The TEM characterization of the lamellar structure of osteoporotic human trabecular bone

The lamellar structure of osteoporotic human trabecular bone was characterized experimentally by means of transmission electron microscopy (TEM). More specifically, the TEM was used to determine if trabecular bone exhibits similar lamellar structural motifs as cortical bone by analyzing unmineralized, mineralized and demineralized bone, and to study the influence of the osteocyte network on the lamellar structure of osteoporotic trabecular bone. Comparison with normal trabecular bone is included. This paper summarizes partial results of a larger study, which addressed the characterization of the hierarchical structure of normal versus osteoporotic human trabecular bone [Rubin, M.A., 2001. Multiscale characterization of the ultrastructure of trabecular bone in osteoporotic and normal humans and in two inbred strains of mice. MS Thesis, Georgia Institute of Technology.] at several structural scales.     

LiI-doped N,N-dimethyl-pyrrolidinium iodide, an archetypal rotator-phase ionic conductor

N,N-Dimethyl-pyrrolidinium iodide, and the effect of doping with LiI, has been investigated using DSC, NMR, and impedance spectroscopy. It was found that the addition of a small amount of LiI enhances the ionic conductivity by up to 3 orders of magnitude for this ionic solid. Furthermore, a slight decrease in phase transition onset temperatures, as well as the appearance of a superimposed narrow line in the (1)H NMR spectra with dopant, suggest that the LiI facilitates the mobility of the matrix material, possibly by the introduction of vacancies within the lattice. (7)Li NMR line width measurements reveal a narrow Li line width, decreasing in width and increasing in intensity with temperature, indicating mobile Li ions.     

Observed effects of a changing step-edge density on thin-film growth dynamics

We grew SrTiO(3) on SrTiO(3)(001) by pulsed laser deposition, while observing x-ray diffraction at the (00(1/2)) position. The drop DeltaI in the x-ray intensity following a laser pulse contains information about plume-surface interactions. Kinematic theory predicts DeltaI/I = -4sigma(1 - sigma), so that DeltaI /I depends only on the amount of deposited material sigma. In contrast, we observed experimentally that |DeltaI /I| < 4sigma(1 - sigma) and that DeltaI /I depends on the phase of x-ray growth oscillations. The combined results suggest a fast smoothing mechanism that depends on surface step-edge density.     

Direct observation of azimuthal correlations between DNA in hydrated aggregates

This study revisits the classical x-ray diffraction patterns from hydrated, noncrystalline fibers originally used to establish the helical structure of DNA. We argue that changes in these diffraction patterns with DNA packing density reveal strong azimuthally dependent interactions between adjacent molecules up to approximately 40 A interaxial or approximately 20 A surface-to-surface separations. These interactions appear to force significant torsional "straightening" of DNA and strong azimuthal alignment of nearest neighbor molecules. The results are in good agreement with the predictions of recent theoretical models relating DNA-DNA interactions to the helical symmetry of their surface charge patterns.     

Analysis of HRTEM images for carbon nanostructure quantification

Image processing algorithms have been developed to extract fringe length, tortuosity and separation from high resolution transmission electron microscopy images. To validate the separation algorithm, a comparison is made between the image-based fringe separation and that obtained by analysis of X-ray diffraction data for a progressively heat-treated carbon black. Agreement is favorable. To illustrate the utility of the analysis parameters for a range of carbon nanostructures, analysis is applied to a series of pyrolytically prepared carbon soots – qualitatively described as containing amorphous, graphitic or fullerenic nanostructure. For all processing, the intermediate image, in the form of a skeletonized binary image of the original high resolution transmission electron micrograph, is shown and found to accurately reflect the nanostructural organization within the carbon as visually observed. Statistical results for each analysis parameter, extracted from the binary images, are presented in the form of histograms and quantitatively distinguish the different carbon nanostructures.     

Alpha,beta-unsaturated imines from titanium hydroamination and functionalization by rhodium C-H activation

Titanium pyrrolyl complexes are effective catalysts for the synthesis of alpha,beta-unsaturated imines, which can be further functionalized using Rh-catalyzed alkene or alkyne insertion into the beta-C-H bond.     

Halide-induced supramolecular ligand rearrangement

A novel reaction involving the halide-induced rearrangement of ligands within supramolecular Rh(I) complexes containing hemilabile ligands is presented. Three analogous bis- and trishemilabile ligands have been synthesized to construct bi- and trimetallic Rh(I) macrocyclic complexes. An intentionally added halide source results in the formal rotation of only one hemilabile ligand along the axis that is perpendicular to the plane defined by the aryl backbone of the hemilabile ligands. X-ray structures, as determined by X-ray crystallography, of key intermediates and products are presented.     

Highly selective reduction of acyclic beta-alkoxy ketones to protected syn-1,3-diols

[reaction: see text] The conversion of 1-(2-methoxyethoxy)ethyl-protected beta-hydroxy ketones to syn-1,3-ethylidene acetals is effected by Et(3)SiH and SnCl(4). This reaction is proposed to proceed via a cyclic oxocarbenium ion intermediate and provides the products in yields that range from 69 to 94% and with diastereoselectivities that are >200:1.     

Cooperative metal-coordination and ion pairing in tripeptide recognition

[structure: see text] The recognition of tripeptides by a metal-centered receptor consisting of a rigid backbone region and variable tripeptide arms is described. The studies showed that the receptor was selective for l-Xxx-l-Lys-l-Lys, with Xxx = His, Cys, and Met, giving association constants near 1.0 x 10(6) M(-)(1). Binding enhancement through cooperative interactions of the peptidic arms is demonstrated.