Crystal structure and local structure of Mg(2-x)Pr(x)Ni4 (x = 0.6 and 1.0) deuteride using in situ neutron total scattering.

We studied crystal structure and local structure of Mg(2-x)Pr(x)Ni4 (x = 0.6 and 1.0) and their deuterides using in situ neutron total scattering and first-principles calculations. The total scattering data were analyzed using Rietveld refinement and pair distribution function analysis (PDF). The crystal structure of Mg(2-x)Pr(x)Ni4 before deuterium absorption was C15b in space group F43m. No difference between the crystal and local (PDF) structures was observed. The crystal structure of Mg1.0Pr1.0Ni4D(∼4) was found to be orthorhombic in space group Pmn2(1), with three deuterium occupation sites: PrNi3 and two types of bipyramidal Pr2MgNi2 that have a plane of symmetry composed of MgNi2. There is no significant difference between the crystal structure and the local structure of Mg1.0Pr1.0Ni4D(∼4). On the other hand, the average crystal structure of the Mg-rich Mg1.4Pr0.6Ni4D(∼3.6) was C15b with two deuterium occupation sites: PrNi3 and MgPrNi2 suggesting that the deuterium occupation shifts away from the Pr2MgNi2 bipyramid. First-principles relaxed structures also showed the shift of the hydrogen occupation site toward the Pr atom of the bipyramid, when induced by Mg substitution for the opposing Pr, resulting in hydrogen occupation in the MgPrNi2 tetrahedral site. The PDF pattern of Mg1.4Pr0.6Ni4D(∼3.6) cannot be refined below 7.2 Šin atomic distances using the C15b structure which was obtained from Rietveld refinement but can be done using an orthorhombic structure. It suggests that Mg1.4Pr0.6Ni4D(∼3.6) was locally distorted to the orthorhombic.

The nanostructure and hydrogenation reaction of Mg50Co50 BCC alloy prepared by ball-milling.

Mg50Co50 alloy before and after hydrogenation was investigated by means of transmission electron microscopy (TEM). Mg50Co50 alloy before hydrogenation was found to contain crystals not larger than 5 nm in size. Selected-area electron diffraction patterns (SAEDPs) revealed that these nanocrystals have a body-centered cubic (BCC) structure with a lattice parameter of about 0.3 nm. Distribution of Mg and Co elements in the Mg50Co50 alloy was uniform, indicated by energy dispersive x-ray spectroscopy (EDS) analysis. Crystallization and decomposition occurred in the Mg50Co50 alloy during hydrogenation. A large number of crystals larger than 10 nm were observed in the hydrogenated sample. The SAEDPs showed polycrystalline rings corresponding to the BCC phase and the Co metal phase. The existence of Mg-rich Mg-Co crystals and Co particles was also confirmed by TEM-EDS analysis.

Hydrogen bonding in sodium alanate: a muon spin rotation study.

We have detected the occurrence of hydrogen bonding involving an interstitial positive muon situated between hydrogen atoms of two independent alanate anions in sodium alanate (NaAlH4). Ti doping, which is known to dramatically improve the hydrogen cycling performance of NaAlH4, reduces the kinetic barrier of the transition of the muon from the muon-dialanate state to a mobile interstitial state. This observation strongly suggests that hydrogen bonding is the primary bottleneck for hydrogen release or uptake in sodium alanate, which might be common to other complex hydrides.

Fibroblast growth factor-induced gene expression and cartilage pattern formation in chick limb bud recombinants.

To clarify the roles of fibroblast growth factors (FGF) in limb cartilage pattern formation, the effects of various FGF on recombinant limbs that were composed of dissociated and reaggregated mesoderm and ectodermal jackets were examined. Fibroblast growth factor-soaked beads were inserted just under the apical ectodermal ridge (AER) of recombinant limbs and the recombinant limbs were grafted and allowed to develop. Control recombinant limbs without FGF beads formed one or two cartilage elements. Recombinants with FGF-4 beads formed up to five cartilage elements, which were aligned along the anteroposterior (AP) axis. Each cartilage element showed digit-like segmentation. In contrast, recombinants with FGF-2 beads showed formation of multiple thick and unsegmented cartilage rods, which elongated inside and outside the AP plane from the distal end of the recombinants. Recombinants with FGF-8 beads formed a truncated cartilage pattern and recombinants with FGF-10 beads formed a cartilage pattern similar to that of the control recombinants. The expression of the Fgf-8, Msx-1 and Hoxa-13 genes in the developing recombinant limbs were examined. FGF-4 induced extension of the length of the Fgf-8-positive epidermis, or AER, along the AP axis 5 days after grafting, at which time the digits are specified. FGF-2 induced expansion of the Msx-1-positive area, first in the proximal direction and then along the dorsoventral axis. The functions of these FGF in recombinant and normal limb patterning are discussed in this paper.

Arylsulfatase exists as non-enzymatic cell surface protein in sea urchin embryos.

The physiological role of arylsulfatase (Ars) and its function during development have yet to be satisfactorily defined in any species, though the proteins are widely distributed and the genes have been cloned from various organisms. Here we report the dual location of two types of Ars in sea urchin embryos. The majority of sea urchin Ars does not exhibit enzyme activity and is extracellularly distributed in aboral ectoderm cells (nonenzymatic Ars). Only a small portion has enzyme activity and is localized in lysosomal vesicles (enzymatic Ars). The elution pattern of Ars proteins processed by DEAE-cellulose or analytical gel-column chromatography reveals that although the molecular radius of enzymatic Ars differs from that of nonenzymatic Ars, they have the same charge. Furthermore, sedimentation analysis shows that purified Ars of sea urchin embryos is soluble in the absence of divalent cations but becomes insoluble in the presence of Ca2+ or Mg2+. Taken together, the present results suggest that non-enzymatic Ars is a new member of the cell surface component or extracellular matrix. It is possible that this cell surface Ars plays an important role in morphogenesis of sea urchin embryos.

Nuclear spin-lattice relaxation mechanisms in kaolinite confirmed by magic-angle spinning.

Spin-lattice relaxation mechanisms in kaolinite have been reinvestigated by magic-angle spinning (MAS) of the sample. MAS is useful to distinguish between relaxation mechanisms: the direct relaxation rate caused by the dipole-dipole interaction with electron spins is not affected by spinning while the spin diffusion-assisted relaxation rate is. Spin diffusion plays a dominant role in 1H relaxation. MAS causes only a slight change in the relaxation behavior, because the dipolar coupling between 1H spins is strong. 29Si relaxes directly through the dipole-dipole interaction with electron spins under spinning conditions higher than 2 kHz. A spin diffusion effect has been clearly observed in the 29Si relaxation of relatively pure samples under static and slow-spinning conditions. 27Al relaxes through three mechanisms: phonon-coupled quadrupole interaction, spin diffusion and dipole-dipole interaction with electron spins. The first mechanism is dominant, while the last is negligibly small. Spin diffusion between 27Al spins is suppressed completely at a spinning rate of 2.5 kHz. We have analyzed the relaxation behavior theoretically and discussed quantitatively. Concentrations of paramagnetic impurities, electron spin-lattice relaxation times and spin diffusion rates have been estimated.