Biomimetic Processing of Gel Glasses and Organic-Inorganic Hybrids

Biological hard tissues like bone and shell show combinations of strength and toughness that are hard to duplicate with synthetic materials. These properties are attained by a composite of organic and inorganic phases with very organized microstructures. The structures are hierarchical in that several different scales of organization contribute to the final properties.Biological systems form by chemical precipitation at room temperature in contrast to synthetic processing, which usually depends on thermal solidification. In principle, chemical solidification can give much more control over composition and structure but is limited by the time taken for diffusion processes in any solid component.A family of solid freeform fabrication methods have recently been developed which allow parts to be built under the direct control of a 3-dimensional CAD drawing without the need for a mold. These methods also offer a way of building composite structures, with full control of structure and composition at the scale of 100 m and up. Since this is a layerwise process, like biological growth, diffusion paths are short and so chemical processing of large parts is feasible.We have been developing an SFF system based on extrusion of a reactive slurry through a 300 m needle. The needle is moved on three axes so as to build up a part. The application of this method to the formation of components from sol-gel glasses and organic-inorganic hybrids is described.     

Crystal structure of β-CaNi5D0.77 by rietveld analysis of neutron powder-diffraction data

β-CaNi₅D_0.77 is orthorhombic (a = 8.6033(13) b = 5.0810(9) c = 7.8557(15)Å, Pmcm, Z = 4, D_x = 6.48 g cm^?3, V = 343.4ų, FW = 1339.8 amu. Rietveld analysis of a neutron powder-diffraction pattern shows that D atoms occupy the centers of [Ni₄Ca₂] square dipyramids (“octahedra”) linked through the Ca atoms at opposite apices and forming chains. About 80% of the deuterium atoms occupy fairly regular sites (DNi = 1.53, 1.80, 1.86, 1.86 Å; DCa = 2.42, 2.45 Å). The remaining 20% occupy very distorted sites (DNi = 1.21, 1.38, 2.07, 2.07 Å; DCa = 2.54, 2.60 Å). The average DD distance in a chain is 4.3 Å.     

One-dimensional nonlinear Laplacians under a 3-point boundary condition

We consider a three-point boundary value problem for operators such as the one-dimensional p-Laplacian, and show when they have solutions or not, and how many. The inverse operators are given by various formulas involving zeros of a real-valued function. They are shown to be orderpreserving, for some parameter values, and non-singleton valued for others. The operators are shown to be m-dissipative in the space of continuous functions.     

Surface energies of chain molecules from homogeneous nucleation

A model for the interpretation of homogeneous nucleation data for chain molecules is presented. The two surface energies σ_s and σ_e are related to interchain and intrachain bonding. Surface energies calculated from experimental data on n-alkanes from octane to dotriacontane and polyethylene agree with estimated values. The results are discussed in relation to surface energies measured from spherulite growth rates in polymers but these values are not known with sufficient reliability to provide a good basis for comparison.     

Determination of lincomycin and tylosin residues in honey using solid-phase extraction and liquid chromatography-atmospheric pressure chemical ionization mass spectrometry

An analytical method for the determination of residues of the antibiotic drugs lincomycin and tylosin in honey was developed. The procedure employed a solid-phase extraction for the isolation of lincomycin and tylosin from diluted honey samples. The antibiotic residues were subsequently analyzed by reversed-phase HPLC with atmospheric pressure chemical ionization mass spectrometric detection. Average analyte recoveries for lincomycin and tylosin ranged from 84 to 107% in replicate sets of honey samples fortified with drug concentrations of 0.01, 0.5, and 10 microg/g. The method detection limits were determined to be 0.007 and 0.01 microg/g for lincomycin and tylosin, respectively.     

A study of oxygen self-diffusion in the C-direction of rutile using a nuclear technique

Oxygen-18 has been used as a tracer to study diffusion in the c-direction of rutile single crystals in the temperature range 1173–1473K. The distribution of the tracer was determined by means of a nuclear technique. The diffusion coefficient can be represented in this temperature range by the equation $\text{D = 2.4 × 10}{}^{\mathrm{?6}}\text{exp}\text{?}\text{(2.826 ± 0.05) × 10}{}^5\text{RT}\text{m}{}^2\text{s}{}^{\mathrm{?1}}$. A diffusion coefficient obtained at 1673 K using a different technique agrees well with the value obtained by extrapolation from the other results. Consideration of the results from specimens with different impurity concentrations leads to the conclusion that the diffusion which has been studied is extrinsic.The results obtained in this investigation are in good agreement with those of Haul and Dümbgen[l] and (by extrapolation) Gruenwald and Gordon [2] but not with those of Doskocil and Pospisil[3] and Bagshaw and Hyde[4].     

On the Compactness of the Nonlinear Evolution Operator in a Banach Space

Let X be a real Banach space and let A(t): X 2^x be dissipativefor all t(0, T). Assume that {A(t)} generates an evolution operatorU(t, s) of type (D, , f). Necessary and sufficient conditionsare given for the compactness of U(t, s) for 0 s < t <T.     

Effects of charge location on the absorptions and lifetimes of protonated tyrosine peptides in vacuo

Nearby charges affect the electronic energy levels of chromophores, with the extent of the effect being determined by the magnitude of the charge and degree of charge-chromophore separation. The molecular configuration dictates the charge-chromophore distance. Hence, in this study, we aim to assess how the location of the charge influences the absorption of a set of model protonated and diprotonated peptide ions, and whether spectral differences are large enough to be identified. The studied ions were the dipeptide YK, the tripeptide KYK (Y = tyrosine; K = lysine) and their complexes with 18-crown-6-ether (CE). The CE targets the ammonium group by forming internal ionic hydrogen bonds and limits the folding of the peptide. In the tripeptide, the distance between the chromophore and the backbone ammonium is enlarged relative to that in the dipeptide. Experiments were performed in an electrostatic ion storage ring using a tunable laser system, and action spectra based on lifetime measurements were obtained in the range from 210 to 310 nm. The spectra are all quite similar though there seems to be some changes in the absorption band between 210 and 250 nm, while in the lower energy band all ions had a maximum absorption at ~275 nm. Lifetimes after photoexcitation were found to shorten upon protonation and lengthen upon CE complexation, in accordance with the increased number of degrees of freedom and an increase in activation energies for dissociation as the mobile proton model is no longer operative.