Date of Award

8-2014

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Legacy Department

Chemical Engineering

Committee Member

Dr. Christopher L. Kitchens, Committee Chair

Committee Member

Dr. David Bruce

Committee Member

Dr. Mark Roberts

Committee Member

Dr. Brian A. Powell

Committee Member

Dr. O. Thompson Mefford

Abstract

Rational design of nanoparticle surface chemistry offers the ability to control nanoparticle characteristics such as size, polydispersity, shape, dispersibility in various solvents, functionality and end fate. Ligand exchange has proved to be is a versatile method for modifying the surface of plasmonic nanoparticles. Ligand exchange has provided a “green” alternative to traditional biphasic syntheses that require large amounts of phase transfer catalysts. Ligand exchange can also be used to reduce the amount of post synthesis processing and waste when it is conducted on nanoparticles that have been synthesized with a method that affords control over nanoparticle size and polydispersity. Ligand exchange is also an important reaction to consider when determining the end fate of nanomaterials due to the fact that when nanoparticles enter the natural environment, they will be exposed to a variety of natural ligands and electrolytes. We have conducted a comprehensive review of ligand exchange literature and used isothermal titration calorimetry to investigate ligand binding and exchange on gold nanoparticles experimentally. We have also investigated the impact that citrate and natural organic matter surface chemistries have on the transport properties of silver nanoparticles. This work has led to a greater understanding of the influencing factors on the mechanism of nanoparticle ligand binding and exchange.

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