Instantaneous characterization of vegetable oils via TAG and FFA profiles by easy ambient sonic-spray ionization mass spectrometry

A fast and reliable method is presented for the analysis of vegetable oils. Easy ambient sonic-spray ionization mass spectrometry (EASI-MS) is shown to efficiently desorb and ionize the main oil constituents from an inert surface under ambient conditions and to provide comprehensive triacylglyceride (TAG) and free fatty acid (FFA) profiles detected mainly as either [ TAG + Na](+) or [FFA - H](-) ions. EASI(+/-)-MS analysis is simple, easily implemented, requires just a tiny droplet of the oil and is performed without any pre-separation or chemical manipulation. It also causes no fragmentation of TAG ions hence diacylglyceride (DAG) and monoacylglyceride (MAG) profiles and contents can also be measured. The EASI(+/-)-MS profiles of TAG and FFA permit authentication and quality control and can be used, for instance, to access levels of adulteration, acidity, oxidation or hydrolysis of vegetable oils in general.

Energy systems contributions in 2,000 m race simulation: a comparison among rowing ergometers and water

This study investigated the energy system contributions of rowers in three different conditions: rowing on an ergometer without and with the slide and rowing in the water. For this purpose, eight rowers were submitted to 2,000 m race simulations in each of the situations defined above. The fractions of the aerobic (W(AER)), anaerobic alactic (W(PCR)) and anaerobic lactic (W([La-])) systems were calculated based on the oxygen uptake, the fast component of excess post-exercise oxygen uptake and changes in net blood lactate, respectively. In the water, the metabolic work was significantly higher [(851 (82) kJ] than during both ergometer [674 (60) kJ] and ergometer with slide [663 (65) kJ] (P <= 0.05). The time in the water [515 (11) s] was higher (P < 0.001) than in the ergometers with [398 (10) s] and without the slide [402 (15) s], resulting in no difference when relative energy expenditure was considered: in the water [99 (9) kJ min(-1)], ergometer without the slide [99.6 (9) kJ min(-1)] and ergometer with the slide [100.2 (9.6) kJ min(-1)]. The respective contributions of the WAER, WPCR and W[La-] systems were water = 87 (2), 7 (2) and 6 (2)%, ergometer = 84 (2), 7 (2) and 9 (2)%, and ergometer with the slide = 84 (2), 7 (2) and 9 (1)%. (V) over dotO(2), HR and lactate were not different among conditions. These results seem to indicate that the ergometer braking system simulates conditions of a bigger and faster boat and not a single scull. Probably, a 2,500 m test should be used to properly simulate in the water single-scull race.

Numerical prediction of gas concentrations and fluctuations above a triangular hill within a turbulent boundary layer

The objective of the present work is to propose a numerical and statistical approach, using computational fluid dynamics, for the study of the atmospheric pollutant dispersion. Modifications in the standard k-epsilon turbulence model and additional equations for the calculation of the variance of concentration are introduced to enhance the prediction of the flow field and scalar quantities. The flow field, the mean concentration and the variance of a flow over a two-dimensional triangular hill, with a finite-size point pollutant source, are calculated by a finite volume code and compared with published experimental results. A modified low Reynolds k-epsilon turbulence model was employed in this work, using the constant of the k-epsilon model C(mu)=0.03 to take into account the inactive atmospheric turbulence. The numerical results for the velocity profiles and the position of the reattachment point are in good agreement with the experimental results. The results for the mean and the variance of the concentration are also in good agreement with experimental results from the literature. (C) 2009 Elsevier Ltd. All rights reserved.

Threshold voltages of SOI MuGFETs

The multiple-gate field-effect transistor (MuGFET) is a device with a gate folded on different sides of the channel region. They are one of the most promising technological solutions to create high-performance ultra-scaled SOI CMOS. In this work, the behavior of the threshold voltage in double-gate, triple-gate and quadruple-gate SOI transistors with different channel doping concentrations is studied through three-dimensional numerical simulation. The results indicated that for double-gate transistors, one or two threshold voltages can be observed, depending on the channel doping concentration. However, in triple-gate and quadruple-gate it is possible to observe up to four threshold voltages due to the corner effect and the different doping concentration between the top and bottom of the Fin. (C) 2008 Elsevier Ltd. All rights reserved.

Vibration-enhanced posture stabilization achieved by tactile supplementation: May blind individuals get extra benefits?

Diminished balance ability poses a serious health risk due to the increased likelihood of falling, and impaired postural stability is significantly associated with blindness and poor vision. Noise stimulation (by improving the detection of sub-threshold somatosensory information) and tactile supplementation (i.e. additional haptic information provided by an external contact surface) have been shown to improve the performance of the postural control system. Moreover, vibratory noise added to the source of tactile supplementation (e.g. applied to a surface that the fingertip touches) has been shown to enhance balance stability more effectively than tactile supplementation alone. In view of the above findings, in addition to the well established consensus that blind subjects show superior abilities in the use of tactile information, we hypothesized that blind subjects may take extra benefits from the vibratory noise added to the tactile supplementation and hence show greater improvements in postural stability than those observed for sighted subjects. If confirmed, this hypothesis may lay the foundation for the development of noise-based assistive devices (e.g. canes, walking sticks) for improving somatosensation and hence prevent falls in blind individuals. (C) 2011 Elsevier Ltd. All rights reserved.

Private valuation of carbon sequestration in forest plantations

Approval of the Clean Development Mechanism, provided for in the Kyoto Protocol, enables countries with afforested land to trade in carbon emissions reduction certificates related to carbon dioxide equivalent quantities (CO(2-e)) stored within a certain forest area. Potential CO(2-e) above base line sequestration was determined for two forest sites on commercial eucalyptus plantations in northern Brazil (Bahia). Compensation values for silvicultural regimes involving rotation lengths greater than economically optimal were computed using the Faustmann formula. Mean values obtained were US$8.16 (MgCO(2-e))(-1) and US $7.19 (MgCO(2-e))(-1) for average and high site indexes, respectively. Results show that carbon supply is more cost-efficient in highly productive sites. Annuities of US$18.8 Mg C(-1) and US$35.1 Mg C(-1) and yearly payments of US$4.4 m(-3) and US$8.2 m(-3) due for each marginal cubic meter produced were computed for high and average sites, respectively. The estimated value of the tonne of carbon defines minimum values to be paid to forest owners, in order to induce a change in silvicultural management regimes. A reduction of carbon supply could be expected as a result of an increase in wood prices, although it would not respond in a regular manner. For both sites, price elasticity of supply was found to be inelastic and increased as rotation length moved further away from economically optimal: 0.24 and 0.27 for age 11 years in average- and high-productivity sites, respectively. This would be due to biomass production potential as a limiting factor; beyond a certain threshold value. an increase in price does not sustain a proportional change in carbon storage supply. The environmental service valuation model proposed might be adequate for assessing potential supply in plantation forestry, from a private landowner perspective, with an economic opportunity cost. The model is not applicable to low commercial value forest plantations. (C) 2009 Elsevier B.V. All rights reserved.

Diet-dependent life history, feeding preference and thermal requirements of the predatory mite Neoseiulus baraki (Acari: Phytoseiidae)

Neoseiulus baraki Athias-Henriot (Acari: Phytoseiidae) has been reported from the Americas, Africa and Asia, often in association with Aceria guerreronis Keifer (Acari: Eriophyidae), one of the most important pests of coconut (Cocos nucifera L.) in diVerent parts of the world. That phytoseiid has been considered one of the most common predators associated with A. guerreronis in Brazil. The objective of this study was to evaluate the feeding preference and the eVect of food items commonly present on coconut fruits and several temperature regimes on the life history of a Brazilian population of N. baraki. Completion of immature development was possible when N. baraki was fed A. guerreronis, Steneotarsonemus concavuscutum Lofego and Gondim Jr., and Tyrophagus putrescentiae (Schrank). Fecundity was highest on T. putrescentiae (39.4 eggs), followed by A. guerreronis (24.8 eggs). In choice tests, irrespective of the food on which N. baraki was reared, a larger number of adults of this predator chose leaf discs containing A. guerreronis than discs containing other food items, demonstrating a preference of the former for the latter as food. Egg to adult thermal developmental time was calculated as 84.2 degree-days, above a threshold of 15.8 degrees C. This lower developmental threshold is higher than previously published for phytoseiid species from higher latitudes. Neoseiulus baraki was shown to have higher biotic potential at 30 degrees C (r(m) 0.29). The results suggest N. baraki to be a promising biological control agent of A. guerreronis, well adapted to survive and develop in areas with relatively high temperatures, where that pest prevails.

Suitability of relative humidity as an estimator of leaf wetness duration

Leaf wetness duration (LWD) is a key parameter in agricultural meteorology since it is related to epidemiology of many important crops, controlling pathogen infection and development rates. Because LWD is not widely measured, several methods have been developed to estimate it from weather data. Among the models used to estimate LWD, those that use physical principles of dew formation and dew and/or rain evaporation have shown good portability and sufficiently accurate results, but their complexity is a disadvantage for operational use. Alternatively, empirical models have been used despite their limitations. The simplest empirical models use only relative humidity data. The objective of this study was to evaluate the performance of three RH-based empirical models to estimate LWD in four regions around the world that have different climate conditions. Hourly LWD, air temperature, and relative humidity data were obtained from Ames, IA (USA), Elora, Ontario (Canada), Florence, Toscany (Italy), and Piracicaba, Sao Paulo State (Brazil). These data were used to evaluate the performance of the following empirical LWD estimation models: constant RH threshold (RH >= 90%); dew point depression (DPD); and extended RH threshold (EXT_RH). Different performance of the models was observed in the four locations. In Ames, Elora and Piracicaba, the RH >= 90% and DPD models underestimated LWD, whereas in Florence these methods overestimated LWD, especially for shorter wet periods. When the EXT_RH model was used, LWD was overestimated for all locations, with a significant increase in the errors. In general, the RH >= 90% model performed best, presenting the highest general fraction of correct estimates (F(C)), between 0.87 and 0.92, and the lowest false alarm ratio (F(AR)), between 0.02 and 0.31. The use of specific thresholds for each location improved accuracy of the RH model substantially, even when independent data were used; MAE ranged from 1.23 to 1.89 h, which is very similar to errors obtained with published physical models for LWD estimation. Based on these results, we concluded that, if calibrated locally, LWD can be estimated with acceptable accuracy by RH above a specific threshold, and that the EXT_RH method was unsuitable for estimating LWD at the locations used in this study. (C) 2007 Elsevier B.V. All rights reserved.

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.

Dissociation of deprotonated microcystin variants by collision-induced dissociation following electrospray ionization

Microcystins (MC) are a family of hepatotoxic cyclic heptapeptides produced by a number of different cyanobacterial species. Considering the recent advances in the characterization of deprotonated peptides by mass spectrometry, the fragmentation behavior of four structurally related microcystin compounds was investigated using collision-induced dissociation (CID) experiments on an orbitrap mass spectrometer. It is demonstrated in this study that significant structural information can be obtained from the CID spectra of deprotonated microcystins. A predominant ring-opening reaction at the isoMeAsp residue, as well as two major complementary fragmentation pathways, was observed, reducing the complexity of the product ion spectra in comparison with spectra observed from protonated species. This proposed fragmentation behavior was applied to characterize [Leu(1)]MC-LR from a cyanobacterial cell extract. In conclusion, CID spectra of microcystins in the negative ion mode provide rich structurally informative mass spectra which greatly enhance confidence in structural assignments, in particular when combined with complementary positive ion CID spectra. Copyright (C) 2011 John Wiley & Sons, Ltd.

Re-examination of the anion derivatives of isoflavones by radical fragmentation in negative electrospray ionization tandem mass spectrometry: experimental and computational studies

This paper reports theoretical and experimental studies of gas-phase fragmentation reactions of four naturally occurring isoflavones. The samples were analyzed in negative ion mode by direct infusion in ESI-QqQ, ESI-QqTOF and ESI-Orbitrap systems. The MS/MS and MS(n) spectra are in agreement with the fragmentation proposals and high-resolution analyses have confirmed the formulae for each ion observed. As expected, compounds with methoxyl aromatic substitution have showed a radical elimination of center dot CH(3) as the main fragmentation pathway. A second radical loss (center dot H) occurs as previously observed for compounds which exhibit a previous homolytic center dot CH(3) cleavage (radical anion) and involves radical resonance to stabilize the anion formed. However, in this study we suggest another mechanism for the formation of the main ions, on the basis of the enthalpies for each species. Compounds without methoxy substituent dissociate at the highest energies and exhibit the deprotonated molecule as the most intense ion. Finally, energy-resolved experiments were carried out to give more details about the gas-phase dissociation reaction of the isoflavones and the results are in agreement with the theoretical approaches. Copyright (C) 2011 John Wiley & Sons, Ltd.

Fragmentation studies and electrospray ionization mass spectrometry of lapachol: protonated, deprotonated and cationized species

Electrospray ionization mass spectrometric analysis of lapachol (2-hydroxy-3-(3-methy1-2-butenyl)-1,4-naphthoquinone) was accomplished in order to elucidate the gas-phase dissociation reactions of this important biologically active natural product. The occurrence of protonated and cationized species in the positive mode and of deprotonated species in the negative mode was explored by means of collision-induced dissociation (CID) experiments. For the protonated molecule, the H(2)O and C(4)H(8) losses occur by two competitive channels. For the deprotonated molecule, the even-electron rule is not conserved, and the radicalar species are eliminated by formation of distonic anions. The fragmentation mechanism for each ion was suggested on the basis of computational thermochemistry. Atomic charges, relative energies, and frontier orbitals were employed aiming at a better understanding of the gas-phase reactivity of lapachol. Potential energy surfaces for fragmentation reactions were obtained by the B3LYP/6-31+G(d,p) model. Copyright (C) 2010 John Wiley & Sons, Ltd.

A plateau detected in lead accumulation in subsurface deciduous enamel from individuals exposed to lead may be useful to identify children and regions exposed to higher levels of lead

In a previous study, we showed 4 times more lead in surface deciduous enamel (1.9-5.9 mu m) of a notoriously contaminated area (Bauru, Sao Paulo State, Brazil) in comparison to samples from a region with no lead contamination described (Ribeirao Preto, Sao Paulo State, Brazil). The samples from the more superficial enamel (1.9-3.18 mu m) showed higher amounts of lead and the highest variability, while in the subsurface enamel (3.18-5.9 mu m) a plateau in lead content was detected in children living in the contaminated environment (around 600 mu g/g). Here we expand our previous study, and use only samples obtained from subsurface enamel (Ribeirao Preto, n = 186; Bauru, n = 20). We tried to distinguish regions with more children with lead above the threshold of 600 mu g/g of lead in enamel. We tested whether differences in the percentage of children with ""high"" lead (>= 600 mu g/g) could be observed among the different Kindergartens studied in Ribeirao Preto. We also tested whether these results were different from the ones provided by conventional comparison of the data. Ribeirao Preto showed almost 4 times less lead than Bauru (p < 0.0001), and a statistically significant difference was found only in Ribeirao Preto between Kindergarten 2 and 5 (p<0.01). Twelve percent of the children from Ribeirao Preto had ""high"" lead, while 55% of the children from Bauru did so. However, when we looked at the percentages of children with ""high"" lead in each Kindergarten, and compared them, a whole new picture emerged, in which we could see children with ""high"" lead concentrated mainly in 3 Kindergartens from Ribeirao Preto, with Kindergarten 5 with 33% of the children with ""high"" lead, being statistically different from all Kindergartens, except 4 and 6. The threshold of 600 mu g/g of lead in subsurface enamel was tentatively settled here after the plateau seen in exposed children, and enabled us to identify locations with more children exposed to a higher amount of lead. (C) 2008 Elsevier Inc. All rights reserved.

Tests for the hysteresis hypothesis in Brazilian industrialized exports: A threshold cointegration analysis

This paper examines the hysteresis hypothesis in the Brazilian industrialized exports using a time series analysis. This hypothesis finds an empirical representation into the nonlinear adjustments of the exported quantity to relative price changes. Thus, the threshold cointegration analysis proposed by Balke and Fomby [Balke, N.S. and Fomby, T.B. Threshold Cointegration. International Economic Review, 1997; 38; 627-645.] was used for estimating models with asymmetric adjustment of the error correction term. Amongst sixteen industrial sectors selected, there was evidence of nonlinearities in the residuals of long-run relationships of supply or demand for exports in nine of them. These nonlinearities represent asymmetric and/or discontinuous responses of exports to different representative measures of real exchange rates, in addition to other components of long-run demand or supply equations. (C) 2007 Elsevier B.V. All rights reserved.

Generation of Naphthoquinone Radical Anions by Electrospray Ionization: Solution, Gas-Phase, and Computational Chemistry Studies

Radical anions are present in several chemical processes, and understanding the reactivity of these species may be described by their thermodynamic properties. Over the last years, the formation of radical ions in the gas phase has been an important issue concerning electrospray ionization mass spectrometry studies. In this work, we report on the generation of radical anions of quinonoid compounds (Q) by electrospray ionization mass spectrometry. The balance between radical anion formation and the deprotonated molecule is also analyzed by influence of the experimental parameters (gas-phase acidity, electron affinity, and reduction potential) and solvent system employed. The gas-phase parameters for formation of radical species and deprotonated species were achieved on the basis of computational thermochemistry. The solution effects on the formation of radical anion (Q(center dot-)) and dianion (Q(2-)) were evaluated on the basis of cyclic voltammetry analysis and the reduction potentials compared with calculated electron affinities. The occurrence of unexpected ions [Q + 15](-) was described as being a reaction between the solvent system and the radical anion, Q(center dot-).The gas-phase chemistry of the electrosprayed radical anions was obtained by collisional-induced dissociation and compared to the relative energy calculations. These results are important for understanding the formation and reactivity of radical anions and to establish their correlation with the reducing properties by electrospray ionization analyses.