Photostability of quantum dots with amphiphilic polymer-based passivation strategies.

Quantum dots (QDs) have many appealing properties for biological fluorescence imaging, but exhibit photostabilities that are dependent upon surface passivation to minimize susceptibility to oxygen and light. Here, through spectroscopy and imaging techniques, we compare the photostability of micelle-encapsulated QDs with QDs passivated with either crosslinked amphiphilic polymers or crosslink-free amphiphilic polymers. Both crosslinked and crosslink-free amphiphilic polymer passivation strategies produced QDs with high photoluminescence stability for exposure to light under ambient conditions. In contrast, micelle encapsulation resulted in QDs with photoluminescence emission levels that were highly sensitive to both light exposure and oxygen, exhibiting a reduction of up to 70% in photoluminescence intensity within twenty minutes of exposure. With the addition of reducing agents, the photoluminescence level of the micelle-encapsulated QDs was significantly stabilized. We conclude that amphiphilic polymers provide coatings with considerably higher integrity and stability than micelle encapsulation, reducing the QDs' sensitivities to oxygen and light, both of which are relevant factors in biological imaging applications.

C60 in water: nanocrystal formation and microbial response.

Upon contact with water, under a variety of conditions, C60 spontaneously forms a stable aggregate with nanoscale dimensions (d = 25-500 nm), termed here "nano-C60". The color, hydrophobicity, and reactivity of individual C60 are substantially altered in this aggregate form. Herein, we provide conclusive lines of evidence demonstrating that in solution these aggregates are crystalline in order and remain as underivatized C60 throughout the formation/stabilization process that can later be chemically reversed. Particle size can be affected by formation parameters such as rates and the pH of the water addition. Once formed, nano-C60 remains stable in solution at or below ionic strengths of 0.05 I for months. In addition to demonstrating aggregate formation and stability over a wide range of conditions, results suggest that prokaryotic exposure to nano-C60 at relatively low concentrations is inhibitory, indicated by lack of growth (> or = 0.4 ppm) and decreased aerobic respiration rates (4 ppm). This work demonstrates the fact that the environmental fate, distribution, and biological risk associated with this important class of engineered nanomaterials will require a model that addresses not only the properties of bulk C60 but also that of the aggregate form generated in aqueous media.

Adsorption of cadmium on anatase nanoparticles-effect of crystal size and pH.

The adsorption and desorption of Cd(2+) to large and nanometer-scale anatase crystals have been studied to determine the relationship between heavy metal adsorption properties and anatase particle size. A solvothermal method was used to synthesize very fine anatase nanocrystals with average grain sizes ranging from 8 to 20 nm. On a surface area basis, it was found that large and nanometer-scale anatase particles had similar maximum Cd(2+) adsorption capacities, while their adsorption slopes differed by more than 1 order of magnitude. The particle-size effect on adsorption is constant over a pH range of 4-7.5. The desorption of Cd(2+) from both particle sizes is completely reversible. The adsorption data have been modeled by the Basic Stern model using three monodentate surface complexes. It is proposed that intraparticle electrostatic repulsion may reduce the adsorption free energy significantly for nanometer-sized particles.

Direct observation of terahertz surface modes in nanometer-sized liquid water pools.

The far-infrared absorption spectrum of nanometer-sized water pools at the core of AOT micelles exhibits a pronounced resonance which is absent in bulk water. The amplitude and spectral position of this resonance are sensitive to the size of the confined water core. This resonance results from size-dependent modifications in the vibrational density of states, and thus has far-reaching implications for chemical processes which involve water sequestered within small cavities. These data represent the first study of the terahertz dielectric properties of confined liquids.

A lost-wax approach to monodisperse colloids and their crystals.

We report a nanoscale "lost-wax" method for forming colloids with size distributions around 5% and their corresponding colloidal crystals. Macroporous polymer templates are first prepared from a silica colloidal crystal. We then use the uniform and interconnected voids of the porous polymer to generate a wide variety of highly monodisperse inorganic, polymeric, and metallic solid and core-shell colloids, as well as hollow colloids with controllable shell thickness, as colloidal crystals. We can also uniformly deform the polymer template to alter colloidal shape and demonstrate the formation of elliptical particles with precisely controlled aspect ratios.

Effect of film thickness on the performance of photopolymers as holographic recording materials.

An important issue in developing applications for photopolymers in holography is the effect of film thickness on recording properties. Now it is possible to create these samples with a much wider range of thickness (d = 20-1400 mum) than was previously available. We exploit these recent advances in photopolymer processing to systematically evaluate how the dynamic range of a photopolymer depends on its thickness. The results illustrate that sample performance increases linearly with thickness as predicted by standard models of volume holography. However, above a critical thickness sample performance degrades, and the angular response of recorded plane-wave holograms shows evidence of grating curvature. These distortions are likely the result of photopolymer shrinkage, which in thicker samples occurs in a nonuniform fashion. This problem limits the performance of these photopolymers and is likely to be an issue for any photopolymer that undergoes comparable polymerization shrinkage.