A series of amphiphilic graft copolymers PHFMA-g-PEG comprising of poly(hexafluorobutyl methacrylate) (PHFMA) backbones and poly(ethylene glycol) (PEG) side chains were synthesized by copolymerization of HFMA and an SPEG macromonomer with a p-vinylbenzyl end group. The SPEG macromonomer was synthesized by reaction of PEG with p-chloromethylstyrene in THF in the presence of NaH. The resultant macromonomer and amphiphilic graft copolymers were characterized by 1H-NMR

19F-NMR and GPC. The HFMA contents in the graft copolymers were calculated by the (—OCH2—CF2—) protons (δ = 4.19) for HFMA and (CH3O—) proton (δ = 3.38) for SPEG macromonomers from 1H-NMR spectra. The critical micelle concentration (CMC) of amphiphilic graft copolymers was measured by surface tension technique

and it showed that the CMC decreased with the increase of HFMA content in the graft copolymers. The interactions between PHFMA-g-PEG and bovine serum albumin (BSA) were studied by fluorescence spectroscopy

photon correlation spectroscopy (PCS) and transmission electron microscopy (TEM). The fluorescence spectrum showed that the fluorescence intensity of BSA increased in PHFMA-g-PEG/BSA solution driven by hydrophobic interactions of fluorinated segments

with increasing ratio of HFMA in PHFMA-g-PEG and increasing concentration of PHFMA-g-PEG

the fluorescence emission intensity of BSA also increased. PCS showed that when BSA was added into PEGF39 aqueous solution

the hydrodynamic diameters and distribution of micelles were increased. TEM micrographs showed that PHFMA-g-PEG mainly formed core-shell structure micelles

when BSA was added

micelles changed into vesicle like core-shell structures. This study may suggest that PHFMAgPEG is a potential copolymer for loading proteins or other hydrophilic bioactive drugs.