Supramolecular Assemblies from Amphiphilic Homopolymers:  Testing the Scope

Abstract

It has been shown by us in a recent communication that homopolymers, in which each repeat unit contains a hydrophilic and a hydrophobic head group, are capable of forming environment dependent micellar or inverse micellar assemblies. A systematic structure-property relationship study is carried out here to test the scope of the design. We show here that the molecular design is indeed broadly applicable and that there is a significant gain in the critical aggregation concentrations of these polymers, compared to the small molecule counterparts. We also show that the design can be tuned to achieve vesicle-type assemblies, which further expands the repertoire of amphiphilic homopolymers in a variety of areas. Characterizations of these assemblies have been carried out using transmission electron microscopy, dynamic light scattering, static light scattering, and dye incorporation experiments.

Self‐Assembled Block Copolymer Aggregates: From Micelles to Vesicles and their Biological Applications

“…Vesicles can be generated from 'polymeric surfactants', [75] amphiphilic 'comb-like' copolymers, [76,77] and somewhat surprisingly alternating copolymers synthesised by free-radical methods. [78] Uzun and co-workers have reported the formation of 'recognition-induced vesicles' through the complementary complexation of modified PS, but these 'homopolymers' are believed to be gradient copolymers rather than pure homopolymers.…”

Investigation on RAFT Polymerization of a Y‐Shaped Amphiphilic Fluorinated Monomer and Anti‐Fog and Oil‐Repellent Properties of the Polymers

“…[10] 1,1,1-tris(hydroxymethyl)ethane, [11] 1,3,5-trisubstituted benzenes, [12] tertiary amines, [13] etc. Herein, we selected epichlorohydrin as the linking reagent for the preparation of the amphiphilic monomer because of its advantages such as simplifying the synthetic procedure, commercial availability, and low cost.…”

Anion–Dipole Interactions Make the Homopolymers Self‐Assemble into Multiple Nanostructures

“…[ 1 ] Since Eisenberg fi rst reported multiple morphologies of amphiphilic block-copolymer of polystyrene-blockpoly(acrylic acid), [ 2 ] a signifi cant amount of efforts have been devoted by Eisenberg, [ 3 ] Wooley, [ 1h ] Bates, [ 4 ] Lodge, Percec, [ 4 ] Pochan, [ 1h ] Armes, [ 5 ] and Thayumanavan [ 6 ] et al to constructing "designed" nanostructures via the self-assembly of amphiphilic polymers, targeting important applications such as drug/gene delivery, molecular imaging, [ 1b , 7 ] among others. Due to the repulsion effect between hydrophobic segment and hydrophilic segment in water, not only amphiphilic block copolymers can self-assemble into multiple nanostructures at different ratio of hydrophobic block and hydrophilic block [ 2,8 ] but also amphiphilic homopolymers incorporated with both hydrophobic unit and hydrophilic unit within the side chain can self-assemble into micelles.…”

“…Due to the repulsion effect between hydrophobic segment and hydrophilic segment in water, not only amphiphilic block copolymers can self-assemble into multiple nanostructures at different ratio of hydrophobic block and hydrophilic block [ 2,8 ] but also amphiphilic homopolymers incorporated with both hydrophobic unit and hydrophilic unit within the side chain can self-assemble into micelles. [ 6,9 ] Hydrogen bond, a weak force, typically having interaction strength between 5 and 60 kJ mol −1 , [ 10 ] can act as a driver of macromolecular assembly and many nanostructures have been constructed via the hydrogen bond-driven self-assembly. [ 9a , 11 ] Other weak forces, such as π-π stacking (the strength of π-π interaction is typically 0−50 kJ mol…”