Tunable Surface Properties from Bioinspired Comb Copolymers

A modular polymer system which incorporates multiple functionalities simultaneously while keeping an identical backbone chemistry is a useful tool in determining necessary functionalities for marine antifouling properties. We have investigated the surface properties and antifouling behavior of polypeptoids, a class of non-natural biomimetic polymers based on an N-substituted glycine backbone, that combine many of the advantageous properties of bulk polymers with those of synthetically produced proteins, including controllable chain shape, sequence, and self-assembled structure. Using thiol-ene click chemistry, thiol functionalized amphiphilic peptoid sequences consisting of hydrophilic methoxyethyl and hydrophobic heptafluorobutyl side chains were attached to polystyrene-block-poly(ethylene oxide-stat-allyl glycidyl ether), creating comb-shaped molecules. Near edge X-ray absorption fine structure spectroscopy (NEXAFS) was used to study the surface characteristics as a function of peptoid length and composition. Only 20{\%} of fluorinated groups in the peptoid were sufficient for promoting surface display of the otherwise hydrophilic PEO/peptoid comb block. Antifouling experiments with spores of the green algae Ulva indicated an influence of sequence.