Environmentally friendly reduction of a platinum catalyst precursor supported on polypyrrole

Supported metals are traditionally prepared by impregnating a support material with the metal precursor solution, followed by reduction in hydrogen at elevated temperatures. In this study, a polymeric support has been considered. Polypyrrole (PPy) has been chemically synthesized using FeCl3 as a doping agent, and it has been impregnated with a H2PtCl6 solution to prepare a catalyst precursor. The restricted thermal stability of polypyrrole does not allow using the traditional reduction in hydrogen at elevated temperature, and chemical reduction under mild conditions using sodium borohydride implies environmental concerns. Therefore, cold RF plasma has been considered an environmentally friendly alternative. Ar plasma leads to a more effective reduction of platinum ions in the chloroplatinic complex anchored onto the polypyrrole chain after impregnation than reduction with sodium borohydride, as has been evidenced by XPS. The increase of RF power enhanced the effectiveness of the Ar plasma treatment. A homogeneous distribution of platinum nanoparticles has been observed by TEM after the reduction treatment with plasma. The Pt/polypyrrol catalyst reduced by Ar plasma at 200 watts effectively catalyzed the aqueous reduction of nitrates with H2 to yield N2, with a very low selectivity to undesired nitrites and ammonium by-products.

Chlorophyll catabolism and gene expression in the peel of ripening banana fruits

The biochemical and molecular basis of chlorophyll (Chl) catabolism in bananas was investigated during ripening at 20°C and at an elevated temperature (35°C) where degreening is inhibited. Biochemical analysis showed that Chl breakdown products could be isolated from fruit ripened at both temperatures. The coloured breakdown products, chlorophyllide and pheophorbide, were not detected at any stage of ripening in the two treatments; however, a non-fluorescent Chl catabolite accumulated to a higher concentration at 20 than at 35°C. To investigate the ripening-related gene expression associated with these changes, a cDNA library was generated from the peel of fruit ripened at 20°C. Differential screening of this library produced 20 non-redundant families of clones including those encoding enzymes involved in ethylene biosynthesis, respiration, starch metabolism, cell wall degradation and other metabolic events. The expression of these genes was followed by northern analysis in fruit ripened at 20 and 35°C.

Moderately High Temperatures Inhibit Ribulose-1,5-Bisphosphate Carboxylase/Oxygenase (Rubisco) Activase-Mediated Activation of Rubisco

We tested the hypothesis that light activation of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) is inhibited by moderately elevated temperature through an effect on Rubisco activase. When cotton (Gossypium hirsutum L.) or wheat (Triticum aestivum L.) leaf tissue was exposed to increasing temperatures in the light, activation of Rubisco was inhibited above 35 and 30°C, respectively, and the relative inhibition was greater for wheat than for cotton. The temperature-induced inhibition of Rubisco activation was fully reversible at temperatures below 40°C. In contrast to activation state, total Rubisco activity was not affected by temperatures as high as 45°C. Nonphotochemical fluorescence quenching increased at temperatures that inhibited Rubisco activation, consistent with inhibition of Calvin cycle activity. Initial and maximal chlorophyll fluorescence were not significantly altered until temperatures exceeded 40°C. Thus, electron transport, as measured by Chl fluorescence, appeared to be more stable to moderately elevated temperatures than Rubisco activation. Western-blot analysis revealed the formation of high-molecular-weight aggregates of activase at temperatures above 40°C for both wheat and cotton when inhibition of Rubisco activation was irreversible. Physical perturbation of other soluble stromal enzymes, including Rubisco, phosphoribulokinase, and glutamine synthetase, was not detected at the elevated temperatures. Our evidence indicates that moderately elevated temperatures inhibit light activation of Rubisco via a direct effect on Rubisco activase.

(Table 1) Lithium contents and isotopic composition in sediments from DSDP Holes 64-477 and 64-477A

Lithium isotopic compositions of hydrothermally altered sediments of Deep Sea Drilling Project (DSDP) site 477/477A, as well as high temperature vent fluids of the Guaymas Basin, have been determined to gain an understanding of lithium exchange during fluid-sediment interaction at this sediment-covered spreading center. Unaltered turbidite of the basin has a d6Li value of -10%, 5-7% heavier than fresh oceanic basalts. Contact metamorphism induced by a shallow sill intrusion results in a decrease of the lithium content of the adjacent sediments and a lighter isotopic value (-8%). Below the sill, sediments altered by a deep-seated hydrothermal system show strong depletions in lithium, while lithium isotopic compositions vary greatly, ranging from -11 to +1%. The shift to lighter composition is the result of preferential retention of the lighter isotope in recrystallized phases after destruction of the primary minerals. The complexity of the isotope profile is attributed to inhomogeneity in mineral composition, the tortuous pathway of fluids and the temperature effect on isotopic fractionation. The range of lithium concentration and d6Li values for the vent fluids sampled in 1982 and 1985 overlaps with that of the sediment-free mid-ocean ridge systems. The lack of a distinct expression of sediment input is explained in terms of a flow-through system with continuous water recharge. The observations on the natural system agree well with the results of laboratory hydrothermal experiments. The experimental study demonstrates the importance of temperature, pressure, water/rock ratio, substrate composition and reaction time on the lithium isotopic composition of the reacted fluid. High temperature authigenic phases do not seem to constitute an important sink for lithium and sediments of a hydrothermal system such as Guaymas are a source of lithium to the ocean. The ready mobility of lithium in the sediment under elevated temperature and pressure conditions also has important implications for lithium cycling in subduction zones.

Stickleback F2 generation transgenerational plasticity experiment: egg and body size data

Nongenetic inheritance mechanisms such as transgenerational plasticity (TGP) can buffer populations against rapid environmental change such as ocean warming. Yet, little is known about how long these effects persist and whether they are cumulative over generations. Here, we tested for adaptive TGP in response to simulated ocean warming across parental and grandparental generations of marine sticklebacks. Grandparents were acclimated for two months during reproductive conditioning, whereas parents experienced developmental acclimation, allowing us to compare the fitness consequences of short-term vs. prolonged exposure to elevated temperature across multiple generations. We found that reproductive output of F1 adults was primarily determined by maternal developmental temperature, but carry-over effects from grandparental acclimation environments resulted in cumulative negative effects of elevated temperature on hatching success. In very early stages of growth, F2 offspring reached larger sizes in their respective paternal and grandparental environment down the paternal line, suggesting that other factors than just the paternal genome may be transferred between generations. In later growth stages, maternal and maternal granddam environments strongly influenced offspring body size, but in opposing directions, indicating that the mechanism(s) underlying the transfer of environmental information may have differed between acute and developmental acclimation experienced by the two generations. Taken together, our results suggest that the fitness consequences of parental and grandparental TGP are highly context dependent, but will play an important role in mediating some of the impacts of rapid climate change in this system.

Gasterosteus aculeatus egg traits and fish lengths vs. experiment setup

1) Our study addresses the role of non-genetic and genetic inheritance in shaping the adaptive potential of populations under a warming ocean scenario. We used a combined experimental approach (transgenerational plasticity and quantitative genetics) to partition the relative contribution of maternal vs. paternal (additive genetic) effects to offspring body size (a key component of fitness), and investigated a potential physiological mechanism (mitochondrial respiration capacities) underlying whole organism growth/size responses. 2) In very early stages of growth (up to 30 days), offspring body size of marine sticklebacks benefited from maternal transgenerational plasticity (TGP): offspring of mothers acclimated to17°C were larger when reared at 17°C, and offspring of mothers acclimated to 21°C were larger when reared at 21°C. The benefits of maternal TGP on body size were stronger and persisted longer (up to 60 days) for offspring reared in the warmer (21°C) environment, suggesting that maternal effects will be highly relevant for climate change scenarios in this system. 3) Mitochondrial respiration capacities measured on mature offspring (F1 adults) matched the pattern of TGP for juvenile body size, providing an intuitive mechanistic basis for the maternal acclimation persisting into adulthood. Size differences between temperatures seen at early growth stages remained in the F1 adults, linking offspring body size to maternal inheritance of mitochondria. 4) Lower maternal variance components in the warmer environment were mostly driven by mothers acclimated to ambient (colder) conditions, further supporting our tenet that maternal effects were stronger at elevated temperature. Importantly, all parent-offspring temperature combination groups showed genotype x environment (GxE) interactions, suggesting that reaction norms have the potential to evolve. 5) To summarise, transgenerational plasticity and genotype x environment interactions work in concert to mediate impacts of ocean warming on metabolic capacity and early growth of marine sticklebacks. TGP can buffer short-term detrimental effects of climate warming and may buy time for genetic adaptation to catch up, therefore markedly contributing to the evolutionary potential and persistence of populations under climate change.

Magnetic state of ocean basalts (Table 1)

The natural remanent magnetization (NRM) of ocean basalts, giving rise to the pattern of marine magnetic anomalies, is known to be of comparatively low intensity for about 20 Ma old oceanic crust. The aim of this study is to detect possible peculiarities in the rock magnetic properties of ocean basalts of this age, and to establish a link between magnetomineralogy, rock magnetic parameters, and the low NRM intensity. Ocean basalts covering ages from 0.7 to 135 Ma were selected for rock magnetic experiments and their room temperature hysteresis parameters, Curie temperature and temperature dependence of saturation magnetization MS(T) was determined and complemented by reflected light microscopy. The majority of samples is magnetically dominated by titanomagnetite and titanomaghemite with increasing oxidation state with age. For these, a strong dependence of hysteresis parameters on the age of the samples is found. The samples have a minimum in saturation magnetization and a maximum in magnetic stability in the age interval ranging from approximately 10 to 40 Ma, coinciding with the age interval of low NRM intensity. The observed change in saturation magnetization is in the same order as that for the NRM intensity. A further peculiarity of the titanomaghemites from this age interval is the shape of their MS(T) curves, which display a maximum above room temperature (Neel P-type) and, sometimes, a self-reversal of magnetization below room temperature (Neel N-type). These special rock magnetic properties can be explained by titanomagnetite low-temperature oxidation and highly oxidized titanomaghemites in the age interval 10-40 Ma. A corresponding measurement of the NRM at elevated temperature allows to identify a maximum in NRM intensity above room temperature for the samples in that age interval. This provides evidence that the NRM is equally carried by titanomaghemites and that the low NRM intensities for about 20 Ma old ocean basalts are caused consequently by the low saturation magnetization of these titanomaghemites.

Combined effects of coral reef foraminifera Marginopora vertebralis and Heterostegina depressa in a multi-fractorial experiment

Warming and changes in ocean carbonate chemistry alter marine coastal ecosystems at an accelerating pace. The interaction between these stressors has been the subject of recent studies on reef organisms such as corals, bryozoa, molluscs, and crustose coralline algae. Here we investigated the combined effects of elevated sea surface temperatures and pCO2 on two species of photosymbiont-bearing coral reef Foraminifera: Heterostegina depressa (hosting diatoms) and Marginopora vertebralis (hosting dinoflagellates). The effects of single and combined stressors were studied by monitoring survivorship, growth, and physiological parameters, such as respiration, photochemistry (pulse amplitude modulation fluorometry and oxygen production), and chl a content. Specimens were exposed in flow-through aquaria for up to seven weeks to combinations of two pCO2 (~790 and ~490 µatm) and two temperature (28 and 31 °C) regimes. Elevated temperature had negative effects on the physiology of both species. Elevated pCO2 had negative effects on growth and apparent photosynthetic rate in H.depressa but a positive effect on effective quantum yield. With increasing pCO2, chl a content decreased in H. depressa and increased in M. vertebralis. The strongest stress responses were observed when the two stressors acted in combination. An interaction term was statistically significant in half of the measured parameters. Further exploration revealed that 75 % of these cases showed a synergistic (= larger than additive) interaction between the two stressors. These results indicate that negative physiological effects on photosymbiont-bearing coral reef Foraminifera are likely to be stronger under simultaneous acidification and temperature rise than what would be expected from the effect of each of the stressors individually.

Microstructure and mechanical properties of high pressure die cast magnesium alloy AE42 with 1% strontium

The addition of 1 wt-%Sr to AE42 results in an improvement in the tensile strength of the alloy at elevated temperatures of 150 and 175degreesC and an improvement in the constant load creep properties at 175degreesC. The improved elevated temperature tensile and creep strength of the alloy can be attributed to the presence of a strontium-containing phase in the microstructure of the alloy along with an increase in the stability of the microstructure of the alloy at high temperatures. (C) 2004 W. S. Maney Son Ltd.

Thermosetting Blends of Polybenzoxazine and Poly(ε-caprolactone): Phase Behavior and Intermolecular Specific Interactions

Polybenzoxazine (PBA-a)/poly(epsilon-caprolactone) (PCL) blends were prepared by an in situ curing reaction of benzoxazine (BA-a) in the presence of PCL. Before curing, the benzoxazine (BA-a)/PCL blends are miscible, which was evidenced by the behaviors of single and composition-dependant glass transition temperature and equilibrium melting point depression. However, the phase separation induced by polymerization was observed after curing at elevated temperature. It was expected that after curing, the PBA-a/PCL blends would be miscible since the phenolic hydroxyls in the PBA-a molecular backbone have the potential to form inter- molecular hydrogen-bonding interactions with the carbonyls of PCL and thus would fulfil the miscibility of the blends. The resulting morphology of the blends prompted an investigation of the status of association between PBA-a and PCL under the curing conditions. Although Fourier-transform infrared spectroscopy (FT-IR) showed that there were intermolecular hydrogen-bonding interactions between PBA-a and PCL at room temperature, especially for the PCL-rich blends, the results of variable temperature FT-IR spectroscopy by the model compound indicate that the phenolic hydroxyl groups could not form efficient intermolecular hydrogen-bonding interactions at elevated temperatures, i.e., the phenolic hydroxyl groups existed mainly in the non-associated form in the system during curing. The results are valuable to understand the effect of curing temperature on the resulting morphology of the thermosetting blends. SEM micrograph of the dichloromethane-etched fracture surface of a 90:10 PBA-a PCL blend showing a heterogeneous morphology.

Coral reefs in a century of rapid environmental change

Coral reefs are the most diverse marine ecosystem and embrace possibly millions of plant, animal and protist species. Mutualistic symbioses are a fundamental feature of coral reefs that have been used to explain their structure, biodiversity and existence. Complex inter-relationships between hosts, habitats and symbionts belie closely coupled nutrient and community dynamics that create the circumstances for something from nothing (or the oasis in a nutrient desert). The flip side of these dynamics is a close dependency between species, which results in a series of non-linear relationships as conditions change. These responses are being highlighted as anthropogenic influences increase across the world's tropical and subtropical coastlines. Caribbean as well as Indo-Pacific coral populations are now in a serious decline in many parts of the world. This has resulted in a significant reorganization of how coral reef ecosystems function. Among the spectra of changes brought about by humans is rapid climate change. Mass coral bleaching - the loss of the dinoflagellate symbionts from reef-building corals - and mortality has affected the world's coral reefs with increasing frequency and intensity since the late 1970s. Mass bleaching events, which often cover thousands of square kilometres of coral reefs, are triggered by small increases (+1-3degreesC) in water temperature. These increases in sea temperature are often seen during warm phase weather conditions (e.g. ENSO) and are increasing in size and magnitude. The loss of living coral cover (e.g. 16% globally in 1998, an exceptionally warm year) is resulting in an as yet unspecified reduction in the abundance of a myriad of other species. Projections from general circulation models (GCM) used to project changes in global temperature indicate that conditions even under the mildest greenhouse gas emission scenarios may exceed the thermal tolerances of most reef-building coral communities. Research must now explore key issues such as the extent to which the thermal tolerances of corals and their symbionts are dynamic if bleaching and disease are linked; how the loss of high densities of reef-building coral will affect other dependent species; and, how the loss of coral populations will affect the millions of people globally who depend on coral reefs for their daily survival.

Scleractinian corals with photoprotective host pigments are hypersensitive to thermal bleaching

Recent episodes of mass coral bleaching, the loss of symbiotic dinoflagellates or photosynthetic pigment from hermatypic corals, have been triggered by elevated sea temperatures. Photosynthetic irradiance is an important secondary factor. Host based pigments (pocilloporins or Green Fluorescent Protein homologues) have been proposed to reduce the impact of elevated temperature by shading the dinoflagellate symbionts of corals, thereby reducing light stress. This study investigates this phenomenon in the reef-building coral Acropora aspera from Heron Island Research Station (Great Barrier Reef, Australia), which occurs as 3 distinct colour morphs. Experimental data showed that the host pigments are photoprotective at normal temperatures or

Testing the 'photoinhibition' model of coral bleaching using chemical inhibitors

Explants of the hard coral Seriatopora hystrix were exposed to sublethal concentrations of the herbicide diuron DCMU (N'-(3,4-dichlorophenyl,-N,N-dimethylurea)) and the heavy metal copper. Pulse amplitude modulated (PAM) chlorophyll fluorescence techniques were used to assess the effects on the photosynthetic efficiency of the algal symbionts in the tissue (in Symbio), and chlorophyll fluorescence and counts of symbiotic algae (normalised to surface area) were used to assess the extent of coral bleaching. At 30 mug DCMU l(-1), there was a reduction in both the maximum effective quantum yield (DeltaF/F-m') and maximum potential quantum yield (F-v/F-m) of the algal symbionts in symbio. Corals subsequently lost their algal symbionts and discoloured (bleached), especially on their upper sunlight-exposed surfaces. At the same DCMU concentration but under low light (5% of growth irradiance), there was a marked reduction in DeltaF/F-m' but only a slight reduction in F-v/F-m and slight loss of algae. Loss of algal symbionts was also noted after a 7 d exposure to concentrations as low as 10 mug DCMU l(-1) under normal growth irradiance, and after 14 d exposure to 10 mug DCMU l(-1) under reduced irradiance. Collectively the results indicate that DCMU-induced bleaching is caused by a light-dependent photoinactivation of algal symbionts, and that bleaching occurs when F-v/F-n, (measured 2 h after sunset) is reduced to a value of less than or equal to 0.6. Elevated copper concentrations (60 mug Cu l(-1) for 10 h) also induced a rapid bleaching in S. hystrix but without affecting the quantum yield of the algae in symbio. Tests with isolated algae indicated that substantially higher concentrations (300 mug Cu l(-1) for 8 h) were needed to significantly reduce the quantum yield. Thus, copper-induced bleaching occurs without affecting the algal photosynthesis and may be related to effects on the host (animal). It is argued that warm-water bleaching of corals resembles both types of chemically induced bleaching, suggesting the need for an integrated model of coral bleaching involving the effect of temperature on both host (coral) and algal symbionts.

Coral bleaching following wintry weather

Extensive coral bleaching Occurred intertidally in early August 2003 in the Capricorn Bunker group (Wistari Reef, Heron and One Tree Islands; Southern Great Barrier Reef). The affected intertidal coral had been exposed to unusually cold (minimum = 13.3degreesC; wet bulb temperature = 9degreesC) and dry winds (44% relative humidity) for 2 d during predawn low tides. Coral bleached in the upper 10 cm of their branches and had less than 0.2 x 10(6) cell cm(-2) as compared with over 2.5 x 10(6), Cell cm(-2) in nonbleached areas. Dark-adapted quantum yields did not differ between symbionts in bleached and nonbleached areas. Exposing symbionts to light, however, led to greater quenching of Photosystem 11 in symbionts in the bleached coral. Bleached areas of the affected colonies had died by September 2003, with areas that were essentially covered by more than 80% living coral decreasing to less than 10% visible living coral cover. By January 2004, coral began to recover, principally from areas of colonies that were not exposed during low tide (i.e., from below dead, upper regions). These data highlight the importance of understanding local weather patterns as well as the effects of longer term trends in global climate.

Phase behavior of a phospholipid/fatty acid/water mixture studied in atomic detail

Molecular dynamics simulations have been used to study the phase behavior of a dipalmitoylphosphatidylcholine (DPPC)/palmitic acid (PA)/water 1:2:20 mixture in atomic detail. Starting from a random solution of DPPC and PA in water, the system adopts either a gel phase at temperatures below similar to 330 K or an inverted hexagonal phase above similar to 330 K in good agreement with experiment. It has also been possible to observe the direct transformation from a gel to an inverted hexagonal phase at elevated temperature (similar to 390 K). During this transformation, a metastable fluid lamellar intermediate is observed. Interlamellar connections or stalks form spontaneously on a nanosecond time scale and subsequently elongate, leading to the formation of an inverted hexagonal phase. This work opens the possibility of studying in detail how the formation of nonlamellar phases is affected by lipid composition and (fusion) peptides and, thus, is an important step toward understanding related biological processes, such as membrane fusion.