Confined water radiolysis in aluminosilicate nanotubes: the importance of charge separation effects.

Imogolite nanotubes are potentially promising co-photocatalysts because they are predicted to have curvature-induced, efficient electron-hole pair separation. This prediction has however not yet been experimentally proven. Here, we investigated the behavior upon irradiation of these inorganic nanotubes as a function of their water content to understand the fate of the generated electrons and holes. Two types of aluminosilicate nanotubes were studied: one was hydrophilic on its external and internal surfaces (IMO-OH) and the other had a hydrophobic internal cavity due to Si-CH3 bonds (IMO-CH3), with the external surface remaining hydrophilic. Picosecond pulse radiolysis experiments demonstrated that the electrons are efficiently driven outward. For imogolite samples with very few external water molecules (around 1% of the total mass), quasi-free electrons were formed. They were able to attach to a water molecule, generating a water radical anion, which ultimately led to dihydrogen. When more external water molecules were present, solvated electrons, precursors of dihydrogen, were formed. In contrast, holes moved towards the internal surface of the tubes. They mainly led to the formation of dihydrogen and of methane in irradiated IMO-CH3. The attachment of the quasi-free electron to water was a very efficient process and accounted for the high dihydrogen production at low relative humidity values. When the water content increased, electron solvation dominated over attachment to water molecules. Electron solvation led to dihydrogen production, albeit to a lesser extent than quasi-free electrons. Our experiments demonstrated the spontaneous curvature-induced charge separation in these inorganic nanotubes, making them very interesting potential co-photocatalysts.

A pressure-actuated flow cell for soft X-ray spectromicroscopy in liquid media.

We present and fully characterize a flow cell dedicated to imaging in liquid at the nanoscale. Its use as a routine sample environment for soft X-ray spectromicroscopy is demonstrated, in particular through the spectral analysis of inorganic particles in water. The care taken in delineating the fluidic pathways and the precision associated with pressure actuation ensure the efficiency of fluid renewal under the beam, which in turn guarantees a successful utilization of this microfluidic tool for in situ kinetic studies. The assembly of the described flow cell necessitates no sophisticated microfabrication and can be easily implemented in any laboratory. Furthermore, the design principles we relied on are transposable to all microscopies involving strongly absorbed radiation (e.g. X-ray, electron), as well as to all kinds of X-ray diffraction/scattering techniques.

Using hydrogen isotope incorporation as a tool to unravel the surfaces of hydrogen-treated nanodiamonds.

We report here on a robust and easy-to-implement method for the labelling of detonation nanodiamonds (DND) with hydrogen isotopes (deuterium and tritium), using thermal annealing performed in a closed system. With this method, we have synthesized and fully characterized (FTIR, Raman, DLS, 3H/2H/1H and 13C MAS NMR) deuterium-treated and tritium-treated DND and demonstrated the usefulness of isotope incorporation in investigating the surface chemistry of such nanomaterials. For instance, surface treatment with deuterium coupled to FTIR spectroscopy allowed us to discriminate the origin of C-H terminations at the DND surface after the hydrogenation process. As a complementary, tritium appeared very useful for quantification purposes, while 1,2,3H NMR confirmed the nature of the C-1,2,3H bonds created. This isotopic study provides new insights into the characteristics of hydrogen-treated DND.

Heavy metal bioaccumulation by the bryophyte Scleropodium purum at three French sites under various influences: rural conditions, traffic, and industry.

An active biomonitoring of the heavy metals pollution experiment was undertaken by means of the bryophyte species Scleropodium purum transplanted at three different sites exposed to rural, traffic, or industrial influences. Concentrations of about 40 elements in S. purum were determined by instrumental neutron activation analysis and inductively coupled plasma mass spectrometry. Accumulation rates of heavy metals were determined in the three sites. These accumulation rates in polluted sites were matched together and also to those recorded at the rural site. The changes of the accumulation rate of heavy metals in S. purum versus their concentrations in PM(10) particles simultaneously collected above show some different accumulation properties of S. purum according to elements and sites. S. purum has a weak efficiency in the three sites to accumulate elements like V, Cr, Cu, Zn, As, Se, Sb, and Pb originating from atmospheric hot sources generally enriched in particulates matter (PM(10)), whereas it is particularly high for Br, Th, and Rb. For other elements, Co, La, Ce, and Hf, and rare earth elements, Fe, Sr, Nb, Ti, Al, and Sc, the collection efficiency by S. purum is intermediate. In the industrial site Dunkerque, a magnification of the collection efficiency by S. purum for elements originating from steel and aluminum productions and petroleum refinement suggests that these metals could be enriched in coarse particles with a better accumulation by the bryophyte with respect to PM10.

Ripening of catanionic aggregates upon dialysis.

We have studied the dialysis of surfactant mixtures of two oppositely charged surfactants (catanionic mixture) by combining HPLC, neutron activation, confocal microscopy, and NMR. In mixtures of n-alkyl trimethylammonium halides and n-fatty acids, we have demonstrated the existence of a specific ratio between both surfactant contents (anionic/cationic almost equal to 2:1) that determines the morphology, the elimination of ions, and the elimination of the soluble cationic surfactant upon dialysis. In mixtures prepared with lower anionic surfactant contents, ill-defined aggregates are formed, and dialysis quickly eliminates the ion pairs (H+X-) formed upon surfactant association and also the cationic surfactant until a limiting 2:1 ratio is reached. By contrast, mixtures prepared above the anionic/cationic 2:1 ratio form micrometer-sized vesicles resistant to dialysis. These closed aggregates retain a significant number of ions (30%) over 1000 hours, and dialysis is unable to eliminate the soluble surfactant. The interactions between surfactants have been estimated by measuring the partitioning of the CTA molecules between the catanionic bilayer, the bulk solution, and mixed micelles when they exist. The mean extraction free energy per CTA in the membrane has been found to increase by 1 kBT to 2 kBT as the soluble surfactant is depleted from the bilayer, which is enough to stop the dialysis. The vesicles produced above the anionic/cationic 2:1 ratio are formed by frozen bilayers and are resistant to extensive dialysis and therefore show an interesting potential for encapsulation as far as durability is concerned.