Quantifying the hydroxyapatite orientation near the ossification front in a piglet femoral condyle using X-ray diffraction tensor tomography

While a detailed knowledge of the hierarchical structure and morphology of the extracellular matrix is considered crucial for understanding the physiological and mechanical properties of bone and cartilage, the orientation of collagen fibres and carbonated hydroxyapatite (HA) crystallites remains a debated topic. Conventional microscopy techniques for orientational imaging require destructive sample sectioning, which both precludes further studies of the intact sample and potentially changes the microstructure. In this work, we use X-ray diffraction tensor tomography to image non-destructively in 3D the HA orientation in a medial femoral condyle of a piglet. By exploiting the anisotropic HA diffraction signal, 3D maps showing systematic local variations of the HA crystallite orientation in the growing subchondral bone and in the adjacent mineralized growth cartilage are obtained. Orientation maps of HA crystallites over a large field of view (~ 3 7 3 7 3 mm3) close to the ossification (bone-growth) front are compared with high-resolution X-ray propagation phase-contrast computed tomography images. The HA crystallites are found to predominantly orient with their crystallite c-axis directed towards the ossification front. Distinct patterns of HA preferred orientation are found in the vicinity of cartilage canals protruding from the subchondral bone. The demonstrated ability of retrieving 3D orientation maps of bone-cartilage structures is expected to give a better understanding of the physiological properties of bones, including their propensity for bone-cartilage diseases

Degradation of the chemotherapy drug 5-fouorouracil on medical-grade silver surfaces

The degradation of the chemotherapy drug 5-fluorouracil by a non-pristine metal surfaces is studied. Using density functional theory, X-ray photoelectron spectroscopy and X-ray absorption spectroscopy we show that the drug is entirely degraded by medical-grade silver surfaces, already at body temperature, and that all of the fluorine has left the molecule, presumably as HF. Remarkably, this degradation is even more severe than that reported previously for 5-fluorouracil on a pristine monocrystalline silver surface (in which case 80% of the drug reacted at body temperature) [1]. We conclude that the observed reaction is due to a reaction pathway, driven by H to F attraction between molecules on the surface, which results in the direct formation of HF; a pathway which is favoured when competing pathways involving reactive Ag surface sites are made unavailable by environmental contamination. Our measurements indicate that realistically cleaned, non-pristine silver alloys, which are typically used in medical applications, can result in severe degradation of 5-fluorouracil, with the release of HF – a finding which may have important implications for the handling of chemotherapy drugs

Graphene coatings for chemotherapy: avoiding silver-mediated degradation

Chemotherapy treatment usually involves the delivery of fluorouracil (5-Fu) together with other drugs through central venous catheters. Catheters and their connectors are increasingly treated with silver or argentic alloys/compounds. Complications arising from broken catheters are common, leading to additional suffering for patients and increased medical costs. Here, we uncover a likely cause of such failure through a study of the surface chemistry relevant to chemotherapy drug delivery, i.e. between 5-Fu and silver. We show that silver catalytically decomposes 5-Fu, compromising the efficacy of the chemotherapy treatment. Furthermore, HF is released as a product, which will be damaging to both patient and catheter. We demonstrate that graphene surfaces inhibit this undesirable reaction and would offer superior performance as nanoscale coatings in cancer treatment applications

Micro X-ray diffraction mapping of a fluorene copolymer fibre

Using raster-scanning wide-angle X-ray scattering, we investigate oriented fibres of the low bandgap conjugated polymer, poly[2,7-(9,9-dioctylfluorene)-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (F8TBT), that was developed in particular for polymer solar cells. For the first time, structural data are provided for F8TBT. Our results demonstrate that the nano-scale structure of this polymer is closely related to the externally observable features of the fibre, and thus emphasise the importance of having full control over the local molecular conformation. Liquid-crystalline phases are observed at elevated temperatures, and the molecular alignment in the drawn fibres yields scattering patterns that are dominated by broad peaks of equatorial diffuse scattering. The significant degree of preferred orientation facilitates the analysis, leading to estimates of (average) nearest-neighbour packing distances and coherence length of this macromolecule. In particular, we observe a pronounced broad signal assigned to packing of the conjugated backbone with an approximate spacing of 4.00–4.39 Å that is coherent over 5-6 polymer segments

Columnar Self-Assembly and Alignment of Planar Carbenium Ions in Langmuir-Blodgett Films

Structural and optical properties of multilayer Langmuir-Blodgett (LB) films of two amphiphilic carbenium salts 2-didecylamino-6,10-bis(dimethylamino)-4,8,12-trioxatriangulenium hexafluorophosphate (ATOTA-1) and 2,6-bis-(decylmethylamino)-10-dimethylamino-4,8,12-trioxatriangulenium hexafluorophosphate (ATOTA-2) are described. The LB films were prepared on lipophilic glass by standard vertical dipping. Grazing incidence X-ray diffraction (GIXD) measurements show that the planar organic cores, in spite of their positive charge, form closely packed columns with a repeating distance of similar to 3.45 angstrom. Specular X-ray reflectivity (SXR) reveals the LB multilayers to consist of Y-type bilayers with thickness 31 angstrom for ATOTA-1 and 41 angstrom for ATOTA-2. This significant difference is ascribed to the different packing motifs of the alkyl chains in the two LB films. GIXD and polarized UV-vis absorption and emission spectroscopy show that the columnar aggregates in the LB films are oriented along the dipping direction. This alignment is attributed to shear effects during LB transfer. The main absorption band of the LB films is blue-shifted compared to that in solution, while the fluorescence is red-shifted by more than 100 nm. These findings suggest the presence of H-aggregates in agreement with the cofacial packing derived from the X-ray measurements. Polarized absorption spectroscopy with variable angle of incidence was used to resolve two perpendicular optical transitions in the visible range, one at 460 nm polarized perpendicular to the columnar direction, in the plane of the film, and one at 420 nm polarized along the film normal

Static and time-resolved 3D imaging of porous media

info:eu-repo/semantics/publishe