A temperature-dependent relative-rate study of the OH initiated oxidation of n-butane: the kinetics of the reactions of the 1-and 2-butoxy radicals

The kinetics of the reactions of 1-and 2-butoxy radicals have been studied using a slow-flow photochemical reactor with GC-FID detection of reactants and products. Branching ratios between decomposition, CH3CH(O-.)CH2CH3 CH3CHO + C2H5, reaction (7), and reaction with oxygen, CH3CH(O-.)CH2CH3 + O-2 -> CH3C(O)C2H5 + HO2, reaction (6), for the 2-butoxy radical and between isomerization, CH3CH2CH2CH2O. -> CH2CH2CH2CH2OH, reaction (9), and reaction with oxygen, CH3CH2CH2CH2O. + O-2 -> C3H7CHO + HO2, reaction (8), for the 1-butoxy radical were measured as a function of oxygen concentration at atmospheric pressure over the temperature range 250-318 K. Evidence for the formation of a small fraction of chemically activated alkoxy radicals generated from the photolysis of alkyl nitrite precursors and from the exothermic reaction of 2-butyl peroxy radicals with NO was observed. The temperature dependence of the rate constant ratios for a thermalized system is given by k(7)/k(6) = 5.4 x 1026 exp[(-47.4 +/- 2.8 kJ mol(-1))/RT] molecule cm(-3) and k(9)/k(8) = 1.98 x 10(23) exp[(-22.6 +/- 3.9 kJ mol(-1))/RT] molecule cm(-3). The results agree well with the available experimental literature data at ambient temperature but the temperature dependence of the rate constant ratios is weaker than in current recommendations.

Verification of cloud-fraction forecasts

Cloud radar and lidar can be used to evaluate the skill of numerical weather prediction models in forecasting the timing and placement of clouds, but care must be taken in choosing the appropriate metric of skill to use due to the non- Gaussian nature of cloud-fraction distributions. We compare the properties of a number of different verification measures and conclude that of existing measures the Log of Odds Ratio is the most suitable for cloud fraction. We also propose a new measure, the Symmetric Extreme Dependency Score, which has very attractive properties, being equitable (for large samples), difficult to hedge and independent of the frequency of occurrence of the quantity being verified. We then use data from five European ground-based sites and seven forecast models, processed using the ‘Cloudnet’ analysis system, to investigate the dependence of forecast skill on cloud fraction threshold (for binary skill scores), height, horizontal scale and (for the Met Office and German Weather Service models) forecast lead time. The models are found to be least skillful at predicting the timing and placement of boundary-layer clouds and most skilful at predicting mid-level clouds, although in the latter case they tend to underestimate mean cloud fraction when cloud is present. It is found that skill decreases approximately inverse-exponentially with forecast lead time, enabling a forecast ‘half-life’ to be estimated. When considering the skill of instantaneous model snapshots, we find typical values ranging between 2.5 and 4.5 days. Copyright c 2009 Royal Meteorological Society

Structures of Pd(CN)2and Pt(CN)2: intrinsically nanocrystalline materials?

Analysis and modeling of X-ray and neutron Bragg and total diffraction data show that the compounds referred to in the literature as “Pd(CN)2”and“Pt(CN)2” are nanocrystalline materials containing of small sheets of vertex-sharing square-planar M(CN)4 units, layered in a disordered manner with an intersheet separation of 3.44 A at 300 K. The small size of the crystallites means that the sheets’ edges form a significant fraction of each material. The Pd(CN)2 nanocrystallites studied using total neutron diffraction are terminated by water and the Pt(CN)2 nanocrystallites by ammonia, in place of half of the terminal cyanide groups, thus maintaining charge neutrality. The neutron samples contain sheets of approximate dimensions 30 A x 30 A. For sheets of the size we describe, our structural models predict compositions of Pd(CN)2-xH2O and Pt(CN)2-yNH3 (x = y = 0.29). These values are in good agreement with those obtained from total neutron diffraction and thermal analysis, and are also supported by infrared and Raman spectroscopy measurements. It is also possible to prepare related compounds Pd(CN)2-pNH3 and Pt(CN)2-qH2O, in which the terminating groups are exchanged. Additional samples showing sheet sizes in the range 10 A x 10 A (y = 0.67) to 80 A x 80 A (p = q = 0.12), as determined by X-ray diffraction, have been prepared. The related mixed-metal phase, Pd1/2Pt1/2(CN)2-qH2O(q = 0.50), is also nanocrystalline (sheet size 15 A x 15 A). In all cases, the interiors of the sheets are isostructural with those found in Ni(CN)2. Removal of the final traces of water or ammonia by heating results in decomposition of the compounds to Pd and Pt metal, or in the case of the mixed-metal cyanide, the alloy, Pd1/2Pt1/2, making it impossible to prepare the simple cyanides, Pd(CN)2, Pt(CN)2 or Pd1/2Pt1/2(CN)2, by this method.

Is silt the most influential soil grain size fraction?

The contribution of individual grain size fractions (2000–500, 500–250, 250–63, 63–2 and < 2 μm) to bulk soil surface area and reactivity is discussed with reference to mineralogical and oxalate and dithionite extractions data. The 63–2 μm fraction contributed up to 56% and 67% of bulk soil volume and BET surface area, respectively. Consideration of these observations and the mineralogy of this fraction suggest that the 63–2 μm fraction may be the most influential for the release of elements via mineral dissolution in the bulk soil.

Regulation of bcl-2 family proteins during development and in response to oxidative stress in cardiac myocytes: association with changes in mitochondrial membrane potential.

Cardiac myocyte apoptosis is potentially important in many cardiac disorders. In other cells, Bcl-2 family proteins and mitochondrial dysfunction are probably key regulators of the apoptotic response. In the present study, we characterized the regulation of antiapoptotic (Bcl-2, Bcl-xL) and proapoptotic (Bad, Bax) Bcl-2 family proteins in the rat heart during development and in oxidative stress-induced apoptosis. Bcl-2 and Bcl-xL were expressed at high levels in the neonate, and their expression was sustained during development. In contrast, although Bad and Bax were present at high levels in neonatal hearts, they were barely detectable in adult hearts. We confirmed that H(2)O(2) induced cardiac myocyte cell death, stimulating poly(ADP-ribose) polymerase proteolysis (from 2 hours), caspase-3 proteolysis (from 2 hours), and DNA fragmentation (from 8 hours). In unstimulated neonatal cardiac myocytes, Bcl-2 and Bcl-xL were associated with the mitochondria, but Bad and Bax were predominantly present in a crude cytosolic fraction. Exposure of myocytes to H(2)O(2) stimulated rapid translocation of Bad (<5 minutes) to the mitochondria. This was followed by the subsequent degradation of Bad and Bcl-2 (from approximately 30 minutes). The levels of the mitochondrial membrane marker cytochrome oxidase remained unchanged. H(2)O(2) also induced translocation of cytochrome c from the mitochondria to the cytosol within 15 to 30 minutes, which was indicative of mitochondrial dysfunction. Myocytes exposed to H(2)O(2) showed an early loss of mitochondrial membrane potential (assessed by fluorescence-activated cell sorter analysis) from 15 to 30 minutes, which was partially restored by approximately 1 hour. However, a subsequent irreversible loss of mitochondrial membrane potential occurred that correlated with cell death. These data suggest that the regulation of Bcl-2 and mitochondrial function are important factors in oxidative stress-induced cardiac myocyte apoptosis.

Constraining the aerosol influence on cloud fraction

Aerosol-cloud interactions have the potential to modify many different cloud properties. There is significant uncertainty in the strength of these aerosol-cloud interactions in analyses of observational data, partly due to the difficulty in separating aerosol effects on clouds from correlations generated by local meteorology. The relationship between aerosol and cloud fraction (CF) is particularly important to determine, due to the strong correlation of CF to other cloud properties and its large impact on radiation. It has also been one of the hardest to quantify from satellites due to the strong meteorological covariations involved. This work presents a new method to analyze the relationship between aerosol optical depth (AOD) and CF. By including information about the cloud droplet number concentration (CDNC), the impact of the meteorological covariations is significantly reduced. This method shows that much of the AOD-CF correlation is explained by relationships other than that mediated by CDNC. By accounting for these, the strength of the global mean AOD-CF relationship is reduced by around 80%. This suggests that the majority of the AOD-CF relationship is due to meteorological covariations, especially in the shallow cumulus regime. Requiring CDNC to mediate the AOD-CF relationship implies an effective anthropogenic radiative forcing from an aerosol influence on liquid CF of −0.48 W m−2 (−0.1 to −0.64 W m−2), although some uncertainty remains due to possible biases in the CDNC retrievals in broken cloud scenes.

Deterpenation of Bergamot Essential Oil Using Liquid-Liquid Extraction: Equilibrium Data of Model Systems at 298.2 K

The deterpenation of bergamot essential oil can be performed by liquid liquid extraction using hydrous ethanol as the solvent. A ternary mixture composed of 1-methyl-4-prop-1-en-2-yl-cydohexene (limonene), 3,7-dimethylocta-1,6-dien-3-yl-acetate (linalyl acetate), and 3,7-dimethylocta-1,6-dien-3-ol (linalool), three major compounds commonly found in bergamot oil, was used to simulate this essential oil. Liquid liquid equilibrium data were experimentally determined for systems containing essential oil compounds, ethanol, and water at 298.2 K and are reported in this paper. The experimental data were correlated using the NRTL and UNIQUAC models, and the mean deviations between calculated and experimental data were lower than 0.0062 in all systems, indicating the good descriptive quality of the molecular models. To verify the effect of the water mass fraction in the solvent and the linalool mass fraction in the terpene phase on the distribution coefficients of the essential oil compounds, nonlinear regression analyses were performed, obtaining mathematical models with correlation coefficient values higher than 0.99. The results show that as the water content in the solvent phase increased, the kappa value decreased, regardless of the type of compound studied. Conversely, as the linalool content increased, the distribution coefficients of hydrocarbon terpene and ester also increased. However, the linalool distribution coefficient values were negatively affected when the terpene alcohol content increased in the terpene phase.

Modelling the warm H(2) infrared emission of the Helix nebula cometary knots

Molecular hydrogen emission is commonly observed in planetary nebulae. Images taken in infrared H(2) emission lines show that at least part of the molecular emission is produced inside the ionized region. In the best studied case, the Helix nebula, the H(2) emission is produced inside cometary knots (CKs), comet-shaped structures believed to be clumps of dense neutral gas embedded within the ionized gas. Most of the H(2) emission of the CKs seems to be produced in a thin layer between the ionized diffuse gas and the neutral material of the knot, in a mini-photodissociation region (mini-PDR). However, PDR models published so far cannot fully explain all the characteristics of the H(2) emission of the CKs. In this work, we use the photoionization code AANGABA to study the H(2) emission of the CKs, particularly that produced in the interface H(+)/H(0) of the knot, where a significant fraction of the H(2) 1-0 S(1) emission seems to be produced. Our results show that the production of molecular hydrogen in such a region may explain several characteristics of the observed emission, particularly the high excitation temperature of the H(2) infrared lines. We find that the temperature derived from H(2) observations, even of a single knot, will depend very strongly on the observed transitions, with much higher temperatures derived from excited levels. We also proposed that the separation between the H alpha and [N II] peak emission observed in the images of CKs may be an effect of the distance of the knot from the star, since for knots farther from the central star the [N II] line is produced closer to the border of the CK than H alpha.

Antipyretic and anti-inflammatory properties of the ethanolic extract, dichloromethane fraction and costunolide from Magnolia ovata (Magnoliaceae)

Aim of the study: Magnolia ovata (A.St.-Hil.) Spreng (formerly Talauma ovata), known as ""pinha-do-brejo"" or ""baguacu"", is a large tree widely distributed in Brazil. Its trunk bark has been used in folk medicine against fever. However, no data have been published to support the antipyretic ethnopharmacological use. This study investigated the antipyretic and anti-inflammatory effects of the ethanolic extract (EEMO). dichloromethane fraction (DCM), and the isolated compound costunolide. Materials and methods: The antipyretic and anti-inflammatory activities were evaluated in experimental models of fever and inflammation in mice. Results: The oral administration of EEMO, DCM and costunolide inhibited carrageenan (Cg)-induced paw oedema (ID(50) 72.35 (38.64-135.46) mg/kg, 5.8 (2.41-14.04) mg/kg and 0.18 (0.12-0.27) mg/kg, respectively) and was effective in abolishing lipopolysaccharide (LPS)-induced fever (30 mg/kg, 4.5 mg/kg and 0.15 mg/kg, respectively). EEMO was also effective in reducing cell migration in the pleurisy model. Intraplantar injection of costunolide also reduced the paw oedema, myeloperoxidase and N-acetyl-glucosaminidase activity induced by Cg in mice. Conclusions: Collectively, these results show, for the first time, that extracts obtained from Magnolia ovata possess antipyretic and anti-inflammatory properties, and costunolide appears to be the compound responsible for these effects. (C) 2009 Elsevier Ireland Ltd. All rights reserved.

A Bayesian Long-term Survival Model Parametrized in the Cured Fraction

The main goal of this paper is to investigate a cure rate model that comprehends some well-known proposals found in the literature. In our work the number of competing causes of the event of interest follows the negative binomial distribution. The model is conveniently reparametrized through the cured fraction, which is then linked to covariates by means of the logistic link. We explore the use of Markov chain Monte Carlo methods to develop a Bayesian analysis in the proposed model. The procedure is illustrated with a numerical example.

Upper limit on the cosmic-ray photon fraction at EeV energies from the Pierre Auger Observatory

From direct observations of the longitudinal development of ultra-high energy air showers performed with the Pierre Auger Observatory, upper limits of 3.8%, 2.4%, 3.5% and 11.7% (at 95% c.l.) are obtained on the fraction of cosmic-ray photons above 2, 3, 5 and 10 EeV (1 EeV equivalent to 10(18) eV), respectively. These are the first experimental limits on ultra-high energy photons at energies below 10 EeV. The results complement previous constraints on top-down models from array data and they reduce systematic uncertainties in the interpretation of shower data in terms of primary flux, nuclear composition and proton-air cross-section. (C) 2009 Elsevier B.V. All rights reserved.

Group 11 (Cu, Ag, Au) promotion of 15%Co/Al(2)O(3) Fischer-Tropsch synthesis catalysts

Co/Al(2)O(3) Fischer-Tropsch synthesis catalysts promoted with different quantities of Group 11 metals (Cu, Ag, Au) were characterized and tested. The presence of relatively small quantities of such metals enhanced Co reducibility and, in the cases of Ag and Au, improved the surface Co metal active site densities. EXAFS experiments with the most loaded catalyst samples show that only Co-Co and Me-Me (Me = Cu, Ag and Au) coordination could be observed. This suggests that the greater fraction of the metals form different phases. However, the reduction promoting effect of the Group 11 metal is severely hampered once the catalyst receives a mild passivation treatment following primary reduction. An explanation in terms of promoter segregation during primary reduction is proposed. At lower promoter levels (0.83%Ag and 1.51%Au) and higher Ag levels (2.76%), significant gains in Co active site densities were achieved resulting in improved CO conversion levels relative to the unpromoted catalyst. Moreover, slight decreases in light product (e.g., CH(4)) selectivity and slight increases in C(5)+ selectivity were achieved. At high Au loading (5.05%), however, too much Au was loaded which, although significantly increasing the fraction of Co reduced, blocked Co surface sites and resulted in decreased Co conversion rates. While Cu facilitated Co reduction, the increased fraction of reduced Co did not translate to improved active site densities. It appears that a fraction of Cu tended to cover the rim of Co clusters, resulting in decreases in CO conversion rates and detrimental increases in light product selectivity. (C) 2009 Elsevier B.V. All rights reserved.

Comparative analysis of the volatile fraction from Annona cherimola Mill. cultivars by solid-phase microextraction and gas chromatography–quadrupole mass spectrometry detection

The analysis of volatile compounds in Funchal, Madeira, Mateus and Perry Vidal cultivars of Annona cherimola Mill. (cherimoya) was carried out by headspace solid-phase microextraction (HS-SPME) combined with gas chromatography–quadrupole mass spectrometry detection (GC–qMSD). HS-SPME technique was optimized in terms of fibre selection, extraction time, extraction temperature and sample amount to reach the best extraction efficiency. The best result was obtained with 2 g of sample, using a divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fibre for 30 min at 30 °C under constant magnetic stirring (800 rpm). After optimization of the extraction methodology, all the cherimoya samples were analysed with the best conditions that allowed to identify about 60 volatile compounds. The major compounds identified in the four cherimoya cultivars were methyl butanoate, butyl butanoate, 3-methylbutyl butanoate, 3-methylbutyl 3-methylbutanoate and 5-hydroxymethyl-2-furfural. These compounds represent 69.08 ± 5.22%, 56.56 ± 15.36%, 56.69 ± 9.28% and 71.82 ± 1.29% of the total volatiles for Funchal, Madeira, Mateus and Perry Vidal cultivars, respectively. This study showed that each cherimoya cultivars have 40 common compounds, corresponding to different chemical families, namely terpenes, esters, alcohols, fatty acids and carbonyl compounds and using PCA, the volatile composition in terms of average peak areas, provided a suitable tool to differentiate among the cherimoya cultivars.

Aditivos químicos ou biológicos na ensilagem de cana-de-açúcar: 2. parâmetros ruminais e degradabilidade da matéria seca e das frações fibrosas

Objetivou-se avaliar o efeito da inclusão de aditivos na ensilagem de cana-de-açúcar (Saccharum officinarum L.) sobre a degradação de MS e de componentes da parede celular e sobre os parâmetros de fermentação ruminal em bovinos alimentados com dietas contendo essas silagens. Utilizaram-se cinco novilhos da raça Nelore providos de cânula ruminal, alocados em delineamento quadrado latino 5 ´ 5 e alimentados com dietas com 65% de volumoso (%) MS. Foram avaliadas cinco silagens (base úmida): controle - cana-de-açúcar, sem aditivos; uréia - cana-de-açúcar + 0,5% ureia; benzoato - cana-de-açúcar + 0,1% de benzoato de sódio; LP - cana-de-açúcar inoculada com Lactobacillus plantarum (1 ´ 10(6) ufc/g MV); LB - cana-de-açúcar inoculada com L. buchneri (3,6 ´ 10(5) ufc/g forragem). A forragem foi armazenada em silos do tipo poço por 90 dias antes do fornecimento aos animais. Os parâmetros ruminais foram afetados de forma moderada pelas silagens e tiveram forte efeito do horário de coleta de amostras. As concentrações molares médias dos ácidos acético, propiônico e butírico foram de 60,9; 19,3 e 10,2 mM, respectivamente. O ambiente ruminal proporcionado por dietas formuladas com silagens de cana-de-açúcar foi satisfatório e similar ao tradicionalmente observado em dietas contendo cana. O uso de aditivos na ensilagem influenciou, de forma não-significativa, a degradabilidade ruminal da MS e da MO, mas não alterou a degradabilidade ruminal da fração fibrosa. Os aditivos aplicados à cana-de-açúcar resultaram em pequenas alterações na maior parte das variáveis avaliadas. Apesar de a degradabilidade ruminal das silagens ter sido pouco afetada pelo uso de aditivos, os valores observados foram próximos aos observados para a cana-de-açúcar in natura.

Purification and renal effects of phospholipase A(2) isolated from Bothrops insularis venom

Bothrops insularis venom contains a variety of substances presumably responsible for several pharmacological effects. We investigated the biochemical and biological effects of phospholipase A(2) protein isolated from B. insularis venom and the chromatographic profile showed 7 main fractions and the main phospholipase A(2) (PLA(2)) enzymatic activity was detected in fractions IV and V. Fraction IV was submitted to a new chromatographic procedure on ion exchange chromatography, which allowed the elution of 5 main fractions designated as lV-1 to IV-5, from which lV-4 constituted the main fraction. The molecular homogeneity of this fraction was characterized by high-performance liquid chromatography (HPLC) and demonstrated by mass spectrometry (MS), which showed a molecular mass of 13984.20 Da; its N-terminal sequence presented a high amino acid identity (up to 95%) with the PLA(2) of Bothrops jararaca and Bothrops asper. Phospholipase A(2) isolated from B. insularis (Bi PLA(2)) venom (10 mu g/mL) was also studied as to its effect on the renal function of isolated perfused kidneys of Wistar rats (n = 6). Bi PLA(2) increased perfusion pressure (PP), renal vascular resistance (RVR), urinary flow (UF) and glomerular filtration rate (GFR). Sodium (%TNa+) and chloride tubular reabsorption (%TCl-) decreased at 120 min, without alteration in potassium transport. In conclusion, PLA(2) isolated from B. insularis venom promoted renal alterations in the isolated perfused rat kidney. (c) 2007 Elsevier Ltd. All rights reserved.