Silica nanospheres (SNSs) of ca. 15 nm in diameter assemble into nanoring structures with the aid of amphiphilic block copolymers containing the oxyethylene side chains poly[(2-ethoxyethyl vinyl ether)-block-(2-methoxyethyl vinyl ether)] [poly(EOVE-b-MOVE)]. Cryo-transmission electron microscope observation confirms that the ring assembly of SNSs occurs in the liquid phase. The SNSs favorably assemble into ring-like nanostructures in the presence of 1-2 wt% EOVE100-b-MOVE310 at pH ∼7.8 and 45 °C. Irregular aggregates of SNSs form at 60 °C, most likely because of the hydrophobic collapse of the thermoresponsive block copolymer. A series of poly(EOVE-b-MOVE) with varying block lengths successfully induce the ring assembly of SNSs, whereas a random copolymer fails, indicating that the polymer's molecular structure critically affects the assembly mode of SNSs. Interestingly, SNSs of a larger size (ca. 30 nm) assemble one-dimensionally into chain-like nanostructures in the presence of EOVE100-b-MOVE310.
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