Reactive magnesium oxide nanoparticles and halogen (Cl2, Br2) adducts of these MgO particles were allowed to contact certain bacteria and spore cells. Bacteriological test data, atomic force microscopy (AFM) images, and electron microscopy (TEM) images are provided, which yield insight into the biocidal action of these nanoscale materials. The tests show that these materials are very effective against Gram-positive and Gram-negative bacteria as well as spores. ζ-Potential measurements show an attractive interaction between the MgO nanoparticles and bacteria and spore cells, which is confirmed by confocal microscopy images. The AFM studies illustrate considerable changes in the cell membranes upon treatment, resulting in the death of the cells. TEM micrographs confirm these results and supply additional information about the processes inside the cells. Overall, the results presented illustrate that dry powder nanoparticulate formulations as well as water slurries are effective. It is proposed that abrasiveness, basic character, electrostatic attraction, and oxidizing power (due to the presence of active halogen) combine to promote these biocidal properties.

XPS studies of solvated metal atom dispersed (SMAD) catalysts coupled with detailed studies of reference compounds were carried out. It was shown that toluene-solvated cobalt atoms nucleate at surface OH groups, and the resultant cobalt oxide surface species serve as sites for nucleation of more cobalt atoms, leading to very small, reactive metallic clusters. The surface of these clusters/particles are partially oxidized by adventitious oxygen or water, but when cobalt loadings of over 4% are used, a major portion of the catalytic particle remains metallic. When solvated cobalt and manganese atoms are mixed together, the manganese atoms deposit first at surface OH sites, and manganese is highly dispersed in this way, but the majority ends up as surface MnO and Mn203. Some of the deposited manganese atoms/clusters serve as nucleation sites for cobalt atoms. In this way a layered catalytic particle is formed: support (Si02 or A1203) covered by manganese oxide which in turn is covered by metallic cobalt. The manganese material serves as a gradient between the ionic support oxide and metallic cobalt, and the composite is quite stable and highly active in catalysis. Also, the manganese serves as a sacrificial metal, serving to scavenge oxidizing moieties (mostly OH groups) on the support surface, thereby allowing cobalt to deposit and remain metallic and very highly dispersed. Sizes of the composite particles are probably 10-30 Á in diameter and are nearly amorphous.

Nanocrystals of MgO and CaO have been prepared by a modified aerogel/hypercritical drying/dehydration method. For nanocrystalline MgO (AP-MgO) surface areas ranged from 250 to 500 m 2 /g, whereas for AP-CaO 100-160 m 2 /g. These materials have been compared with more conventional (CP) microcrystalline samples of lower surface area with regard to (1) morphology (AP-samples (autoclave preparation) are tiny polyhedral crystallites, while CP-samples (conventional preparation) are larger, hexagonal platelets and cubes);(2) residual surface OH (AP-samples have less acidic OH, which are more isolated from each other; (3) acid gas adsorption (AP-samples adsorb more SO 2 and CO 2 at low pressures and room temperature and prefer monodentate rather than bidentate adsorption modes, but at higher pressures CP-samples adsorb more SO 2 and HCl apparently due to the formation of more well ordered multilayers); (4) destructive adsorption of organophosphorus compounds and chlorocarbons (AP-samples are superior due to higher surface areas and higher surface reactivities), and (5) very thin layers of transition metal oxides on the MgO and CaO nanocrystals that significantly enhance destructive adsorption capacities to the point where [M x O y ]AP-MgO and [M x O y ]-AP-CaO become stoichiometric in reaction with CCl 4 . The data are conclusive that the nanocrystals are more reactive than the microcrystals, and this is mainly attributed to morphological differences, including defects. However, intrinsic electronic effects due purely to "smallness" cannot be ruled out.

Particle−particle and particle−substrate interactions cause nanocrystals to self-assemble into superlattice structures upon drying from a colloidal suspension on a solid surface. Rapid dewetting of a volatile solvent, however, can significantly undermine the degree of ordering. We demonstrate here that by increasing the concentration of the nonvolatile dodecanethiol ligand, dewetting can be controlled and gold nanocrystal superlattices can be formed on silicon nitride substrates with long range ordering over several microns. Monolayer and bilayer superlattices can be produced by adjusting the nanocrystal concentration. The superlattice structures are robust and are not perturbed by the final dewetting of the solvent.

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Digestive ripening, heating a colloidal suspension at or near the solvent boiling point in the presence of a surface-active ligand, was applied to polydisperse colloidal gold in toluene using a series of alkylthiols, viz., octyl-, decyl-, dodecyl-, and hexadecylthiols. In all the instances, digestive ripening significantly reduced the average particle size and polydispersity. All the colloids remain suspended in solution above 80 °C, but at room temperature the tendency to form 3D superlattices and precipitate increased with declining alkyl chain length. For example, using octanethiol as the ligand makes the colloids aggregate into big 3D superlattices and precipitate; decane-and dodecanethiol also produce precipitated 3D superlattices along with separate particles, while hexadecanethiol-coated particles remain well separated from each other. The optical spectra at room temperature reveal, apart from the gold plasmon band at 530 nm, a large tail above 700 nm for Au-octanethiol and Au-decanethiol cases and a shoulder at 630 nm for Au-dodecanethiol attributed to the superlattices. Au-hexadecanethiol, on the other hand, shows only the gold plasmon band as expected from separate particles. However, at higher temperatures only the gold plasmon band is observed for all the colloids indicating the dissolution of the superlattices. The aggregation of the particles into 3D superlattices or their stability as a colloidal suspension is qualitatively explained on the basis of decreasing van der Waals attraction between the gold nanoparticles as the separation between them is increased through the alkyl chain length of the capping ligand from octyl to hexadecyl.

We describe a synthetic procedure for preparation of large quantities of monodisperse thiol-stabilized gold colloids in toluene solution. The method is based on the solvated metal atom dispersion technique (SMAD), which is very suitable for preparation of large amounts of metal colloidal solutions, as well as of metal sulfide, metal oxide, and other types of dispersed compounds in different solvents. A combination of two different solvents like acetone and toluene is used for the preparation of the gold colloids. The necessity of initially carrying out the SMAD reaction in acetone comes from its high degree of solvation of gold particles. Acetone acts as a preliminary stabilizing agent. After its removal from the system, the particles are stabilized by dodecanethiol molecules, which enable their very good dispersion in toluene solution. A digestive ripening procedure is carried out with the gold-toluene colloid, and for this purpose pure toluene as solvent is necessary. This has a dramatic effect on the narrowing of particle size distribution and almost monodisperse colloids are obtained (some discussion of the probable mechanism of this remarkable digestive ripening step is given). These colloidal solutions have a great tendency to organize in two- and three-dimensional structures (nanocrystal superlattices, NCSs). We believe that this procedure provides a real opportunity to synthesize large amounts of gold nanocrystals as well as NCSs.

The room-temperature reactions of the chemical warfare agents VX (O-ethyl S-2-(diisopropylamino)ethyl methylphosphonothioate), GD (3,3-dimethyl-2-butyl methylphosphonofluoridate, or Soman), and HD (2,2′-dichloroethyl sulfide, or mustard) with nanosize MgO have been studied using solid-state MAS NMR. All three agents hydrolyze on the surface of the very reactive MgO nanoparticles. VX yields ethyl methylphosphonic acid (EMPA) and methylphosphonic acid (MPA), but no toxic S-(2-diisopropylamino)ethyl methylphosphonothioate (EA-2192). GD forms both GD-acid and MPA. For HD, in addition to hydrolysis to thiodiglycol, about 50% elimination to divinyl sulfide occurs. The reaction kinetics for all three agents are characterized by a fast initial reaction followed by gradual slowing to a steady-state reaction with first-order behavior. The fast reaction is consistent with liquid spreading through the porous nanoparticle aggregates. The steady-state reaction is identified as a gas-phase reaction, mediated by evaporation, once the liquid achieves its volume in the smallest available pores.