Graphene Multi-Protonation: a Cooperative Mechanism for Proton Permeation

The interaction between protons and graphene is attracting a large interest due to recent experiments showing that these charged species permeate through the 2D material following a low barrier (~ 0.8 eV) activated process. A possible explanation involves the flipping of a chemisorbed proton (rotation of the C-H$^+$ bond from one to the other side of the carbon layer) and previous studies have found so far that the energy barriers (around 3.5 eV) are too high to explain the experimental findings. Contrarily to the previously adopted model assuming an isolated proton, in this work we consider protonated graphene at high local coverage and explore the role played by nearby chemisorbed protons in the permeation process. By means of density functional theory calculations exploiting large molecular prototypes for graphene it is found that, when various protons are adsorbed on the same carbon hexagonal ring, the permeation barrier can be reduced down to 1.0 eV. The related mechanism is described in detail and could shed a new light on the interpretation of the experimental observations for proton permeation through graphene.Comment: 16 pages, 5 figure

Green's functions for far-side seismic images: a polar expansion approach

We have computed seismic images of magnetic activity on the far surface of the Sun by using a seismic-holography technique. As in previous works, the method is based on the comparison of waves going in and out of a particular point in the Sun but we have computed here the Green's functions from a spherical polar expansion of the adiabatic wave equations in the Cowling approximation instead of using the ray-path approximation previously used in the far-side holography. A comparison between the results obtained using the ray theory and the spherical polar expansion is shown. We use the gravito-acoustic wave equation in the local plane-parallel limit in both cases and for the latter we take the asymptotic approximation for the radial dependencies of the Green's function. As a result, improved images of the far-side can be obtained from the polar-expansion approximation, especially when combining the Green's functions corresponding to two and three skips. We also show that the phase corrections in the Green's functions due to the incorrect modeling of the uppermost layers of the Sun can be estimated from the eigenfrequencies of the normal modes of oscillation.Comment: 8 pages, 5 figures, Astrophysical Journal, accepted (2010

RNA interference is ineffective as a routine method for gene silencing in chick embryos as monitored by fgf8 silencing.

The in vivo accessibility of the chick embryo makes it a favoured model system for experimental developmental biology. Although the range of available techniques now extends to miss-expression of genes through in ovo electroporation, it remains difficult to knock out individual gene expression. Recently, the possibility of silencing gene expression by RNAi in chick embryos has been reported. However, published studies show only discrete quantitative differences in the expression of the endogenous targeted genes and unclear morphological alterations. To elucidate whether the tools currently available are adequate to silence gene expression sufficiently to produce a clear and specific null-like mutant phenotype, we have performed several experiments with different molecules that trigger RNAi: dsRNA, siRNA, and shRNA produced from a plasmid coexpressing green fluorescent protein as an internal marker. Focussing on fgf8 expression in the developing isthmus, we show that no morphological defects are observed, and that fgf8 expression is neither silenced in embryos microinjected with dsRNA nor in embryos microinjected and electroporated with a pool of siRNAs. Moreover, fgf8 expression was not significantly silenced in most isthmic cells transformed with a plasmid producing engineered shRNAs to fgf8. We also show that siRNA molecules do not spread significantly from cell to cell as reported for invertebrates, suggesting the existence of molecular differences between different model systems that may explain the different responses to RNAi. Although our results are basically in agreement with previously reported studies, we suggest, in contrast to them, that with currently available tools and techniques the number of cells in which fgf8 gene expression is decreased, if any, is not sufficient to generate a detectable mutant phenotype, thus making RNAi useless as a routine method for functional gene analysis in chick embryos

Three-Dimensional Wave Packet Approach for the Quantum Transport of Atoms through Nanoporous Membranes

Quantum phenomena are relevant to the transport of light atoms and molecules through nanoporous two-dimensional (2D) membranes. Indeed, confinement provided by (sub-)nanometer pores enhances quantum effects such as tunneling and zero point energy (ZPE), even leading to quantum sieving of different isotopes of a given element. However, these features are not always taken into account in approaches where classical theories or approximate quantum models are preferred. In this work we present an exact three-dimensional wave packet propagation treatment for simulating the passage of atoms through periodic 2D membranes. Calculations are reported for the transmission of $^3$He and $^4$He through graphdiyne as well as through a holey graphene model. For He-graphdiyne, estimations based on tunneling-corrected transition state theory are correct: both tunneling and ZPE effects are very important but competition between each other leads to a moderately small $^4$He/$^3$He selectivity. Thus, formulations that neglect one or another quantum effect are inappropriate. For the transport of He isotopes through leaky graphene, the computed transmission probabilities are highly structured suggesting widespread selective adsorption resonances and the resulting rate coefficients and selectivity ratios are not in agreement with predictions from transition state theory. Present approach serves as a benchmark for studies of the range of validity of more approximate methods.Comment: 4 figure

X-ray spectral variability of seven LINER nuclei with XMM-Newton and Chandra data

One of the most important features in active galactic nuclei (AGN) is the variability of their emission. Variability has been discovered at X-ray, UV, and radio frequencies on time scales from hours to years. Among the AGN family and according to theoretical studies, Low-Ionization Nuclear Emission Line Region (LINER) nuclei would be variable objects on long time scales. Our purpose is to investigate spectral X-ray variability in LINERs and to understand the nature of these kinds of objects, as well as their accretion mechanism. Chandra and XMM-Newton public archives were used to compile X-ray spectra of seven LINER nuclei at different epochs with time scales of years. To search for variability we fit all the spectra from the same object with a set of models, in order to identify the parameters responsible for the variability pattern. We also analyzed the light curves in order to search for short time scale (from hours to days) variability. Whenever possible, UV variability was also studied. We found spectral variability in four objects, with variations mostly related to hard energies (2-10 keV). These variations are due to changes in the soft excess, and/or changes in the absorber, and/or intrinsic variations of the source. Another two galaxies seem not to vary. Short time scale variations during individual observations were not found. Our analysis confirms the previously reported anticorrelation between the X-ray spectral index and the Eddington ratio, and also the correlation between the X-ray to UV flux ratio and the Eddington ratio. These results support an Advection Dominated Accretion Flow (ADAF) as the accretion mechanism in LINERs.Comment: 35 pages, 53 figures, recently accepted pape