Studies on the orthogonal assembly of β-cyclodextrin-poly (ε-caprolactone) and ferrocene-poly (ethylene oxide).

A biodegradable multi-arm polymer β-cyclodextrin-poly (ε-caprolactone) (CD-PCL) with a ``jellyfish-like'' structure was obtained, in which flexible and hydrophobic PCL arms were selectively grafted to the wide side of the hydrophilic torus-shaped β-CD. The amphiphilic "jellyfish-like'' polymer with a hollow cavity and hydrophobic tails could orthogonally self-assemble into a new amphiphilic supramolecular copolymer CD-PCL/FcPEG with poly (ethylene oxide) end-decorated by ferrocene (FcPEG) in aqueous solution based on terminal hydrophobic interactions. The chemical structures of CD-PCL and CD-PCL/FcPEG were characterized by IR, NMR and UV and their self-assembled structures in water were investigated by transmission electron microscopy (TEM) and dynamic light scattering (DLS). CD-PCL alone self-assembled into nano vesicles in water, while CD-PCL/FcPEG into nanospheres. The supramolecular nanospheres were further investigated by cyclic voltammogram. The results indicated that the ferrocenyl groups which were embedded into the hydrophobic core of the supramolecular nanospheres could not transmit electrons or carry out electrochemical oxidation and reduction reaction.