Discrete cyanide-bridged mixed-valence Co/Fe complexes: Outer-sphere redox behaviour

The outer-sphere redox behaviour of a series of [LnCoIII-NCFeII(CN)(5)](-) (L-n = n-membered pentadentate aza-macrocycle) complexes have been studied as a function of pH and oxidising agent. All the dinuclear complexes show a double protonation process at pH approximate to 2 that produces a shift in their UV/Vis spectra. Oxidation of the different non-protonated and diprotonated complexes has been carried out with peroxodisulfate, and of the non-protonated complexes also with trisoxalatocobaltate(III). The results are in agreement with predictions from the Marcus theory. The oxidation of [Fe(phen)(3)](3+) and [IrCl6](2-) is too fast to be measured, although for the latter the transient observation of the process has been achieved at pH = 0. The study of the kinetics of the outer-sphere redox process, with the S2O82- and [Co(ox)(3)](3-) oxidants, has been carried out as a function of pH, temperature, and pressure. As a whole, the values found for the activation volumes, entropies, and enthalpies are in the following margins, for the diprotonated and non-protonated dinuclear complexes, respectively: DeltaV(not equal) from 11 to 13 and 15 to 20 cm(3) mol(-1); DeltaS(not equal) from 110 to 30 and -60 to -90 J K-1 mol(-1); DeltaH(not equal) from 115 to 80 and 50 to 65 kJ.mol(-1). The thermal activation parameters are clearly dominated by the electrostriction occurring on outer-sphere precursor formation, while the trends found for the values of the volume of activation indicate an important degree of tuning due to the charge distribution during the electron transfer process. The special arrangement on the amine ligands in the isomer trans[(L14CoNCFeII)-N-III(CN)(5)](-) accounts for important differences in solvent-assisted hydrogen bonding occurring within the outer-sphere redox process, as has been established in redox reactions of similar compounds. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).

Effect of the number of shells on the pressure and energy of two-dimensional free bubble clusters

We have performed Surface Evolver simulations of two-dimensional hexagonal bubble clusters consisting of a central bubble of area lambda surrounded by s shells or layers of bubbles of unit area. Clusters of up to twenty layers have been simulated, with lambda varying between 0.01 and 100. In monodisperse clusters (i.e., for lambda = 1) [M.A. Fortes, F Morgan, M. Fatima Vaz, Philos. Mag. Lett. 87 (2007) 561] both the average pressure of the entire Cluster and the pressure in the central bubble are decreasing functions of s and approach 0.9306 for very large s, which is the pressure in a bubble of an infinite monodisperse honeycomb foam. Here we address the effect of changing the central bubble area lambda. For small lambda the pressure in the central bubble and the average pressure were both found to decrease with s, as in monodisperse clusters. However, for large,, the pressure in the central bubble and the average pressure increase with s. The average pressure of large clusters was found to be independent of lambda and to approach 0.9306 asymptotically. We have also determined the cluster surface energies given by the equation of equilibrium for the total energy in terms of the area and the pressure in each bubble. When the pressures in the bubbles are not available, an approximate equation derived by Vaz et al. [M. Fatima Vaz, M.A. Fortes, F. Graner, Philos. Mag. Lett. 82 (2002) 575] was shown to provide good estimations for the cluster energy provided the bubble area distribution is narrow. This approach does not take cluster topology into account. Using this approximate equation, we find a good correlation between Surface Evolver Simulations and the estimated Values of energies and pressures. (C) 2008 Elsevier B.V. All rights reserved.

Re-entrant phase behaviour of network fluids: A patchy particle model with temperature-dependent valence

We study a model consisting of particles with dissimilar bonding sites ("patches"), which exhibits self-assembly into chains connected by Y-junctions, and investigate its phase behaviour by both simulations and theory. We show that, as the energy cost epsilon(j) of forming Y-junctions increases, the extent of the liquid-vapour coexistence region at lower temperatures and densities is reduced. The phase diagram thus acquires a characteristic "pinched" shape in which the liquid branch density decreases as the temperature is lowered. To our knowledge, this is the first model in which the predicted topological phase transition between a fluid composed of short chains and a fluid rich in Y-junctions is actually observed. Above a certain threshold for epsilon(j), condensation ceases to exist because the entropy gain of forming Y-junctions can no longer offset their energy cost. We also show that the properties of these phase diagrams can be understood in terms of a temperature-dependent effective valence of the patchy particles. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3605703]

A Hexanuclear Mixed-Valence Oxovanadium(IV,V) Complex as a Highly Efficient Alkane Oxidation Catalyst

The new hexanuclear mixed-valence vanadium complex [V3O3(OEt)(ashz)(2)(mu-OEt)](2) (1) with an N,O-donor ligand is reported. It acts as a highly efficient catalyst toward alkane oxidations by aqueous H2O2. Remarkably, high turnover numbers up to 25000 with product yields of up to 27% (based on alkane) stand for one of the most active systems for such reactions.

Shells of the limpet Patella aspera as habitat for epibionts

World Congress of Malacology, Universidade dos Açores, Ponta Delgada, 21-28 de julho.

Removal of sulfamethoxazole from solution by raw and chemically treated walnut shells

Purpose: The sorption of sulfamethoxazole, a frequently detected pharmaceutical compound in the environment, onto walnut shells was evaluated. Methods: The sorption proprieties of the raw sorbent were chemically modified and two additional samples were obtained, respectively HCl and NaOH treated. Scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric (TG/DTG) techniques were applied to investigate the effect of the chemical treatments on the shell surface morphology and chemistry. Sorption experiments to investigate the pH effect on the process were carried out between pH 2 and 8. Results: The chemical treatment did not substantially alter the structure of the sorbent (physical and textural characteristics) but modified the surface chemistry of the sorbent (acid–base properties, point of zero charge—pHpzc). The solution pH influences both the sorbent’s surface charge and sulfamethoxazole speciation. The best removal efficiencies were obtained for lower pH values where the neutral and cationic sulfamethoxazole forms are present in the solution. Langmuir and Freundlich isotherms were applied to the experimental adsorption data for sulfamethoxazole sorption at pH 2, 4, and 7 onto raw walnut shell. No statistical difference was found between the two models except for the pH 2 experimental data to which the Freundlich model fitted better. Conclusion: Sorption of sulfamethoxazole was found to be highly pH dependent in the entire pH range studied and for both raw and treated sorbent.

Shells of Patella aspera as 'islands' for epibionts

Copyright © Marine Biological Association of the United Kingdom, 2014.

Effects of emotional valence and three-dimensionality of visual stimuli on brain activation: an fMRI study

BACKGROUND: Examining changes in brain activation linked with emotion-inducing stimuli is essential to the study of emotions. Due to the ecological potential of techniques such as virtual reality (VR), inspection of whether brain activation in response to emotional stimuli can be modulated by the three-dimensional (3D) properties of the images is important. OBJECTIVE: The current study sought to test whether the activation of brain areas involved in the emotional processing of scenarios of different valences can be modulated by 3D. Therefore, the focus was made on the interaction effect between emotion-inducing stimuli of different emotional valences (pleasant, unpleasant and neutral valences) and visualization types (2D, 3D). However, main effects were also analyzed.METHODS: The effect of emotional valence and visualization types and their interaction were analyzed through a 3x2 repeated measures ANOVA. Post-hoc t-tests were performed under a ROI-analysis approach. RESULTS: The results show increased brain activation for the 3D affective-inducing stimuli in comparison with the same stimuli in 2D scenarios, mostly in cortical and subcortical regions that are related to emotional processing, in addition to visual processing regions. CONCLUSIONS: This study has the potential of clarify brain mechanisms involved in the processing of emotional stimuli (scenarios’ valence) and their interaction with three-dimensionality.

Biomimetic mineralization: encapsulation in calcium carbonate shells

Calcium carbonate biomineralization is a self-assembly process that has been studied to be applied in the biomedical field to encapsulate biomolecules. Advantages of engineering mineral capsules include improved drug loading efficiencies and protection against external environment. However, common production methods result in heterogeneous capsules and subject biomolecules to heat and vibration which cause irreversible damage. To overcome these issues, a microfluidic device was designed, manufactured and tested in terms of selectivity for water and oil to produce a W/O/W emulsion. During the development of this work there was one critical challenge: the selective functionalization in closed microfluidic channels. Wet chemical oxidation of PDMS with 1M NaOH, confirmed by FTIR, followed by adsorption of polyelectrolytes - PDADMAC/PSS - confirmed by UV-Vis and AFM results, render the surface of PDMS hydrophilic. UV-Vis spectroscopy also confirmed that this modification did not affect PDMS optical properties, making possible to monitor fluids and droplets. More important, with this approach PDMS remains hydrophilic over time. However, due to equipment constrains selectivity in microchannels was not achieved. Therefore, emulsion studies took place with conventional methods. Several systems were tried, with promising results achieved with CaCO3 in-situ precipitation, without the use of polymers or magnesium. This mineral stabilizes oil droplets in water, but not in air due to incomplete capsule formation.

The natural history of British shells : including figures and descriptions of all the species hitherto discovered in Great Britain, systematically arranged in the Linnean manner, with scientific and general observations on each ; in five volumes /

5