Defense Date

2008

Document Type

Dissertation

Degree Name

Doctor of Philosophy

Department

Chemistry

First Advisor

Dr. Maryanne M. Collinson

Abstract

Magnetic nanoparticles are of great interest for a wide range of applications. This work has focused on three primary forms of iron based nanoparticles and combinations thereof: α-iron, iron oxide, and iron carbide or cementite. The synthesis of several core-shell particles including cementite-iron oxide, α-iron-cementite, and α-iron-iron oxide was accomplished through reverse micelle routes and high temperature decomposition of iron pentacarbonyl in various media. Structural analysis to confirm the structures was performed using extended x-ray absorption fine structure (EXAFS) techniques. A rapid characterization technique was developed utilizing a correlation between Fourier transform infrared spectroscopy and EXAFS to determine the full metal cation distribution between the octahedral and tetrahedral sites in manganese zinc ferrite (MZFO). This method was then used to show that the initial Fe3+ to Fe2+ ratio in MZFO synthesis could be used to design a desired cation distribution and affected the zinc incorporation levels into the resultant ferrite. Functionalization of nanoparticles for aqueous dispersions and ferrofluids has varying degrees of importance, depending on the application. In applications such as magnetic resonance imaging (MRI) where the targets are biological systems, it was important to produce solutions that will not aggregate in the high magnetic field of the MRI. It was also vital to characterize decomposition mechanisms and products that would be presented to the body after use as a contrast agent. This work has provided insight into both the preparation of magnetic samples for MRI applications and implications of the biocompatibility of reactive and decomposition products. Three successful methods of forming dispersions that would not aggregate in the high magnetic field of the MRI were comprised of cysteine/polyethylene glycol (PEG), PEG based ferrofluids, and dopamine/PEG. The dopamine functionalization however showed reactivity with the iron/iron oxide nanoparticles and led to the formation of the cytotoxic dopamine quinone and resulted in the destruction of the nanoparticles. Using all three types of dispersions to compare the iron based nanomaterials, the MRI measurements concluded with the iron oxide ferrofluid yielding the highest R2 enhancement.

Rights

© The Author

Is Part Of

VCU University Archives

Is Part Of

VCU Theses and Dissertations

Date of Submission

June 2008

Included in

Chemistry Commons

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