title: Revealing and tuning the core, structure, properties and function of polymer micelles with lanthanide-coordination complexes.
abstract: Controlling self-assembly processes is of great interest in various fields where multifunctional and tunable materials are designed. We here present the versatility of lanthanide-complex-based micelles (Ln-C3Ms) with tunable coordination structures and corresponding functions (e.g. luminescence and magnetic relaxation enhancement). Micelles are prepared by charge-driven self-assembly of a polycationic-neutral diblock copolymer and anionic coordination complexes formed by Ln(III) ions and the bis-ligand L2EO4, which contains two dipicolinic acid (DPA) ligand groups (L) connected by a tetra-ethylene oxide spacer (EO4). By varying the DPA/Ln ratio, micelles are obtained with similar size but with different stability, different aggregation numbers and different oligomeric and polymeric lanthanide(III) coordination structures in the core. Electron microscopy, light scattering, luminescence spectroscopy and magnetic resonance relaxation experiments provide an unprecedented detailed insight into the core structures of such micelles. Concomitantly, the self-assembly is controlled such that tunable luminescence or magnetic relaxation with Eu-C3Ms, respectively, Gd-C3Ms is achieved, showing potential for applications, e.g. as contrast agents in (pre)clinical imaging. Considering the various lanthanide(III) ions have unique electron configurations with specific physical chemical properties, yet very similar coordination chemistry, the generality of the current coordination-structure based micellar design shows great promise for development of new materials such as, e.g., hypermodal agents.
authors.affiliation: Laboratory of BioNanoTechnology, Wageningen University, Dreijenplein 6, 6703 HB Wageningen, The Netherlands. aldrik.velders@wur.nl.
authors.forename: Junyou
authors.initials: J
authors.lastname: Wang
authors.affiliation: Laboratory of BioNanoTechnology, Wageningen University, Dreijenplein 6, 6703 HB Wageningen, The Netherlands. aldrik.velders@wur.nl.
authors.forename: Andrea
authors.initials: A
authors.lastname: Groeneveld
authors.affiliation: Laboratory of BioNanoTechnology, Wageningen University, Dreijenplein 6, 6703 HB Wageningen, The Netherlands. aldrik.velders@wur.nl.
authors.forename: Maria
authors.initials: M
authors.lastname: Oikonomou
authors.affiliation: Laboratory of Biophysics and Wageningen NMR Centre, Wageningen University, Dreijenplein 3, 6703 HA Wageningen, The Netherlands.
authors.forename: Alena
authors.initials: A
authors.lastname: Prusova
authors.affiliation: Laboratory of Biophysics and Wageningen NMR Centre, Wageningen University, Dreijenplein 3, 6703 HA Wageningen, The Netherlands.
authors.forename: Henk
authors.initials: H
authors.lastname: Van As
authors.affiliation: Wageningen Electron Microscopy Centre, Wageningen University, Droevendaalsesteeg 1, 6708 PB Wageningen, The Netherlands.
authors.forename: Jan W M
authors.initials: JW
authors.lastname: van Lent
authors.affiliation: Laboratory of BioNanoTechnology, Wageningen University, Dreijenplein 6, 6703 HB Wageningen, The Netherlands. aldrik.velders@wur.nl and Interventional Molecular Imaging Laboratory, Department of Radiology, Leiden University Medical Centre, Leiden, The Netherlands.
authors.forename: Aldrik H
authors.initials: AH
authors.lastname: Velders
mesh_terms: D028581:Lanthanoid Series Elements / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008823:Micelles; D009942:Organometallic Compounds / Q000737:chemistry*; D010848:Picolinic Acids / Q000737:chemistry; D011092:Polyethylene Glycols / Q000737:chemistry
chemical_list: D028581:Lanthanoid Series Elements; D008823:Micelles; D009942:Organometallic Compounds; D010848:Picolinic Acids; D011092:Polyethylene Glycols; C004860:dipicolinic acid