A fluorous functional nanospace was created within the fluorine-condensed microgel-core in a star polymer (F-Star), which induced efficient, selective, and stimuli-responsive molecular recognition (see the attached illustration; Macromolecules 2011 , 44, 4574).  F-Stars were efficiently synthesized by locally crosslinking macro-initiators (PMMACl; arms) with a bifunctional methacrylate (12FODMA or EGDMA; core-forming linking agent) in the presence of perfluorinated monomers [RFMA; RF: C4F9 (9F), C6F12H (12F), C6F13 (13F), C8F17 (17F)]. For example, the core-formation with 13FMA led to 13F-Star : Mw = 2.0 x 106; 86 PMMA-arms; 14800 fluorine atoms/core.  The thermal mobility of the fluorine atoms was much smaller in the 13F-Star core than in MMA/13FOMA random and block copolymers with similar fluorine contents, as confirmed by clearly reduced 19F NMR spin-spin relaxation time (T2).  Independent of the total number of fluorine per polymer, all these F-Stars solubilized perfluorinated guests (PFH, PFO, and PFMCH) in DMF.  The solubilization efficiency, or fluorous recognition, apparently depended the number of in-core �CF3 units, rather than the total number of fluorine atoms (�CF3 + �C2F2 �).  F-Stars selectively captured PFO even in the presence of fluorine-containing hydrophobic and hydrophilic compounds (TFMB and TFE, respectively) and also released the guest upon mild heating or addition of excess CHCl3 .

Fluorinated microgel-core star polymers: Fluorous nanocapsules for molecular capture and release

246th National Meeting (2013)

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