4.2. Titanium Dioxide 4947 4.3. Germanium Oxide 4949 4.4. Gallium Oxide and Zinc Oxide 4950 4.5. Mixed-Valence Oxides of Iron and Cobalt (Fe 3 O 4 and Co 3 O 4 ) 4951 4.6. Multicomponent Oxides: BaTiO 3 , BaTiOF 4 , CaMoO 4 , and (Fe,Co) 3 O 4 4952 5. Protein-and Peptide-Directed Syntheses of Non-Oxide Semiconductors 4954 5.1. Introduction 4954 5.2. Biogenic and Biologically-Derived Production of Semiconductor Nanoparticles 4954

Whereas considerable interest exists in self-assembly of well-ordered, porous “inverse opal” structures for optical, electronic, and (bio)chemical applications, uncontrolled defect formation has limited the scale-up and practicality of such approaches. Here we demonstrate a new method for assembling highly ordered, crack-free inverse opal films over a centimeter scale. Multilayered composite colloidal crystal films have been generated via evaporative deposition of polymeric colloidal spheres suspended within a hydrolyzed silicate sol-gel precursor solution. The coassembly of a sacrificial colloidal template with a matrix material avoids the need for liquid infiltration into the preassembled colloidal crystal and minimizes the associated cracking and inhomogeneities of the resulting inverse opal films. We discuss the underlying mechanisms that may account for the formation of large-area defect-free films, their unique preferential growth along the 〈110〉 direction and unusual fracture behavior. We demonstrate that this coassembly approach allows the fabrication of hierarchical structures not achievable by conventional methods, such as multilayered films and deposition onto patterned or curved surfaces. These robust SiO 2 inverse opals can be transformed into various materials that retain the morphology and order of the original films, as exemplified by the reactive conversion into Si or TiO 2 replicas. We show that colloidal coassembly is available for a range of organometallic sol-gel and polymer matrix precursors, and represents a simple, low-cost, scalable method for generating high-quality, chemically tailorable inverse opal films for a variety of applications.

Titanium (Ti) osseointegration is critical for the success of dental and orthopaedic implants. Previous studies have shown that surface roughness at the micro- and submicro-scales promotes osseointegration by enhancing osteoblast differentiation and local factor production. Only relatively recently have the effects of nanoscale roughness on cell response been considered. The aim of the present study was to develop a simple and scalable surface modification treatment that introduces nanoscale features to the surfaces of Ti substrates without greatly affecting other surface features, and to determine the effects of such superimposed nano-features on the differentiation and local factor production of osteoblasts. A simple oxidation treatment was developed for generating controlled nanoscale topographies on Ti surfaces, while retaining the starting micro-/submicro-scale roughness. Such nano-modified surfaces also possessed similar elemental compositions, and exhibited similar contact angles, as the original surfaces, but possessed a different surface crystal structure. MG63 cells were seeded on machined (PT), nano-modified PT (NMPT), sandblasted/acid-etched (SLA), and nano-modified SLA (NMSLA) Ti disks. The results suggested that the introduction of such nanoscale structures in combination with micro-/submicro-scale roughness improves osteoblast differentiation and local factor production, which, in turn, indicates the potential for improved implant osseointegration in vivo.

The carbothermal reduction of silica into silicon requires the use of temperatures well above the silicon melting point (> or =2,000 degrees C). Solid silicon has recently been generated directly from silica at much lower temperatures (< or =850 degrees C) via electrochemical reduction in molten salts. However, the silicon products of such electrochemical reduction did not retain the microscale morphology of the starting silica reactants. Here we demonstrate a low-temperature (650 degrees C) magnesiothermic reduction process for converting three-dimensional nanostructured silica micro-assemblies into microporous nanocrystalline silicon replicas. The intricate nanostructured silica microshells (frustules) of diatoms (unicellular algae) were converted into co-continuous, nanocrystalline mixtures of silicon and magnesia by reaction with magnesium gas. Selective magnesia dissolution then yielded an interconnected network of silicon nanocrystals that retained the starting three-dimensional frustule morphology. The silicon replicas possessed a high specific surface area (>500 m(2) g(-1)), and contained a significant population of micropores (< or =20 A). The silicon replicas were photoluminescent, and exhibited rapid changes in impedance upon exposure to gaseous nitric oxide (suggesting a possible application in microscale gas sensing). This process enables the syntheses of microporous nanocrystalline silicon micro-assemblies with multifarious three-dimensional shapes inherited from biological or synthetic silica templates for sensor, electronic, optical or biomedical applications.