Melanie L. Mastronardi

Preparation of Monodisperse Silicon Nanocrystals Using Density Gradient Ultracentrifugation

We report the preparation of monodisperse silicon nanocrystals (ncSi) by size-separation of polydisperse alkyl-capped ncSi using organic density gradient ultracentrifugation. The ncSi were synthesized by thermal processing of trichlorosilane-derived sol-gel glasses followed by HF etching and surface passivation with alkyl chains and were subsequently fractionated by size using a self-generating density gradient of 40 wt % 2,4,6-tribromotoluene in chlorobenzene. The isolated monodisperse fractions were characterized by photoluminescence spectroscopy and high-angle annular dark-field scanning transmission electron microscopy and determined to have polydispersity index values between 1.04 and 1.06. The ability to isolate monodisperse ncSi will allow for the quantification of the size-dependent structural, optical, electrical, and biological properties of silicon, which will undoubtedly prove useful for tailoring property-specific optoelectronic and biomedical devices.

Silicon Nanocrystal OLEDs: Effect of Organic Capping Group on Performance

The synthesis of highly luminescent, colloidally-stable and organically-capped silicon nanocrystals (ncSi) and their incorporation into a visible wavelength organic light-emitting diode (OLED) is reported. By substituting decyl chains with aromatic allylbenzene capping ligands and size-selecting visible emitting ncSi, superior packing density, enhanced charge transport, and an improved photoluminescence absolute quantum yield of the ncSi is obtained in the active layer of an OLED.

Non-wettable, oxidation-stable, brightly luminescent, perfluorodecyl-capped silicon nanocrystal film.

Here we describe for the first time the synthesis of colloidally stable, brightly luminescent perfluorodecyl-capped silicon nanocrystals and compare the properties of solutions and films made from them with those of their perhydrodecyl-capped relatives. The perfluorodecyl capping group compared to the perhydrodecyl capping group yields superior hydrophobicity and much greater resistance to air oxidation, the enhanced electron-withdrawing character induces blue shifts in the wavelength of photoluminescence, and the lower-frequency carbon-fluorine stretching modes disfavor non-radiative relaxation pathways and boost the absolute photoluminescence quantum yield. Together these attributes bode well for advanced materials and biomedical applications founded upon perfluorodecyl-protected silicon nanocrystals.

Enhanced cellular uptake of size-separated lipophilic silicon nanoparticles

Specific size, shape and surface chemistry influence the biological activity of nanoparticles. In the case of lipophilic nanoparticles, which are widely used in consumer products, there is evidence that particle size and formulation influences skin permeability and that lipophilic particles smaller than 6 nm can embed in lipid bilayers. Since most nanoparticle synthetic procedures result in mixtures of different particles, post-synthetic purification promises to provide insights into nanostructure-function relationships. Here we used size-selective precipitation to separate lipophilic allyl-benzyl-capped silicon nanoparticles into monodisperse fractions within the range of 1 nm to 5 nm. We measured liposomal encapsulation and cellular uptake of the monodisperse particles and found them to have generally low cytotoxicities in Hela cells. However, specific fractions showed reproducibly higher cytotoxicity than other fractions as well as the unseparated ensemble. Measurements indicate that the cytotoxicity mechanism involves oxidative stress and the differential cytotoxicity is due to enhanced cellular uptake by specific fractions. The results indicate that specific particles, with enhanced suitability for incorporation into lipophilic regions of liposomes and subsequent in vitro delivery to cells, are enriched in certain fractions.