Obstructive Sleep Apnoea Syndrome, Endothelial Function and Markers of Endothelialization. Changes after CPAP

STUDY OBJECTIVES: This study tries to assess the endothelial function in vivo using flow-mediated dilatation (FMD) and several biomarkers of endothelium formation/restoration and damage in patients with obstructive sleep apnoea (OSA) syndrome at baseline and after three months with CPAP therapy. DESIGN: Observational study, before and after CPAP therapy. SETTING AND PATIENTS: We studied 30 patients with apnoea/hypopnoea index (AHI) >15/h that were compared with themselves after three months of CPAP therapy. FMD was assessed non-invasively in vivo using the Laser-Doppler flowmetry. Circulating cell-free DNA (cf-DNA) and microparticles (MPs) were measured as markers of endothelial damage and the vascular endothelial growth factor (VEGF) was determined as a marker of endothelial restoration process. MEASUREMENTS AND RESULTS: After three month with CPAP, FMD significantly increased (1072.26 ± 483.21 vs. 1604.38 ± 915.69 PU, p< 0.005) cf-DNA and MPs significantly decreased (187.93 ± 115.81 vs. 121.28 ± 78.98 pg/ml, p<0.01, and 69.60 ± 62.60 vs. 39.82 ± 22.14 U/μL, p<0.05, respectively) and VEGF levels increased (585.02 ± 246.06 vs. 641.11 ± 212.69 pg/ml, p<0.05). These changes were higher in patients with more severe disease. There was a relationship between markers of damage (r = -0.53, p<0.005) but not between markers of damage and restoration, thus suggesting that both types of markers should be measured together. CONCLUSIONS: CPAP therapy improves FMD. This improvement may be related to an increase of endothelial restoration process and a decrease of endothelial damage

Evaluación del potencial agronómico del fríjol "alado" psophocarpus tetragonolobus (l.) d.c. en las condiciones del valle del cauca

En el ensayo se utilizaron cinco accesiones (lCA-66, UPS-018, UPS-020, UPS-139 y UPS-140) de fríjol alado. Se realizó la caracterización botánica y fenológica del cultivo, aspectos referentes al comportamiento agronómico, fauna insectil que visitó el cultivo, enfermedades que lo afectaron y análisis bromatológico. La accesión de mejor comportamiento fue la ICA-66 ya que registró el mayor rendimiento de semillas por planta (120.13g) y raíces tuberosas por planta (60 g). La accesión UPS–140 presentó el mayor valor de proteína en hojas (25.37 %), vainas (17.86%) y semillas (35.03%).In this research five accessions (ICA-66, UPS-018, UPS-020, UPS-139 and UPS-140) of winged beans were used. The botanycal and phenologycal characterization was accomplished and aspects relating to the agronomicalbehavior, insectile fauna visiting the crop, main diseases and bromatologycal analysis were studied too. The accession with better behavior was ICA-66 because of it showed the greater yield of seeds per plant (120.13 g) and tuberose roots per plant (60 g).The accessi onUPS-140 presented the greater value of protein in leaves (25.37%), pods (17.86%) and seeds (35.03%)

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 study of ScVO4 by Raman scattering and ab initio calculations

We report results of experimental and theoretical lattice-dynamics studies on scandium orthovanadate up to 35 GPa. Raman-active modes of the low-pressure zircon phase are measured up to 8.2 GPa, where the onset of an irreversible zircon-to-scheelite phase transition is detected. Raman-active modes in the scheelite structure are observed up to 16.5 GPa. Beyond 18.2 GPa we detected a gradual splitting of the Eg modes of the scheelite phase, indicating the onset of a second phase transition. Raman symmetries, frequencies, and pressure coefficients in the three phases of ScVO4 are discussed in the light of ab initio lattice-dynamics calculations that support the experimental results. The results on all the three phases of ScVO4 are compared with those previously reported for related orthovanadates.We acknowledge the financial support of the Spanish MCYT under Grants No. MAT2007-65990-C03-01/03, No. MAT2010-21270-C04-01/03/04, and No. CSD2007-00045, and the computation time provided by the Red Espanola de Supercomputacion and the supercomputer Atlante. F.J.M. acknowledges also financial support from "Vicerrectorado de Innovacion y Desarrollo de la UPV" (No. PAID-05-2009 through Project No. UPV2010-0096). Some of the authors are members of the MALTA Consolider Team.Panchal, V.; Manjón Herrera, FJ.; Errandonea, D.; Rodriguez-Hernandez, P.; López-Solano, J.; Muñoz, A.; Achary, S.... (2011). High-pressure study of ScVO4 by Raman scattering and ab initio calculations. Physical Review B. 83(6):641111-1-64111-10. https://doi.org/10.1103/PhysRevB.83.064111S641111-164111-10836Shafi, S. P., Kotyk, M. W., Cranswick, L. M. D., Michaelis, V. K., Kroeker, S., & Bieringer, M. (2009). In Situ Powder X-ray Diffraction, Synthesis, and Magnetic Properties of the Defect Zircon Structure ScVO4−x. Inorganic Chemistry, 48(22), 10553-10559. doi:10.1021/ic900927jMullica, D. F., Sappenfield, E. L., Abraham, M. M., Chakoumakos, B. C., & Boatner, L. A. (1996). Structural investigations of several LnVO4 compounds. Inorganica Chimica Acta, 248(1), 85-88. doi:10.1016/0020-1693(95)04971-1Errandonea, D., & Manjón, F. J. (2008). Pressure effects on the structural and electronic properties of ABX4 scintillating crystals. Progress in Materials Science, 53(4), 711-773. doi:10.1016/j.pmatsci.2008.02.001Aldred, A. T. (1984). Cell volumes of APO4, AVO4, and ANbO4 compounds, where A = Sc, Y, La–Lu. Acta Crystallographica Section B Structural Science, 40(6), 569-574. doi:10.1107/s0108768184002718Errandonea, D., Lacomba-Perales, R., Ruiz-Fuertes, J., Segura, A., Achary, S. N., & Tyagi, A. K. (2009). High-pressure structural investigation of several zircon-type orthovanadates. Physical Review B, 79(18). doi:10.1103/physrevb.79.184104López-Solano, J., Rodríguez-Hernández, P., & Muñoz, A. (2009). Ab initiostudy of high-pressure structural properties of the LuVO4and ScVO4zircon-type orthovanadates. High Pressure Research, 29(4), 582-586. doi:10.1080/08957950903417444Manjón, F. J., Rodríguez-Hernández, P., Muñoz, A., Romero, A. H., Errandonea, D., & Syassen, K. (2010). Lattice dynamics ofYVO4at high pressures. Physical Review B, 81(7). doi:10.1103/physrevb.81.075202Wang, X., Loa, I., Syassen, K., Hanfland, M., & Ferrand, B. (2004). Structural properties of the zircon- and scheelite-type phases ofYVO4at high pressure. Physical Review B, 70(6). doi:10.1103/physrevb.70.064109Klotz, S., Chervin, J.-C., Munsch, P., & Le Marchand, G. (2009). Hydrostatic limits of 11 pressure transmitting media. Journal of Physics D: Applied Physics, 42(7), 075413. doi:10.1088/0022-3727/42/7/075413Errandonea, D., Meng, Y., Somayazulu, M., & Häusermann, D. (2005). Pressure-induced transition in titanium metal: a systematic study of the effects of uniaxial stress. Physica B: Condensed Matter, 355(1-4), 116-125. doi:10.1016/j.physb.2004.10.030Mao, H. K., Xu, J., & Bell, P. M. (1986). Calibration of the ruby pressure gauge to 800 kbar under quasi-hydrostatic conditions. Journal of Geophysical Research, 91(B5), 4673. doi:10.1029/jb091ib05p04673Kresse, G., & Furthmüller, J. (1996). Efficient iterative schemes forab initiototal-energy calculations using a plane-wave basis set. Physical Review B, 54(16), 11169-11186. doi:10.1103/physrevb.54.11169Kresse, G., & Joubert, D. (1999). From ultrasoft pseudopotentials to the projector augmented-wave method. Physical Review B, 59(3), 1758-1775. doi:10.1103/physrevb.59.1758Blöchl, P. E. (1994). Projector augmented-wave method. Physical Review B, 50(24), 17953-17979. doi:10.1103/physrevb.50.17953Perdew, J. P., Burke, K., & Ernzerhof, M. (1996). Generalized Gradient Approximation Made Simple. Physical Review Letters, 77(18), 3865-3868. doi:10.1103/physrevlett.77.3865Mujica, A., Rubio, A., Muñoz, A., & Needs, R. J. (2003). High-pressure phases of group-IV, III–V, and II–VI compounds. Reviews of Modern Physics, 75(3), 863-912. doi:10.1103/revmodphys.75.863Guedes, I., Hirano, Y., Grimsditch, M., Wakabayashi, N., Loong, C.-K., & Boatner, L. A. (2001). Raman study of phonon modes in ErVO4 single crystals. Journal of Applied Physics, 90(4), 1843-1846. doi:10.1063/1.1384858Garg, A. B., Rao, R., Sakuntala, T., Wani, B. N., & Vijayakumar, V. (2009). Phase stability of YbVO4 under pressure: In situ x-ray and Raman spectroscopic investigations. Journal of Applied Physics, 106(6), 063513. doi:10.1063/1.3223327Santos, C. C., Silva, E. N., Ayala, A. P., Guedes, I., Pizani, P. S., Loong, C.-K., & Boatner, L. A. (2007). Raman investigations of rare earth orthovanadates. Journal of Applied Physics, 101(5), 053511. doi:10.1063/1.2437676Zhang, F. X., Wang, J. W., Lang, M., Zhang, J. M., Ewing, R. C., & Boatner, L. A. (2009). High-pressure phase transitions ofScPO4andYPO4. Physical Review B, 80(18). doi:10.1103/physrevb.80.184114Tossell, J. A. (1975). Electronic structures of silicon, aluminum, and magnesium in tetrahedral coordination with oxygen from SCF-X.alpha. MO calculations. Journal of the American Chemical Society, 97(17), 4840-4844. doi:10.1021/ja00850a010Rao, R., Garg, A. B., Sakuntala, T., Achary, S. N., & Tyagi, A. K. (2009). High pressure Raman scattering study on the phase stability of LuVO4. Journal of Solid State Chemistry, 182(7), 1879-1883. doi:10.1016/j.jssc.2009.05.003Duclos, S. J., Jayaraman, A., Espinosa, G. P., Cooper, A. S., & Maines, R. G. (1989). Raman and optical absorption studies of the pressure-induced zircon to scheelite structure transformation in TbVO4 and DyV04. Journal of Physics and Chemistry of Solids, 50(8), 769-775. doi:10.1016/0022-3697(89)90055-3Smirnov, M. B., Mirgorodsky, A. P., Kazimirov, V. Y., & Guinebretière, R. (2008). Bond-switching mechanism for the zircon-scheelite phase transition. Physical Review B, 78(9). doi:10.1103/physrevb.78.094109Flórez, M., Contreras-García, J., Recio, J. M., & Marqués, M. (2009). Quantum-mechanical calculations of zircon to scheelite transition pathways inZrSiO4. Physical Review B, 79(10). doi:10.1103/physrevb.79.104101Rousseau, D. L., Bauman, R. P., & Porto, S. P. S. (1981). Normal mode determination in crystals. Journal of Raman Spectroscopy, 10(1), 253-290. doi:10.1002/jrs.1250100152Mittal, R., Garg, A. B., Vijayakumar, V., Achary, S. N., Tyagi, A. K., Godwal, B. K., … Chaplot, S. L. (2008). Investigation of the phase stability of LuVO4at high pressure using powder x-ray diffraction measurements and lattice dynamical calculations. Journal of Physics: Condensed Matter, 20(7), 075223. doi:10.1088/0953-8984/20/7/075223Manjón, F. J., Errandonea, D., Garro, N., Pellicer-Porres, J., Rodríguez-Hernández, P., Radescu, S., … Muñoz, A. (2006). Lattice dynamics study of scheelite tungstates under high pressure I.BaWO4. Physical Review B, 74(14). doi:10.1103/physrevb.74.144111Manjon, F. J., Errandonea, D., Garro, N., Pellicer-Porres, J., López-Solano, J., Rodríguez-Hernández, P., … Muñoz, A. (2006). Lattice dynamics study of scheelite tungstates under high pressure II.PbWO4. Physical Review B, 74(14). doi:10.1103/physrevb.74.144112Panchal, V., Garg, N., & Sharma, S. M. (2006). Raman and x-ray diffraction investigations on BaMoO4under high pressures. Journal of Physics: Condensed Matter, 18(16), 3917-3929. doi:10.1088/0953-8984/18/16/002Hardcastle, F. D., & Wachs, I. E. (1991). Determination of vanadium-oxygen bond distances and bond orders by Raman spectroscopy. The Journal of Physical Chemistry, 95(13), 5031-5041. doi:10.1021/j100166a025Brown, I. D., & Wu, K. K. (1976). Empirical parameters for calculating cation–oxygen bond valences. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, 32(7), 1957-1959. doi:10.1107/s0567740876006869Lacomba-Perales, R., Martinez-García, D., Errandonea, D., Le Godec, Y., Philippe, J., Le Marchand, G., … López-Solano, J. (2010). Experimental and theoretical investigation of the stability of the monoclinicBaWO4-II phase at high pressure and high temperature. Physical Review B, 81(14). doi:10.1103/physrevb.81.144117Tschauner, O., Errandonea, D., & Serghiou, G. (2006). Possible superlattice formation in high-temperature treated carbonaceous MgB2 at elevated pressure. Physica B: Condensed Matter, 371(1), 88-94. doi:10.1016/j.physb.2005.09.042Errandonea, D., Kumar, R. S., Ma, X., & Tu, C. (2008). High-pressure X-ray diffraction study of SrMoO4 and pressure-induced structural changes. Journal of Solid State Chemistry, 181(2), 355-364. doi:10.1016/j.jssc.2007.12.010Errandonea, D., Santamaria-Perez, D., Grover, V., Achary, S. N., & Tyagi, A. K. (2010). High-pressure x-ray diffraction study of bulk and nanocrystalline PbMoO4. Journal of Applied Physics, 108(7), 073518. doi:10.1063/1.3493048Errandonea, D., Santamaria-Perez, D., Bondarenko, T., & Khyzhun, O. (2010). New high-pressure phase of HfTiO4 and ZrTiO4 ceramics. Materials Research Bulletin, 45(11), 1732-1735. doi:10.1016/j.materresbull.2010.06.061Marqués, M., Flórez, M., Recio, J. M., Gerward, L., & Olsen, J. S. (2006). Structure and stability ofZrSiO4under hydrostatic pressure. Physical Review B, 74(1). doi:10.1103/physrevb.74.014104Lacomba-Perales, R., Errandonea, D., Meng, Y., & Bettinelli, M. (2010). High-pressure stability and compressibility ofAPO4(A=La, Nd, Eu, Gd, Er, and Y) orthophosphates: An x-ray diffraction study using synchrotron radiation. Physical Review B, 81(6). doi:10.1103/physrevb.81.064113Long, Y. W., Zhang, W. W., Yang, L. X., Yu, Y., Yu, R. C., Ding, S., … Jin, C. Q. (2005). Pressure-induced structural phase transition in CaCrO4: Evidence from Raman scattering studies. Applied Physics Letters, 87(18), 181901. doi:10.1063/1.2117624Long, Y. W., Yang, L. X., Yu, Y., Li, F. Y., Yu, R. C., Ding, S., … Jin, C. Q. (2006). High-pressure Raman scattering and structural phase transition inYCrO4. Physical Review B, 74(5). doi:10.1103/physrevb.74.054110Errandonea, D., Kumar, R. S., Gracia, L., Beltrán, A., Achary, S. N., & Tyagi, A. K. (2009). Experimental and theoretical investigation ofThGeO4at high pressure. Physical Review B, 80(9). doi:10.1103/physrevb.80.094101Gracia, L., Beltrán, A., & Errandonea, D. (2009). Characterization of theTiSiO4structure and its pressure-induced phase transformations: Density functional theory study. Physical Review B, 80(9). doi:10.1103/physrevb.80.094105Errandonea, D. (2007). Landau theory applied to phase transitions in calcium orthotungstate and isostructural compounds. Europhysics Letters (EPL), 77(5), 56001. doi:10.1209/0295-5075/77/56001Errandonea, D., & Manjón, F. J. (2009). On the ferroelastic nature of the scheelite-to-fergusonite phase transition in orthotungstates and orthomolybdates. Materials Research Bulletin, 44(4), 807-811. doi:10.1016/j.materresbull.2008.09.024Errandonea, D., Pellicer-Porres, J., Manjón, F. J., Segura, A., Ferrer-Roca, C., Kumar, R. S., … Aquilanti, G. (2005). High-pressure structural study of the scheelite tungstatesCaWO4andSrWO4. Physical Review B, 72(17). doi:10.1103/physrevb.72.174106Errandonea, D. (2005). High-pressure X-ray diffraction study of EuWO4 to 12 GPa. physica status solidi (b), 242(14), R125-R127. doi:10.1002/pssb.200541334Begun, G. M., Beall, G. W., Boatner, L. A., & Gregor, W. J. (1981). Raman spectra of the rare earth orthophosphates. Journal of Raman Spectroscopy, 11(4), 273-278. doi:10.1002/jrs.1250110411Podor, R. (1995). Raman spectra of the actinide-bearing monazites. European Journal of Mineralogy, 7(6), 1353-1360. doi:10.1127/ejm/7/6/1353Zhang, C. C., Zhang, Z. M., Dai, R. C., Wang, Z. P., Zhang, J. W., & Ding, Z. J. (2010). High-Pressure Raman and Luminescence Study on the Phase Transition of GdVO4:Eu3+ Microcrystals. The Journal of Physical Chemistry C, 114(42), 18279-18282. doi:10.1021/jp106063cVoron’ko, Y. K., Sobol’, A. A., Shukshin, V. E., Zagumennyĭ, A. I., Zavartsev, Y. D., & Kutovoĭ, S. A. (2009). Raman spectroscopic study of structural disordering in YVO4, GdVO4, and CaWO4 crystals. Physics of the Solid State, 51(9), 1886-1893. doi:10.1134/s1063783409090200Baran, E. J., Escobar, M. E., Fournier, L. L., & Filgueira, R. R. (1981). Die Raman-Spektren der Orthovanadate der Seltenen Erden. Zeitschrift f�r anorganische und allgemeine Chemie, 472(1), 193-199. doi:10.1002/zaac.19814720123Frost, R. L., Henry, D. A., Weier, M. L., & Martens, W. (2006). Raman spectroscopy of three polymorphs of BiVO4: clinobisvanite, dreyerite and pucherite, with comparisons to (VO4)3-bearing minerals: namibite, pottsite and schumacherite. Journal of Raman Spectroscopy, 37(7), 722-732. doi:10.1002/jrs.1499Blin, J. L., Lorriaux-Rubbens, A., Wallart, F., & Wignacourt, J. P. (1996). Synthesis and structural investigation of the Eu1–xBixVO4scheelite phase: X-ray diffraction, Raman scattering and Eu3+luminescence. J. Mater. Chem., 6(3), 385-389. doi:10.1039/jm9960600385Manjón, F. J., Errandonea, D., López-Solano, J., Rodríguez-Hernández, P., & Muñoz, A. (2009). Negative pressures in CaWO4 nanocrystals. Journal of Applied Physics, 105(9), 094321. doi:10.1063/1.3116727Tokunaga, S., Kato, H., & Kudo, A. (2001). Selective Preparation of Monoclinic and Tetragonal BiVO4with Scheelite Structure and Their Photocatalytic Properties. Chemistry of Materials, 13(12), 4624-4628. doi:10.1021/cm0103390Rice, C. E., & Robinson, W. R. (1976). Lanthanum orthovanadate. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, 32(7), 2232-2233. doi:10.1107/s0567740876007450Errandonea, D., Manjón, F. J., Somayazulu, M., & Häusermann, D. (2004). Effects of pressure on the local atomic structure of CaWO4 and YLiF4: mechanism of the scheelite-to-wolframite and scheelite-to-fergusonite transitions. Journal of Solid State Chemistry, 177(4-5), 1087-1097. doi:10.1016/j.jssc.2003.10.01

Structural stability of Fe5Si3 and Ni2Si studied by high-pressure x-ray diffraction and ab initio total-energy calculations

We performed high-pressure angle dispersive x-ray diffraction measurements on Fe5Si3 and Ni2Si up to 75 GPa. Both materials were synthesized in bulk quantities via a solid-state reaction. In the pressure range covered by the experiments, no evidence of the occurrence of phase transitions was observed. On top of that, Fe5Si3 was found to compress isotropically, whereas an anisotropic compression was observed in Ni2Si. The linear incompressibility of Ni2Si along the c-axis is similar in magnitude to the linear incompressibility of diamond. This fact is related to the higher valence-electron charge density of Ni2Si along the c-axis. The observed anisotropic compression of Ni2Si is also related to the layered structure of Ni2Si where hexagonal layers of Ni2+ cations alternate with graphite-like layers formed by (NiSi)2- entities. The experimental results are supported by ab initio total-energy calculations carried out using density functional theory and the pseudopotential method. For Fe5Si3, the calculations also predicted a phase transition at 283 GPa from the hexagonal P63/mcm phase to the cubic structure adopted by Fe and Si in the garnet Fe5Si3O12. The room-temperature equations of state for Fe5Si3 and Ni2Si are also reported and a possible correlation between the bulk modulus of iron silicides and the coordination number of their minority element is discussed. Finally, we report novel descriptions of these structures, in particular of the predicted high-pressure phase of Fe5Si3 (the cation subarray in the garnet Fe5Si3O12), which can be derived from spinel Fe2SiO4 (Fe6Si3O12).Comment: 44 pages, 13 figures, 3 Table

Pressure-Driven Symmetry-Preserving Phase Transitions in Co(IO3)(2)

[EN] High-pressure synchrotron X-ray diffraction studies of cobalt iodate, Co(IO3)(2), reveal a counterintuitive pressure-induced expansion along certain crystallographic directions. High-pressure Raman and infrared spectroscopy, combined with density-functional theory calculations, reveal that with increasing pressure, it becomes energetically favorable for certain I-O bonds to increase in length over the full range of pressure studied up to 28 GPa. This phenomenon is driven by the high-pressure behavior of iodate ion lone electron pairs. Two pressure-induced isosymmetric monoclinic-monoclinic phase transitions are observed at around 3.0 and 9.0 GPa, which are characterized by increasing oxygen coordination of the iodine atoms and the probable formation of pressure-induced metavalent bonds. Pressure-volume equations of state are presented, as well as a detailed discussion of the pressure dependences of the observed Raman- and infrared-active modes, which clarifies previous inconsistencies in the literature.This work was supported by the Generalitat Valenciana under Project PROMETEO 2018/123-EFIMAT and by the Spanish Ministerio de Ciencia, Universidades, e Investigacion under Projects PID2019-106383GB-41/42/43, as well as through MALTA Consolider Team research network (RED2018102612-T). A.M. and P.R.-H. acknowledge computing time provided by Red Espan~ola de Supercomputacion (RES) and the MALTA Consolider Team cluster. D.E. acknowledges the resources and technical assistance provided by the Informatics Service of Universitat de Valencia through the Tirant III cluster. A.L. and D.E. would like to thank the Generalitat Valenciana for the Ph.D. Fellowship no. GRISOLIAP/2019/025. R.T. acknowledges funding from the Spanish Ministerio de Economia y Competitividad (MINECO) via the Juan de la Cierva Formacion fellowship (FJC2018-036185-I). C.P. is thankful for the financial support of the Spanish Mineco Project no. FIS2017-83295-P. E.B would like to thank the University of Valencia for his "Attraccio de Talent" postdoctoral contract (UV-INV_POSTDOC19-1026935). The authors thank Sandrine Beauquis from Symme, Universite Savoie Mont Blanc (France), for her technical assistance concerning the SEM and ADX analyses. PXRD experiments were performed at the MSPD beamline of ALBA Synchrotron (experiment no. 2019083663). IR experiments were performed at the MIRAS beamline of ALBA Synchrotron (experiment no. 2020024118).Liang, A.; Popescu, C.; Manjón, F.; Turnbull, R.; Bandiello, E.; Rodriguez-Hernandez, P.; Muñoz, A.... (2021). Pressure-Driven Symmetry-Preserving Phase Transitions in Co(IO3)(2). The Journal of Physical Chemistry C. 125(31):17448-17461. https://doi.org/10.1021/acs.jpcc.1c0465917448174611253

Understanding the pharmacokinetics of synthetic cathinones: Evaluation of the blood–brain barrier permeability of 13 related compounds in rats

This is the pre-peer reviewed version of the following article:Understanding the pharmacokinetics of synthetic cathinones: Evaluation of the blood–brain barrier permeability of 13 related compounds in rats, which has been published in final form at https://doi.org/10.1111/adb.12979. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.Synthetic cathinones are the second most commonly seized new psychoactive substance family in Europe. These compounds have been related to several intoxication cases, including fatalities. Although the pharmacological effects, metabolism, and pharmacokinetics of cathinones have been studied, there is little information about the permeability of these compounds through the blood–brain barrier (BBB). This is an important parameter to understand the behavior and potency of cathinones. In this work, 13 selected cathinones have been analyzed in telencephalon tissue from Sprague–Dawley rats intraperitoneally dosed at 3 mg/kg. Our results revealed a direct relationship between compound polarity and BBB permeability, with higher permeability for the more polar cathinones. The chemical moieties present in the cathinone had an important impact on the BBB permeability, with lengthening of the α‐alkyl chain or functionalization of the aromatic ring with alkyl moieties resulting in lower concentration in telencephalon tissue. Our data suggest that transport of cathinones is a carrier‐mediated process, similar to cocaine transport across the BBB

Layered topological semimetal GaGeTe: New polytype with non-centrosymmetric structure

[EN] GaGeTe is a layered van der Waals material composed of germanene and GaTe sublayers that has been recently predicted to be a basic Z2 topological semimetal. To date, only one polytype of GaGeTe is known with trigonal centrosymmetric structure (a phase, space group R-3m, No. 166). Here we show that asgrown samples of GaGeTe show traces of at least another polytype with hexagonal noncentrosymmetric structure (f3 phase, space group P63mc, No. 186). Moreover, we suggest that another bulk hexagonal polytype (g phase, space group P-3m1, No. 164) could also be found near room conditions. Both a and f3 polytypes have been identified and characterized by means of X-ray diffraction and Raman scattering measurements with the support of ab initio calculations. We provide the vibrational properties of both polytypes and show that the Raman spectrum reported for GaGeTe almost forty years ago and attributed to the a phase, was, in fact, that of the secondary f3 phase. Additionally, we show that a Fermi resonance occurs in a-GaGeTe under non-resonant excitation conditions, but not under resonant excitation conditions. Theoretical calculations show that bulk f3-GaGeTe is a non-centrosymmetric weak topological semimetal with even smaller lattice thermal conductivity than centrosymmetric bulk aGaGeTe. In perspective, our work paves the way for the control and engineering of GaGeTe polytypes to design and implement complex van der Waals heterostructures formed by a combination of centrosymmetric and non-centrosymmetric layers of up to three different polytypes in a single material, suitable for a number of fundamental studies and technological applications.This publication is part of the project MALTA Consolider Team network (RED2018-102612-T) , financed by MINECO/AEI/10.13039/501100003329; by I ? D ? i projects PID2019-106383 GB -41/42/43 financed by MCIN/AEI/10.13039/501100011033; and by project PROMETEO/2018/123 (EFIMAT) financed by Generalitat Valenciana. E.B. would like to thank the Universitat Politecnica de Valencia for his postdoctoral contract (Ref. PAID -10-21) . AHR was supported by the U.S. Department of Energy (DOE) , Office of Science, Basic Energy Sciences under award DE-SC0021375. We also acknowledge the computational resources awarded by XSEDE, a project supported by National Science Foundation grant number ACI-1053575. The authors also acknowledge the support from the Texas Advances Computer Center (with the Stampede2 and Bridges supercom- puters) . E.L.d.S would like to acknowledge the Network of Extreme Conditions Laboratories (NECL) , financed by FCT and co -financed by NORTE 2020, through the program Portugal 2020 and FEDER; the High Performance Computing Chair-a R & D infrastructure (based at the University of ? Evora; PI: M. Avillez) ; and for the computational support provided by the HPC center OBLIVION -U. ? Evora to perform the lattice thermal conductivity calculations. A.L. and D.E. would like to thank the Generalitat Valenciana for the Ph.D. Fellowship no. GRISOLIAP/2019/025.Gallego-Parra, S.; Bandiello, E.; Liang, A.; Da Silva, EL.; Rodriguez-Hernandez, P.; Muñoz, A.; Radescu, S.... (2022). Layered topological semimetal GaGeTe: New polytype with non-centrosymmetric structure. Materials Today Advances. 16:1-16. https://doi.org/10.1016/j.mtadv.2022.1003091161

Pediatric Parapneumonic Empyema, Spain

Increased incidence is principally due to highly invasive nonvaccine serotypes of pneumococci, especially serotype 1

Chemical pressure effects on the spectroscopic properties of Nd3+-doped gallium nano-garnets

[EN] Nd3+-doped RE3Ga5O12 (RE = Gd, Y, and Lu) nano-crystalline garnets of 40-45 nm in size have been synthesized by a sol-gel method. With the decrease of the RE atom size, the chemical pressure related to the decreasing volumes of the GaO4 tetrahedral, GaO6 octahedral and REO8 dodecahedral units drive the nano-garnets toward a more compacted structure, which is evidenced by the change of the vibrational phonon mode frequencies. The chemical pressure also increases the crystal-field strength felt by the RE3+ ions while decreases the orthorhombic distortion of the REO8 local environment. These effects alter the absorption and emission properties of the Nd3+ ion measured in the near-infrared luminescence range from 0.87 to 1.43 ¿m associated with the 4 F3/2¿4 IJ (J = 9/2, 11/2, 13/2) transitions. The 4 F3/2 luminescence decay curves show non-exponential behavior due to dipole-dipole energy transfer interactions among Nd3+ ions that increases with pressure.Authors are grateful to The Governments of Spain and India for the Indo-Spanish Joint Programme of Bilateral Cooperation in Science and Technology (PRI-PIBIN-2011-1153/DST-INT-Spain-P-38-11). Dr. Venkatramu is grateful to DAE-BRNS, Government of India for the award of DAE Research Award for Young Scientist (No. 2010/20/34/5/BRNS/2223). This work have been partially supported by MINECO under The National Program of Materials (MAT2013-46649-C4-2-P/-3-P/-4-P), The Consolider-Ingenio 2010 Program (MALTA CSD2007-00045), by Fundacion CajaCanarias (ENER-01), and by the EU-FEDER funds. V. Monteseguro wishes to thank MICINN for the FPI grant (BES-2011-044596). Authors also thank Agencia Canaria de Investigacion, Innovacion y Sociedad de la Informacion for the funds given to Universidad de La Laguna, co-financed by The European Social Fund by a percentage of 85%.Monteseguro, V.; Rathaiah, M.; Linganna, K.; Lozano-Gorrin, AD.; Hernandez-Rodriguez, MA.; Martin, IR.; Babu, P.... (2015). Chemical pressure effects on the spectroscopic properties of Nd3+-doped gallium nano-garnets. Optical Materials Express. 5(8):1661-1673. https://doi.org/10.1364/OME.5.001661S1661167358Pollnau, M., Hardman, P. ., Clarkson, W. ., & Hanna, D. . (1998). Upconversion, lifetime quenching, and ground-state bleaching in Nd3+:LiYF4. Optics Communications, 147(1-3), 203-211. doi:10.1016/s0030-4018(97)00524-5Brandle, C. D., & Barns, R. L. (1974). Crystal stoichiometry of Czochralski grown rare-earth gallium garnets. Journal of Crystal Growth, 26(1), 169-170. doi:10.1016/0022-0248(74)90223-1Venkatramu, V., Giarola, M., Mariotto, G., Enzo, S., Polizzi, S., Jayasankar, C. K., … Speghini, A. (2010). Nanocrystalline lanthanide-doped Lu3Ga5O12garnets: interesting materials for light-emitting devices. Nanotechnology, 21(17), 175703. doi:10.1088/0957-4484/21/17/175703Speghini, A., Piccinelli, F., & Bettinelli, M. (2011). Synthesis, characterization and luminescence spectroscopy of oxide nanopowders activated with trivalent lanthanide ions: The garnet family. Optical Materials, 33(3), 247-257. doi:10.1016/j.optmat.2010.10.039Krsmanović, R., Morozov, V. A., Lebedev, O. I., Polizzi, S., Speghini, A., Bettinelli, M., & Tendeloo, G. V. (2007). Structural and luminescence investigation on gadolinium gallium garnet nanocrystalline powders prepared by solution combustion synthesis. Nanotechnology, 18(32), 325604. doi:10.1088/0957-4484/18/32/325604Naccache, R., Vetrone, F., Speghini, A., Bettinelli, M., & Capobianco, J. A. (2008). Cross-Relaxation and Upconversion Processes in Pr3+ Singly Doped and Pr3+/Yb3+ Codoped Nanocrystalline Gd3Ga5O12: The Sensitizer/Activator Relationship. The Journal of Physical Chemistry C, 112(20), 7750-7756. doi:10.1021/jp711494dAntic-Fidancev, E., Hölsä, J., Lastusaari, M., & Lupei, A. (2001). Dopant-host relationships in rare-earth oxides and garnets doped with trivalent rare-earth ions. Physical Review B, 64(19). doi:10.1103/physrevb.64.195108Rodríguez-Carvajal, J. (1993). Recent advances in magnetic structure determination by neutron powder diffraction. Physica B: Condensed Matter, 192(1-2), 55-69. doi:10.1016/0921-4526(93)90108-iMonteseguro, V., Rodríguez-Hernández, P., Ortiz, H. M., Venkatramu, V., Manjón, F. J., Jayasankar, C. K., … Muñoz, A. (2015). Structural, elastic and vibrational properties of nanocrystalline lutetium gallium garnet under high pressure. Physical Chemistry Chemical Physics, 17(14), 9454-9464. doi:10.1039/c4cp05903dRay, S., León-Luis, S. F., Manjón, F. J., Mollar, M. A., Gomis, Ó., Rodríguez-Mendoza, U. R., … Lavín, V. (2014). Broadband, site selective and time resolved photoluminescence spectroscopic studies of finely size-modulated Y2O3:Eu3+ phosphors synthesized by a complex based precursor solution method. Current Applied Physics, 14(1), 72-81. doi:10.1016/j.cap.2013.07.027Nekvasil, V. (1978). The Crystal Field for Nd3+ in Garnets. Physica Status Solidi (b), 87(1), 317-323. doi:10.1002/pssb.2220870137Rodríguez-Mendoza, U. R., León-Luis, S. F., Muñoz-Santiuste, J. E., Jaque, D., & Lavín, V. (2013). Nd3+-doped Ca3Ga2Ge3O12garnet: A new optical pressure sensor. Journal of Applied Physics, 113(21), 213517. doi:10.1063/1.4809217Kaminska, A., Buczko, R., Paszkowicz, W., Przybylińska, H., Werner-Malento, E., Suchocki, A., … Saxena, S. (2011). Merging of the4F3/2level states of Nd3+ions in the photoluminescence spectra of gadolinium-gallium garnets under high pressure. Physical Review B, 84(7). doi:10.1103/physrevb.84.075483Allik, T. H., Stewart, S. A., Sardar, D. K., Quarles, G. J., Powell, R. C., Morrison, C. A., … Pinto, A. A. (1988). Preparation, structure, and spectroscopic properties ofNd3+:{La1−xLux}3[Lu1−yGay]2Ga3O12crystals. Physical Review B, 37(16), 9129-9139. doi:10.1103/physrevb.37.9129Wu, K., Yao, B., Zhang, H., Yu, H., Wang, Z., Wang, J., & Jiang, M. (2010). Growth and properties of Nd:Lu3Ga5O12 laser crystal by floating-zone method. Journal of Crystal Growth, 312(24), 3631-3636. doi:10.1016/j.jcrysgro.2010.09.029Jia, Z., Arcangeli, A., Tao, X., Zhang, J., Dong, C., Jiang, M., … Tonelli, M. (2009). Efficient Nd3+→Yb3+ energy transfer in Nd3+,Yb3+:Gd3Ga5O12 multicenter garnet crystal. Journal of Applied Physics, 105(8), 083113. doi:10.1063/1.3115442Guillot-Noel, O., Bellamy, B., Viana, B., & Gourier, D. (1999). Correlation between rare-earth oscillator strengths and rare-earth–valence-band interactions in neodymium-dopedYMO4(M=V,P, As),Y3Al5O12,andLiYF4matrices. Physical Review B, 60(3), 1668-1677. doi:10.1103/physrevb.60.1668Demidovich, A. A., Shkadarevich, A. P., Danailov, M. B., Apai, P., Gasmi, T., Gribkovskii, V. P., … Batay, L. E. (1998). Comparison of cw laser performance of Nd:KGW, Nd:YAG, Nd:BEL, and Nd:YVO 4 under laser diode pumping. Applied Physics B: Lasers and Optics, 67(1), 11-15. doi:10.1007/s003400050467Inokuti, M., & Hirayama, F. (1965). Influence of Energy Transfer by the Exchange Mechanism on Donor Luminescence. The Journal of Chemical Physics, 43(6), 1978-1989. doi:10.1063/1.1697063Lupei, V., & Lupei, A. (2000). Emission dynamics of the4F3/2level ofNd3+in YAG at low pump intensities. Physical Review B, 61(12), 8087-8098. doi:10.1103/physrevb.61.8087Maeda, K., Wada, N., Umino, M., Abe, M., Takada, Y., Nakano, N., & Kuroda, H. (1984). Concentration Dependence of Fluorescence Lifetime of Nd3+-Doped Gd3Ga5O12Lasers. Japanese Journal of Applied Physics, 23(Part 2, No. 10), L759-L760. doi:10.1143/jjap.23.l759Geusic, J. E., Marcos, H. M., & Van Uitert, L. G. (1964). LASER OSCILLATIONS IN Nd‐DOPED YTTRIUM ALUMINUM, YTTRIUM GALLIUM AND GADOLINIUM GARNETS. Applied Physics Letters, 4(10), 182-184. doi:10.1063/1.1753928Löhring, J., Nicklaus, K., Kujath, N., & Hoffmann, D. (2007). Diode pumped Nd:YGG laser for direct generation of pulsed 935 nm radiation for water vapour measurements. Solid State Lasers XVI: Technology and Devices. doi:10.1117/12.708220Maunier, C., Doualan, J. L., Moncorgé, R., Speghini, A., Bettinelli, M., & Cavalli, E. (2002). Growth, spectroscopic characterization, and laser performance of Nd:LuVO_4, a new infrared laser material that is suitable for diode pumping. Journal of the Optical Society of America B, 19(8), 1794. doi:10.1364/josab.19.00179