Intermolecular Interaction of Polymer Brushes Containing Phosphorylcholine and Inverse-Phosphorylcholine.

Choline phosphate (CP) is a phosphobetaine-type zwitterionic functional group, referred to as inverse phosphorylcholine (PC) due to the reverse orientation of a positively charged quaternary amine and anionic phosphate in contrast to PC lipids in nature. The A unique dipole paring between CP and PC groups has attracted much attention in the biointerface research field. Herein, to evaluate the molecular interaction between the CP and PC groups in water, force-distance curve measurements using scanning probe microscopy (SPM) with a PC-group-functionalized cantilever was carried out on the surface of polymer brushes bearing the CP groups. Three types of methacrylate monomers bearing CP with ethyl (Et), methoxyethyl (MOE), and isopropyl (iPr) phosphates were synthesized in 42-71% yields, and polymerized by surface-initiated atom transfer radical polymerization to form polymer brushes on silicon wafers. The surface free energy of CP-polymer brushes with Et, MOE, and iPr was estimated to be 64.0, 61.4, and 57.4 mN m-1, respectively, based on contact angle measurements. Force-distance curve measurements of polymer brushes having a CP group was conducted in water at 25 °C by SPM using a spherical probe produced by attaching a silica particle (SiP; d = 25 μm) covered with PC or CP groups to a tipless cantilever. Adhesion force larger than 14 nN was observed between the CP-polymer brushes and PC-SiP, whereas PC-polymer brushes revealed extremely low adhesion force of less than 0.6 nN with PC-SiP and propylsilane-modified SiP. The specific attractive molecular interaction between CP and PC groups was quantitatively evaluated.