EXAFS investigation on U(VI) immobilization in hardened cement paste: influence of experimental conditions on speciation

Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the coordination environment of U(VI) in cementitious materials. The EXAFS measurements were carried out on U(VI)-doped samples prepared under varying conditions, such as samples from sorption, hydration and diffusion experiments, and using different cementitious materials, such as crushed hydrated hardened cement paste (HCP) and calcium silicate hydrates (C-S-H). The samples had U(VI) loadings ranging from 1700μg/g to 45000μg/g. Applying principal component analysis (PCA) on 13 EXAFS spectra (each spectra corresponding to aminimum of five different scans) of the low loading samples, one single species is obtained indicating asimilar U(VI) coordination environment for both HCP and C-S-H samples. This result confirms that C-S-H phases control the uptake of U(VI) in the complex cement matrix. The coordination environment structure of this species is similar to aU(VI) surface complex or to U(VI) in uranyl silicate minerals (two axial O atoms at 1.82±0.02 Å; four equatorial O atoms at 2.25±0.01 Å; one Si atom at 3.10±0.03 Å). At high U(VI) loading, PCA revealed asecond U(VI) species, with acoordination environment similar to that of U(VI) in calcium uranate (two axial O atoms at 1.94±0.04 Å; five equatorial O atoms at 2.26±0.01 Å; four Ca atoms at 3.69±0.05 Å and five U atoms at 3.85±0.04 Å). This study suggest that, at low U(VI) loading, U(VI) is bound to C-S-H phases in HCP while at high U(VI) loading, the immobilization of U(VI) in cementitious materials is mainly controlled by the precipitation of acalcium uranate-type phas

Effect of a Novel Nonviral Gene Delivery of BMP-2 on Bone Healing

Background. Gene therapeutic drug delivery approaches have been introduced to improve the efficiency of growth factors at the site of interest. This study investigated the efficacy and safety of a new nonviral copolymer-protected gene vector (COPROG) for the stimulation of bone healing. Methods. In vitro, rat osteoblasts were transfected with COPROG + luciferase plasmid or COPROG + hBMP-2 plasmid. In vivo, rat tibial fractures were intramedullary stabilized with uncoated versus COPROG+hBMP-2-plasmid-coated titanium K-wires. The tibiae were prepared for biomechanical and histological analyses at days 28 and 42 and for transfection/safety study at days 2, 4, 7, 28, and 42. Results. In vitro results showed luciferase expression until day 21, and hBMP-2-protein was measured from day 2 – day 10. In vivo, the local application of hBMP-2-plasmid showed a significantly higher maximum load after 42 days compared to that in the control. The histomorphometric analysis revealed a significantly less mineralized periosteal callus area in the BMP-2 group compared to the control at day 28. The rt-PCR showed no systemic biodistribution of luciferase RNA. Conclusion. A positive effect on fracture healing by nonviral BMP-2 plasmid application from COPROG-coated implants could be shown in this study; however, the effect of the vector may be improved with higher plasmid concentrations. Transfection showed no biodistribution to distant organs and was considered to be safe

Nonlinear Magneto-Optics of Fe Monolayers from first principles: Structural dependence and spin-orbit coupling strength

We calculate the nonlinear magneto-optical response of free-standing fcc (001), (110) and (111) oriented Fe monolayers. The bandstructures are determined from first principles using a full-potential LAPW method with the additional implementation of spin-orbit coupling. The variation of the spin-orbit coupling strength and the nonlinear magneto-optical spectra upon layer orientation are investigated. We find characteristic differences which indicate an enhanced sensitivity of nonlinear magneto-optics to surface orientation and variation of the in-plane lattice constants. In particular the crossover from onedimensional stripe structures to twodimensional films of (111) layers exhibits a clean signature in the nonlinear Kerr-spectra and demonstrates the versatility of nonlinear magneto-optics as a tool for in situ thin-film analysis.Comment: 28 pages, RevTeX, psfig, submitted to PR

MHC-II dynamics are maintained in HLA-DR allotypes to ensure catalyzed peptide exchange.

Presentation of antigenic peptides by major histocompatibility complex class II (MHC-II) proteins determines T helper cell reactivity. The MHC-II genetic locus displays a large degree of allelic polymorphism influencing the peptide repertoire presented by the resulting MHC-II protein allotypes. During antigen processing, the human leukocyte antigen (HLA) molecule HLA-DM (DM) encounters these distinct allotypes and catalyzes exchange of the placeholder peptide CLIP by exploiting dynamic features of MHC-II. Here, we investigate 12 highly abundant CLIP-bound HLA-DRB1 allotypes and correlate dynamics to catalysis by DM. Despite large differences in thermodynamic stability, peptide exchange rates fall into a target range that maintains DM responsiveness. A DM-susceptible conformation is conserved in MHC-II molecules, and allosteric coupling between polymorphic sites affects dynamic states that influence DM catalysis. As exemplified for rheumatoid arthritis, we postulate that intrinsic dynamic features of peptide-MHC-II complexes contribute to the association of individual MHC-II allotypes with autoimmune disease

environmental, earth and planetary science 916 Ni phases formed in cement and cement systems under highly alkaline conditions: an XAFS study

[email protected] X-ray absorption fine structure (XAFS) spectroscopy was applied to assess the solubility-limiting phase of Ni in cement and cement minerals. The study reveals the formation Ni and Al containing hydrotalcite-like layered double hydroxides (Ni-Al LDHs) when cement material (a complex mixture of CaO, SiO 2 , Al 2 O 3 , Fe 2 O 3 and SO 3 ) was treated with Ni in artificial cement pore water under highly alkaline conditions (pH = 13.3). This finding indicates that Ni-Al LDHs and not Ni-hydroxides determine the solubility of Ni in cement materials