Self-assembly of iron oxide precursor micelles driven by magnetic stirring time in sol-gel coatings.

The purpose of this work is to fabricate self-assembled microstructures by the sol-gel method and study the morphological, structural and compositional dependence of ε-Fe2O3 nanoparticles embedded in silica when glycerol (GLY) and cetyl-trimethylammonium bromide (CTAB) are added as steric agents simultaneously. The combined action of a polyalcohol and a surfactant significantly modifies the morphology of the sample giving rise to a different microstructure in each of the studied cases (1, 3 and 7 days of magnetic stirring time). This is due to the fact that the addition of these two compounds leads to a considerable increase in gelation time as GLY can interact with the alkoxide group on the surface of the iron oxide precursor micelle and/or be incorporated into the hydrophilic chains of CTAB. This last effect causes the iron oxide precursor micelles to be interconnected forming aggregates whose size and structure depend on the magnetic stirring time of the sol-gel synthetic route. In this paper, crystalline structure, composition, purity and morphology of the sol-gel coatings densified at 960 °C are examined. Emphasis is placed on the nominal percentage of the different iron oxides found in the samples and on the morphological and structural differences. This work implies the possibility of patterning ε-Fe2O3 nanoparticles in coatings and controlling their purity by an easy one-pot sol-gel method.

Formation of biomineral iron oxides compounds in a Fe hyperaccumulator plant: Imperata cylindrica (L.) P. Beauv.

We report a detailed work of composition and location of naturally formed iron biominerals in plant cells tissues grown in iron rich environments as Imperata cylindrica. This perennial grass grows on the Tinto River banks (Iberian Pyritic Belt) in an extreme acidic ecosystem (pH∼2.3) with high concentration of dissolved iron, sulphate and heavy metals. Iron biominerals were found at the cellular level in tissues of root, stem and leaf both in collected and laboratory-cultivated plants. Iron accumulated in this plant as a mix of iron compounds (mainly as jarosite, ferrihydrite, hematite and spinel phases) was characterized by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), Mössbauer spectroscopy (MS), magnetometry (SQUID), electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX; TEM-EDX; HRSTEM). A low fraction of phosphorous was detected in this iron hyperaccumulator plant. Root and rhizomes tissues present a high proportion of ferromagnetic iron oxide compounds. Iron oxides-rich zones are localized in electron dense intra and inter-cellular aggregates that appear as dark deposits covering the inner membrane and organelles of the cell. This study aims to contribute to a better understanding of the mechanisms of accumulation, transport, distribution of iron in Imperata cylindrica.