The synthesis, structure and CO-releasing properties of a number of new tricarbonyl rhenium(i) complexes with 5-substituted-6-amino-1,3-dimethyluracils are reported and their structural features discussed on the basis of both spectral and X-ray crystallographic analyses. The 5-substituent library includes -N[double bond, length as m-dash]CH-2py (DAAUPic) and -CH[double bond, length as m-dash]N-N[double bond, length as m-dash]CH-2py (FDUHzPic) as additional metal binding components and chloride, acetonitrile or pyridine acting as ancillary ligands. The compounds have been identified by elemental analysis, NMR, MS and IR spectroscopy. In addition, [ReCl(CO)(DAAUPic)], [Re(CO)(FDUHzPic)py]ClO, [Re(CO)(FDUHzPic)py]PF, [ReCl(CO)(FDUHzPic)] and [ReCl(CO)(FDUHzPicH)(HO)] structures have been solved by X-ray diffraction methods. These studies have clearly shown that the preferred coordination mode to rhenium takes place through the (N1F,N52)-pyridin-2-yl-methyleneamine moiety, the uracil coordinative availability (O4-N51 or N6-N51) being used only to bind the second metal center. The CO-releasing ability of these rhenium compounds has been investigated by the reaction with myoglobin; the corresponding studies have revealed that two of the mononuclear complexes and their related binuclear analogues are able to release CO to a moderate extent. This ability has also been theoretically assessed through a QTAIM analysis. The results, although non-conclusive, may explain somehow possible different preferences in CO releasing power after a comparison between the nature of Re-CO links in mononuclear and binuclear compounds.
A 58-year-old woman presented with a pilomatrix carcinoma on the right knee. The tumor developed at the site of a previous lesion that had been present since she was 30 years old. Histologic study showed the presence of basaloid cells with numerous atypical mitoses, shadow cells, and calcification. After several surgical excisions, the tumor mass infiltrated the subcutaneous tissue, muscle, and bone, resulting in inguinal lymph node and pulmonary metastasis. We also review the literature and comment on the histopathologic differences from other cutaneous tumors.
A combination of atomic absorption spectroscopy (AAS), Fourier transform infrared spectroscopy (FTIR), scanning electronic microscopy (SEM), and gas adsorption techniques was used to characterize the effect of 30 % hydrogen peroxide (HP) on enamel surface. To perform the analyses of AAS, 1 ml of 30 % HP was added to 30 mg of a bovine enamel powder sample (150-200 µm fractions) for times of 5, 20, 60, 90, and 120 min; then 5 ml of the solution was withdrawn after each time period to measure [Ca(2+)] ions. The remaining powder was recovered and analyzed by FTIR. For SEM and gas adsorption tests, 4 × 4 mm(2) enamel sectioned samples were polished and 30 % HP was applied on the surface for the same time periods. AAS data show that 30 % HP treatment mobilized calcium from the enamel at all times studied. FTIR spectra showed that the total amount of phosphate and carbonate mineral contents such as amide I decreased significantly. SEM revealed that randomly distributed areas throughout the smooth enamel surface treatment became rougher and more irregular. These alterations indicate that surface damage increases with increasing durations of HP treatment. Gas adsorption analysis proved that bleached enamel is a typically non-porous material with a small specific surface area which decreases slightly with the 30 % HP treatment. In sum, 30 % HP induced a significant alteration of the organic and mineral part of the enamel, leading to the release of calcium and a rougher, more irregular enamel surface on randomly distributed areas.
Pseudoxanthoma elasticum (PXE) is a genetic disease characterized by the calcification of elastin fibers. Our aim was to quantify vascular calcification in the arteries and the deposition of 18F-sodium-fluoride (18F-NaF) in the skin and vessel walls with positron emission tomography/computed tomography. This was an observational study including 18 patients with PXE. Vascular calcification was measured in Agatston units, and deposition in the skin and vessel walls was shown using target-to-background ratio (TBR). Severity of the disease was scored by Phenodex. We found higher vascular calcification in the popliteal, femoral, and aortic arch vessels compared to other vascular regions; however, the uptake of radiotracer was the highest in the aorta and femoral arteries. In the skin, the highest uptake was observed in the neck and the axillae. There was no significant association between 18F-NaF deposition in the arteries or skin and the global Phenodex score. In contrast, the Phenodex score was significantly associated in univariate analyses with the averaged vascular calcium score (p < 0.01). In the neck, patients with higher skin Phenodex scores exhibited higher radiotracer uptake. As a conclusion, because vascular calcification is physiological, our data suggested that the detection of cutaneous (neck) 18F-NaF deposits might serve to monitor the calcification process in the short-term for patients with PXE.
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