Effect of Sm valence changes on photoemission spectra

[[abstract]]We have used low-energy (hν=17–45 eV) photoemission to study thin films of Sm evaporated on Nb. We find that Sm evaporated onto a room-temperature Nb substrate is initially entirely divalent. On a time scale of the order of 50 min at room temperature a valence transition to mixed-valent or trivalent Sm occurs. This is accompanied by dramatic changes in the photoemission spectra, including a large increase in the total yield of photoelectrons and the appearance of a series of new constant-kinetic-energy peaks. The photon-energy dependence of these peaks indicates that they are due to Auger recombination of the Sm 5p level. We also observe a 5p→5d resonance in Sm for the first time. The underlying cause of these effects appears to be an ordering transition in the Sm film, which changes the Sm 5d occupancy and increases the resonance amplitude. This mechanism is evidently a very sensitive indicator of a Sm valence change.[[incitationindex]]SCI[[booktype]]紙本[[booktype]]電子

Structural precursor to the metal-insulator transition in V_2O_3

The temperature dependence of the local structure of V_2O_3 in the vicinity of the metal to insulator transition (MIT) has been investigated using hard X-ray absorption spectroscopy. It is shown that the vanadium pair distance along the hexagonal c-axis changes abruptly at the MIT as expected. However, a continuous increase of the tilt of these pairs sets in already at higher temperatures and reaches its maximum value at the onset of the electronic and magnetic transition. These findings confirm recent theoretical results which claim that electron-lattice coupling is important for the MIT in V_2O_3. Our results suggest that interactions in the basal plane play a decisive role for the MIT and orbital degrees of freedom drive the MIT via changes in hybridization.Comment: 6 pages, 5 figures, 2 table

Evidence for short range orbital order in paramagnetic insulating (Al,V)_2O_3

The local structure of (Al_0.06V_0.94)_2O_3 in the paramagnetic insulating (PI) and antiferromagnetically ordered insulating (AFI) phase has been investigated using hard and soft x-ray absorption techniques. It is shown that: 1) on a local scale, the symmetry of the vanadium sites in both the PI and the AFI phase is the same; and 2) the vanadium 3d - oxygen 2p hybridization, as gauged by the oxygen 1s absorption edge, is the same for both phases, but distinctly different from the paramagnetic metallic phase of pure V_2O_3. These findings can be understood in the context of a recently proposed model which relates the long range monoclinic distortion of the antiferromagnetically ordered state to orbital ordering, if orbital short range order in the PI phase is assumed. The measured anisotropy of the x-ray absorption spectra is discussed in relation to spin-polarized density functional calculations.Comment: 8 pages, 5 figure

Biomechanics of bone-fracture fixation by stiffness-graded plates in comparison with stainless-steel plates

BACKGROUND: In the internal fixation of fractured bone by means of bone-plates fastened to the bone on its tensile surface, an on-going concern has been the excessive stress-shielding of the bone by the excessively-stiff stainless-steel plate. The compressive stress-shielding at the fracture-interface immediately after fracture-fixation delays callus formation and bone healing. Likewise, the tensile stress-shielding of the layer of the bone underneath the plate can cause osteoporosis and decrease in tensile strength of this layer. METHOD: In order to address this problem, we propose to use stiffness-graded plates. Accordingly, we have computed (by finite-element analysis) the stress distribution in the fractured bone fixed by composite plates, whose stiffness is graded both longitudinally and transversely. RESULTS: It can be seen that the stiffness-graded composite-plates cause less stress-shielding (as an example: at 50% of the healing stage, stress at the fracture interface is compressive in nature i.e. 0.002 GPa for stainless steel plate whereas stiffness graded plates provides tensile stress of 0.002 GPa. This means that stiffness graded plate is allowing the 50% healed bone to participate in loadings). Stiffness-graded plates are more flexible, and hence permit more bending of the fractured bone. This results in higher compressive stresses induced at the fractured faces accelerate bone-healing. On the other hand, away from the fracture interface the reduced stiffness and elastic modulus of the plate causes the neutral axis of the composite structure to be lowered into the bone resulting in the higher tensile stress in the bone-layer underneath the plate, wherein is conducive to the bone preserving its tensile strength. CONCLUSION: Stiffness graded plates (with in-built variable stiffness) are deemed to offer less stress-shielding to the bone, providing higher compressive stress at the fractured interface (to induce accelerated healing) as well as higher tensile stress in the intact portion of the bone (to prevent bone remodeling and osteoporosis)

Transcriptional Profiling of Chondrodysplasia Growth Plate Cartilage Reveals Adaptive ER-Stress Networks That Allow Survival but Disrupt Hypertrophy

Metaphyseal chondrodysplasia, Schmid type (MCDS) is characterized by mild short stature and growth plate hypertrophic zone expansion, and caused by collagen X mutations. We recently demonstrated the central importance of ER stress in the pathology of MCDS by recapitulating the disease phenotype by expressing misfolding forms of collagen X (Schmid) or thyroglobulin (Cog) in the hypertrophic zone. Here we characterize the Schmid and Cog ER stress signaling networks by transcriptional profiling of microdissected mutant and wildtype hypertrophic zones. Both models displayed similar unfolded protein responses (UPRs), involving activation of canonical ER stress sensors and upregulation of their downstream targets, including molecular chaperones, foldases, and ER-associated degradation machinery. Also upregulated were the emerging UPR regulators Wfs1 and Syvn1, recently identified UPR components including Armet and Creld2, and genes not previously implicated in ER stress such as Steap1 and Fgf21. Despite upregulation of the Chop/Cebpb pathway, apoptosis was not increased in mutant hypertrophic zones. Ultrastructural analysis of mutant growth plates revealed ER stress and disrupted chondrocyte maturation throughout mutant hypertrophic zones. This disruption was defined by profiling the expression of wildtype growth plate zone gene signatures in the mutant hypertrophic zones. Hypertrophic zone gene upregulation and proliferative zone gene downregulation were both inhibited in Schmid hypertrophic zones, resulting in the persistence of a proliferative chondrocyte-like expression profile in ER-stressed Schmid chondrocytes. Our findings provide a transcriptional map of two chondrocyte UPR gene networks in vivo, and define the consequences of UPR activation for the adaptation, differentiation, and survival of chondrocytes experiencing ER stress during hypertrophy. Thus they provide important insights into ER stress signaling and its impact on cartilage pathophysiology

Clonal heterogeneity and rates of specific chromosome gains are risk predictors in childhood high-hyperdiploid B-cell acute lymphoblastic leukemia

B-cell acute lymphoblastic leukemia (B-ALL) is the commonest childhood cancer. High hyperdiploidy (HHD) identifies the most frequent cytogenetic subgroup in childhood B-ALL. Although hyperdiploidy represents an important prognostic factor in childhood B-ALL, the specific chromosome gains with prognostic value in HHD-B-ALL remain controversial, and the current knowledge about the hierarchy of chromosome gains, clonal heterogeneity and chromosomal instability in HHD-B-ALL remains very limited. We applied automated sequential-iFISH coupled with single-cell computational modeling to identify the specific chromosomal gains of the eight typically gained chromosomes in a large cohort of 72 primary diagnostic (DX, n = 62) and matched relapse (REL, n = 10) samples from HHD-B-ALL patients with either favorable or unfavorable clinical outcome in order to characterize the clonal heterogeneity, specific chromosome gains and clonal evolution. Our data show a high degree of clonal heterogeneity and a hierarchical order of chromosome gains in DX samples of HHD-B-ALL. The rates of specific chromosome gains and clonal heterogeneity found in DX samples differ between HHD-B-ALL patients with favorable or unfavorable clinical outcome. In fact, our comprehensive analyses at DX using a computationally defined risk predictor revealed low levels of trisomies +18+10 and low levels of clonal heterogeneity as robust relapse risk factors in minimal residual disease (MRD)-negative childhood HHD-B-ALL patients: relapse-free survival beyond 5 years: 22.1% versus 87.9%, P < 0.0001 and 33.3% versus 80%, P < 0.0001, respectively. Moreover, longitudinal analysis of matched DX-REL HHD-B-ALL samples revealed distinct patterns of clonal evolution at relapse. Our study offers a reliable prognostic sub-stratification of pediatric MRD-negative HHD-B-ALL patients

Magnetic resonance and X-ray absorption studies of materials for advanced batteries. Semiannual report, October 15, 1996 - March 15, 1997

Although only 5 months have elapsed since the official award date for this new grant, there is progress to report, including work on Li{sub x}V{sub 6}O{sub 13}, Li{sub x}FeS{sub 2}, polymer electrolytes, and lithiated carbon