Role of initial precursors on the liquid-crystalline phase behavior of synthetic aluminogermanate imogolite nanotubes.

HYPOTHESIS: Synthetic imogolite nanotubes form stable colloidal dispersions that may also exhibit a rich liquid-crystalline phase behavior according to the nanotube length to diameter ratio. Anisometric double-walled aluminogermanate nanotubes are now readily available through hydrothermal treatment of germanium and aluminum precursors. This work aims to assess how the self-organization behavior of these nanotubes is influenced by the nature of the precursors. EXPERIMENTS: Five different samples were synthesized by changing the precursors involved in the formation of either inner or outer walls, then fully characterized. From series of aqueous dispersions prepared by osmotic stress, we evaluated the phase behavior by coupling polarized optical observations and small-angle X-ray scattering. FINDINGS: The formation of anisometric nanotubes is achieved whatever the initial conditions. Their structural properties are however affected by the nature of the aluminum salt. For nanotubes synthesized with aluminum perchlorate, the dispersions present an isotropic-to-columnar phase transition with a self-organization of the nanotubes over large distances. By contrast, nanotubes synthesized with chloride and nitrate salts form only nematic or isotropic liquids and tend to group together in bi-dimensional rafts. We suggest that the different phase behaviors are related at the first order to the presence of structural vacancies in the nanotube walls.

Enhanced sieving from exfoliated MoS2 membranes via covalent functionalization.

Nanolaminate membranes made of two-dimensional materials such as graphene oxide are promising candidates for molecular sieving via size-limited diffusion in the two-dimensional capillaries, but high hydrophilicity makes these membranes unstable in water. Here, we report a nanolaminate membrane based on covalently functionalized molybdenum disulfide (MoS2) nanosheets. The functionalized MoS2 membranes demonstrate >90% and ~87% rejection for micropollutants and NaCl, respectively, when operating under reverse osmotic conditions. The sieving performance and water flux of the functionalized MoS2 membranes are attributed both to control of the capillary widths of the nanolaminates and to control of the surface chemistry of the nanosheets. We identify small hydrophobic functional groups, such as the methyl group, as the most promising for water purification. Methyl- functionalized nanosheets show high water permeation rates as confirmed by our molecular dynamic simulations, while maintaining high NaCl rejection. Control of the surface chemistry and the interlayer spacing therefore offers opportunities to tune the selectivity of the membranes while enhancing their stability.

87Sr solid-state NMR as a structurally sensitive tool for the investigation of materials: antiosteoporotic pharmaceuticals and bioactive glasses.

Strontium is an element of fundamental importance in biomedical science. Indeed, it has been demonstrated that Sr(2+) ions can promote bone growth and inhibit bone resorption. Thus, the oral administration of Sr-containing medications has been used clinically to prevent osteoporosis, and Sr-containing biomaterials have been developed for implant and tissue engineering applications. The bioavailability of strontium metal cations in the body and their kinetics of release from materials will depend on their local environment. It is thus crucial to be able to characterize, in detail, strontium environments in disordered phases such as bioactive glasses, to understand their structure and rationalize their properties. In this paper, we demonstrate that (87)Sr NMR spectroscopy can serve as a valuable tool of investigation. First, the implementation of high-sensitivity (87)Sr solid-state NMR experiments is presented using (87)Sr-labeled strontium malonate (with DFS (double field sweep), QCPMG (quadrupolar Carr-Purcell-Meiboom-Gill), and WURST (wideband, uniform rate, and smooth truncation) excitation). Then, it is shown that GIPAW DFT (gauge including projector augmented wave density functional theory) calculations can accurately compute (87)Sr NMR parameters. Last and most importantly, (87)Sr NMR is used for the study of a (Ca,Sr)-silicate bioactive glass of limited Sr content (only ~9 wt %). The spectrum is interpreted using structural models of the glass, which are generated through molecular dynamics (MD) simulations and relaxed by DFT, before performing GIPAW calculations of (87)Sr NMR parameters. Finally, changes in the (87)Sr NMR spectrum after immersion of the glass in simulated body fluid (SBF) are reported and discussed.