Self-Sorting and Co-Assembly 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 hydrogenated 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 H F 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 co-assembly 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 co-assembled 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 co-assembled 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 19 F-MRI make them important tools for synthetic biology.