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

• Published in: Journal of the American Chemical Society 2016-09, Vol.138 (38), p.12655-12663
• Main Authors: Xiao, Qi, Rubien, Jack D, Wang, Zhichun, Reed, Ellen H, Hammer, Daniel A, Sahoo, Dipankar, Heiney, Paul A, Yadavalli, Srujana S, Goulian, Mark, Wilner, Samantha E, Baumgart, Tobias, Vinogradov, Sergei A, Klein, Michael L, Percec, Virgil
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.6b08069

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 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 19F-MRI make them important tools for synthetic biology.