Thermochemistry of bis-arene- and arenetricarbonyl-chromium compounds containing hexamethylbenzene, 1,3,5-trimethylbenzene and naphthalene.

Microcalorimetric measurements at elevated temperatures of the heats of thermal decomposition and iodination have led to values of the standard enthalpies of formation of the following crystalline compounds (values given in kJ mol^?1) at 298K: [Cr(η⁶-1,3,5-C₆H₃(CH₃)₃)₂] = (63±12); [Cr(η⁶-C₆(CH₃)₆)₂] : -(88±12); [Cr(1,2,3,4,4a,8a-η-C₁₀H₈)₂] = (407±11); [Cr(CO)₃(1,2,3,4,4a,8a-η-C₁₀H₈)] = -(258±8). Separate measurements by the vacuum sublimation microcalorimetric technique gave the following values for the enthalpy of sublimation at 298K (kJ mol^?1) : [Cr(η⁶-1,3,5-C₆H₃(CH₃)₃)₂] = (104±1); [Cr(η⁶-C₆(CH₃)₆)₂] = (119±4); [Cr(CO)₃(1,2,3,4,4a,8a-η-C₁₀H₈)] = (107±3). From these and other data, the bond enthalpy contributions of the metal-ligand bonds in the gaseous metal complexes were evaluated as follows: [(η₆-C₆(CH₃)₆)-Cr] (155±7); [(η⁶-C₆H₃(CH₃)₃)-Cr] (151±6); [(1,2,3,4,4a, 8a-η-C₁₀H₈)-Cr](145±6) kJ mol^?1]The question of the transferability of the enthalpy contributions of chromium—ligand bonds between organochronium complexes is discussed with aid of information from structural and spectroscopic investigation. The limitations of the procedure are defined.The thermodynamic data are used to discuss various substitution, redistribution and exchange reaction of Cr(η-arene)₂ and [Cr(CO)₃(η-arene)] compounds.     

Preparation and properties of dinitrogen complexes of molybdenum and tungsten with trimethylphosphine as coligand : III. Synthesis and properties of cis-[W(N2)2(PMe3)4], trans-[W(C2H4)2(PMe3)4] and [M(N2)(PMe3)5] (M = Mo,W). The crystal and molecular structure of [Mo(N2)(PMe3)5]

The reduction of [WCl₄(PMe₃)₃] with dispersed sodium, under dinitrogen, gives cis-[W(N₂)₂(PMe₃)₄], while under ethylene trans-[W(C₂H₄)₂(PMe₃)₄] is obtained. The ethylene complex can also be prepared by displacement of the dinitrogen molecules in cis-[W(N₂)₂(PMe₃)₄] by ethylene at room temperature and pressure. Interaction of cis-[M(N₂)₂(PMe₃)₄] complexes (M = Mo, W), with PMe₃, under helium or argon, yields [M(N₂)(PMe₃)₅]. The molybdenum complex crystallizes in the orthorhombic space group Pnma, with a 22.063(6), b 12.106(4), c 9.745(4) Å. The Mo—P distance trans to the dinitrogen ligand (2.483(7) Å) is slightly longer than the average of the other four Mo—P bonds (2.460(5) Å).     

A Phosphine Functionalized β-Diketimine Ligand for the Synthesis of Manifold Metal Complexes

A bis(diphenyl)-phosphine functionalized β-diketimine (PNac-H) was synthesized as a flexible ligand for transition metal complexes. The newly designed ligand features symmetrically placed phosphine moieties around a β-diketimine unit, forming a PNNP-type pocket. Due to the hard and soft donor atoms (N vs. P) the ligand can stabilize various coordination polyhedra. A complete series ranging from coordination numbers 2 to 6 was realized. Linear, trigonal planar, square planar, tetrahedral, square pyramidal, and octahedral coordination arrangements containing the PNac-ligand around the metal center were observed by using suitable metal sources. Hereby, PNac-H or its anion PNac⁻ acts as mono-, bi- and tetradendate ligand. Such a broad flexibility is unusual for a rigid tetradentate system. The structural motifs were realized by treatment of PNac-H with a series of late transition metal precursors, for example, silver, gold, nickel, copper, platinum, and rhodium. The new complexes have been fully characterized by single crystal X-ray diffraction, NMR, IR, UV/Vis spectroscopy, mass spectrometry as well as elemental analysis. Additionally, selected complexes were investigated regarding their photophysical properties. Thus, PNac-H proved to be an ideal ligand platform for the selective coordination and stabilization of various metal ions in diverse polyhedra and oxidation states.     

Whey proteins eluted reversed phase gradients

The behavior of bovine whey proteins in Reversed-Phase High Performance Liquid Chromatography (RP-HPLC) systems has been investigated. The Linear Solvent Strength (LSS) model has been applied to the separation of these proteins studying how their retention time and band broadening change when different gradient parameters are modified. From our results it is deduced that the LSS model describes the behaviour of the whey proteins in RP-HPLC. Also, it seems that t_s (the retention time for non-retained solutes) depends on the size of these proteins. The good fit observed between experimental data and the equations deduced from the LSS model allows the prediction of a gradient shape that permits a rapid analysis of the above mentioned proteins.     

Fabrication of Bioactive Polyoxymethylene Nanocomposites for Bone Tissue Replacement

Summary: Stearic acid modified nano hydroxyapatite (n-SHA) filled polyoxymethylene (POM) nanocomposites were prepared by melt mixing method for bone tissue replacement and regeneration applications. Contact angle measurements of POM nanocomposites were carried out to understand the effect of n-SHA addition on the hydrophobicity of nanocomposites. The mechanical properties like tensile strength, Young's modulus and elongation at break were found to be increased significantly by the incorporation of n-SHA into the POM matrix. The bone-bonding ability of the nanocomposites was evaluated by examining the apatite formation on their surface after soaking in simulated body fluid (SBF) and apatite formation was studied by atomic force microscopy (AFM). The protein adhesion studies revealed the enhanced biocompatibility of the nanocomposites due to the presence of n-SHA nanofillers on the surface and it provides favorable binding sites for protein adsorption. The significant improvement in the biocompatibility as well as mechanical, thermal and hydrophobic properties of the POM nanocomposites makes it a potential future material for bone implantation.     

Spectra and dose with ANN of 252Cf, 241Am–Be, and 239Pu–Be

Artificial neural networks have been applied to unfold the neutron spectra and to calculate the effective dose, the ambient equivalent dose, and the personal dose equivalent for ²⁵²Cf, ²⁴¹Am–Be, and ²³⁹Pu–Be neutron sources. The count rates that these neutron sources produce in a Bonner Sphere Spectrometer with a ⁶LiI(Eu) were utilized as input in both artificial neural networks. Spectra and the ambient dose equivalent were also obtained with BUNKIUT code and the UTA4 response matrix. With both procedures spectra and ambient dose equivalent agrees in less than 10%. The Artificial neural network technology is an alternative procedure to unfold neutron spectra and to perform neutron dosimetry.