Differential capacitance of ionic liquids according to lattice-gas mean-field model with nearest-neighbor interactions

The Bragg-Williams free energy is used to incorporate nearest-neighbor interactions into the lattice gas model of a solvent-free ionic liquid near a planar electrode. We calculate the differential capacitance from solutions of the mean-field consistency relation, arriving at an explicit expression in the limit of a weakly charged electrode. The two additional material parameters that appear in the theory -- the degree of nonideality and the resistance to concentration changes of each ion type -- give rise to different regimes that we identify and discuss. As the nonideality parameter, which becomes more positive for stronger nearest-neighbor attraction between like-charged ions, increases and the electrode is weakly charged, the differential capacitance is predicted to transition through a divergence and subsequently adopt negative values just before the ionic liquid becomes structurally unstable. This is associated with the spontaneous charging of an electrode at vanishing potential. The physical origin of the divergence and the negative sign of the differential capacitance is a nonmonotonic relationship between surface potential and surface charge density, which reflects the formation of layered domains alternatingly enriched in counterions and coions near the electrode. The decay length of this layered domain pattern, which can be many times larger than the ion size, is reminiscent of the recently introduced concept of "underscreening".Comment: 24 pages, 7 figures, version of record published in The Journal of Chemical Physic

Pore evolution in interstellar ice analogues: simulating the effects of temperature increase

Context. The level of porosity of interstellar ices - largely comprised of amorphous solid water (ASW) - contains clues on the trapping capacity of other volatile species and determines the surface accessibility that is needed for solid state reactions to take place. Aims. Our goal is to simulate the growth of amorphous water ice at low temperature (10 K) and to characterize the evolution of the porosity (and the specific surface area) as a function of temperature (from 10 to 120 K). Methods. Kinetic Monte Carlo simulations are used to mimic the formation and the thermal evolution of pores in amorphous water ice. We follow the accretion of gas-phase water molecules as well as their migration on surfaces with different grid sizes, both at the top growing layer and within the bulk. Results. We show that the porosity characteristics change substantially in water ice as the temperature increases. The total surface of the pores decreases strongly while the total volume decreases only slightly for higher temperatures. This will decrease the overall reaction efficiency, but in parallel, small pores connect and merge, allowing trapped molecules to meet and react within the pores network, providing a pathway to increase the reaction efficiency. We introduce pore coalescence as a new solid state process that may boost the solid state formation of new molecules in space and has not been considered so far.Comment: 9 pages, 8 figures Accepted for publication in A&

Collection and Evaluation of (Q)SAR Models for Mutagenicity and Carcinogenicity

This evaluation of the non-commercial (Q)SARs for mutagenicity and carcinogenicity consisted of a preliminary survey (Phase I), and then of a more detailed analysis of short listed models (Phase II). In Phase I, the models were collected from the literature, and then assessed according to the OECD principles based on the information provided by the authors-. Phase I provided the support for short listing a number of promising models, that were analyzed more in depth in Phase II. In Phase II, the information provided by the authors was completed and complemented with a series of analyses aimed at generating an overall profile of each of the short listed models. The models can be divided into two families based on their target: a) congeneric; and b) non-congeneric sets of chemicals. The QSARs for congeneric chemicals include most of the chemical classes top ranking in the EU High Production Volume list, with the notable exception of the halogenated aliphatics. They almost exclusively aim at modeling Salmonella mutagenicity and rodent carcinogenicity, which are crucial toxicological endpoints in the regulatory context. The lack of models for in vivo genotoxicity should be remarked. Overall the short listed models can be interpreted mechanistically, and agree with, and/or support the available scientific knowledge, and most of the models have good statistics. Based on external prediction tests, the QSARs for the potency of congeneric chemicals are 30 to 70 % correct, whereas the models for discriminating between active and inactive chemicals have considerably higher accuracy (63 to 100 %), thus indicating that predicting intervals is more reliable than predicting individual data points. The internal validation procedures (e.g., cross-validation, etc...) did not seem to be a reliable measure of external predictivity. Among the non-local, or global approaches for non-congeneric data sets, four models based on the use of Structural Alerts (SA) were short listed and investigated in more depth. The four sets did not differ to a large extent in their performance. In the general databases of chemicals the SAs appear to agree around 65% with rodent carcinogenicity data, and 75% with Salmonella mutagenicity data. The SAs based models do not seem to work equally efficiently in the discrimination between active and inactive chemicals within individual chemical classes. Thus, their main role is that of preliminary, or large-scale screenings. A priority for future research on the SAs is their expansion to include alerts for nongenotoxic carcinogens. A general indication of this study, valid for both congeneric and noncongeneric models, is that there is uncertainty associated with (Q)SARs; the level of uncertainty has to be considered when using (Q)SAR in a regulatory context. However, (Q)SARs are not meant to be black-box machines for predictions, but have a much larger scope including organization and rationalization of data, contribution to highlight mechanisms of action, complementation of other data from different sources (e.g., experiments). Using only non-testing methods, the larger the evidence from QSARs (several different models, if available) and other approaches (e.g. chemical categories, read across) the higher the confidence in the prediction.JRC.I.3-Toxicology and chemical substance

Anisotropy studies around the galactic center

We present the first results for anisotropy searches around the galactic center at EeV energies using data from the Pierre Auger Observatory. Our analysis, based on a substantially larger data set, do not support previous claim of anisotropy found in this region by the AGASA and Sugar experiment. Furthermore we place un upper limit on a possible point like source located at the galactic center which exclude several scenarios predicting neutron sources in this location.Comment: 10 pages. 6 figures. Proceeding of the CRIS 2006 conferenc

Dolor abdominal, principal motivo de consulta en obstetricia. Estudio transversal, Hospital Universitario Clínica San Rafael - Bogotá, 2011 a 2012

Se realizó un estudio observacional, de corte transversal en pacientes embarazadas cuyo motivo de consulta al momento del ingreso en el servicio de urgencias obstétricas del Hospital Universitario Clínica San Rafael de la ciudad de Bogotá, fue dolor abdominal , en el período comprendido entre 1 de Junio de 2011, y 31 de Mayo de 2012, con el objetivo de determinar la prevalencia y medir la frecuencia de aquellas que requirieron manejo quirúrgico, definir factores de riesgo asociados a su presentación clínica, como: parto pretérmino, infección de vías urinarias, urolitiasis e infección vaginal y establecer la frecuencia de desenlace perinatal adverso asociado a aquellas pacientes que requirieron manejo quirúrgico."Was performed an observational, cross- sectional study in pregnant patients whose reason for consultation at the time of admission to the emergency obstetric in the Hospital Universitario Clinica San Rafael of Bogotá , was "" abdominal pain "" in the period between 1 June 2011 , and May 31, 2012 , with the objective of determining the prevalence and measure the frequency of those who required surgical management , identify risk factors associated with clinical presentation, such as preterm labor , urinary tract infection , urolithiasis and vaginal infection and to determine the frequency of adverse perinatal outcome associated with those patients requiring surgical management.

High Temperature Stability of Onion-Like Carbon vs Highly Oriented Pyrolytic Graphite

Abstract The thermodynamic stability of onion-like carbon (OLC) nanostructures with respect to highly oriented pyrolytic graphite (HOPG) was determined in the interval 765–1030 K by the electromotive force (emf) measurements of solid electrolyte galvanic cell: (Low) Pt|Cr3C2,CrF2,OLC|CaF2s.c.|Cr3C2,CrF2,HOPG|Pt (High). The free energy change of transformation HOPG = OLC was found positive below 920.6 K crossing the zero value at this temperature. Its trend with temperature was well described by a 3rd degree polynomial. The unexpected too high values of LDrHT LT P ~DcPðTÞ jointly to the HR-TEM, STEM and EELS evidences that showed OLC completely embedded in rigid cages made of a Cr3C2/CrF2 matrix, suggested that carbon in the electrodes experienced different internal pressures. This was confirmed by the evaluation under constant volume of dP dT by the a k ratio for OLC (0.5 MPa K21) and HOPG (8 Pa K21) where a and k are the isobaric thermal expansion and isothermal compressibility coefficients, respectively. The temperature dependency of the pressure was derived and utilized to calculate the enthalpy and entropy changes as function of temperature and pressure. The highest value of the internal pressure experienced by OLC was calculated to be about 7 GPa at the highest temperature. At 920.6 K, DrH and DrS values are 95.8 kJ mol21 and 104.1 JK21 mol21, respectively. The surface contributions to the energetic of the system were evaluated and they were found negligible compared with the bulk terms. As a consequence of the high internal pressure, the values of the enthalpy and entropy changes were mainly attributed to the formation of carbon defects in OLC considered as multishell fullerenes. The change of the carbon defect fraction is reported as a function of temperature

Porosity measurements of interstellar ice mixtures using optical laser interference and extended effective medium approximations

Aims. This article aims to provide an alternative method of measuring the porosity of multi-phase composite ices from their refractive indices and of characterising how the abundance of a premixed contaminant (e.g., CO2) affects the porosity of water-rich ice mixtures during omni-directional deposition. Methods. We combine optical laser interference and extended effective medium approximations (EMAs) to measure the porosity of three astrophysically relevant ice mixtures: H2O:CO2=10:1, 4:1, and 2:1. Infrared spectroscopy is used as a benchmarking test of this new laboratory-based method. Results. By independently monitoring the O-H dangling modes of the different water-rich ice mixtures, we confirm the porosities predicted by the extended EMAs. We also demonstrate that CO2 premixed with water in the gas phase does not significantly affect the ice morphology during omni-directional deposition, as long as the physical conditions favourable to segregation are not reached. We propose a mechanism in which CO2 molecules diffuse on the surface of the growing ice sample prior to being incorporated into the bulk and then fill the pores partly or completely, depending on the relative abundance and the growth temperature.Comment: 9 pages, 6 figures, 1 table. Accepted for publication in A&