Date of Award

Fall 12-2016

Degree Type


Degree Name


Degree Program




Major Professor

Dr. Steven W. Rick

Second Advisor

Dr. Mark L. Trudell

Third Advisor

Dr. Wendy M. Schluchter

Fourth Advisor

Dr. Henry S. Ashbaugh


Polymers that undergo dramatic changes in structural conformations in response to numerous stimuli such as temperature, pH, electric and magnetic fields, light inten- sity, biological molecules, and solvent polarity, are known as stimuli-responsive or ”smart” polymers. There is a broad range of very promising applications of these materials in catalysis, environmental remediation, sensors or actuator systems, and as delivery systems of therapeutic agents. Researchers have been trying to mimic smart polymers based on properties of polymers found in nature such as proteins, carbohydrates and nucleic acids. Novel bio-compatible polymers with a variety of chemical functional groups, diverse topologies, and cross-linking patterns with the ability to self-assemble in vivo are being engineered.

Experimental and theoretical studies indicate that the thermodynamic properties relating to the hydrophobic effects play a pivotal role in determining the self-assembly process in smart polymers. At the same time, computational approaches based on simulation and modeling provide an understanding of this phenomenon on the micro- scopic level. Building empirical models based on statistical mechanics methods and

simulation data helps to design polymeric materials with desirable traits.

My research is mainly focused on investigating physicochemical characteristics of stimuli-responsive polymers under different conditions. I used atomistic molecular dynamics simulations to investigate these effects on polymer conformation. Given the size and complexity of our polymeric systems, we employed Graphical Process- ing Units (GPU) and enhanced sampling techniques such as REDS2 to increase the sampling time. These methods allow for the study of polymeric structural dynamics in solvents of varying polarity and in human skin epidermis.

Our constant pH simulation of poly(methacrylic acid) revealed that the overall response is made up of local and global structural changes. The local structural re- sponse depends on the tacticity of the polymer, which leads to distinct cooperative effects for polymers with varying stereochemistry. Such simulations help to under- stand the principal driving forces behind the mechanism of self-assembly processes.


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