Catalytic effect of MCM-41 in the pyrolysis of tobacco and several substances used as additives in the preparation of commercial cigarettes

Comunicación presentada en forma de póster en el "12th Mediterranean Congress of Chemical Engineering", Barcelona (Spain), November 15-18, 2011.

Kinetic study of thermal 1,3-dipolar cycloaddition of azomethine ylides using differential scanning calorimetry as monitoring window

Kinetics of 1,3-dipolar cycloaddition involving azomethine ylides, generated from thermal [1,2]-prototropy of the corresponding imino ester, employing differential scanning calorimetry (DSC), is surveyed. Glycine and phenylalanine derived imino esters have different behavior. The first one prefers reacting with itself at 75 ºC, rather than with the dipolarophile. However, the α-substituted imino ester gives the cycloadduct at higher temperatures. The thermal dynamic analysis by 1H NMR of the neat reaction mixture of the glycine derivative reveals the presence of signals corresponding to the dipole in very small proportion. The non-isothermal and isothermal DSC curves of the cycloaddition of phenylalaninate and diisobutyl fumarate are obtained from freshly prepared samples. The application of known kinetic models and mathematical multiple non-linear regressions (NLR) allow to determine and to compare Ea, lnA, reaction orders, and reaction enthalpy. Finally a rate equation for each different temperature can be established for this particular thermal cycloaddition.

Extinction trends of threatened invertebrates in peninsular Spain

Using information from two recently published atlases of threatened invertebrate species in peninsular Spain, we examined the climatic, land use and geographic characteristics of the 100 km2 UTM cells with most likelihood of suffering extinctions (extinction cells), as well as the attributes of the species prone to population extinctions. Extinction cells have had significantly (1) lower precipitation values, (2) higher temperatures, (3) higher percentages of anthropic land uses or (4) higher rates of anthropization during the last 20 years than the remaining cells. Nevertheless, probable extinctions may occur under a wide range of climatic and anthropization change rates and these variables can only explain a low proportion (~5 %) of variability in the occurrence or number of extinction cells. Aquatic species seem to suffer higher local extinction rates than terrestrial species. Interestingly, many invertebrate species with approximately 25 or less occurrence cells are on a clear trajectory towards extinction. These results outline the difficulties and uncertainties in relating probable population extinctions with climatic and land use changes in the case of invertebrate data. However, they also suggest that a third of the considered Spanish threatened species could have lost some of their populations, and that current conservation efforts are insufficient to reverse this tendency.

Análisis experimental de la pérdida de adherencia hormigón-acero en hormigones sometidos a altas temperaturas

En el conjunto de materiales de construcción habituales en la edificación y las obras de ingeniería, el hormigón destaca entre otras razones por su excelente comportamiento frente a las altas temperaturas y la exposición al fuego. El presente estudio se centra en la adherencia residual entre el hormigón y las barras de acero corrugado soldable tras exponer probetas a altas temperaturas y enfriarlas hasta temperatura ambiente por convección natural. El estudio incluye hormigones de resistencia convencional, hormigones de alta resistencia y hormigones reforzados con fibras de polipropileno y fibras de acero. La adherencia hormigón-acero se ha medido mediante el conocido ensayo de pull-out. La campaña experimental también ha incluido la resistencia a compresión y la resistencia a tracción indirecta. Parte de las probetas se han ensayado a 28 días de edad a temperatura ambiente. A 60 días de edad se han repetido los ensayos a temperatura ambiente y se han realizado esos mismos ensayos en probetas calentadas en un horno industrial hasta tres rangos de temperatura: 450°C, 650°C y 825°C. Previo al proceso de calentamiento han sido sometidas durante 3 horas a un escalón de secado a 120°C. Mediante la metodología propuesta ha sido posible caracterizar la evolución de la pérdida de adherencia residual entre el acero y el hormigón conforme se exponen los especímenes a temperaturas más elevadas. La adición de fibras no tiene una influencia clara en la adherencia a temperatura ambiente. Sin embargo, sí se ha conseguido determinar una mejora sustancial de la adherencia residual en los hormigones, reforzados con fibras de acero sometidos a altas temperaturas.

Stable carbon and oxygen isotope record of live benthic foraminifera from Swedish fjords

In a previous 16-month seasonal study on living (stained) benthic foraminifera from two fjords on the Swedish west coast, it was reported that foraminifera proliferated in response to phytodetritus input; the strongest response came from the opportunistic species Stainforthia fusiformis. In this study, our objective was to find out if that phytodetritus input resulted in a change in the carbon isotopic composition of the foraminiferal tests. We also wanted to examine if variations in salinity and temperature (due to seasonality or deep-water exchanges) were reflected in the delta18O values. From S. fusiformis that were obtained from the Havstens Fjord (20 m) and the Gullmar Fjord (119 m) during the 16-month study, we developed a time series of delta18O and delta13C. After the spring blooms in the Havstens and the Gullmar Fjord, decreases of about 0.2 per mil to 0.3 per mil in the foraminiferal delta13C values were noted; in the Gullmar Fjord after the autumn blooms, decreases of the same order were also noted. Comparing the Havstens and the Gullmar Fjord, we found a 1 per mil difference in both delta13C and delta18O; we attribute this to hydrographic differences between the two fjords. Using calculated values of delta18O, together with the measured ones, we noticed that S. fusiformis in the Gullmar Fjord seems to calcify close to equilibrium with respect to the oxygen isotopes. During autumn, water temperatures were relatively high in the Havstens Fjord, and foraminiferal abundance in the fjord was also high after a phytodetritus input; but, the measured delta18O values do not reflect these higher temperatures. This apparently contradictory combination of results might be explained by a varying delta18O composition of the water during the year, which counterbalances the temperature effect.

Geochemistry and stable isotope record of the hydtrothermally altered lower sheeted dike complex in ODP Hole 140-504B

Drilling during Legs 137 and 140 of the Ocean Drilling Program deepened Hole 504B, the only hole to penetrate through the volcanic section and into the underlying hydrothermally altered sheeted dike complex, by 438.1 m to a total depth of 2000.4 meters below seafloor. This paper presents the secondary mineralogy, bulk-rock sulfur contents, and stable isotopic (O, S) compositions, plus oxygen isotopic compositions of secondary minerals from the lower sheeted dike complex drilled during Legs 137 and 140. Various evidence indicates higher temperatures of hydrothermal alteration in the lower dikes than in the upper dikes, including: the local presence of secondary clinopyroxene in the lower dikes; secondary anorthite and hornblende in the lower dikes vs. mainly actinolite and albite-oligoclase in the upper dikes; generally increasing Al and Ti contents of amphibole downward in the dike section; and greater 18O depletions of the lower dikes (d18O = 3.6-5.0 per mil) compared with the upper dikes. Early high-temperature alteration stages (T = 350°-500°C) resulted in 18O depletions and losses of metals (Cu, Zn) and sulfur from the rocks. Local incorporation of reduced seawater sulfate led to elevated d34S values of sulfide in the rocks (up to 2.5 per mil). Quartz + epidote formed in crosscutting veins at temperatures of 310°-320°C from more evolved fluids (d18O = 1 per mil). Late-stage lower-temperature (~250°C) reactions producing albite, prehnite, and zeolites in the rocks caused slight 18O enrichments, but these were insufficient to offset the 18O depletions caused by earlier higher-temperature reactions. Addition of anhydrite to the rocks during seawater recharge led to increased S contents of rocks that had previously lost S during axial hydrothermal alteration, and to further increases in d34S values of total S in the rocks (up to 12 per mil). Despite the evidence for seawater recharge to near the base of the sheeted dike complex, the paucity of late zeolites in the lower dikes suggests that late-stage, off-axis circulation was mainly restricted to the volcanics and shallowest dikes, or to localized high-permeability zones (faults) at depth.

Interstitial water chemistry of DSDP Leg 85 sites

The concentration changes in pore waters of dissolved calcium, magnesium, sulfate, strontium, and silica and of alkalinity are controlled by diagenetic reactions occurring within the biogenic sediments of DSDP Sites 572, 573, and 574. Downcore increases in dissolved Sr2 + indicate recrystallization of calcite, and increases in dissolved SiO2 reflect dissolution of amorphous silica. Minor gradients in dissolved Ca(2+) and Mg(2+) suggest little if any influence from reactions involving volcanic sediments or basalt. Differences in interstitial water profiles showing the downhole trends of these chemical species mark variations in carbonate and silica diagenesis, sediment compositions, and sedimentation rate histories among the sites. The location and extent of carbonate diagenesis in these sediments are determined from Sr/Ca distributions between the interstitial waters and the bulk carbonate samples. Pore water strontium increases in the upper 100 to 250 m of sediment are assumed to reflect diffusion from underlying zones where calcite recrystallization has occurred. On the basis of calculations of dissolved strontium production and comparisons between observed and calculated "equilibrium" Sr/Ca ratios of the solids, approximately 30 to 50% of the carbonate has recrystallized in these deeper intervals. These estimates agree with the observed amounts of chalk at these sites. Variations in Sr/Ca ratios of these carbonates reflect differences in calcareous microfossil content, in diagenetic history, and, possibly, in changes in seawater Sr/Ca with time. Samples of porcelanite recovered below 300 m at Site 572 suggest formation at temperatures 20 to 30° C greater than ones estimated assuming oceanic geothermal gradients from sedimentary sections similar to those recovered on Leg 85. The higher temperatures may partially account for higher Sr/Ca ratios determined for recrystallized carbonates from this site.

Isotope characterization and estimated temperature of formation of calcite veins in ODP Sites 124-768 and 124-770 (Table 1)

Secondary carbonate minerals were recovered within the basalts at both ODP Sites 768 and 770 in the Sulu and Celebes seas. Petrographic and X-ray diffraction analyses indicate that the carbonates are calcites. Other alteration products recognized in the thin sections are smectites, iron oxides, and gypsum. The 13C values of carbonates from both sites range from 1.6 per mil to 2.3 per mil, which are indicative of inorganic carbonate formation with no contributions from 13C-depleted sources such as oxidized organic carbon or methane. The oxygen isotopes at Site 770 range from 30.8 per mil to 31.6 per mil, which indicates a pervasive circulation of cold seawater (9° to 12°C) during alteration of the Celebes Sea basalts. In contrast, carbonates associated with Site 768 basalts have less positive d18O values (21.0 per mil to 27.3 per mil). A lighter 18O isotopic signature indicates the formation of secondary calcite at either higher temperatures or in a system closed to seawater. The rapidly deposited pyroclastic flows at Site 768 would have limited water access to the crust very soon after its formation, which leads us to speculate that the carbonates in the Sulu Sea basalts were formed by isotopically modified fluids resulting from basalt alteration in a closed system.

Hydrothermal deposition of cerium hydroxycarbonate thin films on glass

The first success in the preparation of rare earth hydroxycarbonate thin films has been achieved. Cerium hydroxycarbonate films were prepared by a hydrothermal deposition method, the sample of a single orthorhombic phase was deposited at a lower temperature while those of orthorhombic and hexagonal phases were obtained at higher temperatures. The crystals in the films could be ellipsoidal, prismatic, or rhombic, depending on the deposition conditions applied. The thin films could be candidates for developing novel optical materials and for advanced ceramics processing. (C) 2003 Elsevier Science B.V. All rights reserved.

Adventitious root formation in cuttings of Backhousia citriodora F. Muell 2. Seasonal influences of temperature, rainfall, flowering and auxins on the stock plant

A 2-year study was carried out on established trees at two sites in southeastern Queensland, Australia, to identify environmental factors that influenced rooting of Backhousia citriodora from cuttings. Complex interactions of rainfall events above 20 mm from the preceding month and mean maximum temperature on stock plants resulted in a correlation with rooting success of r = 0.81 and 0.74 for sites at The University Of Queensland, Gatton Campus, and Cedar Glen, respectively. A more detailed investigation under controlled environmental conditions showed that maintaining stock plants at temperatures between 10 and 30degreesC had no direct effect on rooting capacity. However, temperature was correlated with growth, which may have an indirect effect on root formation. In spring floral initiation was found to only delay rooting and had no effect on the final rooting percentage. A series of seasonal experiments demonstrated that application of the auxins indole-3-acetic acid, indole-3-butyric acid and napthaleneacetic acid over a range of concentrations (1000-8000 mug/ml) did not significantly increase rooting compared to the control and there is no practical advantage in applying auxins. Seasonal results and the temperature experiment also suggest that under a glasshouse environment with higher temperatures in winter and an adequate supply of water, B. citriodora cuttings can be successfully rooted over the whole year. (C) 2004 Elsevier B.V. All rights reserved.

Temperature-dependent sex ratio in a bird

To our knowledge, there is, so far, no evidence that incubation temperature can affect sex ratios in birds, although this is common in reptiles. Here, we show that incubation temperature does affect sex ratios in megapodes, which are exceptional among birds because they use environmental heat sources for incubation. In the Australian brush-turkey Alectura lathami, a mound-building megapode, more males hatch at low incubation temperatures and more females hatch at high temperatures, whereas the proportion is 1 : 1 at the average temperature found in natural mounds. Chicks from lower temperatures weigh less, which probably affects offspring survival, but are not smaller. Megapodes possess heteromorphic sex chromosomes like other birds, which eliminates temperature-dependent sex determination, as described for reptiles, as the mechanism behind the skewed sex ratios at high and low temperatures. Instead, our data suggest a sex-biased temperature-sensitive embryo mortality because mortality was greater at the lower and higher temperatures, and minimal at the middle temperature where the sex ratio was 1 : 1.

Miscibility and phase separation in blends of phenolphthalein poly(aryl ether ketone) and poly(ethylene oxide): a differential scanning calorimetric study

Miscibility and phase separation in the blends of phenolphthalein poly(aryl ether ketone) (PPAEK) and poly(ethylene oxide) (PEO) were investigated by means of differential scanning calorimetry (DSC). The PPAEK/PEO blends prepared by solution casting from N,N-dimethylformamide (DMF) displayed single composition-dependent glass transition temperatures (T-g), intermediate between those of the pure components, suggesting that the blend system is miscible in the amorphous state at all compositions. All the blends underwent phase separation at higher temperatures and the system exhibited a lower critical solution temperature (LCST) behavior. A step-heating thermal analysis was designed to determine the phase boundaries with DSC. The significant changes in the thermal properties of blends were utilized to judge the mixing status for the blends and the phase diagram was thus established. (C) 2004 Elsevier B.V. All rights reserved.

Vitamin B-12 release from P(HEMA-co-THFMA) in water and SBF: A model drug release study

A model drug release study on the ingress of water and Kokubo simulated body fluid (SBF) into poly(2-hydroxyethyl methacrylate) (THFMA) and its copolymers with tetrahydrofurfuryl methacrylate (THFMA) loaded with vitamin B-12 was undertaken over the temperature range 298-318 K. The polymers were studied as cylinders and were loaded with either 5 or 10 wt-% of the drug. The drug release from the polymers was found to follow a Fickian diffusion mechanism in the early stages of the drug release, with higher normalized release rates at higher temperatures and higher drug loadings. The normalized release rates were also found to be higher for the SBF solution than for water. The copolymer composition was found to have a significant effect on the rate of release of the drug, with the rate falling rapidly between HEMA mole fractions of 1.0 and 0.8, but for lower mole fractions of HEMA the normalized release rate decreased more slowly. This behaviour followed the trend found for the changes in the equilibrium penetrant contents for the copolymers.

An ESR study of the radiolysis of semi-crystalline ethylene-propylene copolymers containing DOP mobilizer

The radiolysis of a poly(ethylene-co-propylene), Elpro, marketed by Thai Polypropylene Co. Ltd for the manufacture of medical goods has been investigated at 77 K. Calcium stearate was blended with the Elpro as a processing aid; and dioctyl phthalate, DOP, was added in various amounts as a radiation stabilizer. The ESR spectra of Elpro and Elpro+Ca were very similar and characterized principally by the presence of PP a-carbon radicals. The spectra of the samples containing DOP were similar to those for Elpro but with an additional narrow singlet arising from DOP radicals. On annealing the irradiated polymers to higher temperatures, the singlet was lost between 250 and 270 K, and at room temperature the principal radicals remaining were allyl radicals. The G-values for radical formation at 77 K for Elpro and Elpro+Ca at 77 K were 3.0 and 3.2, respectively, but incorporation of DOP resulted in lower G-values, ranging from 1.6 to 1.4 for 0.5 and 2.5 phr DOP, respectively.(c) 2005 Wiley Periodicals, Inc.

Altitudinal variation in behavioural thermoregulation: Local adaptation vs. plasticity in California grasshoppers

We investigated the adaptive significance of behavioural thermoregulation in univoltine populations of the grasshopper Melanoplus sanguinipes along an altitudinal gradient in California using laboratory tests of animals raised under different temperatures. Trials consisted of continuous body temperature measurements with semi-implanted microprobes in a test arena, and observation and simultaneous recording of behavioural responses. These responses included mobility, basking and orientation of the body axes (aspect angle) towards a radiation source. Mobility and basking are determined by the altitudinal origin of the parental generation and not by the temperature treatments. With increasing altitude, individuals tend increasingly to raise body temperatures via mobility and increased basking. In contrast, body orientation towards the radiation source is influenced by the temperature treatments but not by the altitude of origin. Individuals experiencing higher temperatures during rearing show a lower tendency to lateral flanking. We conclude that body orientation responses are not adapted locally. In contrast other components of the behavioural syndrome that increase body temperature, such as mobility and basking, are adaptive in response to local selection pressure. The thermoregulatory syndrome of these grasshoppers is an important contribution to life-history adaptations that appropriately match season lengths.