Cubic boron nitride (cBN) is a well known superhard material that has a wide range of industrial applications. Nanostructuring of cBN is an effective way to improve its hardness by virtue of the Hall-Petch effect--the tendency for hardness to increase with decreasing grain size. Polycrystalline cBN materials are often synthesized by using the martensitic transformation of a graphite-like BN precursor, in which high pressures and temperatures lead to puckering of the BN layers. Such approaches have led to synthetic polycrystalline cBN having grain sizes as small as ∼14 nm (refs 1, 2, 4, 5). Here we report the formation of cBN with a nanostructure dominated by fine twin domains of average thickness ∼3.8 nm. This nanotwinned cBN was synthesized from specially prepared BN precursor nanoparticles possessing onion-like nested structures with intrinsically puckered BN layers and numerous stacking faults. The resulting nanotwinned cBN bulk samples are optically transparent with a striking combination of physical properties: an extremely high Vickers hardness (exceeding 100 GPa, the optimal hardness of synthetic diamond), a high oxidization temperature (∼1,294 °C) and a large fracture toughness (>12 MPa m(1/2), well beyond the toughness of commercial cemented tungsten carbide, ∼10 MPa m(1/2)). We show that hardening of cBN is continuous with decreasing twin thickness down to the smallest sizes investigated, contrasting with the expected reverse Hall-Petch effect below a critical grain size or the twin thickness of ∼10-15 nm found in metals and alloys.

Seeding and autocatalytic reduction of platinum salts in aqueous surfactant solution using ascorbic acid as the reductant leads to remarkable dendritic metal nanostructures. In micellar surfactant solutions, spherical dendritic metal nanostructures are obtained, and the smallest of these nanodendrites resemble assemblies of joined nanoparticles and the nanodendrites are single crystals. With liposomes as the template, dendritic platinum sheets in the form of thin circular disks or solid foamlike nanomaterials can be made. Synthetic control over the morphology of these nanodendrites, nanosheets, and nanostructured foams is realized by using a tin-porphyrin photocatalyst to conveniently and effectively produce a large initial population of catalytic growth centers. The concentration of seed particles determines the ultimate average size and uniformity of these novel two- and three-dimensional platinum nanostructures.

Micellar nanoparticles made of surfactants and polymers have attracted wide attention in the materials and biomedical community for controlled drug delivery, molecular imaging, and sensing; however, their long-term stability remains a topic of intense study. Here we report a new class of robust, ultrafine silica core-shell nanoparticles formed from silica cross-linked, individual block copolymer micelles. Compared with pure polymeric micelles, the main advantage of the new core-shell nanoparticles is that they have significantly improved stability and do not break down during dilution. We also studied the drug loading and release properties of the silica cross-linked micellar particles, and we found that the new core-shell nanoparticles have a slower release rate which allows the entrapped molecules to be slowly released over a much longer period of time under the same experimental conditions. A range of functional groups can be easily incorporated through co-condensation with the silica matrix. The potential to deliver hydrophobic agents into cancer cells has been demonstrated. Because of their unique structures and properties, these novel core-shell nanoparticles could potentially provide a new nanomedicine platform for imaging, detection, and treatment, as well as novel colloidal particles and building blocks for mutlifunctional materials.

Nanostructured films and coatings with controlled surface area, porosity, crystalline orientation, grain sizes, and crystal morphologies are desirable for many applications, including microelectronic devices, chemical and biological sensing and diagnosis, energy conversion and storage (photovoltaic cells, batteries and capacitors, and hydrogen-storage devices), lightemitting displays, catalysis, drug delivery, separation, and optical storage. Meeting the demands of these potential applications, however, will require reliable and economic processes for the production of a large supply of high-quality nanomaterials. Gas-phase reactions [1] have been extensively used to prepare oriented nanostructures including carbon nanotubes, [2,3] ZnO nanowires, [4,5] and many other oxide and non-oxide semiconductor materials, [6,7] but these methods typically require high temperatures (∼ 500-1100°C) and vacuum conditions, which limit the choice of substrate and the economic viability of high-volume production. These limitations have stimulated research on solution-phase synthesis (sometimes referred to as the soft solution route or chemical bath deposition), which offers the potential for low-cost, industrial-scale manufacturing. Low-temperature (typically < 100°C), aqueous-phase approaches are particularly attractive because of their low energy requirements, and safe and environmentally benign processing conditions.In aqueous-phase synthesis, oriented nanocrystalline films are deposited on a substrate in aqueous media by heterogeneous nucleation and subsequent growth. The resultant film structure is controlled by a complicated set of coupled processes in both the solution and solid phases. Heterogeneous nuclea- 335Nanostructured films with controlled architectures are desirable for many applications in optics, electronics, biology, medicine, and energy/chemical conversions. Low-temperature, aqueous chemical routes have been widely investigated for the synthesis of continuous films, and arrays of oriented nanorods and nanotubes. More recently, aqueous-phase routes have been used to produce films composed of more complex crystal structures. In this paper, we discuss recent progress in the synthesis of complex nanostructures through sequential nucleation and growth processes. We first review the use of multistage, seeded-growth methods to synthesize a wide range of nanostructures, including oriented nanowires, nanotubes, and nanoneedles, as well as laminated films, columns, and multilayer heterostructures. We then describe more recent work on the application of sequential nucleation and growth to the systematic assembly of large arrays of hierarchical, complex, oriented, and ordered crystal architectures. The multistage aqueous chemical route is shown to be applicable to several technologically important materials, and therefore may play a key role in advancing complex nanomaterials into applications.-[*] Dr.

Porous aluminium oxide films with precisely controlled thickness down to several angstroms are deposited on particle surfaces from dense aluminium alkoxide hybrid polymer films by molecular layer deposition. Porous structures are obtained by either mild water etching at room temperature or calcination in air at elevated temperatures.

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Microscale four-leaf clover-shaped structures are formed by self-assembly of anionic and cationic porphyrins. Depending on the metal complexed in the porphyrin macrocycle (Zn or Sn), the porphyrin cores are either electron donors or electron acceptors. All four combinations of these two metals in cationic tetra(N-ethanol-4-pyridinium)porphyrin and anionic tetra(sulfonatophenyl)porphyrin result in related cloverlike structures with similar crystalline packing indicated by X-ray diffraction patterns. The clover morphology transforms as the ionic strength and temperature of the self-assembly reaction are increased, but the structures maintain 4-fold symmetry. The ability to alter the electronic and photophysical properties of these solids (e.g., by altering the metals in the porphyrins) and to vary cooperative interactions between the porphyrin subunits raises the possibility of producing binary solids with tunable functionality. For example, we show that the clovers derived from anionic Zn porphyrins (electron donors) and cationic Sn porphyrins (electron acceptors) are photoconductors, but when the metals are reversed in the two porphyrins, the resulting clovers are insulators.

Hybrid silicate materials derived from organo-bridged silsesquioxane precursors, RO3-Si-R'-Si-OR3, where R and R' are organic ligands, represent a remarkably diverse class of nanocomposites capable of forming both Si-O-Si and Si-C-Si bonds with molecular scale homogeneity. Recently, in an effort to better control their structure and function, surfactant-directed self-assembly or self-directed assembly has been used to synthesize hierarchical organo-bridged polysilsesquioxanes that exhibit order over multiple length scales. Here we report the synthesis and self-directed assembly of an optically active azobenzene-bridged silsesquioxane, 4,4'-bis(3-triethoxysilylpropylureido)azobenzene 1. Hydrogen-bonding interactions between the three active centers of the bis-ureide groups (-NH-CO-NH) combined with pi-pi interactions between the azobenzene groups serve to self-assemble 1 into a highly ordered lamellar mesostructure in which the d-spacing is optically controlled through photoisomerization of the azobenzene moiety before or after assembly.