Platinum nanoparticles incorporated in silsesquioxane for use in LbL films for the simultaneous detection of dopamine and ascorbic acid

We describe the preparation of platinum nanoparticles (PtNPs) using the 3-n-propylpyridinium silsesquioxane chloride (SiPy+Cl-) as a nanoreactor and stabilizer. The formation of PtNPs was monitored by UV-Vis spectroscopy by measuring the decrease in the intensity of the band at 375 nm, which is attributed to the electronic absorption of PtCl62- ions. TEM images of Pt-SiPy+Cl- nanohybrid indicated an average size of 3-40 nm for PtNPs. The Pt-SiPy+Cl- was used as a polycation in the preparation of layer-by-layer films (LbL) on a glass substrate coated with fluorine-doped tin oxide (FTO) alternating with the polyanion poly(vinyl sulfonic acid) (PVS). The films were electrochemically tested in sulfuric acid to confirm the deposition of Pt-SiPy+Cl- onto the LbL films, observing the adsorption and desorption of hydrogen (E-pa = 0.1 V) and by the redox process of formation for PtO with E-pa = 1.3 V and E-pc = 0.65 V. FTIR and Raman spectra confirmed the presence of the PVS and Pt-SiPy+Cl- in the LbL films. A linear increase in the absorbance in the UV-Vis spectra of the Pt-SiPy+Cl- at 258 nm (pi -> pi* transition of the pyridine groups) with a number of Pt-SiPy+Cl-/PVS or PVS/SiPy+Cl- bilayers (R = 0.992) was observed. These LbL films were tested for the determination of dopamine (DA) in the presence of ascorbic acid (AA) with a detection limit (DL) on the order of 2.6 x 10(-6) mol L-1 and a quantification limit (QL) of 8.6 x 10(-6) mol L-1. The films exhibited a good repeatability and reproducibility, providing a potential difference of 550 mV for the oxidation of DA with AA interferent.

Surface ecophysiological behavior across vegetation and moisture gradients in tropical South America

Surface ecophysiology at five sites in tropical South America across vegetation and moisture gradients is investigated. From the moist northwest (Manaus) to the relatively dry southeast (Pé de Gigante, state of São Paulo) simulated seasonal cycles of latent and sensible heat, and carbon flux produced with the Simple Biosphere Model (SiB3) are confronted with observational data. In the northwest, abundant moisture is available, suggesting that the ecosystem is light-limited. In these wettest regions, Bowen ratio is consistently low, with little or no annual cycle. Carbon flux shows little or no annual cycle as well; efflux and uptake are determined by high-frequency variability in light and moisture availability. Moving downgradient in annual precipitation amount, dry season length is more clearly defined. In these regions, a dry season sink of carbon is observed and simulated. This sink is the result of the combination of increased photosynthetic production due to higher light levels, and decreased respiratory efflux due to soil drying. The differential response time of photosynthetic and respiratory processes produce observed annual cycles of net carbon flux. In drier regions, moisture and carbon fluxes are in-phase; there is carbon uptake during seasonal rains and efflux during the dry season. At the driest site, there is also a large annual cycle in latent and sensible heat flux.

Molecular origin of charge traps in polyfluorene-based semiconductors

The comprehensive control of morphology and structure is of extreme importance in semiconducting polymers when used as active layers in optoelectronic devices. In the work reported here, a systematic investigation of the structural and dynamical properties of poly(9,9-di-n-octyl-fluorene-alt-benzothiadiazole), known as F8BT, and their correlation with electrical properties is presented when the material is used as an active layer in optoelectronic devices. By means of X-ray diffraction, one observes that in thick layer films (thickness of about 4 μm) grown by drop-cast deposition, a solvent induced crystalline phase exists which evolves to a stable phase as the temperature is raised. This was not observed in thin films (thickness of about 250 nm) prepared by spin-coating within the investigated temperature range. By modeling the current-voltages characteristics of both thick and thin film devices, important information on the influence of crystallization on the trapping states could be drawn. Furthermore, the temperature dependence of the charge carrier mobility was found to be closely related to that of the molecular relaxation processes. The understanding of the nature of such molecular relaxations, measured by solid-state nuclear magnetic resonance methods, allows one to understand the importance of molecular relaxations and microstructure changes on the trap states of the system.

Gradients in the number of species at reef-seagrass ecotones explained by gradients in abundance

[EN] Gradients in the composition and diversity (e.g. number of species) of faunal assemblages are common at ecotones between juxtaposed habitats. Patterns in the number of species, however, can be confounded by patterns in abundance of individuals, because more species tend to be found wherever there are more individuals. We tested whether proximity to reefs influenced patterns in the composition and diversity (‘species density’ = number of species per area and ‘species richness’ = number of species per number of individuals) of prosobranch gastropods in meadows of two seagrasses with different physiognomy: Posidonia and Amphibolis. A change in the species composition was observed from reef-seagrass edges towards the interiors of Amphibolis, but not in Posidonia meadows. Similarly, the abundance of gastropods and species density was higher at edges relative to interiors of Amphibolis meadows, but not in Posidonia meadows. However, species richness was not affected by proximity to reefs in either type of seagrass meadow. The higher number of species at the reef-Amphibolis edge was therefore a consequence of higher abundance, rather than species richness per se. These results suggest that patterns in the composition and diversity of fauna with proximity to adjacent habitats, and the underlying processes that they reflect, likely depend on the physiognomy of the habitat.

Parallel divergent adaptation along replicated altitudinal gradients in Alpine trout

Background The European trout (Salmo trutta species complex) occurs across a very wide altitudinal range from lowland rivers to alpine streams. Historically, the major European river systems contained different, evolutionarily distinct trout lineages, and some of this genetic diversity has persisted in spite of extensive human-mediated translocations. We used AFLP-based genome scans to investigate the extent of potentially adaptive divergence among major drainages and along altitudinal gradients replicated in several rivers. Results The proportion of loci showing evidence of divergent selection was larger between drainages than along altitudinal transects within drainages. This suggests divergent selection is stronger between drainages, or adaptive divergence is constrained by gene flow among populations within drainages, although the latter could not be confirmed at a more local scale. Still, altitudinal divergence occurred and, at approximately 2% of the markers, parallel changes of the AFLP band frequencies with altitude were observed suggesting that altitude may well be an important source of divergent selection within rivers. Conclusions Our results indicate that adaptive genetic divergence is common both between major European river systems and along altitudinal gradients within drainages. Alpine trout appear to be a promising model system to investigate the relative roles of divergent selection and gene flow in promoting or preventing adaptation to climate gradients.