The use of advanced diffraction methods in the study of the structure of a bioactive calcia: silica sol-gel glass.

Sol-gel derived calcium silicate glasses may be useful for the regeneration of damaged bone. The mechanism of bioactivity is as yet only partially understood but has been strongly linked to calcium dissolution from the glass matrix. In addition to the usual laboratory-based characterisation methods, we have used neutron diffraction with isotopic substitution to gain new insights into the nature of the atomic-scale calcium environment in bioactive sol-gel glasses, and have also used high energy X-ray total diffraction to probe the nature of the processes initiated when bioactive glass is immersed in vitro in simulated body fluid. The data obtained point to a complex calcium environment in which calcium is loosely bound within the glass network and may therefore be regarded as facile. Complex multi-stage dissolution and mineral growth phases were observed as a function of reaction time between 1 min and 30 days, leading eventually, via octacalcium phosphate, to the formation of a disordered hydroxyapatite (HA) layer on the glass surface. This methodology provides insight into the structure of key sites in these materials and key stages involved in their reactions, and thereby more generally into the behaviour of bone-regenerative materials that may facilitate improvements in tissue engineering applications.

Electronic interaction in an outer-sphere mixed-valence double salt: a polarized neutron diffraction study of K(3)(MnO(4))(2).

The mixed-valence double salt K(3)(MnO(4))(2) crystallizes in space group P2(1)/m with Z = 2. The manganese centers Mn1 and Mn2 constitute discrete "permanganate", [Mn(VII)O(4)](-), and "manganate", [Mn(VI)O(4)](2-), ions, respectively. There is a spin-ordering transition to an antiferromagnetic state at ca. T = 5 K. The spin-density distribution in the paramagnetic phase at T = 10 K has been determined by polarized neutron diffraction, confirming that unpaired spin is largely confined to the nominal manganate ion Mn2. Through use of both Fourier refinement and maximum entropy methods, the spin on Mn1 is estimated as 1.75 +/- 1% of one unpaired electron with an upper limit of 2.5%.

Structural studies of bioactivity in sol-gel-derived glasses by X-ray spectroscopy.

Extended X-ray absorption fine structure spectroscopy and X-ray absorption near edge structure, X-ray fluorescence spectroscopy, and X-ray powder diffraction have been used to study the local calcium environment in four sol-gel-derived bioactive calcium silicate glasses of the general formula (CaO)(x)(SiO(2))(1-x). The formation of a hydroxyapatite layer on the composition with the highest bioactivity (x = 0.3) with time has been studied, in an in vitro environment, by immersion in simulated body fluid (SBF) at 37 degrees C. The calcium oxygen environment in the four compositions has been shown to be six-coordinate in character. Both the extended X-ray absorption fine structure spectroscopy and X-ray absorption near edge structure show a gradual increase in coordination number and Ca--O bond distance with longer exposure to SBF. X-ray fluorescence show that calcium is quickly lost from the samples on exposure to SBF and the calcium concentration then recovers with time. There is clear evidence that the recovery of calcium content is due to the formation of a CaO-P(2)O(5)-rich layer. Annealing of samples at 650 degrees C shows the presence of what, on the length scales probed by X-ray diffraction, appears to be noncrystalline calcium phosphate after 1 h of exposure to an SBF solution, which becomes more crystalline on longer exposure.

Structural study of the thermal and photochemical spin states in the spin crossover complex [Fe(phen)2(NCSe)2].

The first structural data for [Fe(phen)(2)(NCSe)(2)] (obtained using the extraction method of sample preparation) in its high-spin, low-spin and LIESST induced metastable high-spin states have been recorded using synchrotron radiation single crystal diffraction. The space group for all of the spin states was found to be Pbcn. On cooling from the high-spin state (HS-1) at 292 K through the spin crossover at about 235 K to the low-spin state at 100 K (LS-1) the iron coordination environment changed to a more regular octahedral geometry and the Fe-N bond lengths decreased by 0.216 and 0.196 A (Fe-N(phen)) and 0.147 A (Fe-N(CSe)). When the low-spin state was illuminated with visible light at about 26 K, the structure of this LIESST induced metastable high-spin state (HS-2) was very similar to that of HS-1 with regards to the Fe-phen bond lengths, but there were some differences in the bond lengths in the Fe-NCSe unit between HS-1 and HS-2. When HS-2 was warmed in the dark to 50 K, the resultant low-spin state (LS-2) had an essentially identical structure to LS-1. In all spin states, all of the shortest intermolecular contacts (in terms of van der Waals radii) involved the NCSe ligand, which may be important in describing the cooperativity in the solid state. The quality of the samples was confirmed by magnetic susceptibility and IR measurements.

Hypoxia-targeting copper bis(selenosemicarbazone) complexes: comparison with their sulfur analogues.

The first copper bis(selenosemicarbazone) complexes have been synthesized, using the ligands glyoxal bis(selenosemicarbazone), pyruvaldehyde bis(selenosemicarbazone), and 2,3-butanedione bis(selenosemicarbazone). Their spectroscopic properties indicate that they are structurally analogous to their well-known square-planar sulfur-containing counterparts, the copper bis(thiosemicarbazone) complexes. Spectroscopic comparison of the sulfur- and selenium-containing complexes provides insight into their electronic structure. The effects on spectroscopic and redox properties of replacing sulfur with selenium, and of successive addition of methyl groups to the ligand backbone, are rationalized in terms of their electronic structure using spin-unrestricted density functional calculations. These suggest that, like the sulfur analogues, the complexes have a very low-lying empty ligand-based pi-orbital immediately above the LUMO, while the LUMO itself has d(x2)-(y2) character (i.e., is the spin partner of the HOMO). Replacement of S by Se shifts the oxidation potentials much more than the reduction potentials, whereas alkylation of the ligand backbone shifts the reduction potentials more than the oxidation potentials. This suggests that oxidation and reduction involve spatially different orbitals, with the additional electron in the reduced species occupying the ligand-based pi-orbital rather than d(x2)-(y2). Density functional calculations on the putative singlet Cu(I)-reduced species suggest that this ligand pi-character could be brought about by distortion away from planarity during reduction, allowing the low-lying ligand pi-LUMO to mix into the d(x2)-(y2)-based HOMO. The analogy in the structure and reduction behavior between the sulfur- and selenium-containing complexes suggests that labeled with positron emitting isotopes of copper (Cu-60, Cu-62, Cu-64), the complexes warrant biological evaluation as radiopharmaceuticals for imaging of tissue perfusion and hypoxia.