The high-pressure behavior of CaMoO4

We report a high-pressure study of tetragonal scheelite-type CaMoO4 up to 29 GPa. In order to characterize its high-pressure behavior, we have combined Raman and optical-absorption measurements with density-functional theory calculations. We have found evidence of a pressure-induced phase transition near 15 GPa. Experiments and calculations agree in assigning the high-pressure phase to a monoclinic fergusonite-type structure. The reported results are consistent with previous powder x-ray-diffraction experiments, but are in contradiction with the conclusions obtained from earlier Raman measurements, which support the existence of more than one phase transition in the pressure range covered by our studies. The observed scheelite-fergusonite transition induces significant changes in the electronic band gap and phonon spectrum of CaMoO4. We have determined the pressure evolution of the band gap for the low- and high-pressure phases as well as the frequencies and pressure dependences of the Raman-active and infrared-active modes. In addition, based upon calculations of the phonon dispersion of the scheelite phase, carried out at a pressure higher than the transition pressure, we propose a possible mechanism for the reported phase transition. Furthermore, from the calculations we determined the pressure dependence of the unit-cell parameters and atomic positions of the different phases and their room-temperature equations of state. These results are compared with previous experiments showing a very good agreement. Finally, information on bond compressibility is reported and correlated with the macroscopic compressibility of CaMoO4. The reported results are of interest for the many technological applications of this oxide.Comment: 36 pages, 10 figures, 8 table

Zircon to monazite phase transition in CeVO4

X-ray diffraction and Raman-scattering measurements on cerium vanadate have been performed up to 12 and 16 GPa, respectively. Experiments reveal that at 5.3 GPa the onset of a pressure-induced irreversible phase transition from the zircon to the monazite structure. Beyond this pressure, diffraction peaks and Raman-active modes of the monazite phase are measured. The zircon to monazite transition in CeVO4 is distinctive among the other rare-earth orthovanadates. We also observed softening of external translational Eg and internal B2g bending modes. We attributed it to mechanical instabilities of zircon phase against the pressure-induced distortion. We additionally report lattice-dynamical and total-energy calculations which are in agreement with the experimental results. Finally, the effect of non-hydrostatic stresses on the structural sequence is studied and the equations of state of different phases are reported.Comment: 45 pages, 8 figures, 8 table

High-pressure polymorphs of TbVO4: A Raman and ab initio study

Raman measurements on TbVO4 show the occurrence of three pressure-induced phase transitions. The first one, an irreversible transition from the zircon to the scheelite structure, occurs beyond 6.7 GPa. In addition, two reversible transformations take place at 26.7 and 34.4 GPa. The last transition was never reported before. The experimental findings are supported by structural and lattice-dynamics calculations that helped us to identify the post-scheelite phase as a monoclinic fergusonite structure. According to the calculations, the third transition involves a symmetry increase. An orthorhombic structure is proposed for the phase found above 34.4 GPa. The results have been compared with previous studies in TbVO4 and discussed in comparison with related compounds. The calculated equations of state are reported for the different polymorphs of TbVO4. A compressibility increase is caused by the third transition. It is associated to a bond-strength decrease, which is related to a coordination increase and a delocalization of Tb f-electrons. (C) 2013 Elsevier B.V. All rights reserved.Research supported by the Spanish MINECO (Grants No.: MAT2010-21270-C04-01/03/04), MALTA Consolider (CSD2007-00045), and Vicerrectorado de Investigacion y Desarrollo of UPV (UPV2011-0966/0914). The authors also acknowledge the computing time provided by Red Espanola de Supercomputacion and MALTA-Cluster.Errandonea, D.; Manjón Herrera, FJ.; Muñoz, A.; Rodríguez-Hernández, P.; Panchal, V.; Achary, SN.; Tyagi, AK. (2013). High-pressure polymorphs of TbVO4: A Raman and ab initio study. Journal of Alloys and Compounds. 577:327-335. https://doi.org/10.1016/j.jallcom.2013.06.008S32733557

Biomolecule surface patterning may enhance membrane association

Under dehydration conditions, amphipathic Late Embryogenesis Abundant (LEA) proteins fold spontaneously from a random conformation into alpha-helical structures and this transition is promoted by the presence of membranes. To gain insight into the thermodynamics of membrane association we model the resulting alpha-helical structures as infinite rigid cylinders patterned with hydrophobic and hydrophilic stripes oriented parallel to their axis. Statistical thermodynamic calculations using Single Chain Mean Field (SCMF) theory show that the relative thickness of the stripes controls the free energy of interaction of the alpha-helices with a phospholipid bilayer, as does the bilayer structure and the depth of the equilibrium penetration of the cylinders into the bilayer. The results may suggest the optimal thickness of the stripes to mimic the association of such protein with membranes.Comment: Published in ACS Nano http://pubs.acs.org/doi/pdf/10.1021/nn204736

Calibration of multi-layered probes with low/high magnetic moments

We present a comprehensive method for visualisation and quantification of the magnetic stray field of magnetic force microscopy (MFM) probes, applied to the particular case of custom-made multi-layered probes with controllable high/low magnetic moment states. The probes consist of two decoupled magnetic layers separated by a non-magnetic interlayer, which results in four stable magnetic states: ±ferromagnetic (FM) and ±antiferromagnetic (A-FM). Direct visualisation of the stray field surrounding the probe apex using electron holography convincingly demonstrates a striking difference in the spatial distribution and strength of the magnetic flux in FM and A-FM states. In situ MFM studies of reference samples are used to determine the probe switching fields and spatial resolution. Furthermore, quantitative values of the probe magnetic moments are obtained by determining their real space tip transfer function (RSTTF). We also map the local Hall voltage in graphene Hall nanosensors induced by the probes in different states. The measured transport properties of nanosensors and RSTTF outcomes are introduced as an input in a numerical model of Hall devices to verify the probe magnetic moments. The modelling results fully match the experimental measurements, outlining an all-inclusive method for the calibration of complex magnetic probes with a controllable low/high magnetic moment

Flexible CO₂ sensor architecture with selective nitrogen functionalities by one-step laser-induced conversion of versatile organic ink

Nitrogen-doped carbons (NC) are a class of sustainable materials for selective CO2 adsorption. We introduce a versatile concept to fabricate flexible NC-based sensor architectures for room-temperature sensing of CO2 in a one-step laser conversion of primary coatings cast from abundant precursors. By the unidirectional energy impact in conjunction with depth-dependent attenuation of the laser beam, a layered sensor heterostructure with porous transducer and active sensor layer is formed. Comprehensive microscopic and spectroscopic cross-sectional analyses confirm the preservation of a high content of imidazolic nitrogen in the sensor. The performance was optimized in terms of material morphology, chemical composition, and surface chemistry to achieve a linear relative resistive response of up to ∆R/R0 = -14.3% (10% of CO2). Thermodynamic analysis yields ΔadsH values of -35.6 kJ·mol-1 and 34.1 kJ·mol-1 for H2O and CO2, respectively. The sensor is operable even in humid environments (e.g., ∆R/R0,RH=80% = 0.53%) and shows good performance upon strong mechanical deformation