Open Access Dissertation
Date of Award
Physics and Astronomy
Soft matter systems of colloidal particles, polymers, amphiphiles and liquid crystals are ubiquitous in our everyday life. Food, plastics, soap and even human body is comprised of soft materials. Research conducted to understand the behavior of these soft matter systems at molecular level is essential for many interdisciplinary fields of study as well as important for many technological applications.
We used gold nanoparticles (Au NPs) to investigate the length-scale dependent dynamics in semidilute poly(ethylene glycol) (PEG)-water, bovine serum albumin (BSA)-phosphate buffer, dextran and particulate solutions. In case of PEG-water solutions, fluctuation correlation spectroscopy was used to measure the diffusion coefficients (D) of the NPs as a function of their radius, Ro (2.5-10 nm), PEG volume fraction 0-0.37, and molecular weight, Mw (5 kg/mol and 35 kg/mol). Our results indicate that the radius of gyration, Rg of the polymer chain is the crossover length scale for the NPs experiencing nanoviscosity or macroviscosity.
In BSA-phosphate buffer solutions, we observed a monolayer formation at the NP surface with a thickness of 3.8 nm. The thickness of the adsorbed layer was independent of NP size. Best fit was obtained by the anticooperative binding model with the Hill coefficient of n = 0.63. Dissociation constant (KD) increased with particle size indicating stronger interaction of BSA with smaller sized NPs.
We also contrasted the diffusion of gold nanoparticles (AuNPs) in crowded solutions of randomly branched polymer (dextran) and rigid, spherical particles (silica) to understand the roles played by the probe size and structure of the crowding agent in determining the probe diffusion. AuNPs of two different sizes (2.5 nm & 10 nm), dextran of molecular weight 70 kDa and silica particles of radius 10 nm were used. Our results indicated that the AuNP diffusion can be described using the bulk viscosity of the matrix and hydrodynamically dextran behaved similar to soft colloid. In all situations, we observed normal diffusion except for 2.5 nm sized AuNP particles in dextran solution at higher volume fraction. This was caused by transient trapping of particles within the random branches. The results showed the importance of macromolecular architecture in determining the transport properties in intracellular matrix and in cells with spiny dendrites.
Kohli, Indermeet, "Diffusion Of Gold Nanoparticles In Synthetic And Biopolymer Solutions" (2013). Wayne State University Dissertations. 777.