Stimuli-Responsive Aqueous Micelles from an ABC Metallo-Supramolecular Triblock Copolymer

Abstract

A metallo-supramolecular ABC triblock copolymer containing a bis(2,2‘:6‘,2‘ ‘-terpyridine)ruthenium(II) complex as a supramolecular connection between the constituting poly(styrene)-block-poly(2-vinylpyridine) diblock and poly(ethylene oxide) block (PS32-b-P2VP13-[Ru]-PEO70) has been prepared. This copolymer was further utilized in order to prepare aqueous micelles consisting of a PS core, a pH-sensitive P2VP shell, and a PEO corona. The accordingly formed micelles have been characterized by a combination of dynamic light scattering, transmission electron microscopy, and atomic force microscopy. Spherical micelles and a minor fraction of bigger aggregates were observed by these three independent techniques. The pH sensitivity of the P2VP shell could be demonstrated and the reversibility of the metallo-supramolecular complex investigated utilizing a strong competitive ligand.

New Functional Polymers and Materials Based on 2,2′:6′,2″‐Terpyridine Metal Complexes

“…Moreover, more complex systems using PS 32 -P2VP 13 ± [Ru II ]±PEG 70 block copolymers have also been prepared. [54] Up to now, few reports on terpyridine functionalized polymeric resins or beads have appeared in literature, compared to bipyridine functionalized ones. [7] The main applications of such species lie in the area of heterogeneous catalysis.…”

Transport and Electro‐Optical Properties in Polymeric Self‐Assembled Systems

“…blocks. The interactions can be ionic [43,[53][54][55][56][57][58][59][60][61][62][63][64][65][66], in which case the term ionic self-assembly can be used [42]; they can be hydrogen bonds or their combinations [10,11,21,22,34,; they can be coordinative [89][90][91][92][93]; or they can in principle be any sufficiently strong attractive interaction or their combination. Over the years, several examples have arisen of physical interactions that enable one to prepare polymer-like materials (Figs.…”

“…3.3 and 3.4). For example, ionically interacting sites at the ends of telechelic polystyrene and poly(ethylene oxide) form "ionic multiblock copolymers" [55], the combination of four hydrogen bonds leads to linear polymeric supramolecules [6,10,11] where self-assembly can be achieved [94] and coordination bonds can be used to prepare polymers [7,8,95] and "coordinative block copolymers" [91,92].…”

Development of acid-sensitive copolymer micelles for drug delivery

“…For example, a poly(2-vinylpyridine)-block-poly(ethylene oxide)(P2VP-b-PEO) copolymer undergoes spontaneous and reversible micellization in aqueous solutions as the pH is increased from acidic to neutral or basic [19]. P2VP has also been incorporated into triblock copolymers that form micelles having pH sensitivity [20,21]. Armes and coworkers have prepared a series of block copolymers having tertiary amine groups.…”