Counterion-Mediated Hierarchical Self-Assembly of an ABC Miktoarm Star Terpolymer

Abstract

Directed self-assembly processes of polymeric systems represent a powerful approach for the generation of structural hierarchy in analogy to biological systems. Herein, we utilize triiodide as a strongly polarizable counterion to induce hierarchical self-assembly of an ABC miktoarm star terpolymer comprising a polybutadiene (PB), a poly(tert-butyl methacrylate) (PtBMA), and a poly(N-methyl-2-vinylpyridinium) (P2VPq) segment. Hereby, the miktoarm architecture in conjunction with an increasing ratio of triiodide versus iodide counterions allows for a stepwise assembly of spherical micelles as initial building blocks into cylindrical structures and superstructures thereof. Finally, micrometer-sized multicompartment particles with a periodic lamellar fine structure are observed, for which we introduce the term "woodlouse". The counterion-mediated decrease in hydrophilicity of the corona-forming P2VPq block is the underlying trigger to induce this hierarchical structure formation. All individual steps and the corresponding intermediates toward these well-defined superstructures were intensively studied by scattering and electron microscopic techniques, including transmission electron microtomography.

Limiting the valence: advancements and new perspectives on patchy colloids, soft functionalized nanoparticles and biomolecules

“…193 Similar results can be obtained by imposing different topological constraints, for instance by binding three homopolymers together. Changing the way in which the three types of polymers are linked together controls the functionality of the system: triblock copolymer chains 196 and stars 195 have been shown to self-assemble into patchy particles that then form string-and sheet-like superstructures or even open lamellar and cylindrical aggregates depending on the concentration of particular ions (that modifies the solubility of one of the arms), the volumes occupied by the different groups and/or the solvent quality. 195,196 Finally, very promising polymeric macromolecules that have been recently shown to self-assemble into soft functionalized units are diblock copolymer stars, also referred to as telechelic star polymers (TSPs).…”

Synthesis and Complexation of Well-Defined Labeled Poly(N,N-dimethylaminoethyl methacrylate)s (PDMAEMA)

“…Polymers 2015, 7, page-page 10 After quaternization, the copolymers show different absorption spectra: first, an additional signal at 290 nm can be seen which, according to literature, can be attributed to the presence of I3 − (absorption maxima at 290 and 360 nm) [50][51][52][53][54][55]. Second, the absorption band of the dye is shifted to higher λmax.…”

Preparation of cylindrical multi-compartment micelles by the hierarchical self-assembly of ABC triblock polymer in solution

“…The degree of 25 polymerization (DP) of PnBA was calculated with the area ratio of the peak at δ = 2.3 ppm that was assigned to the hydrogen of the methine group in nBA repeating unit to the peak at δ = 3.8 ppm that was assigned to the hydrogen of methylene in EDMAT (Table 1). 5 is the DLS curves for the micelles obtained before and after dialysis, the 10 relative data are shown in Table2. At the primary step as shown in Fig.…”

“…In the selected solvent for one block where the other two blocks are insoluble, the insoluble two blocks form a micelle core. 1,[5][6][7][8][9][10] Large number of microsegments are formed in the cores and shells of MCMs, leading to a complex micellar morphology. 1,[5][6][7][8][9][10] Large number of microsegments are formed in the cores and shells of MCMs, leading to a complex micellar morphology.…”