Influence of soil type on TiO2 nanoparticle fate in an agro-ecosystem.

Nanoparticles (NPs) and in particular TiO2-NPs are increasingly included in commercial goods leading to their accumulation in sewage sludge which is spread on agricultural soils as fertilizers in many countries. Crop plants are thus a very likely point of entry for NPs in the food chain up to humans. So far, soil influence on NP fate has been under-investigated. In this article, we studied the partitioning of TiO2-NPs between soil and soil leachate, their uptake and biotransformation in wheat seedlings and their impact on plant development after exposure on 4 different types of soil with different characteristics: soil texture (from sandy to clayey), soil pH, cationic exchange capacity, organic matter content. Results suggest that a NP contamination occurring on agricultural soils will mainly lead to NP accumulation in soil (increase of Ti concentration up to 302% in sand) but to low to negligible transfer to soil leachate and plant shoot. In our experimental conditions, no sign of acute phytotoxicity has been detected (growth, biomass, chlorophyll content). Clay content above 6% together with organic matter content above 1.5% lead to translocation factor from soil to plant leaves below 2.5% (i.e. below 13mgTi·kg-1 dry leaves). Taken together, our results suggest low risk of crop contamination in an agro-ecosystem.

Pressure effect on the crystal lattice of unconventional superconductor UCoGe.

High-pressure techniques were used to determine the structural behaviour of the superconducting ferromagnet UCoGe up to 30 GPa enabling us to determine the link between the effect of pressure on the material magnetic properties and crystal structure. The TiNiSi type structure of UCoGe was preserved up to the highest pressure. The a direction, equivalent to the shortest U-U links, was identified as the critical soft direction. The data are compared with the structural variations in UCoGe α-hydride, which becomes non-magnetic and non-superconducting despite a volume expansion. We show that at least in this case, but probably more generally, the structure impact of hydrogenation is definitely not equivalent to negative pressure.

Evidence of flexibility in the nanoporous iron(iii) carboxylate MIL-89.

The very large expansion upon adsorption of liquids, up to 160% in cell volume, has been observed in the iron(iii) trans,trans muconate MIL-89 [(MIL = Material Institut Lavoisier]. The structure of lutidine-containing MIL-89 (lutidine = 2,6-dimethylpyridine) has been determined using X-ray powder diffraction and computer simulations. Finally, the consequences of adsorption of various polar and apolar liquids have been evaluated using ex situ synchrotron X-ray powder diffraction data and reveals that the swelling behavior of MIL-89 is selective but slightly different from the MIL-88 analogues.

Role of solvent-host interactions that lead to very large swelling of hybrid frameworks.

An unusually large expansion upon solvent adsorption occurs without apparent bond breaking in the network of a series of isoreticular chromium(III) or iron(III) diarboxylates labeled MIL-88A to D [dicarbox = fumarate (88A); terephthalate (1,4-BDC) (88B); 2,6-naphthalenedicarboxylate (2,6-NDC) (88C); and 4-4'-biphenyldicarboxylate (4-4'-BPDC) (88D)]. This reversible "breathing" motion was analyzed in terms of cell dimensions (extent of breathing), movements within the framework (mechanism of transformation), and the interactions between the guests and the skeleton. In situ techniques show that these flexible solids are highly selective absorbents and that this selectivity is strongly dependent on the nature of the organic linker.

A chromium terephthalate-based solid with unusually large pore volumes and surface area.

We combined targeted chemistry and computational design to create a crystal structure for porous chromium terephthalate, MIL-101, with very large pore sizes and surface area. Its zeotype cubic structure has a giant cell volume (approximately 702,000 cubic angstroms), a hierarchy of extra-large pore sizes (approximately 30 to 34 angstroms), and a Langmuir surface area for N2 of approximately 5900 +/- 300 square meters per gram. Beside the usual properties of porous compounds, this solid has potential as a nanomold for monodisperse nanomaterials, as illustrated here by the incorporation of Keggin polyanions within the cages.