The effect of compressive strain on the Raman modes of the dry and hydrated BaCe0.8Y0.2O3 proton conductor

The BaCe0.8Y0.2O3-{\delta} proton conductor under hydration and under compressive strain has been analyzed with high pressure Raman spectroscopy and high pressure x-ray diffraction. The pressure dependent variation of the Ag and B2g bending modes from the O-Ce-O unit is suppressed when the proton conductor is hydrated, affecting directly the proton transfer by locally changing the electron density of the oxygen ions. Compressive strain causes a hardening of the Ce-O stretching bond. The activation barrier for proton conductivity is raised, in line with recent findings using high pressure and high temperature impedance spectroscopy. The increasing Raman frequency of the B1g and B3g modes thus implies that the phonons become hardened and increase the vibration energy in the a-c crystal plane upon compressive strain, whereas phonons are relaxed in the b-axis, and thus reveal softening of the Ag and B2g modes. Lattice toughening in the a-c crystal plane raises therefore a higher activation barrier for proton transfer and thus anisotropic conductivity. The experimental findings of the interaction of protons with the ceramic host lattice under external strain may provide a general guideline for yet to develop epitaxial strained proton conducting thin film systems with high proton mobility and low activation energy

Magmatic to solid-state evolution of a shallow emplaced agpaitic tinguaite (the Suc de Sara dyke, Velay volcanic province, France): implications for peralkaline melt segregation and extraction in ascending magmas

In the last decades the mush model has been generalized to the complete trans-crustal magmatic system in which differentiation would be driven by segregation and extraction of trapped melts from crystal-rich mushes. Melt extraction processes involved are porous flow and strain localization, the latter being regarded as the main process acting during transfer through dykes and necks along which high differential stresses are acting on. We combine structural measurements together with petrological analyses and textural observations to constrain the model of emplacement and finally emphasize how shear deformation and strain localization structures promoted the residual melt segregation that occurred in a shallow silica-undersaturated peralkaline intrusion (Suc de Sara, Velay volcanic province, French Massif Central). In this study, we demonstrate that segregation and subsequent extraction of the CO2-rich residual melt occurred during magma ascent and final emplacement of the Suc de Sara tinguaite. Contrasting features of shear deformation between the margins that exhibited different permeabilities highlight that melt segregation started by compaction as a loose packing of emerging microlites and continued with melt filling of an anastomosed C/C′ band network developing in the crystal-rich mush subjected to high shear strain. Subsequent melt extraction throughout the country rock was controlled by the permeability of the hanging wall. Along the western hanging wall of the intrusion, extraction of the residual melt was prevented by the 15 cm thick chilled margin. In contrast, segregated melt circulated through the highly porous and permeable eastern margin, causing the fenitization of the country rock.</p

The experimental power of FR900359 to study Gq-regulated biological processes.

Despite the discovery of heterotrimeric αβγ G proteins ∼25 years ago, their selective perturbation by cell-permeable inhibitors remains a fundamental challenge. Here we report that the plant-derived depsipeptide FR900359 (FR) is ideally suited to this task. Using a multifaceted approach we systematically characterize FR as a selective inhibitor of Gq/11/14 over all other mammalian Gα isoforms and elaborate its molecular mechanism of action. We also use FR to investigate whether inhibition of Gq proteins is an effective post-receptor strategy to target oncogenic signalling, using melanoma as a model system. FR suppresses many of the hallmark features that are central to the malignancy of melanoma cells, thereby providing new opportunities for therapeutic intervention. Just as pertussis toxin is used extensively to probe and inhibit the signalling of Gi/o proteins, we anticipate that FR will at least be its equivalent for investigating the biological relevance of Gq

The structural and dynamics neutron study of proton conductors: Difficulties and improvement procedures in protonated perovskite

With the expected development of Hydrogen as energy vector, there is a great impetus on the study of thermally stable proton conductors, the core of fuel cells, electrolysers and potential CO2 converters. Prior to a successful industrial application one should first well determine their extremely complex physical and chemical behaviour related to the unique character of the proton. The difficulties in comprehension of the nature of mobile protonic species, their location (especially the differentiation between bulk and surface species) as well as local and long range dynamics are different as a function of the hydration level: i) in hydrates the number of protons not really involved in the conduction is much larger than that of protonic conducting species, ii) in non-hydrated materials, the total amount of conducting protons can be very small, as dopants in semiconductors, and similar to that arising from surface water and physisorbed protonic moieties. The attempts and difficulties to locate and identify the protonic species and their dynamics using the neutron techniques are discussed in the light of representative examples, with emphasis on proton conducting perovskites

Raman Intensity: An Important Tool in the Study οf Nanomaterials and Nanostructures

Analysis of the relative and absolute Raman intensity is very important and powerful tool which allows to understand and characterize the modifications of the crystal/amorphous structure due to: (i) changes of the symmetry, e.g. substitution of the B site ion by the rare earth/lanthanide one and incorporation of mobile species in the case of high temperature protonic conducting perovskites; (ii) changes of the short/long range order, e.g. existence/disappearance of the nanoregions in the case of $PbMg_{1/3}Nb_{2/3}O_{3-x}PbTiO_3$ (PMN-PT) relaxor ferroelectric perovskites; (iii) changes of the nanostructure, e.g. depolymerisation of the Si-O network due to the substitution of the $Si^{4+}$ ions (and associated covalent bonds) by the $M^+$ cations (forming ionic bonds) or by the incorporation of the metal nanoprecipitates in the case of glasses, glazes and enamels

Raman Intensity: An Important Tool in the Study οf Nanomaterials and Nanostructures

Analysis of the relative and absolute Raman intensity is very important and powerful tool which allows to understand and characterize the modifications of the crystal/amorphous structure due to: (i) changes of the symmetry, e.g. substitution of the B site ion by the rare earth/lanthanide one and incorporation of mobile species in the case of high temperature protonic conducting perovskites; (ii) changes of the short/long range order, e.g. existence/disappearance of the nanoregions in the case of $PbMg_{1/3}Nb_{2/3}O_{3-x}PbTiO_3$ (PMN-PT) relaxor ferroelectric perovskites; (iii) changes of the nanostructure, e.g. depolymerisation of the Si-O network due to the substitution of the $Si^{4+}$ ions (and associated covalent bonds) by the $M^+$ cations (forming ionic bonds) or by the incorporation of the metal nanoprecipitates in the case of glasses, glazes and enamels

Distribution of relaxation times in PMN single crystal

The dielectric permittivity of PMN single crystal was measured in the frequency range from 20 Hz to 3 GHz. Dielectric dispersion was observed in all investigated frequency range. From the frequency dependence of the real and imaginary parts of dielectric permittvity, the distribution of relaxation times was calculated. The low frequency limit of the distribution of the relaxation times diverge according to the Vogel – Fulcher law with the freezing temperature T$_{0}$ = 228 K, which is in good agreement with mean relaxation time temperature dependence obtained from Cole – Cole equation. Broadening of the relaxation time distribution function at low temperatures indicates the existence of two different components making contribution to the total dielectric spectrum of PMN