Date of Award

1-1-2011

Document Type

Campus Access Thesis

Department

Chemistry and Biochemistry

Sub-Department

Chemistry

First Advisor

Ken D Shimizu

Abstract

Recently, a new type of stimuli-responsive polymer, named solvent programmable polymers (SPPs), was developed by ring-opening metathesis polymerization (ROMP) based on monomers containing recognition groups that display restricted rotation. We could modulate the binding properties of the SPPs by heating in polar or non-polar solvents (water/acetonitrile). The SPPs are also able to remember their stimuli-induced binding properties even when removed from the switching environment. In this project, our goal is to use these tunable polymer gels for the separation of mixture solutions of different analytes. First, we synthesized the SPP gels and verified their switching and memory properties. Next, we individually measured the binding capacities of the SPPs against a wide range of potential analytes and selected potential analytes pairs for selective separation by different affinity SPPs. We identified potential analytes pairs that have similar binding capacities with the SPPs in one state but have different binding capacities with the SPPs in another state. Then we tested the ability of the SPPs in different states to separate binary solutions of analytes. And we found analytes pairs: 5-aminoquinoline and EA9A, 8-aminoquinoline and 1-naphthylamine, can use the SPPs for tunable separations. Thus these SPPs demonstrate the tunable separation abilities with analytes mixture solutions.

The second project is the synthesis of well controlled cobaltocenium-containing homopolymer by "living" ROMP. Cobaltocenium-containing polymers are much less common than ferrocene-containing polymers, because the cobaltocene is easily oxidized and the cobaltocenium salts are very inert to be modified. Based on several coblatocenium-containing polymers reported recently, we developed the first well controlled cobaltocenium-containing homopolymer by living ROMP, and we checked the living polymerization by kinetic study. Since the special electrochemical, catalytical, and optical properties of cobaltocenium, we believe this metallocene-containing polymer would have many interesting applications such as electrodes sensoring materials.

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