Tuesday, November 6, 2007 - 1:35 PM
264e

Templated Synthesis Of Mesoporous Hollow Inorganic Nanoparticles

Spyros Monastiriotis, Chemical Engineering, The Graduate Center and The City College of the City University of New York, 140th Street at Convent Avenue, New York, NY 10031 and Alexander Couzis, Chemical Engineering, The City College of the City University of New York, 140th Street at Convent Avenue, New York, NY 10031.

This research focuses on the development of facile scalable methods for the fabrication of porous hollow silica spheres using equilibrium vesicles as templates. As part of the overall project we want to understand how to control pore density and size, as well as the shell thickness. These are the key parameters that control the mass transfer process through the shell and provide the connectivity between the interior hollow space and the exterior environment. The pore structure is determined by the displaying of pore templating entities on the vesicle's outer surface that prevent the silica from depositing and polymerizing in those locations. In effect, the vesicles are templating the structure at two length scales that are decoupled from each other. The first scale determines the diameter of the spheres, which is in the range of 50 to 200 nm and can be tuned by controlling the size of the templating vesicle and the thickness of the inorganic deposited layer. The second length scale determines the porosity of the shell and can be smaller than 5 nm in diameter, again tunable via the molecular weight and molecular shape of the pore templating entity. In this presentation we report on our findings using a catanionic system of equilibrium vesicles that consist of cetyltrimethylammonium bromide (CTAB) and sodium perfluorooctanate (FC7). The vesicle size is tuned by the composition of the two surfactants and characterized using Cryo-Transmission Electron Microscopy and light scattering. The pore-forming entity consists of PEG-lipid amphiphiles that display the PEG functionality of the outer vesicle surface. Adding 2% mole PEG (MW ~ 2000)-amphiphile relative to the total surfactant (CTAB + FC7) into a vesicle solution we observe using light scattering an increase of the average diameter by 7 to 8 nm, which implies that the PEG-amphiphile is at the intermediate state of mushroom – brush regime. Following the incorporation of the PEG, the solution pH is adjusted to a value in the range of 3 to 4.5, and we then introduce the silica precursor (tetramethoxy silane (TMOS)) to the vesicles suspension. Silica deposits and grows around the equilibrium vesicles resulting in the formation of hollow capsules. In the paper we discuss the effects of pH on the structure of the resulting hollow capsules. The templated particles have been characterized using a combination of microscopy techniques (Cryo-Transmission Electron Microscopy and Atomic Force Microscopy) and dynamic light scattering.