High-pressure structural investigation of several zircon-type orthovanadates

Room temperature angle-dispersive x-ray diffraction measurements on zircon-type EuVO4, LuVO4, and ScVO4 were performed up to 27 GPa. In the three compounds we found evidence of a pressure-induced structural phase transformation from zircon to a scheelite-type structure. The onset of the transition is near 8 GPa, but the transition is sluggish and the low- and high-pressure phases coexist in a pressure range of about 10 GPa. In EuVO4 and LuVO4 a second transition to a M-fergusonite-type phase was found near 21 GPa. The equations of state for the zircon and scheelite phases are also determined. Among the three studied compounds, we found that ScVO4 is less compressible than EuVO4 and LuVO4, being the most incompressible orthovanadate studied to date. The sequence of structural transitions and compressibilities are discussed in comparison with other zircon-type oxides.Comment: 34 pages, 2 Tables, 11 Figure

Impact of torrential rain on coastal ecosystem at kalpakkam, southeast coast of India

1609-1615The present study focuses on the drastic changes observed in the coastal ecosystem at Kalpakkam during flooding event due to huge rainfall that occurred in and around northern Tamil Nadu during December 2015. A significant increase in hydrological parameters (nitrate, phosphate, silicate, total nitrogen and phosphorous) was recorded as compared to previous years (2006-2014). In the present instance, the coastal water salinity which was about 19 psu was the lowest as compared to the data available since 1979. The phytoplankton population density was severely affected by the runoff. The present observed density 1.4 x 104 cells l-1 was the lowest among the available data at this coast. Availability of green algae species in the coastal waters was significantly high (10 species, 17 % of total species) as compared to previous reports. One of the most interesting features of this study was the observation of epibiosis on zooplankton in massive numbers. A comparison of previous occurrences of epibiotic relationship in plankton community with the present observation showed a staggering increase in epibiosis to 38 % of zooplankton species as compared to 5-13 % during 2008-2014

High-Temperature Phonon Spectra of Multiferroic BiFeO3 from Inelastic Neutron Spectroscopy

We report inelastic neutron scattering measurements of the phonon spectra in a pure powder sample of the multiferroic material BiFeO3. A high-temperature range was covered to unravel the changes in the phonon dynamics across the Neel (T_N ~ 650 K) and Curie (T_C ~ 1100 K) temperatures. Experimental results are accompanied by ab-initio lattice dynamical simulations of phonon density of states to enable microscopic interpretations of the observed data. The calculations reproduce well the observed vibrational features and provide the partial atomic vibrational components. Our results reveal clearly the signature of three different phase transitions both in the diffraction patterns and phonon spectra. The phonon modes are found to be most affected by the transition at the T_C. The spectroscopic evidence for the existence of a different structural modification just below the decomposition limit (T_D ~ 1240 K) is unambiguous indicating strong structural changes that may be related to oxygen vacancies and concomitant Fe3+ to Fe2+ reduction and spin transition

Phonons and Colossal Thermal Expansion Behavior of Ag3Co(CN)6 and Ag3Fe(CN)6

Recently colossal positive volume thermal expansion has been found in the framework compounds Ag3Co(CN)6 and Ag3Fe(CN)6. Phonon spectra have been measured using the inelastic neutron scattering technique as a function of temperature and pressure. The data has been analyzed using ab-initio calculations. We find that the bonding is very similar in both compounds. At ambient pressure modes in the intermediate frequency part of the vibrational spectra in the Co compound are shifted to slightly higher energies as compared to the Fe compound. The temperature dependence of the phonon spectra gives evidence for large explicit anharmonic contribution to the total anharmonicity for low-energy modes below 5 meV. We found that modes are mainly affected by the change in the size of unit cell, which in turn changes the bond lengths and vibrational frequencies. Thermal expansion has been calculated via the volume dependence of phonon spectra. Our analysis indicates that Ag phonon modes in the energy range from 2 to 5 meV are strongly anharmonic and major contributors to thermal expansion in both compounds. The application of pressure hardens the low-energy part of the phonon spectra involving Ag vibrations and confirms the highly anharmonic nature of these modes.Comment: 19 pages, 14 figures and one tabl

Preparation, structural characterisation and antibacterial properties of Ga-doped sol-gel phosphate-based glass

A sol-gel preparation of Ga-doped phosphate-based glass with potential application in antimicrobial devices has been developed. Samples of composition (CaO)(0.30)(Na2O)(0.20-x) (Ga2O3) (x) (P2O5)(0.50) where x = 0 and 0.03 were prepared, and the structure and properties of the gallium-doped sample compared with those of the sample containing no gallium. Analysis of the P-31 MAS NMR data demonstrated that addition of gallium to the sol-gel reaction increases the connectivity of the phosphate network at the expense of hydroxyl groups. This premise is supported by the results of the elemental analysis, which showed that the gallium-free sample contains significantly more hydrogen and by FTIR spectroscopy, which revealed a higher concentration of -OH groups in that sample. Ga K-edge extended X-ray absorption fine structure and X-ray absorption near-edge structure data revealed that the gallium ions are coordinated by six oxygen atoms. In agreement with the X-ray absorption data, the high-energy XRD results also suggest that the Ga3+ ions are octahedrally coordinated with respect to oxygen. Antimicrobial studies demonstrated that the sample containing Ga3+ ions had significant activity against Staphylococcus aureus compared to the control

New polymorph of InVO4: A high-pressure structure with six-coordinated vanadium

This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in Inorganic Chemestry, copyright © American Chemical Society after peer review. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/ic402043xA new wolframite-type polymorph of InVO4 is identified under compression near 7 GPa by in situ high-pressure (HP) X-ray diffraction (XRD) and Raman spectroscopic investigations on the stable orthorhombic InVO4. The structural transition is accompanied by a large volume collapse (Delta V/V = -14%) and a drastic increase in bulk modulus (from 69 to 168 GPa). Both techniques also show the existence of a third phase coexisting with the low- and high-pressure phases in a limited pressure range close to the transition pressure. XRD studies revealed a highly anisotropic compression in orthorhombic InVO4. In addition, the compressibility becomes nonlinear in the HP polymorph. The volume collapse in the lattice is related to an increase of the polyhedral coordination around the vanadium atoms. The transformation is not fully reversible. The drastic change in the polyhedral arrangement observed at the transition is indicative of a reconstructive phase transformation. The HP phase here found is the only modification of InVO4 reported to date with 6-fold coordinated vanadium atoms. Finally, Raman frequencies and pressure coefficients in the low- and high-pressure phases of InVO4 are reported.This research supported by the Spanish government MINECO under Grant Nos. MAT2010-21270-C04-01/04 and CSD2007-00045. O.G. acknowledges support from Vicerrectorado de Investigacion y Desarrollo of UPV (Grant No. UPV2011-0914 PAID-05-11 and UPV2011-0966 PAID-06-11). S.N.A. acknowledges support provided by Universitat de Valencia during his visit to it. B.G.-D. acknowledges the financial support from MINECO through the FPI program.Errandonea, D.; Gomis Hilario, O.; García-Domene, B.; Pellicer Porres, J.; Katari, V.; Achary, SN.; Tyagi, AK.... (2013). New polymorph of InVO4: A high-pressure structure with six-coordinated vanadium. Inorganic Chemistry. 52(21):12790-12798. https://doi.org/10.1021/ic402043xS1279012798522

High-pressure structural and vibrational properties of monazite-type BiPO4, LaPO4, CePO4, and PrPO4

[EN] Monazite-type BiPO4, LaPO4, CePO4, and PrPO4 have been studied under high pressure by ab initio simulations and Raman spectroscopy measurements in the pressure range of stability of the monazite structure. A good agreement between experimental and theoretical Raman-active mode frequencies and pressure coefficients has been found which has allowed us to discuss the nature of the Raman-active modes. Besides, calculations have provided us with information on how the crystal structure is modified by pressure. This information has allowed us to determine the equation of state and the isothermal compressibility tensor of the four studied compounds. In addition, the information obtained on the polyhedral compressibility has been used to explain the anisotropic axial compressibility and the bulk compressibility of monazite phosphates. Finally, we have carried out a systematic discussion on the high-pressure behavior of the four studied phosphates in comparison to results of previous studies.The authors are thankful for the financial support to this research from the Spanish Ministerio de Economia y Competitividad, the Spanish Research Agency, and the European Fund for Regional Development under Grant Nos: MAT2016-75586-C4-1-P/2-P/3-P and MAT2015-71070-REDC. AM and PR-H acknowledge computing time provided by Red Espanola de Supercomputacion (RES) and MALTA-Cluster.Errandonea, D.; Gomis, O.; Rodríguez Hernández, P.; Muñoz, A.; Ruiz Fuertes, J.; Gupta, M.; Achary, S.... (2018). High-pressure structural and vibrational properties of monazite-type BiPO4, LaPO4, CePO4, and PrPO4. Journal of Physics Condensed Matter. 30(6). https://doi.org/10.1088/1361-648X/aaa20dS30

Wheat genetic resources have avoided disease pandemics, improved food security, and reduced environmental footprints: A review of historical impacts and future opportunities

The use of plant genetic resources (PGR)—wild relatives, landraces, and isolated breeding gene pools—has had substantial impacts on wheat breeding for resistance to biotic and abiotic stresses, while increasing nutritional value, end-use quality, and grain yield. In the Global South, post-Green Revolution genetic yield gains are generally achieved with minimal additional inputs. As a result, production has increased, and millions of hectares of natural ecosystems have been spared. Without PGR-derived disease resistance, fungicide use would have easily doubled, massively increasing selection pressure for fungicide resistance. It is estimated that in wheat, a billion liters of fungicide application have been avoided just since 2000. This review presents examples of successful use of PGR including the relentless battle against wheat rust epidemics/pandemics, defending against diseases that jump species barriers like blast, biofortification giving nutrient-dense varieties and the use of novel genetic variation for improving polygenic traits like climate resilience. Crop breeding genepools urgently need to be diversified to increase yields across a range of environments (>200 Mha globally), under less predictable weather and biotic stress pressure, while increasing input use efficiency. Given that the ~0.8 m PGR in wheat collections worldwide are relatively untapped and massive impacts of the tiny fraction studied, larger scale screenings and introgression promise solutions to emerging challenges, facilitated by advanced phenomic and genomic tools. The first translocations in wheat to modify rhizosphere microbiome interaction (reducing biological nitrification, reducing greenhouse gases, and increasing nitrogen use efficiency) is a landmark proof of concept. Phenomics and next-generation sequencing have already elucidated exotic haplotypes associated with biotic and complex abiotic traits now mainstreamed in breeding. Big data from decades of global yield trials can elucidate the benefits of PGR across environments. This kind of impact cannot be achieved without widescale sharing of germplasm and other breeding technologies through networks and public–private partnerships in a pre-competitive space