724 research outputs found
High pressure behaviour of AIP04-5 in penetrating/ non penetrating pressure medium
No full textAluminophosphate are objects of a growing research interest due to their potential technologieal and industriaI applications [e.g 1,2]. Their large channels serve as ideaI host for organie compounds and small polymers. Among those, AIP0-5 is a synthetic zeolite characterized by an open-framework of (P,AI)O4 tetrahedra. The tetrahedra are connected to form six-and twelve-membered rings, in such a way that a large channel (0~7.3À), parallel to the [001] direction, occurs. Klap et al. [3] underlines that every crystal of AIP0-5 is built up by three different microdomains, in which the positions of the framework oxygen atoms are slightly different; the main effect of the structural disorder is the very large anisotropie displacement parameters of the framework oxygens. We performed two in situ single-crystal synchrotron X-ray diffraction experiments using both penetrating (methanol:ethanol:H20 mix, m:e:w) and non-penetrating (silicon oil) pressure media [4]. The structure refinements showed that: 1) for compression in m:e:w mix, H20 molecules are absorbed at low-P regime, forming a H20-network by H-bonding interaction; 2) the elastic parameters of the super-hydrated AIP04 5 are different if compared to the one compressed in silicon oil; 3) the structural deformation mechanisms of super-hydrated and regular AIP04 -5 are different; 4) evidence of a incommensurately modulated structure occur (according to [3]), and there is an evolution of the non-Bragg reflections with pressure.
The author acknowledges the ltalian Ministry of Education, MIUR-Project: "Futuro in Ricerca 2012 -ImPACT-RBFR12CLQD".
[lJ Tang Z.K. et al. Applied Physies Letters 1998; 73, 2287-2289.
[2] Yang W.S. et al. Microporous and mesoporous materials 20i6; 219,87-92. [3J Klap G.J. et al. Mieroporous and mesoporous materials 2000; 38,403-412. [4J Gatta, G.D. Mieroporous and Mesoporous Material 2010; 128, 78-84
F.C. Hawthorne, Landmark papers : structure topology
No full textIn this second volume of the Mineralogical Society’s ‘Landmark’ series, Prof. Frank Hawthorne has selected a number of key papers, some of which are true milestones of mineralogy and crystallography, showing the acceleration of research and the increase in knowledge in the field of crystal-chemistry. The papers follow in chronological sequence, allowing the reader to see how crystallography and, particularly, mineralogy have evolved during the last 80 years. He has chosen the papers on the basis of three related aspects: (a) the nature of chemical bonds, and (b) their relation to bond topology, leading to (c) the prediction of bond topologies and their hierarchical organization. His commentaries on the selected papers provided a coherent narrative thread running through the volume. In the first chapter ‘Bond topology and Minerals’, Hawthorne reviews the long history of the mineralogy and crystallography, reporting the evolution of the knowledge and the experimental findings in the last 2,000 years. The author introduces the mathematical concept of topology and how to use this tool for the description of the structural configuration in crystals. In addition, he discusses the motivation of mineralogists for understanding and developing principles of bond topology. In chapter 2, two milestone papers by Linus Pauling (both published in 1929) on the structure of complex ionic crystals are reported and enriched with comments. Chapter 3 is devoted to a further milestone paper for mineralogy written by W.L. Bragg (1930), on the structure classification of the silicate minerals, the isomorphous replacement in silicates and on the application of the Pauling’s rules to this class of minerals. In Chapter 4, we jump to the 1970s with the paper of P.B. Moore (1970) on the stereoisomerism among octahedral and tetrahedral chains. Moore based his study not on a specific mineral structure, but examined the different ways in which polyhedra could link via vertices to form chains. He defines the concept of ‘‘structural hierarchy’’ as a general scheme that ties together a certain number of arrangements. An extension of the structural analysis of Moore is found in chapter 6, which is devoted to his systematic study of edge-sharing clusters, deriving the possible arrangements based solely on topological and geometrical principles according to the notions of energy minima and stability (Moore 1974). Chapter 5 deals with the paper by Brown and Shannon (1973), on the empirical bond-valence/ bond-length curves for oxides. A further refinement of the Brown and Shannon approach, into a comprehensive theory that addresses many aspects of the chemical bonding, was developed by Brown (1981), and is presented in chapter 8. Bond-valence analysis of inorganic crystal structures is an essential check on the validity of any structure determination. In his commentary on chapter 8, Hawthorne outlines the critical points introduced by Brown in the bond-valence theory, with interesting application in mineralogy, and presents the bond-valence theory as a molecular orbital theory and as an ionic theory. Chapter 7 is devoted to the paper by L.S. Dent Glasser (1979) on non-existent silicates, emphasizing that the observed arrangements in silicates represent only a small fraction of those topologically possible. Chapter 9 deals with the paper of Hawthorne (1983) on the graphical enumeration of polyhedral clusters. The author developed a ‘‘structural hierarchy’’ hypothesis which has an energetic basis and relates to paragenetic sequences. An example is Bowen’s reaction series shown as a function of the polymerization characteristic of the structure involved. A related topic is covered in chapter 10, which discusses the energetic content of bond topology with reference to the paper by Burdett et al. (1984). The last paper of this collection constituting chapter 11 is devoted to the role of OH and H2O in oxide and oxysalt minerals, based on Hawthorne (1992). The author analysed the roleplayed by (OH) , (H2O)0, (H3O)+ and (H5O2)2+ in controlling bonding topology, topological dimensionality and the role of H2O as a bond-valence transformer, which bears on the, often highly selective, uptake of interstitial cations by environmentally significant minerals. Chapter 12 is the coda, focusing on the prediction of bond topology and of the stoichiometry of stable compounds in a given chemical system. I think that the re-publication of these landmark papers, accompanied by the commentaries of Prof. Hawthorne, will be useful not only for undergraduate or PhD students, but for all structural mineralogists. This collection provides valuable insights into the evolution of structural mineralogy and its wider application to the petrology. As several of the milestone papers collected in this book are published in German journals (Zeitschrift fu ̈r Kristallographie, Neues Jahrbuch fu ̈r Mineralogie Monatshefte), I did a little inquiry and I found that these journals are often not readily available in departmental libraries, and so this is another good reason to have this book in your own library. In conclusion, I warmly recommend this volume to all mineralogists and to Earth sciences libraries.
G. DIEGO GATT
Phase relationships in grunerite-garnet-bearing amphibolites in the systemCFMASH, with applications to metamorphic rocks from the Central Zone of the Limpopo Belt, South Africa.
No full textA petrogenetic grid in the model system CaO–FeO–MgO–Al2O3–SiO2–H2O is presented, illustrating the phase relationships among the minerals grunerite, hornblende, garnet, clinopyroxene, chlorite, olivine, anorthite, zoisite and aluminosilicates, with quartz and H2O in excess. The grid was calculated with the computer softwarethermocalc, using an upgraded version of the internally consistent thermodynamic dataset HP98 and non-ideal mixing activity models for all solid solutions. From this grid, quantitative phase diagrams (P–T pseudosections) are derived and employed to infer a P–T path for grunerite–garnet-bearing amphibolites from the Endora Klippe, part of the Venetia Klippen Complex within the Central Zone of the Limpopo Belt. Agreement between calculated and observed mineral assemblages and garnet zonation indicates that this part of the Central Zone underwent a prograde temperature and pressure increase from c. 540 °C/4.5 kbar to 650 °C/6.5 kbar, followed by a post-peak metamorphic pressure decrease. The inferred P–T path supports a geotectonic model suggesting that the area surrounding the Venetia kimberlite pipes represents the amphibolite-facies roof zone of migmatitic gneisses and granulites that occur widely within the Central Zone. In addition, the P–T path conforms to an interpretation that the Proterozoic evolution of the Central Zone was controlled by horizontal tectonics, causing stacking and differential heating at c. 2.0 Ga
Manganese incorporation in synthetic hercynite
No full textManganese incorporation in synthetic hercynite, and partitioning between hercynite and silicate melt synthesized at 1.0 GPa, 1250°C, and at an f O2 buffered by Fe–FeO, has been studied by X-ray absorption spectroscopy and single-crystal X-ray structure refinement. Spectra indicate the presence of both Mn2+ and Mn3+ (and possibly also Mn4+) in synthetic hercynite and partitioning of Mn2+ into the melt phase, and Mn3+ into hercynite, respectively, under run conditions. X-ray refinement is consistent with partial disorder of Fe and Al across tetrahedral and octahedral sites. A higher than expected degree of Fe-Al disorder in the Mn-bearing hercynite can be explained by preferential incorporation of Mn2+ onto the tetrahedral site, and indicates that Fe-Al disorder in pure, stoichiometric hercynite cannot necessarily be used to determine closure temperatures in natural spinel. However, partitioning of Mn2+ and Mn3+ between melt and hercynite suggests that Mn incorporation in hercynite could be used as a measure of f O2 conditions in magmas during spinel crystallization
Ultra-fast escape of a deformable jet-propelled body
No full textIn this work a cephalopod-like deformable body that fills an internal cavity with fluid and expels it to propel an escape manoeuvre, while undergoing a drastic external shape change through shrinking, is shown to employ viscous as well as mainly inviscid hydrodynamic mechanisms to power an impressively fast start. First, we show that recovery of added-mass energy enables a shrinking rocket in a dense inviscid flow to achieve greater escape speed than an identical rocket in a vacuum. Next, we extend the shrinking body results of Weymouth & Triantafyllou (J. Fluid Mech., vol. 702, 2012, pp. 470–487) to three-dimensional bodies and show that three hydrodynamic mechanisms must be combined to achieve rapid escape performance in a viscous fluid: added-mass energy recovery; flow separation elimination; and an optimized energy storage and recovery. In particular, we show that the mechanism of separation elimination achieved through rapid body shrinking, coordinated with the mechanism of recovering the initially imparted added-mass energy, is critical to achieving a high escape speed. Hence a flexible, collapsing body can be vastly superior to a rigid-shell jet-propelled body
High-brilliance X-ray system for high-pressure in-house research: applications for studies of superhard materials
No full textNewly installed, at Bayerisches Geoinstitut, X-ray system consists of three major components:
RIGAKU FR-D high-brilliance source, Osmic’s Confocal Max-Flux optics, and SMART APEX 4K
CCD area detector. We tested the system for single-crystal structural studies on example of garnet,
Co3Al2Si3O12, for powder diffraction analysis on example of a small sample of boron carbide, B4C,
recovered after treatment in a multi-anvil apparatus, and for in situ experiments at high pressure
on example of FeO compressed in a diamond anvil cell to >100 GPa. In all the cases, the system
demonstrated its reliability and provided results comparable with those obtained using the best currently
available instruments. Using a new X-ray system, we measured the compressibility of superhard
nanocrystalline diamond at pressures up to 26 GPa and found it to be extremely incompressible with
KT = 488(4) GPa, K' = 3.1(2), and V0 = 3.401(6) cm3/mol
A Letter from Sir Charles G.D. Roberts (A Personal Memoir)
No full textSkala recounts her first and subsequent meetings with Charles G.D. Roberts whom she met when he was in his late seventies, and she in her teens. Roberts was a man of paradox, an author of emotionally-distanced verse yet a man of strong sentiment. He was a chameleon, a person who was everything to everybody; he played the role of gentle poet, mentor, and editor; he was a husband, father, and friend. He wrote about unique characters, animal or human, and he was quite naturally an elitist, though his "elite" could have been chosen from all ranks of society, and, indeed, from all societies. Also discussed are some of the critical views on Roberts' work, praiseworthy and not, as well as Roberts' own critical assessment of Skala's early verse
Sunitinib treatment exacerbates intratumoral heterogeneity in metastatic renal cancer
No full textThis work was supported by the Chief Scientist Office, Scotland (ETM37; to G.D. Stewart, A.C.P. Riddick, M. Aitchison, and D.J. Harrison), Cancer Research UK (Experimental Cancer Medicine Centre; to T. Powles, London and D.J. Harrison, Edinburgh), Medical Research Council (to A. Laird and D.J. Harrison), Royal College of Surgeons of Edinburgh (to A. Laird), Melville Trust (to A. Laird), Medical Research Council (MC_UU_12018/25; to I.M. Overton), Royal Society of Edinburgh Scottish Government Fellowship cofunded by Marie Curie Actions (to I.M. Overton), Renal Cancer Research Fund (to G.D. Stewart), Kidney Cancer Scotland (to G.D. Stewart) and an educational grant from Pfizer (to T. Powles).Purpose: The aim of this study was to investigate the effect of VEGF targeted therapy (sunitinib) on molecular intratumoral heterogeneity (ITH) in metastatic clear cell renal cancer (mccRCC). Experimental design: Multiple tumor samples (n=187 samples) were taken from the primary renal tumors of mccRCC patients who were sunitinib treated (n=23, SuMR clinical trial) or untreated (n=23, SCOTRRCC study). ITH of pathological grade, DNA (aCGH), mRNA (Illumina Beadarray) and candidate proteins (reverse phase protein array) were evaluated using unsupervised and supervised analyses (driver mutations, hypoxia and stromal related genes). ITH was analysed using intratumoral protein variance distributions and distribution of individual patient aCGH and gene expression clustering. Results: Tumor grade heterogeneity was greater in treated compared to untreated tumors (P=0.002). In unsupervised analysis, sunitinib therapy was not associated with increased ITH in DNA or mRNA. However, there was an increase in ITH for the driver mutation gene signature (DNA and mRNA) as well as increasing variability of protein expression with treatment (p<0.05). Despite this variability, significant chromosomal and transcript changes to key targets of sunitinib, such as VHL, PBRM1 and CAIX, occurred in the treated samples. Conclusions: These findings suggest that sunitinib treatment has significant effects on the expression and ITH of key tumor and treatment specific genes/proteins in mccRCC. The results, based on primary tumor analysis, do not support the hypothesis that resistant clones are selected and predominate following targeted therapy.Peer reviewe
A low temperature X-ray single-crystal diffraction and polarised infra-red study of epidote
No full textThe effects of low-temperature on the crystal structure of a natural epidote [Ca1.925Fe0.745Al2.265Ti0.004 Si3.037O12(OH), a = 8.8924(7), b = 5.6214(3), c = 10.1547(6) angstrom and beta = 115.396(8)degrees at room conditions, Sp. Gr. P2(1)/m] have been investigated with a series of structure refinements down to 100 K on the basis of X-ray single-crystal diffraction data. The reflection conditions confirm that the space group is maintained within the T-range investigated. Structural refinements at all temperatures show the presence of Fe3+ at the octahedral M(3) site only [%Fe(M3) = 70.6(4)% at 295 K]. Only one independent proton site was located and two possible H-bonds occur, with O(10) as donor and O(4) and O(2) as acceptors. The H-bonding scheme is maintained down to 100 K and is supported by single crystal room-T polarised FTIR data. FTIR Spectra over the region 4,000-2,500 cm(-1) are dominated by the presence of a strongly pleochroic absorption feature which can be assigned to protonation of O(10)-O(4). Previously unobserved splitting of this absorption features is consistent with a NNN influence due to the presence of Al and Fe3+ on the nearby M(3) site. An additional relatively minor absorption feature in FTIR spectra can be tentatively assigned to protonation of O(10)-O(2). Low-T does not affect significantly the tetrahedral and octahedral bond distances and angles, even when distances are corrected for "rigid body motions". A more significant effect is observed for the bond distances of the distorted Ca(1)- and Ca(2)-polyhedra, especially when corrected for "non-correlated motion". The main low-T effect is observed on the vibrational regime of the atomic sites, and in particular for the two Ca-sites. A significant reduction of the magnitude of the thermal displacement ellipsoids, with a variation of U-eq (defined as one-third of the trace of the orthogonalised U-ij tensor) by similar to 40% is observed for the Ca-sites between 295 and 100 K. Within the same T-range, the U-eq of the octahedral and oxygen sites decrease similarly by similar to 35%, whereas those of the tetrahedral cations by similar to 22%.</p
A single-crystal neutron and X-ray diffraction study of elbaite
No full textThe crystal chemistry and crystal structure of gem-quality elbaite from the Pederneira mine, São José da Safira, Minas Gerais, Brazil, were investigated by electron microprobe analysis in wavelength dispersive mode, un-polarized Fourier transform infrared spectroscopy, single-crystal neutron and X-ray diffraction. The average chemical formula of the sample resulted X (Na0.73Ca0.06□0.21) Y (Al1.24Li1.02Fe0.41Mn0.18Mg0.07) Z Al6T Si6O18B (BO3)3V (OH)3W (OH0.46F0.54) and the chemical analysis showed an almost homogeneous distribution of the principal elements over the crystal, with significant amounts of Fe (wt% FeO ~ 3.1) and Mn (wt% MnO ~ 1.3) which substitute YAl. The infrared spectrum over the diagnostic range of fundamental hydroxyl stretching vibrations is characterized by three strong absorption bands at 3,591 (ν1), 3,562 (ν2), and 3,491 (ν3) cm−1, respectively. The neutron structure refinement showed: (a) the presence of boron at the B site only and (b) the absence (at a significant level) of aluminum at the T site, which appears to be fully occupied by silicon. Only one proton site was successfully located. The H bond configuration is described with O3 as “donor” and O5 as “acceptor.” The O3–H bond distance corrected for “riding motion” is 0.9834 Å, and H···O5 = 2.238(7) Å, O3···O5 = 3.152(4) Å and O3–H···O5 = 157.7(5)°. The reasons of the positional disorder at the O1 and O2 sites, observed in both neutron and X-ray refinements, are discussed
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