Lanthanide-Dipicolinic Acid Coordination Driven Micelles with Enhanced Stability and Tunable Function

Lanthanide-incorporated polymer micelles have been prepared driven by the lanthanide-dipicolinic acid (Ln-DPA) coordination. The terdentate DPA ligand is grafted to the PVP block of a diblock copolymer poly(4-vinylpyridine)-b-poly(ethylene oxide) (P4VP48-b-PEO193). Upon addition of Eu(III) ions to a solution of the DPA16-g-P4VP48-b-PEO193 block copolymer, intermolecular cross-links form and the ligand-carrying blocks assemble, leading to the formation of micelles, stabilized by the hydrophilic PEO blocks. The DPA exhibits a dual function in this study. First, the chelate group strongly coordinates to Eu(III) in a three to one ratio, and leads to high stability of the formed micelles, as proven by light scattering and luminescence spectroscopy. Second, DPA acts as an antenna that transfers energy to the Eu(III) ion and dramatically enhances the luminescence emission. The Eu(III) emission is moreover most sensitive for local environment and allows to shine light on the internal structure of this class of self-assembled 36 nm size soft nanoparticles. With the same strategy gadolinium(III) can be incorporated providing micelles which show enhanced magnetic relaxation rates. Micelles capping a mixture of Eu(III) and Gd(III) show both enhanced luminescence emission and magnetic relaxation rates, and the functions can be tuned by regulating the mixing ratio of Eu(III) and Gd(III), showing great potential for developing multimodal imaging agents for diagnostic as well as therapeutic applications