Local structure at Mn2+ ions in vacuum annealed small cubic ZnS nanocrystals self-assembled into a mesoporous structure.

A mesoporous structure of self-assembled nanocrystals of cubic ZnS doped with Mn2+ ions with a homogeneous distribution of pores of similar size was synthesized at room temperature by a surfactant-assisted liquid-liquid reaction. The component nanocrystals exhibit a high crystallinity and a tight size distribution centered at 2 nm, as well as the narrowest Electron Paramagnetic Resonance (EPR) spectra linewidth and the best resolution reported so-far, effects attributed to self-assembling. The observed EPR spectra consist of lines from the substitutional Mn2+(I) and surface Mn2+(II) and Mn2+(III) centers. Here we show that, in contrast with previous reports, our EPR spectra are highly sensitive to structural changes during pulse annealing in vacuum up to 500 degrees C. The changes are related to the transformation of the surface Mn2+ centers in new Mn2+ centers, attributed to an oxidation process in which the thermal decomposition of the Tween 20 additive, also observed by EPR, seems to be involved. We have also been able to observe, for the first time by EPR spectroscopy, the formation of the ZnO phase and the nanocrystals size increase, which occur during annealing up to 500 degrees C, structural changes confirmed by XRD and TEM observations on the samples previously investigated by EPR.

Localization of Mn2+ ions in mesoporous NnS.

Nanocrystalline cubic ZnS doped with 0.2% mol manganese, exhibiting a stable mesoporous structure, was synthesized at room temperature by a non toxic surfactant-assisted liquid-liquid reaction. The X-ray diffraction measurements demonstrate the formation of a sponge-like mesoporous material built from cubic ZnS nanocrystals of 1.8 nm average sizes, with a tight distribution of pores of 1.8 nm mean diameter. The transmission electron microscopy images confirm the formation of the mesoporous structure with walls of 3.1 nm mean thickness built from cubic ZnS nanocrystallites of 2.1 nm average size. The resulting tight distribution of crystallites and pores yields a well resolved Electron Paramagnetic Resonance spectrum, with the narrowest reported component lines attributed to three types of isolated Mn2+ centers, called Mn2+(I), Mn2+(II) and Mn2+(III). From the analysis of the spin Hamiltonian parameters it is shown that in the Mn2+(I) centers the paramagnetic ion is situated at substitutional Zn sites in the ZnS nanocrystals, being also subjected to a small axial distortion. The relative concentration changes under thermal treatment experiments strongly suggest that in both Mn2+(II) and Mn2+(III) centers the Mn2+ ion is localized on the surface of the ZnS nanocrystallites, being bond to an oxygen ion in the first case and to an additional water molecule in the second case.

[Duodenal biliary ileus]. / Ileusul biliar duodenal.

A clinical observation is presented, of a patient that underwent emergency surgery for biliary ileus located in the duodenum. The particularity of the case consisted in the presence of a double bilio-digestive fistula: between the cholecyst and the stomach, and between the cholecyst and the duodenum. The rarity and the clinical characteristics of this syndrome described by Bouveret are stressed. The aspect and the extension of the lesions found during surgery have made necessary to apply an exceptional surgical solution which consisted in cholecystectomy and antrectomy with gastro-jejunal anastomosis, excluding the sutured duodenum from the digestive pathway.