Optimization and Characterization of Fluorinated Zwitterionic Polymeric Coatings via Surface-initiated Atom Transfer Radical Polymerization
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Zwitterionic materials form strong hydration layers that effectively prevent protein adsorption but have a low fouling-release rate, whereas fluorinated materials, even though they have a high adsorption rate, still have a high fouling-release rate due to their low surface free energy. In this work, a series of zwitterionic and fluorinated monomers was synthesized and grafted onto surfaces via surface-initiated atom transfer radical polymerization (SI-ATRP). Ligand selection and solvent screening were performed to achieve a well-defined polymer brush thickness and surface uniformity. Comprehensive characterization, including ellipsometry, Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), sum frequency generation (SFG), and surface plasmon resonance (SPR), confirmed the structures, hydration behavior, and protein adsorption. Moderate fluorination preserved antifouling behavior, while high fluorination introduced hydrophobicity and reduced performance. Our results provide practical design principles for next-generation antifouling coatings.