Off-campus UMass Amherst users: To download campus access dissertations, please use the following link to log into our proxy server with your UMass Amherst user name and password.
Non-UMass Amherst users: Please talk to your librarian about requesting this dissertation through interlibrary loan.
Dissertations that have an embargo placed on them will not be available to anyone until the embargo expires.
Open Access Dissertation
Doctor of Philosophy (PhD)
Polymer Science and Engineering
Year Degree Awarded
Polymer and Organic Materials
This thesis describes the synthesis of chemically functionalized nanoparticles and their behavior at interfaces and in conjunction with polymers. Solid-liquid, liquid-liquid, and air-liquid interfaces are useful platforms for studying nanoparticle assembly, especially when nanoparticles are functionalized to enable their segregation to the interface.
At the liquid-liquid interface, double emulsions droplets, both oil-in-water-in-oil and water-in-oil-in-water, stabilized with nanoparticles were prepared. This involved gold nanoparticles stabilizing oil-in-water droplets, and CdSe quantum dots stabilizing water-in-oil droplets. These double emulsion droplets were by simply shaking to give polydisperse droplets, or in a well-defined fashion by microcapillary flow focusing. When nanoparticle-stabilized double emulsions were sized using glass microcapillary devices, they formed a variety of interesting structures that demonstrated the importance of having nanoparticles in the emulsion.
Ligand-functionalized nanoparticles proved emenable to triggered disruption and inversion processes. Two different tetrahydropyranyl protecting groups were employed in the ligand shell of gold nanoparticles enabling an ‘in situ’ droplet inversion, in the presence of acid using either added H+ or photogenerated acid to trigger the desired inversion.
Considering the liquid-solid interface, amphiphilic phosphorylcholine substituted polyolefins stabilized droplets were used to pick up various types of nanoparticles from substrates, and transport the nanoparticles in a fluid driven system. Specifically, decoration of oil-in water droplets with pentafluorophenyl ester groups enabled efficient removal of amine functionalized silica nanoparticles adsorbed on a substrate.
At the air-liquid interface, Langmuir films of gold nanoparticles were prepared where the nanoparticles contained cyclic olefins in their ligand periphery. The films were crosslinked by introduction of a water soluble ruthenium benzylidene catalyst to the aqueous sub-phase, affording two-dimensional elastic networks at the air-water interface.
Bolukbasi, Irem, "Tailoring nanoparticles and polymers for cooperative interfacial and surface interactions" (2015). Doctoral Dissertations. 286.