Nanometer‐Sized Fluorous Fullerene Vesicles in Water and on Solid Surfaces

Abstract

A lipid molecule has a polar head / nonpolar aliphatic tail structural motif, and, in water, forms a bilayer vesicle, in which the polar heads are exposed to the aqueous environment and the aliphatic tails cluster together to form the core of the bilayer membrane. [1] The lipid vesicle is mechanically labile because of the polymorphic behavior of the aliphatic chains. Although the polar head / nonpolar tail motif is universally accepted, the question may arise as to whether such a binary motif is mandatory for vesicle formation in aqueous media. We report herein that fluorous fullerene anion 1 a, which features a nonpolar/polar/nonpolar ternary motif (Scheme 1 and Figure 1 a), spontaneously forms vesicles with an average diameter of 36 nm in water that expose its nonpolar fluorous chains to the aqueous environment. These Supporting information for this article is available on the WWW under http://dx.

Self‐Assembly of Fullerene‐Based Janus Particles in Solution: Effects of Molecular Architecture and Solvent

“…Therefore, the outer and inner layers of the vesicles are formed by AC 60 , while the hydrophobic C 60 s are located in the middle region between these two AC 60 layers to form a bilayer structure in the vesicles. This is also consistent with the previously reported self‐assembled bilayer vesicles from amphiphilic fullerene derivatives in fullerene‐phobic solvents 13d–f. 19 Interestingly, when the vesicles are subjected to ultrasonication in THF solution, the measured R h value remains constant for at least 5 h (see Figure S8 in the Supporting Information), indicating that the vesicles prepared in THF are quite stable and robust.…”

“…Because the layer thickness values are much larger than the long‐axis dimensions of AC 60 –C 60 and AC 60 –2C 60 , which are ca. 4 nm in the fully extended conformation (see Figure S6 in the Supporting Information), it is suggested that the vesicles are constructed by a double‐layer molecular packing model 13d–f. 19 The vesicular morphologies were further confirmed by light scattering experiments.…”

Synthesis of Carbon Monoxide from Hydrogen and Magnesite/Dolomite

“…The hollow vesicular structure of V1 in water was established previously through combined dynamic and static light scattering analysis 4b. 7 Unlike the preparation of lipid vesicles, there was no need for purification to obtain the narrow size distribution. An aqueous solution of FT‐Man 1 was added to this solution of V1 to obtain a solution of Man‐coated vesicle V2 ([ F8K ]=[ 1 ]=0.2 m M ), which was characterized as described in the following paragraph.…”

“…We report here that this robustness allows us to noncovalently load ligand molecules for protein recognition without affecting the structural integrity of the capsular structure of the vesicles. The key interaction for the self‐assembly is the noncovalent fluorous interaction5, 6 between a fullerene vesicle covered with perfluorooctyl chains ( V1 , Figure 1)7 and fluorous‐tagged (FT) molecules (Figure 2). 5 Thus, the functionalization of the fluorous vesicle V1 with FT‐Man 1 forms a Man‐coated vesicle V2 (= 1/V1 , Figure 1), which then forms a vesicle coated with concanavalin A (ConA; V3 ) (Figure 1, inset).…”

Fullerene Derivatives That Bear Aliphatic Chains as Unusual Surfactants: Hierarchical Self‐Organization, Diverse Morphologies, and Functions

“…There are reports on assemblies comprising C 60 -based nonpolar/polar/nonpolar ternary motifs. [43][44][45] Upon assembly, the hydrophobic tail group protrudes into the environment. In these examples, in addition to the hydrophobic effect, both the presence of the diphenylA C H T U N G T R E N N U N G ester group [43] or the potassium counterion [44] introduced other driving forces for the assemblies.…”