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.
Achiral multi-chain benzil derivatives provide a missing link between mirror symmetry breaking phenomena in fluid systems of polycatenar and bent-core liquid crystals.
The first single-diamond cubic phase in al iquid crystal is reported. This skeletal structure with the Fd " 3mspace group is formed by self-assembly of bolaamphiphiles with swallow-tailed lateral chains.I tc onsists of bundles of pconjugated p-terphenyl rods fused into an infinite network by hydrogen-bonded spheres at tetrahedral four-way junctions. We also present aq uantitative model relating molecular architecture to the space-filling requirements of six possible bicontinuous cubic phases,t hat is,t he single-and doublenetwork versions of gyroid, diamond, and "plumber'sn ightmare".Among the most intriguing self-assembled nano-and mesoscale soft-matter structures are the cubic phases formed by lyotropic and thermotropic liquid crystals (LCs), by block copolymers, [1,2] and by nanoparticle arrays. [3][4][5] Tw o classes of cubic phases can be distinguished, the "bicontinuous" and the "micellar" types. [6,7] Them icellar phases represent periodic arrays of spheres on ac ubic lattice, whereas the bicontinuous phases are more complex and usually formed by two networks divided by aminimal surface with aconstant mean curvature.Depending on the symmetry, the double gyroid (DG, Ia " 3d,Q 230 ), the double diamond (DD; Pn " 3m,Q 224 ), and the body-centered plumber'sn ightmare ("double primitive") cubic phases (DP; Im3 m,Q 229 )w ith junction valencies of n = 3, 4, and 6, respectively,c an be distinguished (Figure 1a-c). Figure 6. Models showing a) the micellar Fd " 3m cubic phase [27,28] and b) the new SD bicontinuous cubic phase of compounds 1/18-11/22.
Spontaneous mirror-symmetry breaking is a fundamental process for development of chirality in natural and in artificial self-assembled systems. A series of triple chain azobenzene based rod-like compounds is investigated that show mirror-symmetry breaking in an isotropic liquid occurring adjacent to a lamellar LC phase. The transition between the lamellar phase and the symmetry-broken liquid is affected by trans-cis photoisomerization, which allows a fast and reversible photoinduced switching between chiral and achiral states with non-polarized light.
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