Structure resolution of Ba5Al3F19 and investigation of fluorine ion dynamics by synchrotron powder diffraction, variable-temperature solid-state NMR, and quantum computations

The room temperature structure of Ba(5)Al(3)F(19) has been solved using electron microscopy and synchrotron powder diffraction data. One-dimensional (1D) (27)Al and ultrafast magic-angle-spinning (MAS) (19)F NMR spectra have been recorded and are in agreement with the proposed structural model for Ba(5)Al(3)F(19). The (19)F isotropic chemical shift and (27)Al quadrupolar parameters have been calculated using the CASTEP code from the experimental and density functional theory geometry-optimized structures. After optimization, the calculated NMR parameters of both the (19)F and (27)Al nuclei show improved consistency with the experimental values, demonstrating that the geometry optimization step is necessary to obtain more accurate and reliable structural data. This also enables a complete and unambiguous assignment of the (19)F MAS NMR spectrum of Ba(5)Al(3)F(19). Variable-temperature 1D MAS (19)F NMR experiments have been carried out, showing the occurrence of fluorine ion mobility. Complementary insights were obtained from both two-dimensional (2D) exchange and 2D double-quantum dipolar recoupling NMR experiments, and a detailed analysis of the anionic motion in Ba(5)Al(3)F(19) is proposed, including the distinction between reorientational processes and chemical exchange involving bond breaking and re-formation.     

Application of thermal analysis in preservation and restoration of historic masonry materials

Thermal analysis techniques have been used in characterizing building materials from significant historic properties in the Charleston, South Carolina area. Determining the chemical and physical effects of deterioration resulting from long periods of exposure is a first step in formulating preservation strategies. In this regard, simultaneous thermal analysis coupled with evolved gas analysis has been used to study reactions between air, seawater, and masonry materials. Further, the traditional petrographic identification of mortar composition is greatly facilitated through use of thermal analysis. Simultaneous thermal analysis allows for an exact determination of the calcium carbonate content in mortars as an alternative to the use of an inferred value based on chemical analysis data. The partial dissolution of calcium carbonate in the presence of sea salt is a major deterioration process. Further, natural cements manufactured in the United States are identified, in part, based on their thermogravimetric (TG) traces and their evolved gases. The data indicates that natural cements form some carbonate phases in addition to the major hydrate phases. Clay bricks are found to exhibit interaction with sea water, with uptake of bicarbonate suggested. Additionally, there is evidence of re-hydroxylation in the 160 year old bricks. The bricks made in coastal zones contain a considerable free silica fraction that is composed of a small percentage of cristobalite. The silica content of the clay bricks is seen to result in very high thermal expansion coefficients in the area of 10 × 10⁻⁶ to 12 × 10⁻⁶ K⁻¹. These studies provide guidance in restoration efforts where authenticity of cements is important. In the event that replacement bricks are required, matching the thermal expansion coefficient of the original bricks is a requirement for preservation of the masonry structure.     

Puroindoline-a, a lipid binding protein from common wheat, spontaneously forms prolate protein micelles in solution

The self-assembly in solution of puroindoline-a (Pin-a), an amphiphilic lipid binding protein from common wheat, was investigated by small angle neutron scattering, dynamic light scattering and size exclusion chromatography. Pin-a was found to form monodisperse prolate ellipsoidal micelles with a major axial radius of 112 ± 4.5 ? and minor axial radius of 40.4 ± 0.18 ?. These protein micelles were formed by the spontaneous self-assembly of 38 Pin-a molecules in solution and were stable over a wide pH range (3.5-11) and at elevated temperatures (20-65 °C). Pin-a micelles could be disrupted upon addition of the non-ionic surfactant dodecyl-β-maltoside, suggesting that the protein self-assembly is driven by hydrophobic forces, consisting of intermolecular interactions between Trp residues located within a well-defined Trp-rich domain of Pin-a.     

Fluorescence lifetime imaging of oxygen in living cells

The usefulness of the fluorescent probe ruthenium tris(2,2′-dipyridyl) dichloride hydrate (RTDP) for the quantitative imaging of oxygen in single cells was investigated utilizing fluorescence lifetime imaging. The results indicate that the fluorescence behavior of RTDP in the presence of oxygen can be described by the Stem-Volmer equation. This shows that fluorescence quenching by oxygen is a dynamic quenching process. In addition, it was demonstrated that the fluorescence lifetime of RTDP is insensitive to pH, ion concentration, and cellular contents. This implies that a simple calibration procedure in buffers can be used to quantify oxygen concentrations within cells. First fluorescence imaging experiments on J774 macrophages show a nonuniform fluorescence intensity and a uniform fluorescence lifetime image. This indicates that the RTDP is heterogeneously partitioned throughout the cells, while the oxygen concentration is constant.     

Generation of ultraviolet broadband light in a single-mode fiber

Ultraviolet broadband light spanning 337–405 nm was produced in a single-mode optical fiber primarily by stimulated Raman scattering. Pulses of 4 ns duration at 337 nm were coupled into a 50 m long ultraviolet-grade fiber featuring single-mode operation in the 320–450 nm range. Significant spectral broadening was achieved with pulses of only ∼10 W peak power. Our experiments demonstrate the potential for a source with ∼10⁴ times the spectral radiance of a quartz tungsten halogen lamp, which is currently used for many applications in this wavelength range. PACS 42.65.Ky; 42.81.Wg     

Circuit preserving edge maps

It is proved that any one-to-one edge map f from a 3-connected graph G onto a graph G′, G and G′ possibly infinite, satisfying f(C) is a circuit in G′ whenever C is a circuit in G is induced by a vertex isomorphism. This generalizes a result of Whitney which hypothesizes f(C) is a circuit in G′ if and only if C is a circuit in G.