities for ethanol oxidation were 50% higher on SnO(2)@Pt/C than on PtSn/C E-tek. In the polarization curve, the mass current density for ethanol oxidation was higher at all potentials for SnO(2)@Pt/C when compared to Pt/C and PtSn/C E-tek. At 0.5 V, the current mass density for ethanol oxidation on SnO(2)@Pt was 2.3 times of that for the same process on the commercial material. The electrocatalytic activity of SnO(2)@Pt/C for ethanol oxidation was associated with an increase in the electrochemically active surface area. However, an electronic effect should also be considered because the Pt shell changes its electronic structure in the presence of the foreign core. (C) 2010 Elsevier B.V. All rights reserved.

Renal C-type natriuretic peptide and natriuretic peptide receptor B mRNA expression are affected by water deprivation in the Spinifex Hopping mouse

This study investigated the effect of water deprivation on the expression of C-type natriuretic peptide (CNP) and natriuretic peptide receptor B (NPR-B) mRNA, and the ability of NPR-B to generate cGMP in the Spinifex Hopping mouse, Notomys alexis. This rodent is a native of central and western Australia that is well adapted to survive in arid environments. Initially, CNP and NPR-B cDNAs (partial for NPR-B) were cloned and sequenced, and were shown to have high homology with those of rat and mouse. RT-PCR analysis showed CNP mRNA expression in the kidney, proximal and distal colon and small intestine, whilst NPR-B mRNA expression was found in the kidney, proximal and distal colon and the atria. Using a semi-quantitative multiplex PCR technique, the expression of renal CNP and NPR-B mRNA was determined in 7- and 14-day water-deprived hopping mice, in parallel with control hopping mice (access to water). Water deprivation significantly decreased the relative levels of CNP and NPR-B mRNA expression in both the 7- and 14-day water-deprived hopping mice, when compared to control hopping mice. In contrast, the ability of CNP to stimulate cGMP production was significantly increased after 14 days of water deprivation. This study shows that alterations in the renal CNP/NPR-B system may be an important physiological adjustment when water is scarce.

Effect of exercise on protein kinase C activity and localization in human skeletal muscle

To investigate the effect of exercise on protein kinase C (PKC) activity and localization in human skeletal muscle, eight healthy men performed cycle  ergometer exercise for 40 min at 76±1% the peak pulmonary O₂ uptake (V_O2peak), with muscle samples obtained at rest and after 5 and 40 min of exercise. PKC expression, phosphorylation and activities were examined by immunoblotting and in vitro kinase assays of fractionated and whole tissue preparations. In response to exercise, total PKC activity was slightly higher at 40 min in an enriched membrane fraction, and using a pSer-PKC-substrate motif antibody it was revealed that exercise increased the serine phosphorylation of a ∼50 kDa protein. There were no changes in conventional PKC (cPKC) or PKCθ activities; however, atypical PKC (aPKC) activity was ∼70% higher at 5 and 40 min, and aPKC expression and Thr^410/403 phosphorylation were unaltered by exercise. There were no effects of exercise on the abundance of PKCα, PKCδ, PKCθ and aPKC within cytosolic or enriched membrane fractions of skeletal muscle. These data indicate that aPKC, but not cPKC or PKCθ, are activated by exercise in contracting muscle suggesting a potential role for aPKC in the regulation of skeletal muscle function and metabolism during exercise in humans.

Improved endothelial function following a 14 month resistance exercise training program in adults with type 2 diabetes

Objective
We examined the effect of a 14-month progressive resistance training (PRT) program on endothelial function in both a supervised training (Center) group and non-supervised training (Home) group of patients with type 2 diabetes. We studied 28 men and women with type 2 diabetes who participated in a 14-month PRT involving an initial 2-month supervised program and a 12-month maintenance program.

Methods
Endothelial function testing was performed through laser doppler flow responses in the skin microcirculation to iontophoresis of acetylcholine (ACh) and sodium nitroprusside (NaNP) and doses of 4, 8 and 16 mC were used. Measurements of vascular response (VR), HbA1c, weight and blood pressure were performed at 0, 2 and 14 months.

Results
VR to ACh and NaNP was significantly increased at 14 months compared with baseline in both the Center and Home groups. However, no between-group differences were observed. A significant correlation was observed between HbA1c and VR to ACh at baseline and 8 weeks using 8 mC dose of ACh. There was a strong correlation between HbA1c at baseline and VR at 14 months using all three doses of ACh (4 mC:r = −0.546, p = 0.003, 8 mC:r = −0.470, p = 0.002, 16 mC:r = −0.547, p = 0.006).

Conclusions/interpretation
Endothelial function is improved following 14 months of PRT in type 2 diabetes both in a supervised and non-supervised program. Strong correlations with HbA1c including initial HbA1c levels suggest that glycemic control may be an important factor in long-term regulation of endothelial function.