Many natural proteins contain multiple repeats of functional domains that bind their targets with high avidity and specificity; therefore, multiblock hybrid copolymers containing functional sequences identified from the natural biopolymers will elicit highly coordinated and dynamic interactions with the targeted cells. In this work, tetrazine ligation, the ultrafast cycloaddition of s-tetrazine (Tz) with trans-cyclooctene (TCO) derivatives, is applied to the synthesis of multiblock copolymers using homo-difunctional Tz and TCO derivatives as the building blocks. Monomeric building blocks are selected for the polymerization to be carried out at the immiscible solvent interface. As the polymerization proceeded, high molecular weight polymer fibers were pulled out of the interface. Compared to the corresponding solution phase polymerization, the interfacial process gave rise to polymers with a higher molecular weight and a narrower molecular weight distribution. Inspection of the micron-sized fibers by FIB-SEM revealed the presence of nanosized pores in the fiber interior. The bioorthogonal nature of the tetrazine ligation permits facile incorporation of functional peptides into the multiblock constructs. When an RGD-based peptidic building block was included in the monomer mixture, interfacial bioorthogonal polymerization resulted in the production of cell-adhesive microfibers. The modular approaches allow facile substitution of the polymer and peptide segments to fine-tune the materials properties for applications in tissue engineering.

Functional multiblock hybrid copolymers via interfacial bioorthogonal polymerization

248th National Meeting (2014)

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