Enzymatic Synthesis and Polymerization of Saccharide-Vinyl Monomers in Aqueous Systems

Carbohydrates are a renewable biomass in which they are formed regularly through photosynthetic reactions in plants. The varieties of different carbohydrates in nature is abundant. However, the utilization of carbohydrates as polymeric materials only arose in the last few decades due to several reasons: First, most polymers are generated from fossil resources that are predicted to be exhausted in the next several hundred years. Therefore, carbohydrates offer an alternative renewable feedstock for this purpose. Second, the human awareness of creating more sustainable polymers, that have less impact on the environment compared to the fossil-based polymers, was improved. Third, novel functional polymeric materials can be developed when resources with complex functionalities, like carbohydrates, are incorporated in the polymeric structures. For example, in recent years, it was reported that glycopolymers which are comprised of carbohydrates as pendant moieties have been developed and are suitable for applications such as disease inhibitors, biosensors, and drug delivery systems. Glycomonomers, the precursor of these glycopolymers, consist of saccharide units that are linked to some polymerizable groups. Currently, vinyl groups are the most exploited ones. This thesis discusses the synthesis of several glycomonomers and polymerization of the monomers via environmentally friendly methods. The synthesis of saccharide-vinyl (macro)monomers utilized carbohydrates as starting materials and enzymes as biocatalyst. In addition, the glycomonomers were successfully polymerized by reversible addition–fragmentation chain transfer polymerization, free radical polymerization (FRP), and enzyme-mediated FRP in aqueous solvents. Double-hydrophilic and amphiphilic block glycopolymers were prepared and their self-assembly resulting in polymeric micelles was studied