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A novel route for the synthesis of boehmite nanospheres with a hollow core and the shell composed of highly crumpled AlOOH nanosheets by oxidizing Al nanopowder in pure water under mild processing conditions is described. The stepwise events of Al transformation into boehmite are followed by monitoring the pH in the reaction medium. A mechanism of formation of hollow AlOOH nanospheres with a well-defined shape and crystallinity is proposed which includes the hydration of the Al oxide passivation layer, local corrosion of metallic Al accompanied by hydrogen evolution, the rupture of the protective layer, the dissolution of Al from the particle interior and the deposition of AlOOH nanosheets on the outer surface. In contrast to previously reported methods of boehmite nanoparticle synthesis, the proposed method is simple, and environmentally friendly and allows the generation of hydrogen gas as a by-product. Due to their high surface area and high, slit-shaped nanoporosity, the synthesized AlOOH nanostructures hold promise for the development of more effective catalysts, adsorbents, vaccines and drug carriers.

Oxidation of aluminum nanopowders obtained by electro-exploded wires is studied. Particle size distributions are obtained from transmission electron microscopy (TEM) images. Thermo-gravimetric (TG) experiments are complemented by TEM and XRD studies of partially oxidized particles. Qualitatively, oxidation follows the mechanism developed for coarser aluminum powder and resulting in formation of hollow oxide shells. Sintering of particles is also observed. The TG results are processed to account explicitly for the particle size distribution and spherical shapes, so that oxidation of particles of different sizes is characterized. The apparent activation energy is obtained as a function of the reaction progress using model-free isoconversion processing of experimental data. A complete phenomenological oxidation model is then proposed assuming a spherically symmetric geometry. The oxidation kinetics of aluminum powder is shown to be unaffected by particle sizes reduced down to tens of nm. The apparent activation energy describing growth of amorphous alumina is increasing at the very early stages of oxidation. The higher activation energy is likely associated with an increasing homogeneity in the growing amorphous oxide layer, initially containing multiple defects and imperfections. The trends describing changes in both activation energy and pre-exponent of the growing amorphous oxide are useful for predicting ignition delays of aluminum particles. The kinetic trends describing activation energies and pre-exponents in a broader range of the oxide thicknesses are useful for prediction of aging behavior of aluminum powders.

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Owing to their unique physicochemical properties, nanomaterials have become a focus of multidisciplinary research efforts including investigations of their interactions with tumor cells and stromal compartment of tumor microenvironment (TME) toward the development of next-generation anticancer therapies. Here, we report that agglomerates of radially assembled Al hydroxide crumpled nanosheets exhibit anticancer activity due to their selective adsorption properties and positive charge. This effect was demonstrated in vitro by decreased proliferation and viability of tumor cells, and further confirmed in two murine cancer models. Moreover, Al hydroxide nanosheets almost completely inhibited the growth of murine melanoma in vivo in combination with a minimally effective dose of doxorubicin. Our direct molecular dynamics simulation demonstrated that Al hydroxide nanosheets can cause significant ion imbalance in the living cell perimembranous space through the selective adsorption of extracellular anionic species. This approach to TME dysregulation could lay the foundation for development of novel anticancer therapy strategies.

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