Molecular dynamics simulations of oxygen diffusion in GdBaCo2O5.5

International audienceThe mechanisms of oxygen diffusion in GdBaCo2O5.5 compound are investigated by molecular dynamics simulations. The results confirm that diffusion is mainly bidimensional with oxygen moving in the a,b plane while diffusion along the c axis is much more difficult. Between 1000 and 1600 K, the activation energy for diffusion is about 0.6 eV, close to experimental values. Going deeper inside the oxygen diffusion mechanism, we see that this diffusion occurs mainly in the cobalt planes while most of the oxygen vacancies are kept in the Gd planes. Analysis of oxygen motions show that Gd planes can be seen as source-sink for the oxygen vacancies rather than as fast pathways

Thermodynamics of hydration and oxidation in the proton conductor Gd-doped barium cerate from density functional theory calculations

International audienceHydration and oxidation of gadolinium-doped barium cerate, a system with highly promising properties when used as electrolyte for protonic ceramic fuel cells, are investigated by means of density functional calculations. The energy landscape of oxygen vacancies and interstitial protons in this strongly distorted orthorhombic perovskite is computed. Although the most stable sites for protons are found in the close vicinity of the dopant, the picture of a very complex energy landscape emerges, in which some sites far away from Gd are found more stable than other ones in its close vicinity, due to the highly distorted geometry of the hostmaterials. The fully hydrated phase can be approximated by a structure with 16 local minima. Both hydration (water incorporation) and oxidation (oxygen incorporation) are found to be exothermic processeswith reaction enthalpies of−1.34 eV/H2Omolecule and −0.70 eV/O atom, respectively. The hole polaron resulting from the exothermic incorporation of oxygen is found localized on oxygens around the dopant (small polaron) and carries a spin magnetic moment. Finally, the competition between hydration and oxidation is studied and discussed as a function of oxygen and water partial pressures

Getting elections right? Measuring electoral integrity

Holding elections has become a global norm. Unfortunately, the integrity of elections varies strongly, ranging from “free and fair” elections with genuine contestation to “façade” elections marred by manipulation and fraud. Clearly, electoral integrity is a topic of increasing concern. Yet electoral integrity is notoriously difficult to measure, and hence taking stock of the available data is important. This article compares cross-national data sets measuring electoral integrity. The first part evaluates how the different data sets (a) conceptualize electoral integrity, (b) move from concepts to indicators, and (c) move from indicators to data. The second part analyses how different data sets code the same elections, seeking to explain the sources of disagreement about electoral integrity. The sample analysed comprises 746 elections in 95 third and fourth wave regimes from 1974 until 2009. I find that conceptual and measurement choices affect disagreement about election integrity, and also find that elections of lower integrity and post-conflict elections generate higher disagreement about election integrity. The article concludes with a discussion of results and suggestions for future research

Clinical Study Is IgG4-Related Disease a Cause of Xerostomia? A Cohort Study of 60 Patients

Objective. Immunoglobulin-G4-(IgG4-) related disease (IgG4 RD) is a fibrosing process characterized by a significant infiltration of IgG4-secreting plasma cells. IgG4 RD can affect almost all organs including salivary glands. Whether IgG4 RD plays a role in the development of sicca syndrome and particularly dry mouth syndrome remains to be investigated. Methods. We conducted a monocentric cohort study for two years to search for IgG4 RD features in patients with dry mouth syndrome using immunostainings of labial salivary gland specimens with anti-IgG4 antibody. Results. Among 60 patients presenting with dry mouth syndrome who underwent labial salivary gland biopsy, 18 showed positive immunostaining with the anti-IgG4 antibody including 4 patients with typical systemic IgG4 RD. Five also fulfilled criteria for Sjögren's syndrome. Conclusion. These findings suggest that clinical forms of IgG4 RD salivary involvement without salivary swelling may occur. This salivary involvement is probably overlooked in everyday practice and could represent a mild form of IgG4 RD

Clinical Study Is IgG4-Related Disease a Cause of Xerostomia? A Cohort Study of 60 Patients

Objective. Immunoglobulin-G4-(IgG4-) related disease (IgG4 RD) is a fibrosing process characterized by a significant infiltration of IgG4-secreting plasma cells. IgG4 RD can affect almost all organs including salivary glands. Whether IgG4 RD plays a role in the development of sicca syndrome and particularly dry mouth syndrome remains to be investigated. Methods. We conducted a monocentric cohort study for two years to search for IgG4 RD features in patients with dry mouth syndrome using immunostainings of labial salivary gland specimens with anti-IgG4 antibody. Results. Among 60 patients presenting with dry mouth syndrome who underwent labial salivary gland biopsy, 18 showed positive immunostaining with the anti-IgG4 antibody including 4 patients with typical systemic IgG4 RD. Five also fulfilled criteria for Sjögren's syndrome. Conclusion. These findings suggest that clinical forms of IgG4 RD salivary involvement without salivary swelling may occur. This salivary involvement is probably overlooked in everyday practice and could represent a mild form of IgG4 RD

Fermi level shift in carbon nanotubes by dye confinement

International audienceDye confinement into carbon nanotube significantly affects the electronic charge density distribution of the final hybrid system. Using the electron-phonon coupling sensitivity of the Raman G-band, we quantify experimentally how charge transfer from thiophene oligomers to single walled carbon nanotube is modulated by the diameter of the nano-container and its metallic or semiconducting character. This charge transfer is shown to restore the electron-phonon coupling into defected metallic nanotubes. For sub-nanometer diameter tube, an electron transfer optically activated is observed when the excitation energy matches the HOMO-LUMO transition of the confined oligothiophene. This electron doping accounts for an important enhancement of the photoluminescence intensity up to a factor of nearly six for optimal confinement configuration. This electron transfer shifts the Fermi level, acting on the photoluminescence efficiency. Therefore, thiophene oligomer encapsulation allows modulating the electronic structure and then the optical properties of the hybrid system

Global hybrids from the semiclassical atom theory satisfying the local density linear response

We propose global hybrid approximations of the exchange-correlation (XC) energy functional which reproduce well the modified fourth-order gradient expansion of the exchange energy in the semiclassical limit of many-electron neutral atoms and recover the full local density approximation (LDA) linear response. These XC functionals represent the hybrid versions of the APBE functional [Phys. Rev. Lett. 106, 186406, (2011)] yet employing an additional correlation functional which uses the localization concept of the correlation energy density to improve the compatibility with the Hartree-Fock exchange as well as the coupling-constant-resolved XC potential energy. Broad energetical and structural testings, including thermochemistry and geometry, transition metal complexes, non-covalent interactions, gold clusters and small gold-molecule interfaces, as well as an analysis of the hybrid parameters, show that our construction is quite robust. In particular, our testing shows that the resulting hybrid, including 20\% of Hartree-Fock exchange and named hAPBE, performs remarkably well for a broad palette of systems and properties, being generally better than popular hybrids (PBE0 and B3LYP). Semi-empirical dispersion corrections are also provided.Comment: 12 pages, 4 figure

The initial molecular response predicts the deep molecular response but not treatment-free remission maintenance in a real-world chronic myeloid leukemia cohort

In chronic myeloid leukemia, the identification of early molecular predictors of stable treatment-free remission (TFR) after tyrosine kinase inhibitor (TKI) discontinuation is challenging. The predictive values of residual disease (BCR::ABL1 quantification) at months 3 and 6 and more recently, BCR::ABL1 transcript halving time (HT) have been described, but no study compared the predictive value of different early parameters. Using a real-world cohort of 408 patients, we compared the performance of the ELTS score, BCR::ABL1 HT, and residual disease at month 3 and 6 to predict the molecular response, achievement of the TKI discontinuation criteria, and TFR maintenance. The performances of BCR::ABL1 HT and residual disease at month 3 were similar. Residual disease at month 6 displayed the best performance for predicting the optimal response (area under the ROC curve between 0.81 and 0.92; cut-off values: 0.11% for MR4 at month 24 and 0.12% for MR4.5 at month 48). Conversely, no early parameter predicted reaching the TKI discontinuation criteria and TFR maintenance. We obtained similar results when patients were divided in subgroups by first-line treatment (imatinib vs second generation TKI, 2G-TKI). We identified a relationship between ELTS score, earlier milestones and TFR maintenance only in the 2G-TKI group. In conclusion, this first comparative study of early therapeutic response parameters showed that they are excellent indicators of TKI efficacy (BCR::ABL1 transcript reduction) and best responders. Conversely, they did not predict the achievement of the TKI discontinuation criteria and TFR maintenance, suggesting that other parameters are involved in TFR maintenance