Self-Assembly of Janus Dendrimers into Uniform Dendrimersomes and Other Complex Architectures

Abstract

Self-assembled nanostructures obtained from natural and synthetic amphiphiles serve as mimics of biological membranes and enable the delivery of drugs, proteins, genes, and imaging agents. Yet the precise molecular arrangements demanded by these functions are difficult to achieve. Libraries of amphiphilic Janus dendrimers, prepared by facile coupling of tailored hydrophilic and hydrophobic branched segments, have been screened by cryogenic transmission electron microscopy, revealing a rich palette of morphologies in water, including vesicles, denoted dendrimersomes, cubosomes, disks, tubular vesicles, and helical ribbons. Dendrimersomes marry the stability and mechanical strength obtainable from polymersomes with the biological function of stabilized phospholipid liposomes, plus superior uniformity of size, ease of formation, and chemical functionalization. This modular synthesis strategy provides access to systematic tuning of molecular structure and of self-assembled architecture.

Arrays of giant octagonal and square cylinders by liquid crystalline self-assembly of X-shaped polyphilic molecules

“…To each of its ends, a glycerol groups (A) was attached, capable of forming a cooperative and dynamic hydrogen-bonding network. Hence, these compounds represent Janus-type [27][28][29][30][31][32][33] X-shaped quaternary amphiphiles. An equivalent series of compounds 2 was also synthesized, having a shorter C 10 F 21 segment instead of the C 12 F 25 segment.…”

Self-assembly of amphiphilic Janus dendrimers into uniform onion-like dendrimersomes with predictable size and number of bilayers

“…2). "Single-single" amphiphilic Janus dendrimer refers to a compound constructed from a "single" hydrophilic and a "single" hydrophobic dendron (28), rather than from "twin" hydrophilic and "twin" hydrophobic dendrons (26,27). This modular synthetic approach involves coupling of the hydrophilic acids 3b and 5a-e with the hydrophobic amine minidendron (41) 8a, or hydrophobic acid minidendron 3a with the hydrophilic amine 8b.…”

GdDOTAGA(C18)2: an efficient amphiphilic Gd(iii) chelate for the preparation of self-assembled high relaxivity MRI nanoprobes

“…1,2 The versatility of nanosystems allows tuneable surface modification and loading with different chemicals (drugs, imaging agents, targeting vectors) with the aim of fine-optimizing the biological properties of the nanocarriers, while simultaneously enabling them to perform diagnostically and/or therapeutically important functions. 3,4 Lipid-containing nanoparticles (LNPs), 5 like micelles, liposomes, and solid lipid nanoparticles, or other similar nanosystems (such as the recently developed dendrimersomes) [6][7][8] are based on supramolecular aggregates obtained by spontaneous assembling in aqueous solution of phospholipids alone or in mixture with other amphiphilic molecules. Such objects have been frequently used as nanocarriers for drug delivery and imaging applications due to their great chemical versatility that allows the loading of hydrophobic, amphiphilic, and hydrophilic substances, and surface decoration with targeting vectors, blood lifetime modulators, and diagnostic agents.…”