Date of Completion

8-6-2018

Embargo Period

8-6-2018

Keywords

Polyethylene Oxide, Hydration, Atomistic Simulation, Molecular Dynamics, Polymer brush, Solutions

Major Advisor

Elena E. Dormidontova

Associate Advisor

Gayanath W. Fernando

Associate Advisor

Jose A. Gascon

Field of Study

Physics

Degree

Doctor of Philosophy

Open Access

Open Access

Abstract

Amphiphilic water-soluble polymers are actively used in designing novel nanomaterials and have been the subject of extensive experimental and simulation studies. Polyethylene oxide (PEO) is a water soluble, biocompatible, non-toxic synthetic polymer capable of preventing protein adsorption which is widely used in industry and biomedicine for protein crystallization, control of particle aggregation and drug delivery. Most of the applications of PEO and PEO-based nanoparticles are utilized in an aqueous environment as PEO is highly soluble in water due to its ability to form hydrogen bonds with water and therefore understanding the role of water on the conformation and dynamics of PEO and PEO-based nanomaterials is essential in improving and designing new nanomaterials for a variety of applications. Using all-atom molecular dynamics simulations, we studied PEO in bulk solutions, under nanoconfinement in carbon nanotubes and in nanostructures (PEO brushes grafted to a planar surface and nanoparticles). In the bulk solution, we find that PEO forms a globule like structure in hexane, coil-like structure in water or benzene and an extended rod-like or helical structure is isobutyric acid. The conformation and mobility of PEO in water and in isobutyric acid is dictated by the hydrogen bonding with PEO. As part of our confinement studies, we found that PEO is spontaneously encapsulated from aqueous solution into carbon nanotubes and forms rod-like, helical and wrapped chain conformation depending on the size of the carbon nanotube. The stable helix inside the carbon-nanotube is a consequence of the stable water arrangement around PEO. ii As part of our studies of PEO brushes we investigated PEO grafted to gold nanoparticles and planar gold surfaces at varying grafting densities. We found that PEO hydration in the brush depends on grafting density and for gold nanoparticles also varies with the radial distance and nanoparticle radius of curvature. Our simulation results agree well with the classical scaling theories and we were able to explain the curvature dependent hydration based on bulk-solution PEO behavior

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