Characterization of O(2) ((1)Delta(g))-Derived Oxidation Products of Tryptophan: A Combination of Tandem Mass Spectrometry Analyses and Isotopic Labeling Studies

The fragmentation mechanisms of singlet oxygen [O(2) ((1)Delta(g))]-derived oxidation products of tryptophan (W) were analyzed using collision-induced dissociation coupled with (18)O-isotopic labeling experiments and accurate mass measurements. The five identified oxidized products, namely two isomeric alcohols (trans and cis WOH), two isomeric hydroperoxides (trans and cis WOOH), and N-formylkynurenine (FMK), were shown to share some common fragment ions and losses of small neutral molecules. Conversely, each oxidation product has its own fragmentation mechanism and intermediates, which were confirmed by (18)O-labeling studies. Isomeric WOH lost mainly H(2)O + CO, while WOOH showed preferential elimination of C(2)H(5)NO(3) by two distinct mechanisms. Differences in the spatial arrangement of the two isomeric WOHs led to differences in the intensities of the fragment ions. The same behavior was also found for trans and cis WOOH. FMK was shown to dissociate by a diverse range of mechanisms, with the loss of ammonia the most favored route. MS/MS analyses, (18)O-labeling, and H(2)(18)O experiments demonstrated the ability of FMK to exchange its oxygen atoms with water. Moreover, this approach also revealed that the carbonyl group has more pronounced oxygen exchange ability compared with the formyl group. The understanding of fragmentation mechanisms involved in O(2) ((1)Delta(g))-mediated oxidation of W provides a useful step toward the structural characterization of oxidized peptides and proteins. (J Am Soc Mass Spectrom 2009, 20, 188-197) (C) 2009 Published by Elsevier Inc. on behalf of American Society for Mass Spectrometry

Detection and Characterization of Cholesterol-Oxidized Products Using HPLC Coupled to Dopant Assisted Atmospheric Pressure Photoionization Tandem Mass Spectrometry

Oxidation of cholesterol (Ch) by a variety of reactive oxygen species gives rise mainly to hydroperoxides and aldehydes. Despite the growing interest in Ch-oxidized products, the detection and characterization of these products is still a matter of concern. In this work, the main Ch-oxidized products, namely, 3 beta-hydroxycholest-5-ene-7 alpha-hydroperoxide (7 alpha-OOH), 3 beta-5 alpha-cholest-6-ene-5-hydroperoxide (5 alpha-OOH), 3 beta-hydroxycholest-4-ene-6 alpha-hydroperoxide (6 alpha-OOH), 3 beta-hydroxycholest-4-ene-6 beta-hydroperoxide (6 beta-OOH), and 3 beta-hydroxy-5 beta-hydroxy-B-norcholestane-6 beta-carboxaldehyde (ChAld), were detected in the same analysis using high-performance liquid chromatography (HPLC) coupled to dopant assisted atmospheric pressure photoionization tandem mass spectrometry. The use of selected reaction monitoring mode (SRM) allowed a sensitive detection of each oxidized product, while the enhanced product ion mode (EPI) helped to improve the confidence of the analyses. Isotopic labeling experiments enabled one to elucidate mechanistic features during fragmentation processes. The characteristic fragmentation pattern of Ch-oxidized products is the consecutive loss of 1120 molecules, yielding cationic fragments at m/z 401, 383, and 365. Homolytic scissions of the peroxide bond are also seen. With (18)O-labeling approach, it was possible to establish a fragmentation order for each isomer. The SRM transitions ratio along with EPI and (18)O-labeled experiments give detailed information about differences for water elimination, allowing a proper discrimination between the isomers:Phis is of special interest considering the emerging role of Ch-oxidized products in the development of diseases.

Isotopic view of vegetation and carbon and nitrogen cycles in a cerrado ecosystem, southeastern Brazil

Carbon and nitrogen biogeochemical cycles in savannas are strongly regulated by the seasonal distribution of precipitation and pulses of nutrients released during the wetting of the dry soil and are critical to the dynamics of microorganisms and vegetation. The objective of this study was to investigate the spatial and temporal variability of C and N isotope ratios as indicators of the cycling of these elements in a cerrado sensu stricto area, within a protected area in a State Park in the state of São Paulo, Brazil. The foliar δ13C and δ15N values varied from -33.6 to -24.4 ‰ and -2.5 to 4.5 ‰, respectively. The δ13C values showed a consistent relationship with canopy height, revealing the importance of structure of the canopy over the C isotopic signature of the vegetation. Carbon isotopic variations associated with the length of the dry season indicated the importance of recent fixed C to the integrated isotopic signature of the leaf organic C. The studied Cerrado species showed a depleted foliar δ15N, but a wide range of foliar Nitrogen with no difference among canopy heights. However, seasonal variability was observed, with foliar δ15N values being higher in the transition period between dry and rainy seasons. The variation of the foliar C and N isotope ratios presented here was consistent with highly diverse vegetation with high energy available but low availability of water and N.

Analytical procedures for determining Pb and Sr isotopic compositions in water samples by ID-TIMS

Few articles deal with lead and strontium isotopic analysis of water samples. The aim of this study was to define the chemical procedures for Pb and Sr isotopic analyses of groundwater samples from an urban sedimentary aquifer. Thirty lead and fourteen strontium isotopic analyses were performed to test different analytical procedures. Pb and Sr isotopic ratios as well as Sr concentration did not vary using different chemical procedures. However, the Pb concentrations were very dependent on the different procedures. Therefore, the choice of the best analytical procedure was based on the Pb results, which indicated a higher reproducibility from samples that had been filtered and acidified before the evaporation, had their residues totally dissolved, and were purified by ion chromatography using the Biorad® column. Our results showed no changes in Pb ratios with the storage time.

Carbon Stocks and Isotopic Composition of the Organic Matter in Soils Covered by Native Vegetation and Pasture in Sorocaba, SP, Brazil

Land cover change constitutes one of main way of alteration of soil organic matter in both quantitative and qualitative terms. The goal of this study was to compare the carbon stock and the isotopic signature of the organic matter in the soil of areas with different land use,covered with forest and grass (pasture). The study area is located at Sorocaba, SP, Brazil. Using un-deformed soil samples, we measured the carbon content and bulk density. The isotopic signature of soil carbon was determined through the analysis of isotopic ratio (12)C/(13)C. The pasture soil stocks 48% less carbon than the soil covered by natural forest. The isotopic signature indicated that 42.2% of organic matter of the soil covered by pasture is originated from grasses. This characterizes a highly degradation of organic matter in the environment, both quantitatively and qualitatively. Hence, some guidelines of recuperation are described in order to restore the soil organic matter, structure and porosity.

Geodynamic evolution of the SW Variscides: Orogenic collapse shown by new tectonometamorphic and isotopic data from western Ossa-Morena Zone, SW Iberia

The pre-Mesozoic geodynamic evolution of SW Iberia has been investigated on the basis of detailed structural analysis, isotope dating, and petrologic study of high-pressure (HP) rocks, revealing the superposition of several tectonometamorphic events: (1) An HP event older than circa 358 Ma is recorded in basic rocks preserved inside marbles, which suggests subduction of a continental margin. The deformation associated with this stage is recorded by a refractory graphite fabric and noncoaxial mesoscopic structures found within the host metasediments. The sense of shear is top to south, revealing thrusting synthetic with subduction (underthrusting) to the north. (2) Recrystallization before circa 358 Ma is due to a regional-scale thermal episode and magmatism. (3) Noncoaxial deformation with top to north sense of shear in northward dipping large-scale shear zones is associated with pervasive hydration and metamorphic retrogression under mostly greenschist facies. This indicates exhumation by normal faulting in a detachment zone confined to the top to north and north dipping shear zones during postorogenic collapse soon after 358 Ma ago (inversion of earlier top to south thrusts). (4) Static recrystallization at circa 318 Ma is due to regional-scale granitic intrusions. Citation: Rosas, F. M., F. O. Marques, M. Ballevre, and C. Tassinari (2008), Geodynamic evolution of the SW Variscides: Orogenic collapse shown by new tectonometamorphic and isotopic data from western Ossa-Morena Zone, SW Iberia, Tectonics, 27, TC6008, doi:10.1029/2008TC002333.

Isotopic determination of silicon by mass spectrometry in plants and soils labeled with Si-30

A method for isotopic determination of silicon by mass spectrometry in plants and soils labeled with Si-30 is reported. The development of this method is for use with studies involving the physiological process of absorption, transport, and redistribution of Si in the soil-plant system by use of the stable isotope Si-30 as a tracer. The procedure leads to SiF4 formation, and the isotopic determination of Si was based on the measurements of the (SiF3+)-Si-28, (SiF3+)-Si-29, and (SiF3+)-Si-30 signals. Relative standard deviation of Si-30 abundance measurements (n = 6) were lower than 0.1%, and the detection limit was 0.5 mg Si (dry mass).

Abnormally increased effective connectivity between parahippocampal gyrus and ventromedial prefrontal regions during emotion labeling in bipolar disorder

Emotional liability and mood dysregulation characterize bipolar disorder (BID), yet no study has examined effective connectivity between parahippocampal gyrus and prefrontal cortical regions in ventromedial and dorsal/lateral neural systems subserving mood regulation in BD. Participants comprised 46 individuals (age range: 18-56 years): 21 with a DSM-IV diagnosis of BID, type I currently remitted; and 25 age- and gender-matched healthy controls (HC). Participants performed an event-related functional magnetic resonance imaging paradigm, viewing mild and intense happy and neutral faces. We employed dynamic causal modeling (I)CM) to identify significant alterations in effective connectivity between BD and HC. Bayes model selection was used to determine the best model. The right parahippocampal gyrus (PHG) and right subgenual cingulate gyrus (sgCG) were included as representative regions of the ventromedial neural system. The right dorsolateral prefrontal cortex (DLPFC) region was included as representative of the dorsal/lateral neural system. Right PHG-sgCG effective connectivity was significantly greater in BD than HC, reflecting more rapid, forward PHG-sgCG signaling in BD than HC. There was no between-group difference in sgCG-DLPFC effective connectivity. In BD, abnormally increased right PHG-sgCG effective connectivity and reduced right PHG activity to emotional stimuli suggest a dysfunctional ventromedial neural system implicated in early stimulus appraisal, encoding and automatic regulation of emotion that may represent a pathophysiological functional neural mechanism for mood dysregulation in BD. (C) 2009 Elsevier Ireland Ltd. All rights reserved.

The use of fluorescein for labeling genomic probes in the checkerboard DNA-DNA hybridization method

Molecular methods that permit the simultaneous detection and quantification of a large number of microbial species are currently employed in the evaluation of complex ecosystems. The checkerboard DNA-DNA hybridization technique enables the simultaneous identification of distinct bacterial. species in a large number of dental samples. The original technique employed digoxigenin-labeled whole genomic DNA probes which were detected by chemiluminescence. In this study, we present an alternative protocol for labeling and detecting whole genomic DNA probes in the Checkerboard DNA-DNA hybridization method. Whole genomic DNA was extracted from five bacterial species and labeled with fluorescein. The fluorescein labeled whole genomic DNA probes were hybridized against whole genomic DNA or subgingival plaque samples in a checkerboard hybridization format, followed by chemiluminescent detection. Our results reveal that fluorescein is a viable and adequate alternative labeling reagent to be employed in the checkerboard DNA-DNA hybridization technique. (c) 2007 Elsevier GmbH. All rights reserved.

Nitrogen fluxes from treefrogs to tank epiphytic bromeliads: an isotopic and physiological approach

Diverse invertebrate and vertebrate species live in association with plants of the large Neotropical family Bromeliaceae. Although previous studies have assumed that debris of associated organisms improves plant nutrition, so far little evidence supports this assumption. In this study we used isotopic ((15)N) and physiological methods to investigate if the treefrog Scinax hayii, which uses the tank epiphytic bromeliad Vriesea bituminosa as a diurnal shelter, contributes to host plant nutrition. In the field, bromeliads with frogs had higher stable N isotopic composition (delta(15)N) values than those without frogs. Similar results were obtained from a controlled greenhouse experiment. Linear mixing models showed that frog feces and dead termites used to simulate insects that eventually fall inside the bromeliad tank contributed, respectively, 27.7% (+/- 0.07 SE) and 49.6% (+/- 0.50 SE) of the total N of V. bituminosa. Net photosynthetic rate was higher in plants that received feces and termites than in controls; however, this effect was only detected in the rainy, but not in the dry season. These results demonstrate for the first time that vertebrates contribute to bromeliad nutrition, and that this benefit is seasonally restricted. Since amphibian-bromeliad associations occur in diverse habitats in South and Central America, this mechanism for deriving nutrients may be important in bromeliad systems throughout the Neotropics.

Adapting Web content for low-literacy readers by using lexical elaboration and named entities labeling

This paper presents an approach for assisting low-literacy readers in accessing Web online information. The oEducational FACILITAo tool is a Web content adaptation tool that provides innovative features and follows more intuitive interaction models regarding accessibility concerns. Especially, we propose an interaction model and a Web application that explore the natural language processing tasks of lexical elaboration and named entity labeling for improving Web accessibility. We report on the results obtained from a pilot study on usability analysis carried out with low-literacy users. The preliminary results show that oEducational FACILITAo improves the comprehension of text elements, although the assistance mechanisms might also confuse users when word sense ambiguity is introduced, by gathering, for a complex word, a list of synonyms with multiple meanings. This fact evokes a future solution in which the correct sense for a complex word in a sentence is identified, solving this pervasive characteristic of natural languages. The pilot study also identified that experienced computer users find the tool to be more useful than novice computer users do.

Arterial spin labeling of cerebral perfusion territories using a seperate labeling coil

Purpose: To obtain cerebral perfusion territories of the left, the right. and the posterior circulation in humans with high signal-to-noise ratio (SNR) and robust delineation. Materials and Methods: Continuous arterial spin labeling (CASL) was implemented using a dedicated radio frequency (RF) coil. positioned over the neck, to label the major cerebral feeding arteries in humans. Selective labeling was achieved by flow-driven adiabatic fast passage and by tilting the longitudinal labeling gradient about the Y-axis by theta = +/- 60 degrees. Results: Mean cerebral blood flow (CBF) values in gray matter (GM) and white matter (WM) were 74 +/- 13 mL center dot 100 g(-1) center dot minute(-1) and 14 +/- 13 mL center dot 100 g(-1) center dot minute(-1), respectively (N = 14). There were no signal differences between left and right hemispheres when theta = 0 degrees (P > 0.19), indicating efficient labeling of both hemispheres. When theta = +60 degrees, the signal in GM on the left hemisphere, 0.07 +/- 0.06%, was 92% lower than on the right hemisphere. 0.85 +/- 0.30% (P < 1 x 10(-9)). while for theta = -60 degrees, the signal in the right hemisphere. 0.16 +/- 0.13%, was 82% lower than on the contralateral side. 0.89 +/- 0.22% (P < 1 x 10(-10)). Similar attenuations were obtained in WM. Conclusion: Clear delineation of the left and right cerebral perfusion territories was obtained, allowing discrimination of the anterior and posterior circulation in each hemisphere.

The link between partial melting, granitization and granulite development in central Ribeira Fold Belt, SE Brazil: New evidence from elemental and Sr-Nd isotopic geochemistry

Elemental and Sr-Nd isotopic data on metatexites, diatexites, orthogneisses and charnockites from the central Ribeira Fold Belt indicate that they are LILE-enriched weakly peraluminous granodiorites. Harker and Th-Hf-La correlation trends suggest that these rocks represent a co-genetic sequence, whereas variations on CaO, MnO, Y and HREE for charnockites can be explained by garnet consumption during granulitic metamorphism. Similar REE patterns and isotopic results of epsilon(565)(Nd) = -5.4 to -7.3 and (87)Sr/(86)Sr(565) = 0.706-0.711 for metatexites, diatexites, orthogneisses and charnockites, as well as similar T(DM) ages between 2.0 and 1.5 Ga are consistent with evolution from a relatively homogeneous and enriched common crustal (metasedimentary) protolith. Results suggest a genetic link between metatexites, diatexites, orthogneisses and charnockites and a two-step process for charnockite development: (a) generation of the hydrated igneous protoliths by anatexis of metasedimentary rocks; (b) continuous high-grade metamorphism that transformed the ""S-type granitoids"" (leucosomes and diatexites) into orthogneisses and, as metamorphism and dehydration progressed, into charnockites. (C) 2011 Elsevier Ltd. All rights reserved.

Post-collisional lamprophyric event in Sierra Norte, Cordoba, Argentina: Mineralogical, geochemical and isotopic characteristics

Over 20 lamprophyre dykes, varying in width between a few centimeters and several meters, have been identified in central Sierra Norte - Eastern Pampean Ranges, Cordoba, Argentina. Their mineralogy and chemistry indicate that they are part of the calc-alkaline lamprophyres clan (CAL). They contain phenocrysts of magnesiohomblende +/- augite set in a groundmass of magnesiohornblende, calcic-plagioclase, alkali feldspar, and opaque minerals, which designate them as spessartite-type lamprophyres. Alteration products include chlorite, calcite and iron oxides after malfic phenocrysts, though some are partially replaced by actinolite. Feldspars are replaced by carbonate and clay minerals. The dykes are relatively primitive, and show restricted major element variation (SiO(2) 51.1-55.3 wt.%, Al(2)O(3) 12-16.6 wt.%, total alkalies 1.5-4.7 wt.%), high Mg# (55-77), high Cr contents (27-988 ppm) and moderate to high Ni contents (60-190 ppm). Lamprophyre LILE (e.g. Rb averages 110 ppm, Sr 211-387 ppm, Ba 203-452 ppm) are high relative to HFSE (e.g., Ta 0.2-1.6 ppm, Nb 4-11 ppm, Y 17-21 ppm), and are enriched in LREE (30-70 times chondrite). They are characterized by relatively high (208)Pb/(204)Pb (38.8-39.9), (207)Pb/(204)Pb(similar to 15.7), and (206)Pb/(204)Pb (18.7-20.1), combined with low (epsilon)epsilon(Nd) (-4.69 to -1.52) and a relative moderately high ((87)Sr/(86)Sr)(i) of 0.7055-0.7074. The Rb-Sr whole rock isochron indicates an Early Ordovician age of 485 +/- 25 Ma. The calculated T(DM) (1.7 Ga) suggests that these rocks appear to have originated from a reservoir that was created during a mantle metasomatism event related to the Pampean orogeny. The Sierra Norte lamprophyres show affinities with a subduction-related magma in an active continental margin. Their geochemical and isotopic features suggest a multicomponent source, composed of enriched mantle material variably contaminated by crustal components. The lamprophyric suite emplacement occurred at the dawning stage of the Pampean orogeny, in a regional post-collisional extensional setting developed in the Sierra Norte-Ambargasta batholith (SNAB) in Early Ordovician times. (C) 2008 Published by Elsevier Ltd.

Sr-Nd isotopic evidence for crustal contamination in the Niquelandia complex, Goias, Central Brazil

The Niquelandia complex is a Neoproterozoic mafic-ultramafic intrusion resulting from fractional crystallization of primary picritic basalt intrusions. It consists of two layered sequences: a lower and larger one (LS), where four stratigraphic units exhibit an upward decrease of ultramafic layers and increase of gabbroic layers; an upper, smaller sequence (US), separated from LS by a high-temperature shear zone and consisting of two stratigraphic units (gabbros + anorthosites and amphibolites). Nd and Sr isotopic analyses and rare earth element (REE) profiles provide evidence that the complex suffered important crustal contamination. The LS isotopic array trends from a DM region with positive epsilon Nd and moderately positive epsilon Sr towards a field occupied by crustal xenoliths, especially abundant in the upper LS (negative epsilon Nd and large, positive E:Sr). Each LS stratigraphic unit is distinct from the next underlying unit, showing lower epsilon Nd and higher epsilon Sr, suggesting inputs of fresh magma and mixing with the contaminated, residual magma. The US is characterised by a relatively high variation of epsilon Nd and constant epsilon Sr. REE patterns vary within each unit from LREE depleted to LREE enriched in the samples having lower epsilon Nd and higher epsilon Sr. The contamination process has been modelled by using the EC-AFC algorithms from [Spera, F.J., Bohrson, W.A., 2001. Energy-constrained open-system magmatic processes 1: general model and energy-constrained assimilation and fractional crystallization (EC-AFC) formulation. J. Petrology 42, 999-1018]. The differences between the LS and US isotopic arrays are consistent with contamination by the same crustal component, provided that its melting degree was higher in LS than in US. The different degrees of anatexis are explained by the heat budget released from the magma, higher in LS (because of its larger mass) than in US. Comparison of the correlations between isotopes and incompatible trace element ratios of the models and of the gabbros shows some differences, which are demonstrably related with the variable amount of cumulus phases and trapped melt in the gabbros. (c) 2007 Elsevier Ltd. All rights reserved.