Document Type


Date of Degree

Summer 2016

Degree Name

PhD (Doctor of Philosophy)

Degree In


First Advisor

Larsen, Sarah C

First Committee Member

Grassian, Vicki H

Second Committee Member

Geng, M Lei

Third Committee Member

MacGillivray, Leonard R

Fourth Committee Member

Wohlgenannt, Markus


Primarily concerned with manipulation and study of matter at the nanoscale, the concept of nanoscience encompasses ideas such as nanomaterial synthesis, characterization, and applications to modern scientific and societal problems. These problems encompass a broad range of issues such as energy storage and conversion, medical diagnostics and treatment, environmental remediation and detection, carbon economy and as well as many others. Silica nanoparticles of porous morphology have broad application to many of these issues. In particular, the utility of silica nanoparticles is facilitated by their large intrinsic surface area, tunable surface chemistry, and synthetic variability in both their size and morphology. This facilitates applications to these problems. However, extensive characterization and deeper understanding is needed before full implementation in key applications can be realized.

The work described in this thesis aims to explore fundamental and applied characterization of silica nanoparticles that might be used in biomedical and environmental applications. Fundamental studies of functionalized nanomaterials using NMR spectroscopy reveal complex, dynamic phenomena related to-and ultimately deriving from-the intrinsic and/or modified surface chemistry. Applied studies of nanomaterial-biological interfaces demonstrate free radical chemistry as dominating the toxic response of the materials when exposed to biological systems of interest. Characterization of protein adsorbed on the interface reinforces the ubiquitous nature of protein adsorption on nanomaterial surface in biological and environmental media. Overall, this work illuminates and highlights complex changes that take place in aqueous solution for silica nanoparticles of varied morphology and surface chemistry.


EPR, Mesoporous Silica, Nano-Bio, Nanotoxicity, NMR, Supramolecular


xiv, 168 pages


Includes bibliographical references (pages 157-168).


Copyright 2016 Sean E. Lehman

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Chemistry Commons