Self-assembly of novel lipid-mimicking brush polymers in nanoscale thin films

A series of well-defined poly(oxy(11-phosphorylcholineundecylthiomethyl)ethylene-ran-oxy(n-dodecylthiomethyl)ethylene) (PECH-PCm: m = 0-100 mol% phosphorylcholine (PC)) polymers were used to prepare nanoscale thin films that were characterized by synchrotron X-ray reflectivity (XR) analysis. The quantitative XR analysis provided structural insights into the PECH-PCm thin films. The PECH-PC0 polymer film formed a well-ordered in-plane oriented molecular multibilayer structure, whose individual layers consisted of two sublayers. One sublayer was composed of the fully extended backbones and inner part of the bristles, exhibiting a relatively low electron density, whereas the other sublayer was composed of a bilayer of the outer parts of the bristles without interdigitation. The PECH-PC100 polymer film also formed a well-ordered in-plane oriented molecular multibilayer structure, the individual layers of which were composed of four sublayers rather than two. The bristles in the layer were interdigitated in part via the zwitterionic interactions of the PC end groups. Surprisingly, regardless of the copolymer composition, the PECH-PCm random copolymer molecules in the thin films self-assembled to form a multilayered structure that resembled the structure formed by the PECH-PC100 polymer. These properties have not been observed in other conventional random brush copolymer films. The remarkable multibilayer structures originated from the zwitterionic PC end groups and their favorable interactions and interdigitated structures, which overcame any negative contributions caused by the heterogeneity of the bristles. The unique self-assembly properties of the PECH-PCm polymers always provide a PC-rich surface. The PECH-PCm random copolymers successfully mimicked the molecular bilayer structures formed by natural lipids.