Characterization Techniques for Aggregated Nanomaterials in Biological and Environmental Systems

Abstract

Nanoparticles, which are defined as objects with characteristic lengths in the 10^-9 – 10^-7 m (nanoscale) size range, are used with increasing frequency in a wide of applications, leading to increases in nanomaterial interactions with biological and environmental systems. There is therefore considerable interest in studying the influence nanomaterials can have when inside the human body or dispersed in the ambient environment. However, nanoparticles persist as homo aggregates or heterogeneous mixtures with organic matters, such as proteins, in biological and environmental systems. A large and growing body of research confirm that nanomaterial morphology as well as the degree of aggregation between nanomaterials influences nanomaterial interactions with their surroundings. Specifically, the structures/morphologies of nanoparticles determine their overall surface areas and corresponding surface reactivity (e.g. their catalytic activity). Nanoparticle transport properties (e.g. diffusion coefficient and extent of cellular uptake) are also determined by both their structures and surface properties. Unfortunately, techniques to characterize nanomaterial size and shape quantitatively, when nanomaterials have complex geometries or persist as aggregates, are lacking. Hydrodynamic sizes of nanoparticles and their aggregates can be inferred by dynamic light scattering (DLS) or nanoparticle tracking analysis (NTA). However, since these techniques are relied on the scattering light intensity properties, sizes of polydisperse sub 30 nm particles cannot be effectively measured in those techniques. For structure inference of aggregated nanomaterials, microscopy images have been used for qualitative visual analysis, but the quantitative morphology analysis technique is yet to be developed. Five studies in this dissertation are hence aimed to develop new techniques to provide improved morphology characterization of aggregated nanomaterials in various biological and environmental colloidal systems. Aggregation mechanism and behavior of nanoparticles in surrounding were examined as a function of their quantified aggregate morphologies. The first three studies (Chapters 2, 3, and 4) introduced a new gas-phase particle size measurement system, a liquid nebulization-ion mobility spectrometry (LN-IMS) technique, to characterize nanomaterials (down to 5 nm in characteristic size) and nanoparticle-protein conjugates. In other two studies (Chapters 5 and 6), three dimensional structures of homo-aggregates were quantified with the fractal aggregate model, and resulted fractal structures of aggregates were correlated to their transport properties in surroundings.