Biological interface study of HA/ZrO2 graded composite in a dog lumbar vertebra bone defect model

This study compared bony fusion in autologous bone grafting with HA/ZrO₂ graded composite in terms of mineral depositions, histological characteristics, and biomechanical properties of bonding interface. Twenty-four beagle dogs were established four places of bone defect in two adjacent lumbar vertebral bodies (L4 and L5) and were successively implanted with HA/ZrO₂ graded composite (group A), HA/ZrO₂ unilayer composite (group B), pure ZrO₂ (group C), and pure HA (group D). After operation, lumbar vertebral specimens were respectively harvested per time at week 6, 12, and 16. Then, the bony fusion interface was evaluated by fluorescence microscope and computer image analysis system to measure mineral apposition rates (MAR). Histological analysis of specimen was used to determine bone bonding rates (BBR) and possible foreign body reactions associated with each groups. And interface bonding force between implant and autogenous bone was quantified with biomechanical push-out test. Compared with other groups, group A led to significantly higher MAR from week 6 to 12 (p < 0.05). Histologically, new bony tissue and hyaline cartilage were seen around the HA/ZrO₂ graded composite, accompanied by mild chronic inflammation. And the BBR of HA/ZrO₂ graded composite were the highest (p < 0.05), while reaching (90.3 ± 3.8) % at week 16. Moreover, the biomechanical push-out tests revealed that the maximum interface shear strength of group A was respectively (2.64 ± 0.16) MPa, (2.95 ± 0.19) MPa, and (3.45 ± 0.23) MPa at week 6, 12, and 16, which all possessed significantly statistical differences with other three groups (p < 0.05).     

Nanoparticle supported bis (cyclopentadienyl) zirconium dichloride catalysts for styrene polymerization

Heterogeneous nanoparticle NA-MgO-MAO/NA-TiO₂ (anatase)-MAO supported bis (cyclopentadienyl) zirconium dichloride (Cp₂ZrCl₂) are synthesized and used for the polymerization of styrene monomer. The supporting process is confirmed via X-ray photoelectron spectroscopy (XPS) and FTIR. Characterization of the obtained polymer is done by gel permeation chromatography (GPC), ¹³C NMR spectroscopy and differential scanning calorimetry (DSC).     

Heterometallic (ZrIII)2—Al hydrides [(Cp2Zr)2(μ-H)](μ-H)2AlX2 (X = Cl or Br): preparative synthesis and reactivity. Molecular structure of [(Cp2Zr)2(μ-Cl)](μ-H)2AlCl2

A procedure was developed for the synthesis of trinuclear cyclic (Zr^III)₂—Al hydrides [(Cp₂Zr)₂(μ-H)](μ-H)₂AlX₂ (X = Cl (1a) or Br (1b)). These complexes were prepared in 60–65% yields by the reaction of Cp₂ZrX₂ with LiAlH₄ in the presence of CoBr₂ and tolane. The structures of complexes 1a and 1b and iodide 1c (X = I) were studied by NMR spectroscopy in solvents of different basicities (toluene, THF, and pyridine). Complex 1a is unsolvated and monomeric in all solvents; complex 1b, in toluene and THF; complex 1c, in toluene only. At room temperature, complex 1a does not catalyze hydrogenation of hex-1-ene and does not react with tolane, but reacts with the latter at high temperature to give bis(η⁵-cyclopentadienyl)-2,3,4,5-tetraphenylzirconacyclopentadiene. The reaction of equivalent amounts of complex 1a and HCl produces the [(Cp₂Zr)₂(μ-Cl)](μ-H)₂AlCl₂ complex. The structure of the latter was established by X-ray diffraction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2418–2423, November, 2005.     

Interactions of hafnocene and zirconocene dihydrides with acetylenes. Synthesis of the first acetylene complex of hafnium

The first acetylene complex of hafnium, Cp₂Hf[Me₃SiC=CHf(H)Cp₂], was synthesized by the reaction of hafnocene dihydride Cp₂HfH₂ with bis(trimethylsilyl)acetylene in benzene. The reaction is accompanied by elimination of the Me₃Si group from the molecule of the initial acetylene, as a result of which the acetylenide derivative of hafnium Cp₂Hf(C=CSiMe₃)(H) acts as an acetylene ligand in the complex. Under analogous conditions, the reaction of zirconocene dihydride Cp₂ZrH₂ with bis(trimethylsilyl)acetylene affords an analogous acetylene complex of zirconium Cp₂Zr(M₃SiC=CZr(H)Cp₂]. Reactions of Cp₂HfH₂ with tolane and 3-hexyne proceed differently than the reaction with bis(trimethylsilyl)acetylene. Here the corresponding hafnacyclopentadiene metallacycles are the final products. For preliminary communication, see Ref. 3. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 853–856, April, 1997.     

Carbon?hydrogen versus carbon?heteroatom activation by a high‐valent zirconium‐imido complex

A density functional theory (DFT) study of carbon? hydrogen versus carbon? heteroatom bond activation is presented. Heteroatom groups (X) investigated include X = F, Cl, OH, SH, NH₂, PH₂. The activating model complex is a prototypical d⁰ zirconium‐imide. While C? X activation has a thermodynamic advantage over C? H activation, the former has been found to have a kinetic advantage. Implications for catalytic hydrocarbon functionalization and phosphine–ligand degradation are discussed. The present results for a high‐valent metal complex are compared/contrasted with low‐valent bond activating complexes. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Crystal structure, phase transition and anisotropic thermal expansion of barium zirconium diorthophosphate, BaZr(PO4)2

The crystal structure of BaZr(PO₄)₂ at 298 K was determined from conventional X-ray powder diffraction data using direct methods, and it was further refined by the Rietveld method. The structure was monoclinic (space group C2/m, Z=2) with , , , β=93.086(1)° and . Final reliability indices were R_wp=8.21%, R_p=5.64% and R_B=2.92%. The atom arrangement is similar to that of yavapaiite (KFe(SO₄)₂), however, these crystal structures differ distinctly in the coordination numbers of barium and potassium atoms; the former is tenfold coordinated, whereas the latter is sixfold coordinated. The powder specimens were also examined by high-temperature XRD and DTA to reveal the occurrence of a phase transition from monoclinic to orthorhombic at 732 K during heating. Upon cooling the reverse transition occurred at 710 K. The monoclinic crystal expanded almost one-dimensionally along [503] during the heating process. The orthorhombic phase also showed a tendency to expand one-dimensionally along the c-axis above 732 K.     

Aktivierungsanalytische Untersuchung von Zirkoniumlegierungen

Durch Aktivierungsanalyse mit Reaktorneutronen (zerstörungsfrei und mit chemischer Aufarbeitung) sowie mittels zerstörungsfreier Untersuchungen an einem Neutronengenerator wurden O, Al, Si, P, Mn, Cu, Nb, Mo, Cd, Ti, Cr und Hf in Zirkoniumlegierungen bestimmt.