Integer spin-chain antiferromagnetism of the 4d oxide CaRuO3 with post-perovskite structure

A quasi-one dimensional magnetism was discovered in the post-perovskite CaRuO3 (Ru4+: 4d4, Cmcm), which is iso-compositional with the perovskite CaRuO3 (Pbnm). An antiferromagnetic spin-chain function with -J/kB = 350 K well reproduces the experimental curve of the magnetic susceptibility vs. temperature, suggesting long-range antiferromagnetic correlations. The anisotropic magnetism is probably owing to the dyz - 2p- dzx and dzx - 2p- dyz superexchange bonds along a-axis. The Sommerfeld coefficient of the specific heat is fairly small, 0.16(2) mJ mol-1 K-2, indicating that the magnetism reflects localized nature of the 4d electrons. As far as we know, this is the first observation of an integer (S = 1) spin-chain antiferromagnetism in the 4d electron system.Comment: Accepted for publication in Phys. Rev.

The Mantle Transition Zone Beneath West Antarctica: Seismic Evidence for Hydration and Thermal Upwellings

Although prior work suggests that a mantle plume is associated with Cenozoic rifting and volcanism in West Antarctica, the existence of a plume remains conjectural. Here we use P wave receiver functions (PRFs) from the Antarctic POLENET array to estimate mantle transition zone thickness, which is sensitive to temperature perturbations, throughout previously unstudied parts of West Antarctica. We obtain over 8000 high-quality PRFs using an iterative, time domain deconvolution method filtered with a Gaussian width of 0.5 and 1.0, corresponding to frequencies less than ∼0.24 and ∼0.48 Hz, respectively. Single-station and common conversion point stacks, migrated to depth using the AK135 velocity model, indicate that mantle transition zone thickness throughout most of West Antarctica does not differ significantly from the global average, except in two locations; one small region exhibits a vertically thinned (210 ± 15 km) transition zone beneath the Ruppert Coast of Marie Byrd Land and another laterally broader region shows slight, vertical thinning (225 ± 25 km) beneath the Bentley Subglacial Trench. We also observe the 520 discontinuity and a prominent negative peak above the mantle transition zone throughout much of West Antarctica. These results suggest that the mantle transition zone may be hotter than average in two places, possibly due to upwelling from the lower mantle, but not broadly across West Antarctica. Furthermore, we propose that the transition zone may be hydrated due to \u3e100 million years of subduction beneath the region during the early Mesozoic

Rutile/TiO 2 II phase equilibria

The transition between rutile and α-PbO 2 structured TiO 2 (TiO 2 II) has been investigated at 700–1,200 °C and 4.2–9.6 GPa. Hydrothermal phase equilibrium experiments were performed in the multi-anvil apparatus to bracket the phase boundary at 700, 1,000, and 1,200 °C. The equilibrium phase boundary is described by the equation: P (GPa)=1.29+0.0065 T ( °C). In addition, growth of TiO 2 II was observed in experiments at 500 and 600 °C, although growth of rutile was too slow to bracket unambiguously the equilibrium boundary at these temperatures. Water was not detected in either rutile or TiO 2 II, and dry synthesis experiments at 1,200 °C were consistent with the phase boundary determined in the fluid-bearing experiments, suggesting that the equilibrium is unaffected by the presence of water. Our bracket of the phase boundary at 700 °C is consistent with the reversed, dry experiments of Akaogi et al. (1992) and the reversals of Olsen et al. (1999). The new data suggest that the phase boundary is linear, in agreement with Akaogi et al. (1992), but in striking contrast to the phase diagram inferred by Olsen et al. (1999). The natural occurrence of TiO 2 II requires formation pressures considerably higher than the graphite–diamond phase boundary.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/42229/1/s00410-003-0445-2.pd

Thermodynamics of pyrope-majorite, Mg3Al2Si3O12-Mg4Si4O12, solid solution from atomistic model calculations

Static lattice energy calculations, based on empirical pair potentials have been performed for a large set of different structures with compositions between pyrope and majorite, and with different states of order of octahedral cations. The energies have been cluster expanded using pair and quaternary terms. The derived ordering constants have been used to constrain Monte Carlo simulations of temperature-dependent properties in the ranges of 1073 3673K and 0 20 GPa. The free energies of mixing have been calculated using the method of thermodynamic integration. At zero pressure the cubic/tetragonal transition is predicted for pure majorite at 3300 K. The transition temperature decreases with the increase of the pyrope mole fraction. A miscibility gap associated with the transition starts to develop at about 2000K and xmaj 0.8, and widens with the decrease in temperature and the increase in pressure. Activity composition relations in the range of 0 20 GPa and 1073 2673K are described with the help of a high-order Redlich Kister polynomial

Molecular imaging of glioblastoma multiforme using anti-insulin-like growth factor-binding protein-7 single-domain antibodies

BACKGROUND: Insulin-like growth factor-binding protein 7 (IGFBP7) is an abundant, selective and accessible biomarker of glioblastoma multiforme (GBM) tumour vessels. In this study, an anti-IGFBP7 single-domain antibody (sdAb) was developed to target GBM vessels for molecular imaging applications. METHODS: Human GBM was modelled in mice by intracranial implantation of U87MG.EGFRvIII cells. An anti-IGFBP7 sdAb, isolated from an immune llama library by panning, was assessed in vitro for its binding affinity using surface plasmon resonance and by ex vivo immunobinding on mouse and human GBM tissue. Tumour targeting by Cy5.5-labelled anti-IGFBP7 sdAb as well as by anti-IGFBP7 sdAb conjugated to PEGylated Fe3O4 nanoparticles (NPs)-Cy5.5 were assessed in U87MG.EGFRvIII tumour-bearing mice in vivo using optical imaging and in brain sections using fluorescent microscopy. RESULTS: Surface plasmon resonance analyses revealed a medium affinity (KD\ufffd40\ufffd50 nM) binding of the anti-IGFBP7 sdAb to the purified antigen. The anti-IGFBP7 sdAb also selectively bound to both mouse and human GBM vessels, but not normal brain vessels in tissue sections. In vivo, intravenously injected anti-IGFBP7 sdAb-Cy5.5 bound to GBM vessels creating high imaging signal in the intracranial tumour. Similarly, the anti-IGFBP7 sdAb-functionalised PEGylated Fe3O4 NP-Cy5.5 demonstrated enhanced tumour signal compared with non-targeted NPs. Fluorescent microscopy confirmed the presence of anti-IGFBP7 sdAb and anti-IGFBP7 sdAb- PEGylated Fe3O4 NPs selectively in GBM vessels. CONCLUSIONS: Anti-IGFBP7 sdAbs are novel GBM vessel-targeting moieties suitable for molecular imaging.Peer reviewed: YesNRC publication: Ye

Atomistic model of diopside–K-jadeite (CaMgSi2O6–KAlSi2O6) solid solution

Atomistic model was proposed to describe the thermodynamics of mixing in the diopside–K-jadeite solid solution (CaMgSi2O6–KAlSi2O6). The simulations were based on minimization of the latticeenergies of 800 structures within a 2 × 2 × 4 supercell of C2/c diopside with the compositions betweenCaMgSi2O6 and KAlSi2O6 and with variable degrees of order/disorder in the arrangement of Ca/K cations in M2 site and Mg/Al in Ml site. The energy minimization was performed with the help of a force-field model. The results of the calculations were used to define a generalized Ising model, which included 37 pair interaction parameters. Isotherms of the enthalpy of mixing within the range of 273–2023 K were calculated with a Monte Carlo algorithm, while the Gibbs free energies of mixing were obtained by thermodynamic integration of the enthalpies of mixing. The calculated T–X diagram for the system CaMgSi2O6–KAlSi2O6 at temperatures below 1000 K shows several miscibility gaps, which are separated by intervals of stability of intermediate ordered compounds. At temperatures above 1000 K a homogeneous solid solution is formed. The standard thermodynamic properties of K-adeite (KAlSi2O6) evaluated from quantum mechanical calculations were used to determine location of several mineral reactions with the participation of the diopside–K-jadeite solid solution. The results of the simulations suggest that the low content of KalSi2O6 in natural clinopyroxenes is not related to crystal chemical factors preventing isomorphism, but is determined by relatively high standard enthalpy of this end member

Heat capacity and phase equilibria of hollandite polymorph of KAlSi 3 O 8

The low-temperature heat capacity ( C p ) of KAlSi 3 O 8 with a hollandite structure was measured over the range of 5–303 K with a physical properties measurement system. The standard entropy of KAlSi 3 O 8 hollandite is 166.2±0.2 J mol −1  K −1 , including an 18.7 J mol −1  K −1 contribution from the configurational entropy due to disorder of Al and Si in the octahedral sites. The entropy of K 2 Si 4 O 9 with a wadeite structure (Si-wadeite) was also estimated to facilitate calculation of phase equilibria in the system K 2 O–Al 2 O 3 –SiO 2 . The calculated phase equilibria obtained using Perple_x are in general agreement with experimental studies. Calculated phase relations in the system K 2 O–Al 2 O 3 –SiO 2 confirm a substantial stability field for kyanite–stishovite/coesite–Si-wadeite intervening between KAlSi 3 O 8 hollandite and sanidine. The upper stability of kyanite is bounded by the reaction kyanite (Al 2 SiO 5 ) = corundum (Al 2 O 3 )  + stishovite (SiO 2 ), which is located at 13–14 GPa for 1,100–1,400 K. The entropy and enthalpy of formation for K-cymrite (KAlSi 3 O 8 ·H 2 O) were modified to better fit global best-fit compilations of thermodynamic data and experimental studies. Thermodynamic calculations were undertaken on the reaction of K-cymrite to KAlSi 3 O 8 hollandite +  H 2 O, which is located at 8.3–10.0 GPa for the temperature range 800–1,600 K, well inside the stability field of stishovite. The reaction of muscovite to KAlSi 3 O 8 hollandite + corundum + H 2 O is placed at 10.0–10.6 GPa for the temperature range 900–1,500 K, in reasonable agreement with some but not all experiments on this reaction.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/46910/1/269_2006_Article_63.pd