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| - Y-Shaped Amphiphilic Brushes with Switchable MicellarSurface Structures
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| - We observed novel nanoscale surface structures of segregated pinned micelles and craterlikemicelles formed by grafted Y-shaped molecules and their reversible reorganization in selective solvents.The Y-shaped molecules have two incompatible polymer chains (polystyrene and poly(tert-butyl acrylate))attached to a functional stemlike segment capable of covalent grafting to a functionalized silicon surface.Postgrafting hydrolysis of poly(tert-butyl acrylate) arms imparts amphiphilicity to the brush. We demonstratedthat spatial constraints induced by a chemical junction of two relatively short (6−10 nm) dissimilar arms insuch Y-shaped molecules lead to the formation of segregated micellar surface nanostructures in the graftedlayer. We proposed a model of these segregated pinned micelles and the corresponding reverse micelles(craterlike structures) featuring different segregation states of hydrophobic polystyrene and hydrophilic poly(acrylic acid) arms. The arms undergo conformational rearrangements in selective solvents in a controlledand reversible fashion. These nanoscale structural reorganizations define adaptive macroscopic wettingsurface properties of the amphiphilic Y-shaped brushes. This surface structure and switchable behaviorcan be considered as a promising way toward the patterning of solid substrates with adaptive nanowells,which could be used for trapping of adsorbing nanoscale objects.
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