Stably Grafting Polymer Brushes on Both Active and Inert Surfaces Using Tadpole-Like Single-Chain Particles with an Interactive "Head".

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We report a "grafting to" method for stably grafting high-molecular-weight polymer brushes on both active and inert surfaces using tadpole-like single-chain particles (TSCPs) with an interactive "head" as grafting units. The TSCPs can be efficiently synthesized through intrachain cross-linking one block of a diblock copolymer; the "head" is the intrachain cross-linked single-chain particle, and the "tail" is a linear polymer chain that has a contour length up to micrometers. When grafted to a surface, the "head", integrating numerous interacting groups, can synergize multiple weak interactions with the surface, thereby enabling stable grafting of the "tail" on both active and traditionally challenging inert surfaces. Because the structural parameters and composition of the "heads" and "tails" can be separately adjusted over a wide range, the interactivity of the "heads" with the surface and properties of the brushes can be controlled orthogonally, accomplishing surface brushes that cannot be achieved by existing methods.