Doctoral Dissertations

Date of Award

5-2012

Degree Type

Dissertation

Degree Name

Doctor of Philosophy

Major

Chemistry

Major Professor

Jimmy W. Mays

Committee Members

Bin Zhao, Shawn Campagna, Roberto S. Benson

Abstract

This dissertation presents a review on state-of-the-art research of well-defined charged block copolymers, including synthesis, characterization, bulk morphology and self-assembly in aqueous solution of amphiphilic block polyelectrolytes. In Chapter 1, as a general introduction, experimental observations and theoretical calculations devoted towards understanding morphological behavior in charged block copolymer systems are reviewed along with some of the new emerging research directions. Further investigation of charged systems is urged in order to fully understand their morphological behavior and to directly target structures for the tremendous potential in technological applications. Following this background, in Chapters 2, 3, 4 and 5 are presented the design and synthesis of a series of well-defined block copolymers composed of charged and neutral block copolymers with full characterization: sulfonated polystyrene-b-fluorinated polyisoprene (sPS-b-fPI) and polystyrene-b-sulfonated poly(1,3-cyclohexadiene) (PS-b-sPCHD). Their bulk morphological behaviors in melts and self-assembly of sPS-b-fPI, PS-b-sPCHD in water were investigated. Some unique behaviors of sPS-b-fPI were discovered. The mechanisms for formation of novel nanostructures in aqueous solution are discussed in details in Chapter 4. Spherical and vesicular structures were formed from strong electrolyte block copolymers, e.g. PS-b-sPCHD. Detailed light scattering and transmission electron microscopy were applied to characterize these structures. The abnormal formation of vesicles as well as microstructure effects on self-assembly is discussed in Chapter 5. In Chapter 6, we describe the successful synthesis of a well-defined acid-based block copolymers containing polyisoprene while maintaining the integrity of the iv functionality (double bonds) of polyisoprene. A general purification method is also presented in order to remove homo polyisoprene, polystyrene, and PS-b-PI in the di-, and tri-block copolymers. The self-assembly of PS-b-PI-b-PAA triblock terpolymers was studied in order to form multicompartmental structures in aqueous environments. In the last Chapter 7, detailed synthesis and characterization of a novel conjugate: poly(L-leucine) grafted hyaluronan (HA) (HA-g-PLeu) are presented. This work describes a new method to synthesize HA-g-PLeu via a “grafting onto” strategy. Due to the amphiphilic nature of this graft copolymers, a “local network” formed by self-assembly which was characterized by atomic force microscopy and light scattering. The secondary structure of the polypeptide was revealed by circular dichroism.

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