title: Hierarchical Micelles via Polyphilic Interactions: Hydrogen-Bonded Supramolecular Dendrons and Double Immiscible Polymers.
abstract: We report a simple strategy to form three-phase segregated hierarchical micelles via a counterbalanced phase segregation/self-assembly process. Our methodology relies on a cooperative polyphilic phase segregation, paralleled by a self-assembly process induced by hydrogen-bonds to afford the generation of supramolecular multicompartment dendrons. The versatile preparation of such hierarchical morphologies is evidenced on the basis of a series of supramolecular dendrons, composed of semifluorinated copolymers, homopolymers, or nonfluorinated polymers. We do have designed and prepared mid- and α,ω-barbiturate (Ba) functionalized poly(n-butyl acrylates), Ba-(PnBuA-Ba)2, together with a series of heterocomplementary α,ω-Hamilton wedge (HW) functionalized polymers via reversible addition-fragmentation chain transfer (co)polymerization. To enable subtle phase segregation processes, the semifluorinated homo- and copolymers HW-P(nBuA-co-PFPA)-HW (prepared via copolymerization of nBuA with 2,2,3,3,3-pentafluoropropyl acrylate (PFPA)) and HW-PPFPA-HW, as well as the nonfluorinated polymer HW-PnBuA-HW and HW-PI-HW (PI, polyisoprene), have been generated. Selective intermolecular complexation between Ba-(PnBuA-Ba)2 and the complementary polymers (such as HW-P(nBuA-co-PFPA)-HW, HW-PPFPA-HW or HW-PI-HW) leads to the successful generation of supramolecular dendrons as evidenced by (1)H NMR and diffusion-ordered NMR spectroscopy, together with the formation of well-defined disc-like nano-objects as demonstrated by microscopy investigations. Transmission electron microscopy demonstrates a unique, uncommon phase behavior showing remarkable three-phase segregated hierarchical micelles, indicative of the desired micellar multicompartments.
authors.affiliation: Chair of Macromolecular Chemistry, Faculty of Natural Science II (Chemistry, Physics, and Mathematics) and ‡Physical Chemistry, Faculty of Natural Sciences II (Chemistry, Physics, and Mathematics), Martin Luther University Halle-Wittenberg , von-Danckelmann-Platz 4, Halle (Saale) D-06120, Germany.
authors.forename: Senbin
authors.initials: S
authors.lastname: Chen
authors.affiliation: Chair of Macromolecular Chemistry, Faculty of Natural Science II (Chemistry, Physics, and Mathematics) and ‡Physical Chemistry, Faculty of Natural Sciences II (Chemistry, Physics, and Mathematics), Martin Luther University Halle-Wittenberg , von-Danckelmann-Platz 4, Halle (Saale) D-06120, Germany.
authors.forename: Bob-Dan
authors.initials: BD
authors.lastname: Lechner
authors.affiliation: Chair of Macromolecular Chemistry, Faculty of Natural Science II (Chemistry, Physics, and Mathematics) and ‡Physical Chemistry, Faculty of Natural Sciences II (Chemistry, Physics, and Mathematics), Martin Luther University Halle-Wittenberg , von-Danckelmann-Platz 4, Halle (Saale) D-06120, Germany.
authors.forename: Annette
authors.initials: A
authors.lastname: Meister
authors.affiliation: Chair of Macromolecular Chemistry, Faculty of Natural Science II (Chemistry, Physics, and Mathematics) and ‡Physical Chemistry, Faculty of Natural Sciences II (Chemistry, Physics, and Mathematics), Martin Luther University Halle-Wittenberg , von-Danckelmann-Platz 4, Halle (Saale) D-06120, Germany.
authors.forename: Wolfgang H
authors.initials: WH
authors.lastname: Binder
mesh_terms: D000179:Acrylates / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D006860:Hydrogen Bonding; D009682:Magnetic Resonance Spectroscopy; D008823:Micelles; D015394:Molecular Structure; D049329:Nanostructures / Q000737:chemistry*; D058105:Polymerization; D011108:Polymers / Q000737:chemistry*
chemical_list: D000179:Acrylates; D008823:Micelles; D011108:Polymers; D006859:Hydrogen; C036658:acrylic acid
keywords: Hierarchical micelles; RAFT polymerization; polyphilic phase segregation; supramolecular compartments; supramolecular dendron