Continuous Curvature Change into Controllable and Responsive Onion-like Vesicles by Rigid Sphere–Rod Amphiphiles

Abstract

We observe the formation of highly controllable and responsive onion-like vesicles by using rigid sphere−rod amphiphilic hybrid macromolecules, composed of charged, hydrophilic Keggintype clusters (spheres) and hydrophobic rod-like oligofluorenes (OFs). Unlike the commonly used approach, which mainly relies on chain bending of flexible molecules to satisfy different curvatures in onion-like vesicles, the rigid hybrids form flexible interdigitations by tuning the angles between OFs, leading to the formation of bilayers with different sizes. The self-assembled vesicles possess complete onion-like structures from most inner to outer layers, and their size (layer number) can be accurately manipulated by different solution conditions including solvent polarity, ionic strength, temperature, and hybrid concentration, with fixed interbilayer distance under all conditions. Moreover, the vesicle size (layer number) shows excellent reversibility to the change of temperature. The charged feature of spheres, rod length, and overall hybrid architecture shows significant effects on the formation of such onion-like vesicles.

Open and Closed Layered Nanostructures with Sub-10 nm Periodicity Self-Assembled from Hydrophilic [60]Fullerene-Based Giant Surfactants

“…19,22,26 Recently, some work showed that amphiphilic molecules with comparable hydrophobic and hydrophilic parts can form layered nanostructures in solution. 33,51 However, it is worth noting that the close-layered nanostructure (onion-like micelle) was obtained both in the present simulation and in the corresponding experiment.…”

“…24 Some work on giant surfactant molecules with the same approximate sizes of head and tails have attracted some interest recently. 32,33 ■ EXPERIMRNTAL SECTION Materials. Synthesis.…”

“…The character of the polymer tails tethered to the rigid heads plays a vital role in the self-assembled morphologies . Some work on giant surfactant molecules with the same approximate sizes of head and tails have attracted some interest recently. , …”

Nanostructured Polymer Composite Electrolytes with Self-Assembled Polyoxometalate Networks for Proton Conduction

“…Polyoxometalates (POMs), the molecularly welldefined clusters of metal oxides, 32 are widely used as functional inorganic nanobuilding blocks for the preparation of hybrid polymer nanocomposites. [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47] Moreover, the multicharged anionic characteristic and the high ion-dissociation ability of POMs make them promising molecular electrolytes to transport cations such as protons and lithium ions for energy applications. [48][49][50] Recently, the excellent proton conductivity, electrochemical stability, and water-retention ability of POMs have attracted special interest to develop POM-polymer composite electrolytes for proton conduction.…”

Screw dislocation-induced pyramidal crystallization of dendron-like macromolecules featuring asymmetric geometry

“…[14][15][16][17][18][19][20][21][22][23][24][25] Due to the anisotropy as well as the rigid domains, they have enriched the phase diagrams by self-assembling into diverse nanostructures in the bulk, at the interface, or in solutions. 38,39,[45][46][47][48][49][50][51][52][53][54][55] The topological design featured by breaking the geometrical symmetry of MJPs has elucidated its influence on phase behaviors. 56,57 When increasing the degree of asymmetry, continuous changes in crystalline and quasicrystalline phases were achieved in bulk, indicating the influence of domain volume fractions on the interface curvatures.…”