Self-Sorting and Coassembly of Fluorinated, Hydrogenated, and Hybrid Janus Dendrimers into Dendrimersomes

The modular synthesis of a library containing seven self-assembling amphiphilic Janus dendrimers is reported. Three of these molecules contain environmentally friendly chiral-racemic fluorinated dendrons in their hydrophobic part (R-F), one contains achiral hydrogenated dendrons (R-H), while one denoted hybrid Janus dendrimer, contains a combination of chiral-racemic fluorinated and achiral hydro genated dendrons (R-HF) in its hydrophobic part. Two Janus dendrimers contain either chiral-racemic fluorinated dendrons and a green fluorescent dye conjugated to its hydrophilic part (R-F-NBD) or achiral hydrogenated and a red fluorescent dye in its hydrophilic part (R-H-RhB). These R-F, R-H, and R-HF Janus dendrimers self-assembled into unilamellar or onion-like soft vesicular dendrimersomes (DSs), with similar thicknesses to biological membranes by simple injection from ethanol solution into water or buffer. Since R-F and R-H dendrons are not miscible, R-F-NBD and R-H-RhB were employed to investigate by fluorescence microscopy the self-sorting and coassembly of R-F and R-H as well as of phospholipids into hybrid DSs mediated by the hybrid hydrogenated-fluorinated R-HF Janus dendrimer. The hybrid R-HF Janus dendrimer coassembled with both R-F and R-H. Three-component hybrid DSs containing R-H, R-F, and R-HF were formed when the proportion of R-HF was higher than 40%. With low concentration of R-HF and in its absence, R-H and R-F self-sorted into individual R-H or R-F DSs. Phospholipids were also coassembled with hybrid R-HF Janus dendrimers. The simple synthesis and self-assembly of DSs and hybrid DSs, their similar thickness with biological membranes and their imaging by fluorescence and F-19-MRI make them important tools for synthetic biology.