Function targeted monomer development for ring-opening metathesis polymerization: Fundamentals and applications

In this thesis, the results of a comprehensive study on the development and use of ring-opening metathesis polymerization (ROMP) for the synthesis of new materials with nano- and biotechnological applications is presented. To accomplish this task, an extensive development of functionalized monomers for ROMP was carried out. Utilizing 5-exo-norbornen-2-ol as a core starting material, dozens of new monomers were prepared in high yield with a wide range of useful functionality. Intermediates suitable for further functional group transformations were synthesized as especially versatile synthons. Utilizing simple organic transformations, several novel doubly polymerizable norbornenyl-modified thiophenes and terthiophenes were synthesized and studied as precursors to networked films of conducting polymers. Advances in polymer drug delivery were made with the isolation of norbornenyl-modified anti-cancer drugs. Using these monomers, well-defined block copolymers containing multiple drugs were prepared and found to be monodispersed, despite the wide-ranging functionality present in the monomers.; We also have achieved the synthesis of nanoparticle/polymer hybrid materials. In this strategy, a norbornenyl-modified thiol was used to anchor initiating norbornene groups on the gold nanoparticle surface. Sequential addition of ROMP catalyst and other monomers led to the isolation of core-shell inorganic/organic structures with tailorable functionality. Finally, a strategy for the isolation of DNA-block copolymer conjugates was developed. Post-polymerization modification was used to couple DNA strands to the backbone of monodispersed ROMP polymers and block copolymers. The recognition properties of the DNA were not adversely affected by attachment to the polymer.