Development of Functional Biointerface Using Mixed Zwitterionic Silatranes

Strategies to design multifunctional interfaces for biosensors have been extensively investigated to acquire optimal sensitivity, specificity, and accuracy. However, heterogeneous ingredients in clinical samples inevitably generate background signals, exposing challenges in biosensor performance. Polymer coating has been recognized as a crucial method to functionalize biointerfaces by providing tailored properties that are essential for interacting with biological systems. Herein, we introduce for the first time two oligomeric silatranes, MPS-MPC_<i>n</i> and MPS-PEGMACOOH_<i>m</i>, which were copolymerized from mercaptopropylsilatrane (MPS) with either zwitterionic monomer 2-methacryloyloxyethyl phosphorylcholine (MPC) or carboxylated poly(ethylene glycol) methacrylate (PEGMACOOH) through thiol-ene polymerization. These oligomeric silatranes were prepared individually and in combinations in acidic and nonacid solvents for deposition on silicon wafers. Afterward, coating properties, including wettability, thickness, and elemental composition, were characterized by contact angle meter, ellipsometer, and X-ray photoelectron spectroscopy (XPS), respectively. Importantly, MPS-MPC_<i>n</i> polymers were found to form thin films with high hydrophilicity and superior fouling repulsion to bacteria and protein, while mixed coating involving 70% MPS-PEGMACOOH_2.5 and 30% MPS-MPC_2.5 exhibited thinnest coating with best wettability among COOH-terminated coatings. Furthermore, the functional COOH group in the coated surfaces was exploited for postmodification with biological molecules via intermediated <i>N</i>-hydroxysuccinimide (NHS) ester group by amine coupling chemistry. Once again, the combination of 70% MPS-PEGMACOOH_2.5 and 30% MPS-MPC_2.5 provided an ultimate reduction in nonspecific adsorption (NSA) and established a finest signal discrimination through enzyme-linked immunosorbent assay. Consequently, these novel mixed oligomeric silatranes offer a promising approach for the construction of biosensor interfaces with dual functions in both nonspecific binding prevention and conjugation of biomolecules.