Abstract
Self-assembly of block copolymers is a significant area of polymer science. The self-assembly of completely water-soluble block copolymers is of particular interest, albeit a challenging task. In the present work the self-assembly of a linear-brush architecture block copolymer, namely poly(N-vinylpyrrolidone)-b-poly(oligoethylene glycol methacrylate) (PVP-b-POEGMA), in water is studied. Moreover, the assembled structures are crosslinked via α-CD host/guest complexation in a supramolecular way. The crosslinking shifts the equilibrium toward aggregate formation without switching off the dynamic equilibrium of double hydrophilic block copolymer (DHBC). As a consequence, the self-assembly efficiency is improved without extinguishing the unique DHBC self-assembly behavior. In addition, decrosslinking could be induced without a change in concentration by adding a competing complexation agent for α-CD. The self-assembly behavior was followed by DLS measurement, while the presence of the particles could be observed via cryo-TEM before and after crosslinking.
Highlights
Block copolymer self-assembly has been in the focus of researchers in recent decades
Minor differences in the elugrams of block copolymer sample and blends are observed even at homo polymer contents of 10 wt%, which indicates a purity of 90% or better for the block copolymers. The presence of both blocks was observed in the NMR spectrum (Fig. S7†) and a similar diffusion coefficient was determined for both blocks in Diffusion-ordered spectroscopy (DOSY) (Fig. S8†), which indicates block copolymer formation
A-CD presents an interesting crosslinking behavior that shi s the equilibrium toward aggregate formation without switching off the dynamic equilibrium of linear-brush double hydrophilic block copolymer (DHBC)
Summary
Block copolymer self-assembly has been in the focus of researchers in recent decades. Such a stimuli responsive block is capable of switching from hydrophilic to hydrophobic upon application of heat,[14,15] pH change[16,17] or redox reactions[18,19] to facilitate a self-assembly process In this case the self-assembly is rather driven via hydrophobicity induced aggregation
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