Design, Synthesis, and Applications of Functional Hyperbranched Poly(arylene oxindole)s

Nature has inspired scientists to push the boundaries of science. Branched macromolecular structures resemble branching found in nature from the nano to macro-scale (e.g. from veins to trees). The focal point of this thesis is a hyperbranched poly(arylene oxindole) (HBPAO) three-dimensional structure. HBPAOs have a globular, dendritic architecture with abundant functional groups, intramolecular cavities, tunable solubility and are facilely synthesized in a one-step polymerization. By exploiting unique extraordinary properties of the HBPAO, we report diverse smart material applications in two distinct fields. Catalysis enables us to perform reactions more efficiently and plays an important role both in industry and in academia. HBPAOs potentially provide a mimic of enzyme pockets, nature's best catalysts, improving catalytic efficiency compared to their non-supported corresponding catalysts. Cooperative effects within the macromolecular network, both by bringing reagents in close proximity or by bimetallic hydride transfer, thus improving catalytic efficiency are reported in this thesis. Hyperbranched polymers (HBPs) are expected to play an important role in biomedical science in the future. The versatility of HBPAOs is demonstrated by reporting two bioapplications, tissue engineering and formation of nanocarriers. The unique advantages, such as cytocompatibility and multivalent character, of HBPAOs make them outstanding candidates for bioapplications. Hydrophobic HBP-based bioapplications are scarcely reported, yet the provided examples involving hydrophobic HBPAOs prove their potential. We also report a synthetic methodology protocol useful to material science, chemical biology or medicinal chemistry. By merging dehydrogenative activation and cross-coupling, we report a prior non-existent one-step alternative to an often-used multi-step synthesis. The methodology also provides a valuable alternative synthesis to an important building block necessary to prepare HBPAOs.status: publishe