Self-Assembly into Multicompartment Micelles and Selective Solubilization by Hydrophilic−Lipophilic−Fluorophilic Block Copolymers

Abstract

Amphiphilic linear ternary block copolymers (ABC) were synthesized in three consecutive steps by the reversible additionfragmentation chain transfer (RAFT) method. Using oligo(ethylene oxide) monomethyl ether acrylate, benzyl acrylate, and 1H,1H-perfluorobutyl acrylate monomers, the triblock copolymers consist of a hydrophilic (A), a lipophilic (B), and a fluorophilic (C) block. The block sequence of the triphilic copolymers was varied systematically to provide all possible variations: ABC, ACB, and BAC. All blocks have glass transition temperatures below 0 °C. Self-assembly into spherical micellar aggregates was observed in aqueous solution, where hydrophobic cores undergo local phase separation into various ultrastructures as shown by cryogenic transmission electron microscopy (cryo-TEM). Selective solubilization of substantial quantities of hydrocarbon and fluorocarbon low molar mass compounds by the lipophilic and fluorophilic block, respectively, is demonstrated.

Precise hierarchical self-assembly of multicompartment micelles

“…3e,f). Most importantly, we find homogeneous populations and not just single events among polydisperse mixtures31353638394344. This is significant, considering the delicate interplay of various thermodynamic factors and the shallow differences in free energy between the MCMs with various patches.…”

An injectable, thermosensitive and multicompartment hydrogel for simultaneous encapsulation and independent release of a drug cocktail as an effective combination therapy platform

“…Firstly, the cooperative assembly behavior and the possible fusion of two types of nanoparticles were investigated to exam the formation of different compartments in the hydrogel formulation. Our previous study and other reports on multicompartment micelles have demonstrated that immiscible hydrocarbons and fluorocarbons were inclined to microphase separation and form their own compartments in the micellar core, which was usually observed by transmission electron microscope (TEM) [38,51]. As to this aspect, the FRET technology was utilized to investigate the incompatible property of selected nanoparticles, which might result in the multicompartment hydrogel formation.…”

Solution self-assembly of poly(ethylene oxide)-block-poly(furfuryl glycidyl ether)-block-poly(allyl glycidyl ether) based triblock terpolymers: a field-flow fractionation study

“…As an example, the attachment of fluorocarbons significantly increases the hydrophobicity and has been shown to lead to additional compartmentalization within the (hydrophobic) core of micellar aggregates. 2c, 8 On the other hand, carboxy groups can serve as a model example to increase the hydrophilicity and to implement stimuli-responsive solution behavior based on changes in either pH value or ionic strength. 2b,9 To investigate the variety of morphologies formed by such triblock terpolymers, dynamic (DLS) and static (SLS) light scattering techniques are commonly used, and are often supported by cryogenic transmission electron microscopy (cryo-TEM).…”