Date of Award

12-2006

Degree Type

Dissertation

Degree Name

Ph.D.

Degree Program

Chemistry

Department

Chemistry

Major Professor

O'Connor, Charles

Second Advisor

Wiley,John

Third Advisor

Stokes, Kevin

Fourth Advisor

Harmjanz, Michael

Fifth Advisor

Zhou, Weilie

Abstract

In this thesis, a new synthetic methodology for the high yield synthesis of spineltype transition metal ferrite nanoparticles has been developed. This approach is based on the complexation of the first-row transition metal cations with diethylene glycol (DEG) followed by the hydrolysis of the resulting chelate iron alkoxide complexes in the presence of an alkaline hydroxide. Due to the passivation of their surfaces with DEG molecules, the as-prepared nanoparticles are stable against agglomeration and can be easily dispersed in polar protic solvents (water, alcohols, etc.). Alternatively, a postsynthesis passivation with carboxylate ions can render the iron oxide nanocrystals highly dispersible in non-polar solvents. Optimization of the reaction conditions suggested that the size of the nanocrystals could be controlled by changing the complexing strength of the reaction medium. This hypothesis was verified in the case of the Fe3O4 nanoparticles: their sizes vary from 5.7 nm when the reaction is performed in neat diethylene glycol to 16.8 nm in N-methyl diethanolamine (NMDEA), whereas a 1:1 (%wt) mixture of these solvents yields nanocrystals with an average size of and 12.7 nm. A detailed characterization by using a wide variety of techniques, including powder X-Ray diffraction, IR spectroscopy, thermogravimetric analysis (TGA), transmission electron microscopy (TEM) and 1H-NMR spectrometry was performed in order to elucidate the composition and the morphology of the variable-sized iron oxide nanoparticles. Both finite size and interparticle interaction effects were identified to influence the magnetic behavior of the oleate-capped nanosized particles. At low temperatures the Fe3O4 nanocrystals exhibit a ferromagnetic behavior with blocking temperatures which increase with the average particle size, whereas at room temperature, except for the largest nanoparticles, they undergo a superparamagnetic relaxation. We exploited the high surface reactivity of the 10 nm Fe3O4 nanoparticles to attach 2-3 nm gold grains to their surfaces through a simple, two-step chemically controlled procedure. By chemically bonding bioactive molecules to the attached Au nanoparticles these novel nanoarchitectures open up new opportunities for the implementation of the magnetic nanoparticles as a platform for various applications in the biomedical field.

Rights

The University of New Orleans and its agents retain the non-exclusive license to archive and make accessible this dissertation or thesis in whole or in part in all forms of media, now or hereafter known. The author retains all other ownership rights to the copyright of the thesis or dissertation.

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