[18O]-Oxygen incorporation reveals novel pathways in spiroacetal biosynthesis by Bactrocera cacuminata and B. cucumis

The origins of the oxygen atoms in 1,7-dioxaspiro[5.5]undecane (1) and hydroxyspiroacetal (2) from Bactrocera cacuminata, and in 2,8-dimethyl-1,7-dioxaspiro[5.5]undecane (3) and hydroxyspiroacetal (4) from B. cucumis, have been investigated by incorporation studies from both [18O2]-dioxygen and [18O]-water. Combined GC-MS examination and high-field NMR analysis have demonstrated that all oxygen atoms in 1 and 2 from B. cacuminata are dioxygen derived, but in contrast, the spiroacetals 3 and 4 from B. cucumis incorporate one ring oxygen from water and one ring oxygen (and the hydroxyl oxygen in 4) from [18O2]-dioxygen. These results reveal not only the generality of monoxygenase mediation of spiroacetal formation in Bactrocera sp., but also an unexpected complexity in their biosynthesis. A general paradigm accommodating these and other observations is presented.

Effect of maternal epidural analgesia on fetal intrapartum oxygen saturation

The use of maternal epidural analgesia in labor may be associated with nonreassuring fetal heart rate (FHR) patterns. Fetal oxygen saturation (FSpO(2)) monitoring may improve assessment of fetal well-being during this time. Mean FSpO(2) values were compared over seven 5-minute epochs: 5 minutes prior to an epidural event (combined insertion of epidural/top-up epidural analgesia and infusion pump bolus), to 30 minutes following the event, including possible effects of maternal position and FHR pattern on FSpO(2) values. Mean FSpO(2) values were significantly different between the 5 minutes prior (49.5%) versus 16-20 minutes (44.3%, p

Calculation of resonances and product state distributions for the unimolecular dissociation of H2S

Resonance phenomena associated with the unimolecular dissociation of H2S --> SH + H have been investigated quantum mechanically by the Lanczos homogeneous filter diagonalization method using a newly developed potential energy surface (J. Chem. Phys. 2001, 114, 320). Resonance energies, widths (rates), and product state distributions have been obtained. Both dissociation rates and product state distributions of SH show, strong fluctuations, indicating that the dissociation of H2S is essentially irregular. Statistical analysis of neighboring level spacing and width distributions also confirms this behavior. The dissociation rates and product state distributions are compared to the predictions of quantum phase space theory.

Role of oxygen in the nitrous oxide/carbon reaction

An investigation of the role of oxygen in the nitrous oxide/carbon reaction was carried out on various carbon samples (both graphitic and nongraphitic) over a range of temperatures and partial pressures. Previous work reported that oxygen strongly inhibited the nitrous oxide/carbon reaction. Large ratios of O-2/N2O were used in all previous work. In this work, the O-2/N2O ratio was kept below 1, and we found that oxygen did not inhibit the rate of the C + N2O reaction. Instead, the rate of the reaction in the presence of oxygen was essentially that predicted by the two independent reactions, nitrous oxide/carbon and oxygen/carbon, occurring simultaneously. A simple theoretical explanation is given for the observations, both past and present, on the basis of competitive chemisorption of nitrous oxide and oxygen on active sites.

Caenorhabditis elegans mutants resistant to phosphine toxicity show increased longevity and cross-resistance to the synergistic action of oxygen

Phosphine (hydrogen phosphide, PH3) is the fumigant most widely used to protect stored products from pest infestation. Despite the importance of this chemical, little is known about its mode of action. We have created three phosphine-resistant lines (pre-1, pre-7, pre-33) in the model organism C. elegans, with LC50 values 2, 5, and 9 times greater than the fully susceptible parental strain. Molecular oxygen was shown to be an extremely effective synergist with phosphine as, under hyperoxic conditions, 100% mortality was observed in wild-type nematodes exposed to 0.1 mg/l phosphine, a nonlethal concentration in air. All three mutants were resistant to the synergistic effects of oxygen in proportion to their resistance to phosphine with one mutant, pre-33, showing complete resistance to this synergism. We take the proportionality of cross-resistance between phosphine and the synergistic effect of oxygen to imply that all three mutants circumvent a mechanism of phosphine toxicity that is directly coupled to oxygen metabolism. Compared with the wild-type strain, all three mutants have an extended average life expectancy of from 12.5 to 25.3%. This is consistent with the proposed involvement of oxidative stress in both phosphine toxicity and ageing. Because the wild-type and mutant nematodes develop at the same rate, the longevity is unlikely to be caused by a clk-type reduction in oxidative metabolism, a potential alternative mechanism of phosphine resistance.

A model to investigate hepatic extraction of oxygen during anaesthesia in the dog

Measurement of hepatic oxygen extraction was performed on six healthy Greyhound dogs over a two hour period. The Greyhounds were anaesthetised and a right subcostal surgical incision performed. Ultrasonic flow transducers were used to measure flow rate in the hepatic artery and the portal vein. The blood oxygen tensions in arterial blood and in the portal and hepatic veins were also measured. Hepatic oxygen extraction remained stable throughout the study, despite a steady decline in arterial blood pressure. The methodology described in this study provides a direct measure of oxygen uptake by the liver in the dog and could readily be used to investigate hepatic uptake of drugs. (C) 2003 Elsevier Ltd. All rights reserved.

A comparison of two methods for the calculation of accumulated oxygen deficit

The aim of this study was to compare accumulated oxygen deficit data derived using two different exercise protocols with the aim of producing a less time-consuming test specifically for use with athletes. Six road and four track male endurance cyclists performed two series of cycle ergometer tests. The first series involved five 10 min sub-maximal cycle exercise bouts, a (V) over dotO(2peak) test and a 115% (V) over dotO(2peak) test. Data from these tests were used to estimate the accumulated oxygen deficit according to the calculations of Medbo et al. (1988). In the second series of tests, participants performed a 15 min incremental cycle ergometer test followed, 2 min later, by a 2 min variable resistance test in which they completed as much work as possible while pedalling at a constant rate. Analysis revealed that the accumulated oxygen deficit calculated from the first series of tests was higher (P< 0.02) than that calculated from the second series: 52.3 +/- 11.7 and 43.9 +/- 6.4 ml . kg(-1), respectively (mean +/- s). Other significant differences between the two protocols were observed for (V) over dot O-2peak, total work and maximal heart rate; all were higher during the modified protocol (P

Ichthyotoxicity of Chattonella marina (Raphidophyceae) to damselfish (Acanthochromis polycanthus): the synergistic role of reactive oxygen species and free fatty acids

This investigation aimed to elucidate the relative roles of putative brevetoxins, reactive oxygen species and free fatty acids as the toxic principle of the raphidophyte Chattonella marina, using damselfish as the bioassay. Our investigations on Australian C. marina demonstrated an absence or only very low concentrations of brevetoxin-like compounds by radio-receptor binding assay and liquid chromatography-mass spectroscopy techniques. Chattonella is unique in its ability to produce levels of reactive oxygen species 100 times higher than most other algal species. However, high levels of superoxide on their own were found not to cause fish mortalities. Lipid analysis revealed this raphidophyte to contain high concentrations of the polyunsaturated fatty acid eicosapentaenoic acid (EPA; 18-23% of fatty acids), which has demonstrated toxic properties to marine organisms. Using damselfish as a model organism, we demonstrated that the free fatty acid (FFA) form of EPA produced a mortality and fish behavioural response similar to fish exposed to C. marina cells. This effect was not apparent when fish were exposed to other lipid fractions including a triglyceride containing fish oil, docosahexaenoate-enriched ethyl ester, or pure brevetoxin standards. The presence of superoxide together with low concentrations of EPA accelerated fish mortality rate threefold. We conclude that the enhancement of ichthyotoxicity of EPA in the presence of superoxide can account for the high C. marina fish killing potential. (C) 2003 Elsevier B.V All rights reserved.

Symphysis-fundal height curve in the diagnosis of fetal growth deviations

OBJECTIVE: To validate a new symphysis-fundal curve for screening fetal growth deviations and to compare its performance with the standard curve adopted by the Brazilian Ministry of Health. METHODS: Observational study including a total of 753 low-risk pregnant women with gestational age above 27 weeks between March to October 2006 in the city of João Pessoa, Northeastern Brazil. Symphisys-fundal was measured using a standard technique recommended by the Brazilian Ministry of Health. Estimated fetal weight assessed through ultrasound using the Brazilian fetal weight chart for gestational age was the gold standard. A subsample of 122 women with neonatal weight measurements was taken up to seven days after estimated fetal weight measurements and symphisys-fundal classification was compared with Lubchenco growth reference curve as gold standard. Sensitivity, specificity, positive and negative predictive values were calculated. The McNemar χ2 test was used for comparing sensitivity of both symphisys-fundal curves studied. RESULTS: The sensitivity of the new curve for detecting small for gestational age fetuses was 51.6% while that of the Brazilian Ministry of Health reference curve was significantly lower (12.5%). In the subsample using neonatal weight as gold standard, the sensitivity of the new reference curve was 85.7% while that of the Brazilian Ministry of Health was 42.9% for detecting small for gestational age. CONCLUSIONS: The diagnostic performance of the new curve for detecting small for gestational age fetuses was significantly higher than that of the Brazilian Ministry of Health reference curve.

Anaerobic bacteria: an investigation of metabolic important enzymes: a novel type of oxygen reductase and enzymes of the tetrapyrrole biosynthesis

Desulfovibrio desulfuricans was the first species of a sulphatereducing bacterium to be isolated, in 1895. Since that time, many questions were raised in the scientific community regarding the metabolic and ecological aspects of these bacteria. At present, there is still a myriad of open questions remaining to be answered to enlarge our knowledge of the metabolic pathways operative in these bacteria that have implications in the sulfur cycle, in biocorrosion, namely in sewers and in oil and gas systems, and in bioremediation of several toxic metals. The work presented in this dissertation aimed at contributing with new insights of enzymes involved in two different metabolic systems on Desulfovibrio species, namely enzymes that play a role in the response to oxidative stress and that are involved in the haem biosynthetic pathway.(...)

Evaluation of the Electric Vehicle Impact in the Power Demand Curve in a Smart Grid Environment

Smart grids with an intensive penetration of distributed energy resources will play an important role in future power system scenarios. The intermittent nature of renewable energy sources brings new challenges, requiring an efficient management of those sources. Additional storage resources can be beneficially used to address this problem; the massive use of electric vehicles, particularly of vehicle-to-grid (usually referred as gridable vehicles or V2G), becomes a very relevant issue. This paper addresses the impact of Electric Vehicles (EVs) in system operation costs and in power demand curve for a distribution network with large penetration of Distributed Generation (DG) units. An efficient management methodology for EVs charging and discharging is proposed, considering a multi-objective optimization problem. The main goals of the proposed methodology are: to minimize the system operation costs and to minimize the difference between the minimum and maximum system demand (leveling the power demand curve). The proposed methodology perform the day-ahead scheduling of distributed energy resources in a distribution network with high penetration of DG and a large number of electric vehicles. It is used a 32-bus distribution network in the case study section considering different scenarios of EVs penetration to analyze their impact in the network and in the other energy resources management.

One-step preparation of optically transparent Ni-Fe oxide film electrocatalyst for oxygen evolution reaction

Optically transparent cocatalyst film materials is very desirable for improved photoelectrochemical (PEC)oxygen evolution reaction (OER) over light harvesting photoelectrodes which require the exciting light to irradiate through the cocatalyst side, i.e., front-side illumination. In view of the reaction overpotential at electrode/electrolyte interface, the OER electrocatalysts have been extensively used as cocatalysts for PEC water oxidation on photoanode. In this work, the feasibility of a one-step fabrication of the transparent thin film catalyst for efficient electrochemical OER is investigated. The Ni-Fe bimetal oxide films, 200 nm in thickness, are used for study. Using a reactive magnetron co-sputtering technique, transparent(> 50% in wavelength range 500-2000 nm) Ni-Fe oxide films with high electrocatalytic activities were successfully prepared at room temperature. Upon optimization, the as-prepared bimetal oxide film with atomic ratio of Fe/Ni = 3:7 demonstrates the lowest overpotential for the OER in aqueous KOH solution, as low as 329 mV at current density of 2 mA cm 2, which is 135 and 108 mV lower than that of as-sputtered FeOx and NiOx thin films, respectively. It appears that this fabrication strategy is very promising to deposit optically transparent cocatalyst films on photoabsorbers for efficient PEC water splitting.

RuSe Electrocatalysts and Single Wall Carbon Nanohorns Supports for the Oxygen Reduction Reaction

Selenium modified ruthenium electrocatalysts supported on carbon black were synthesized using NaBH4 reduction of the metal precursor. Prepared Ru/C electrocatalysts showed high dispersion and very small averaged particle size. These Ru/C electrocatalysts were subsequently modified with Se following two procedures: (a) preformed Ru/carbon catalyst was mixed with SeO2 in xylene and reduced in H2 and (b) Ru metal precursor was mixed with SeO2 followed by reduction with NaBH4. The XRD patterns indicate that a pyrite-type structure was obtained at higher annealing temperatures, regardless of the Ru:Se molar ratio used in the preparation step. A pyrite-type structure also emerged in samples that were not calcined; however, in this case, the pyrite-type structure was only prominent for samples with higher Ru:Se ratios. The characterization of the RuSe/C electrocatalysts suggested that the Se in noncalcined samples was present mainly as an amorphous skin. Preliminary study of activity toward oxygen reduction reaction (ORR) using electrocatalysts with a Ru:Se ratio of 1:0.7 indicated that annealing after modification with Se had a detrimental effect on their activity. This result could be related to the increased particle size of crystalline RuSe2 in heat-treated samples. Higher activity of not annealed RuSe/C catalysts could also be a result of the structure containing amorphous Se skin on the Ru crystal. The electrode obtained using not calcined RuSe showed a very promising performance with a slightly lower activity and higher overpotential in comparison with a commercial Pt/C electrode. Single wall carbon nanohorns (SWNH) were considered for application as ORR electrocatalysts' supports. The characterization of SWNH was carried out regarding their tolerance toward strong catalyzed corrosion conditions. Tests indicated that SWNH have a three times higher electrochemical surface area (ESA) loss than carbon black or Pt commercial electrodes.

Correlação da Variação dos Níveis de NT-ProBNP com a Modificação da Capacidade Funcional em Doentes com Insuficiência Cardíaca Crónica

OBJECTIVE: We set out to evaluate whether changes in N-terminal pro-brain natriuretic peptide (proBNP) can predict changes in functional capacity, as determined by cardiopulmonary exercise testing (CPET), in patients with chronic heart failure (CHF) due to dilated cardiomyopathy (DCM). METHODS: We studied 37 patients with CHF due to DCM, 81% non-ischemic, 28 male, who performed symptom-limited treadmill CPET, with the modified Bruce protocol, in two consecutive evaluations, with determination of proBNP after 10 minutes rest prior to CPET. The time between evaluations was 9.6+/-5.5 months, and age at first evaluation was 41.1+/-13.9 years (21 to 67). RESULTS IN THE FIRST AND SECOND EVALUATIONS RESPECTIVELY WERE: NYHA functional class >II 51% and 16% (p<0.001), sinus rhythm 89% and 86.5% (NS), left ventricular ejection fraction 24.9+/-8.9% and 26.6+/-8.6% (NS), creatinine 1.03+/-0.25 and 1.09+/-0.42 mg/dl (NS), taking ACE inhibitors or ARBs 94.5% and 100% (NS), beta-blockers 73% and 97.3% (p<0.001), and spironolactone 89% and 89% (NS). We analyzed the absolute and percentage variation (AV and PV) in peak oxygen uptake (pVO2--ml/kg/min) and proBNP (pg/ml) between the two evaluations. RESULTS: (1) pVO2 AV: -17.4 to 15.2 (1.9+/-5.7); pVO2 PV: -56.1 to 84% (11.0+/-25.2); proBNP AV: -12850 to 5983 (-778.4+/-3332.5); proBNP PV: -99.0 to 379.5% (-8.8+/-86.3); (2) The correlations obtained--r value and p value [r (p)]--are shown in the table below; (3) We considered that a coefficient of variation of pVO2 PV of >10% represented a significant change in functional capacity. On ROC curve analysis, a proBNP PV value of 28% showed 80% sensitivity and 79% specificity for pVO2 PV of >10% (AUC=0.876, p=0.01, 95% CI 0.75 to 0.99). CONCLUSIONS: In patients with CHF due to DCM, changes in proBNP values correlate with variations in pVO2, as assessed by CPET. However, our results suggest that only a proBNP PV of >28% predicts a significant change in functional capacity.