A multiplexed separation of iron oxide nanocrystals using variable magnetic fields.

The size-dependent magnetic properties of nanocrystals are exploited in a separation process that distinguishes particles based on their diameter. By varying the magnetic field strength, four populations of magnetic materials were isolated from a mixture. This separation is most effective for nanocrystals with diameters between 4 and 16 nm.

Reaction of water-stable C60 aggregates with ozone.

While the reactivity of C60 has been described in a variety of organic solvents, little information is available regarding aqueous-based reactions due to solubility limitations. In this study, a reaction between C60, as a nanoscale suspension, and dissolved ozone in the aqueous phase was investigated. Findings indicate a facile reaction occurs, resulting in aggregate dissolution concurrent with formation of water-soluble fullerene oxide species. Product analyses, including 13C NMR, MS (LDI), FTIR, UV-Vis, and XPS, indicate highly oxidized fullerene with an average of approximately 29 oxygen additions per molecule, arranged in repeating hydroxyl and hemiketal functionalities. These findings are significant in that they (1) demonstrate the feasibility of other aqueous-based fullerene chemistries, including those for alternative synthesis routes, which might otherwise be considered prohibitive on the basis of solubility limitations, and (2) imply that the aqueous reactivity of fullerene-based materials must be considered appropriately for accurate assessment of their transport, fate, and potential risk(s) in environmental systems.

Forming biocompatible and nonaggregated nanocrystals in water using amphiphilic polymers.

High-quality nanocrystals formed in organic solvents can be completely solubilized in water using amphiphilic copolymers containing poly(ethylene glycol) or PEG. These copolymers are generated using a maleic anhydride coupling scheme that permits the coupling of a wide variety of PEG polymers, both unfunctionalized and functionalized, to hydrophobic tails. Thermogravimetric analysis, size exclusion chromatography, cryogenic transmission electron microscopy, and infrared spectroscopy all indicate that the copolymers effectively coat the nanocrystals surfaces. The composite nanocrystal-polymer assemblies can be targeted to recognize cancer cells with Her2 receptor and are biocompatible if their surface coatings contain PEG. In the particular case of semiconductor nanocrystals (e.g., quantum dots), the materials in water have the same optical spectra as well as quantum yield as those formed initially in organic solutions.

Low-field magnetic separation of monodisperse Fe3O4 nanocrystals.

Magnetic separations at very low magnetic field gradients (<100 tesla per meter) can now be applied to diverse problems, such as point-of-use water purification and the simultaneous separation of complex mixtures. High-surface area and monodisperse magnetite (Fe3O4) nanocrystals (NCs) were shown to respond to low fields in a size-dependent fashion. The particles apparently do not act independently in the separation but rather reversibly aggregate through the resulting high-field gradients present at their surfaces. Using the high specific surface area of Fe3O4 NCs that were 12 nanometers in diameter, we reduced the mass of waste associated with arsenic removal from water by orders of magnitude. Additionally, the size dependence of magnetic separation permitted mixtures of 4- and 12-nanometer-sized Fe3O4 NCs to be separated by the application of different magnetic fields.

Antibacterial activity of fullerene water suspensions: effects of preparation method and particle size.

Fullerene research in biological systems has been hindered by the compound's relative insolubility in water. However, C60 molecules can be made to aggregate, forming stable fullerene water suspensions (FWS) whose properties differ from those of bulk solid C60. There are many different protocols for making FWS. This paper explores four of these methods and establishes the antibacterial activity of each resulting suspension, including a suspension made without intermediary solvents. The aggregates in each polydisperse suspension were separated by size using differential centrifugation and tested for antibacterial activity using Bacillus subtilis as a test organism. All suspensions exhibited relatively strong antibacterial activity. Fractions containing smaller aggregates had greater antibacterial activity, although the increase in toxicity was disproportionately higher than the associated increase in putative surface area. This suggests the need for improved understanding of the behavior of FWS towards organisms and in the environment to determine how C60 can be safely used and disposed.

Solvothermal synthesis and characterization of anatase TiO2 nanocrystals with ultrahigh surface area.

Phase-pure, ultrafine nanocrystalline anatase with high specific surface area (up to 250 m(2) g(-1)) was obtained upon injection of a titanium alkoxide precursor into ethanol with designed volume of water under mild solvothermal conditions (<200 degrees C, 2 h). Primary particle sizes were tuned by adjusting various reaction parameters, with the smallest grain sizes occurring at low temperatures (140-150 degrees C), low initial alkoxide concentrations, and intermediate hydrolysis ratios (r identical with[H2O]/[Ti(OR)4]=5-10). Additionally, variations in the reaction temperature result in changes in particle morphology and distribution, with high-temperature samples exhibiting bimodal distributions of small spherical and larger cubic particles that suggest grain growth via Ostwald ripening. A crystalline product with high thermal stability and specific surface area up to 5 times that of commercial nano-titania can be obtained at a relatively low temperature of 150 degrees C. The physical properties of the titania samples obtained in this study suggest they might be well suited for catalytic applications.

Characterization of nanocrystalline CdSe by size exclusion chromatography.

High-performance size exclusion chromatography (HPSEC) is a powerful tool for probing the size and size distribution of complex materials. Here we report its application to the analysis of cadmium selenide nanocrystals produced in organic solvents. If nanocrystal-column interactions are minimized, this method provides an accurate measure of nanocrystal hydrodynamic diameter directly in solution; such information is complementary to TEM in that it can measure the thickness of various capping agents. While the resolution of single-pass HPSEC is limited to 1 nm, we show here that recycling size exclusion chromatography can be applied to assess the fine details of a sample's distribution. Finally, semiconductor nanocrystals can be made a variety of shapes whose optical characteristics are difficult to distinguish. HPSEC can be applied to the general problem of shape separations which we demonstrate with a tetrapod material.

Analytical ultracentrifugation for characterizing nanocrystals and their bioconjugates.

Analytical ultracentrifugation (AU) provides a general way to probe the polydispersity of nanoparticles and the formation of bioconjugates in solution. Unconjugated gold nanocrystals show sedimentation coefficient distributions that are in agreement with size distributions as measured by TEM. AU is sensitive to the size/shape changes elicited by conjugation, in this case to lactose repressor (LacI). AU data reveal saturating protein concentrations for conjugates that correspond to the measured stoichiometry of the complex under these conditions.

Virus crystals as nanocomposite scaffolds.

The generation of long-range three-dimensional nanoscopic patterns is a major goal in materials chemistry. Here we report a strategy for creating such systems using virus crystals as scaffolds which can be infiltrated with metal specifically palladium and platinum. The inorganic component effectively packs within the porous macromolecular crystal architecture, providing a route for patterning these materials on the nanometer length scale. To verify the quality of the metal infiltration, SEM-EDX was used to determine the homogeneous distribution of metal across the crystal, and TEM was used to confirm that the metal was confined within the porous structure of the crystal.

Synthesis of monodisperse iron oxide nanocrystals by thermal decomposition of iron carboxylate salts.

Iron oxide (Fe(3)O(4), magnetite) nanocrystals of 6 to 30 nm with narrow size distributions (sigma = 5-10%) were prepared by the pyrolysis of iron carboxylate salts.

Recycling size exclusion chromatography for the analysis and separation of nanocrystalline gold.

Recycling size exclusion chromatography (RSEC) provides a high-resolution technique for the analysis and separation of materials based on size. We show here the application of this method to gold nanocrystals stabilized by thiols. Alternate recycling is more effective at separating nanomaterials as compared to closed-loop recycling because of its improved efficiency and high resolution. With the use of this technique, we find the resolution ratio of nanocrystal separation increases with the square root of the cycle number, in good agreement with theory. The increased resolution of the size exclusion chromatograms permits the use of RSEC in the baseline separation of nanocrystals which differ by only 6 A in size. In addition to separations, RSEC is valuable as an analytical tool. For example, after recycling processes an initially broad and chromatographic feature from a gold nanocrystal solution resolves into three distinct peaks. Transmission electron microscopy of collected fractions reveals that these peaks correspond to distinct populations of gold nanoparticles with narrowly defined sizes.