Self-Organization of Water-Soluble Complexes of a Poly(2-vinylpyridinium)-block-poly(ethylene oxide) Diblock with Fluorinated Anionic Surfactants

Complex coacervate core micelles

“…For f + ≠ 0.5, this value is shifted to higher (f + N 0.5) or lower (f + b 0.5) pH values. And similarly, a pH induced displacement of the preferred micellar composition, PMC (see also Section 5.2), from f + = 0.5, has been observed, [44,68,100,184] when experiments were not performed at pH = 0.5•(pK b + pK a ) [60]. Hence, C3Ms are formed in a narrow region around charge stoichiometry; i.e.…”

“…For one or more weak polyelectrolyte blocks however, α − =α + depends on solution pH and is not necessarily unity, so that the PMC corresponds to f + = 0.5 only if pH = 0.5•(pK a + pK b ). Hence, upon increasing f + from 0 to 1, several solutions properties, such as viscosity, conductivity, I SLS , exhibit an extremum at f + = 0.5 for C3Ms of two quenched polyelectrolytes at any pH, while the position of this extremum is pH dependent as soon as one weak polyelectrolyte is involved [68,184]. The PMC appears to be independent of N corona [27,89].…”

“…The formation of coordination bonds between polyelectrolyte blocks and metal ions in the C3M core, has been studied by attenuated total reflectance infrared spectroscopy (ATR-FTIR) [156]. Atomic force microscopy (AFM), [15,87,106,[184][185][186]199,231,241] transmission electron microscopy (TEM), [63,68,136,138,158,166,178,184,229] and cryogenic transmission electron microscopy (cryo-TEM) [3,45,[152][153][154]181,182] have been used to visualize (the core of) C3Ms. Potentiometric titrations have been performed to study the binding equilibrium between the oppositely charged species [68].…”

“…Ionic-neutral block, graft, and statistical copolymers have been complexed with a wide variety of oppositely charged surfactants, such as AOT, [ [133,139] DDDAB, [135,137] DTAB, [136] DODAB, [135,137] DPC, [136] DTAB, [60,61,105,[124][125][126][127][128][129]174] FSA, [184] FSE, [184] CTAB, [130][131][132]137,167] OA, [70] SD, [185] SDS, [57,68,69,125,126,225,239] SFD, [185] TDS, [68] TOMAB, [135,137] TDTAB, [136] bile salts, [47] and fatty acid salts [46]. Comicellization of surfactants with oppositely charged flexible copolymers, typically leads to the formation of core-shell aggregates, with a disordered core consisting of one to several hundred surfactant micelles connected by the polyelectrolyte copolymer blocks, surrounded by a solvent-swollen shell of the neutral copolymer blocks [60,124,125,…”

Supramolecular Assemblies from Poly(styrene)-block-poly(4-vinylpyridine) Diblock Copolymers Mixed with 6-Hydroxy-2-naphthoic Acid

“…Association of small organic molecules with one of the polymer blocks of the starting block copolymers via weak forces of attractions, like electrostatic interactions, van der Waals forces and hydrogen bonding, has become a widely adopted approach for the fine-tuning of the block copolymer morphology in solution [14], bulk [15,16] and in thin films [17][18][19][20][21][22][23][24][25][26][27]. In a further step, the interacting small molecules can be removed by dissolution in a selective solvent, and nanoporous materials can be obtained [17,18].…”