Graduation Year

2010

Document Type

Dissertation

Degree

Ph.D.

Degree Granting Department

Chemical Engineering

Major Professor

Ryan G. Toomey, Ph.D.

Committee Member

Vinay Gupta, Ph.D.

Committee Member

Norma Alcantar, Ph.D.

Committee Member

John Wolan, Ph.D.

Committee Member

Martin Muschol, Ph.D.

Committee Member

Ashok Kumar, Ph.D.

Keywords

Poly(NIPAAm-co-MaBP), water, AIBN, free radical polymerization, hydrogels, hydrophilic, hydrophobic, pH, neutron reflection, FTIR, Hofmeister series, solid phase peptide synthesis, cloud point, demixing temperature

Abstract

The overall thrust of this dissertation is to gain a comprehensive understanding over the factors that govern the performance and behavior of ultra-thin, cross-linked polymer films. Poly(NIPAAm) was used as a model polymer to study volume phase transition in surface tethered networks.

Poly(NIPAAm) undergoes a reversible phase transition at approximately 32°C between a swollen hydrophilic random coil to a collapsed hydrophobic globule state, thought to be caused by increased hydrophobic attractions between the isopropyl groups at elevated temperatures. We present a simple photochemical technique for fabricating structured polymer networks, enabling the construction of responsive surfaces with unique properties. The approach is based on the photo-cross-linking of copolymers synthesized from N-isopropylacrylamide and methacroyloxybenzophenone (MaBP). In order correlate layer swelling to the MaBP content, we have studied the swelling behavior of such layers in contact with aqueous solutions with neutron reflection.

The cross-linked networks provide a three-dimensional scaffold to host a variety of functionalities. These networks serve as a platform which can be used to amplify small local perturbations induced by various stimuli like temperature, pH, solvent, ionic strength and peptide modified hydrogels to bring about a macroscopic change. Neutron reflection experiments have shown that the volume-phase transition of a surface-tethered, cross-linked poly(NIPAAm) network coincided with the two-phase region of uncross-linked poly(NIPAAm) in solution. Parallel measurements with ATR-FTIR investigating the effect of temperature, pH and salts suggest that the discontinuous transition is the result of cooperative dehydration of the isopropyl groups, with water remaining confined between amide groups in the collapsed state as weakly hydrogen bonded bridges. Hybrid polymers with specific peptide sequences have shown specific response to external cues such as pH and metal ions exhibiting unique phase behavior.

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