Responsive Shape Change of Sub-5 nm Thin, Janus Polymer Nanoplates

Responsive shape changes in soft materials have attracted significant attention in recent years. Despite extensive studies, it is still challenging to prepare nanoscale assemblies with responsive behaviors. Herein we report on the fabrication and pH-responsive properties of sub-5 nm thin, Janus polymer nanoplates prepared via crystallization-driven self-assembly of poly(ε-caprolactone)-b-poly(acrylic acid) (PCL-b-PAA) followed by cross-linking and disassembly. The resultant Janus nanoplate is comprised of partially cross-linked PAA and tethered PCL brush layers with an overall thickness of ∼4 nm. We show that pronounced and reversible shape changes from nanoplates to nanobowls can be realized in such a thin free-standing film. This shape change is achieved by exceptionally small stress-a few orders of magnitude smaller than conventional hydrogel bilayers. These three-dimensional ultrathin nanobowls are also mechanically stable, which is attributed to the tortoise-shell-like crystalline domains formed in the nanoconfined curved space. Our results pave a way to a new class of free-standing, ultrathin polymer Janus nanoplates that may find applications in nanomotors and nanoactuators.