Dendritic domains with hexagonal symmetry formed by x-shaped bolapolyphiles in lipid membranes.
A novel class of bolapolyphile (BP) molecules are shown to integrate into phospholipid bilayers and self-assemble into unique sixfold symmetric domains of snowflake-like dendritic shapes. The BPs comprise three philicities: a lipophilic, rigid, π-π stacking core; two flexible lipophilic side chains; and two hydrophilic, hydrogen-bonding head groups. Confocal microscopy, differential scanning calorimetry, XRD, and solid-state NMR spectroscopy confirm BP-rich domains with transmembrane-oriented BPs and three to four lipid molecules per BP. Both species remain well organized even above the main 1,2-dipalmitoyl-sn-glycero-3-phosphocholine transition. The BP molecules only dissolve in the fluid membrane above 70 °C. Structural variations of the BP demonstrate that head-group hydrogen bonding is a prerequisite for domain formation. Independent of the head group, the BPs reduce membrane corrugation. In conclusion, the BPs form nanofilaments by π stacking of aromatic cores, which reduce membrane corrugation and possibly fuse into a hexagonal network in the dendritic domains.
Institut für Chemie, Martin-Luther-Universität Halle-Wittenberg, 06120 Halle (Saale) (Germany).|ZIK HALOmem, Martin-Luther-Universität Halle-Wittenberg, 06120 Halle (Saale) (Germany).
Stefan
S
Werner
Institut für Chemie, Martin-Luther-Universität Halle-Wittenberg, 06120 Halle (Saale) (Germany).
Helgard
H
Ebert
Institut für Chemie, Martin-Luther-Universität Halle-Wittenberg, 06120 Halle (Saale) (Germany).
Bob-Dan
BD
Lechner
Institut für Physik - NMR, Martin-Luther-Universität Halle-Wittenberg, 06120 Halle (Saale) (Germany).
Frank
F
Lange
Institut für Physik - NMR, Martin-Luther-Universität Halle-Wittenberg, 06120 Halle (Saale) (Germany).
Anja
A
Achilles
Institut für Physik - NMR, Martin-Luther-Universität Halle-Wittenberg, 06120 Halle (Saale) (Germany).
Ruth
R
Bärenwald
Institut für Chemie, Martin-Luther-Universität Halle-Wittenberg, 06120 Halle (Saale) (Germany).
Silvio
S
Poppe
Institut für Chemie, Martin-Luther-Universität Halle-Wittenberg, 06120 Halle (Saale) (Germany).
Alfred
A
Blume
Institut für Physik - NMR, Martin-Luther-Universität Halle-Wittenberg, 06120 Halle (Saale) (Germany). kay.saalwaechter@physik.uni-halle.de.
Kay
K
Saalwächter
Institut für Chemie, Martin-Luther-Universität Halle-Wittenberg, 06120 Halle (Saale) (Germany). carsten.tschierske@chemie.uni-halle.de.
Carsten
C
Tschierske
Institut für Chemie, Martin-Luther-Universität Halle-Wittenberg, 06120 Halle (Saale) (Germany). kirsten.bacia@chemie.uni-halle.de.|ZIK HALOmem, Martin-Luther-Universität Halle-Wittenberg, 06120 Halle (Saale) (Germany). kirsten.bacia@chemie.uni-halle.de.
Kirsten
K
Bacia
bolapolyphiles; lipids; membranes; pi interactions; self-assembly