Synthesis and characterization of perfluoro-tert-butyl semifluorinated amphiphilic polymers and their potential application in hydrophobic drug deliveryElectronic supplementary information (ESI) available: MALDI-MS, 1H 19F and 13C NMR spectra. TEM image and T1 and T2 relaxation curves. See DOI: 10.1039/c4py00882k

Semifluorinated polymer surfactants, composed of a monomethyl poly(ethylene glycol) (mPEG) hydrophilic head group and 1, 2, or 3 perfluoro- tert -butyl (PFtB) groups as the fluorophilic tail, were synthesized, and their aqueous self-assemblies were investigated as a potential design for theranostic nanoparticles. Polymers with three PFtB groups (PFtB TRI ) solely formed stable, spherical micelles, approximately 12 nm in size. These PFtB TRI surfactants demonstrate similar characteristics to those of polymers with linear perfluorocarbon tails, despite large differences in the tail structure. For example, PFtB polymer solutions stably emulsified 20 v/v% sevoflurane with perfluorooctyl bromide (PFOB) as a stabilizer. However, these PFtB polymers have the additional potential to serve as F-MRI contrast agents. PFtB TRI micelles gave one narrow 19 F-NMR signal in D 2 O, with T 1 and T 2 parameters of approximately 500 and 100 ms, respectively. 19 F-MR images of PFtB polymer solutions at 1 mM gave an intense signal at 4.7 T without sensitizers or selective excitation sequences. These preliminary data demonstrate the potential of PFtB polymers as a basic design, which can be further modified to serve as dual drug-delivery and imaging vehicles. Semifluorinated polymer surfactants containing one, two, or three perfluoro- tert -butyl groups were synthesized and fully characterized. Theranostic applications are discussed.