Chirality Induction through Nano-Phase Separation: Alternating Network Gyroid Phase by Thermotropic Self-Assembly of X-Shaped Bolapolyphiles.

The single gyroid phase as well as the alternating double network gyroid, composed of two alternating single gyroid networks, hold a significant place in ordered nanoscale morphologies for their potential applications as photonic crystals, metamaterials and templates for porous ceramics and metals. Here, we report the first alternating network cubic liquid crystals. They form through self-assembly of X-shaped polyphiles, where glycerol-capped terphenyl rods lie on the gyroid surface while semiperfluorinated and aliphatic side-chains fill their respective separate channel networks. This new self-assembly mode can be considered as a two-color symmetry-broken double gyroid morphology, providing a tailored way to fabricate novel chiral structures with sub-10 nm periodicities using achiral compounds.

Transition from nematic to gyroid-type cubic soft self-assembly by side-chain engineering of π-conjugated sticky rods.

A sequence of liquid crystalline phases, involving cybotactic nematics, a lamellar phase, bicontinuous cubics and triangular honeycombs, was observed for oligo(phenylene ethynylene) based X-shaped bolapolyphiles with two long lateral alkyl chains and sticky ends provided by glycerol groups. In the cubic phase with Ia3[combining macron]d lattice - which is tailored by alkyl chain engineering - the aromatic cores are organized on the gyroid minimal surface in 3D curved layers of almost parallel aligned π-conjugated rods. It is shown that this type of cubic phase is a general mode of soft self-assembly of X-shaped bolapolyphiles at the cross-over from the (long or short range) lamellar to the triangular honeycomb-like organization. Cubic phase formation is found only in a narrow range with respect to temperature and chain-length for the non-fluorinated compounds and in much wider ranges for related core-fluorinated molecules.

Self-Assembly of X-Shaped Bolapolyphiles in Lipid Membranes: Solid-State NMR Investigations.

A novel class of rigid-rod bolapolyphilic molecules with three philicities (rigid aromatic core, mobile aliphatic side chains, polar end groups) has recently been demonstrated to incorporate into and span lipid membranes, and to exhibit a rich variety of self-organization modes, including macroscopically ordered snowflake structures with 6-fold symmetry. In order to support a structural model and to better understand the self-organization on a molecular scale, we here report on proton and carbon-13 high-resolution magic-angle spinning solid-state NMR investigations of two different bolapolyphiles (BPs) in model membranes of two different phospholipids (DPPC, DOPC). We elucidate the changes in molecular dynamics associated with three new phase transitions detected by calorimetry in composite membranes of different composition, namely, a change in π-π-packing, the melting of lipid tails associated with the superstructure, and the dissolution and onset of free rotation of the BPs. We derive dynamic order parameters associated with different H-H and C-H bond directions of the BPs, demonstrating that the aromatic cores are well packed below the final phase transition, showing only 180° flips of the phenyl ring, and that they perform free rotations with additional oscillations of the long axis when dissolved in the fluid membrane. Our data suggests that BPs not only form ordered superstructures, but also rather homogeneously dispersed π-packed filaments within the lipid gel phase, thus reducing the corrugation of large vesicles.

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.

Temperature-dependent in-plane structure formation of an X-shaped bolapolyphile within lipid bilayers.

Polyphilic compound B12 is an X-shaped molecule with a stiff aromatic core, flexible aliphatic side chains, and hydrophilic end groups. Forming a thermotropic triangular honeycomb phase in the bulk between 177 and 182 °C but no lyotropic phases, it is designed to fit into DPPC or DMPC lipid bilayers, in which it phase separates at room temperature, as observed in giant unilamellar vesicles (GUVs) by fluorescence microscopy. TEM investigations of bilayer aggregates support the incorporation of B12 into intact membranes. The temperature-dependent behavior of the mixed samples was followed by differential scanning calorimetry (DSC), FT-IR spectroscopy, fluorescence spectroscopy, and X-ray scattering. DSC results support in-membrane phase separation, where a reduced main transition and new B12-related transitions indicate the incorporation of lipids into the B12-rich phase. The phase separation was confirmed by X-ray scattering, where two different lamellar repeat distances are visible over a wide temperature range. Polarized ATR-FTIR and fluorescence anisotropy experiments support the transmembrane orientation of B12, and FT-IR spectra further prove a stepwise "melting" of the lipid chains. The data suggest that in the B12-rich domains the DPPC chains are still rigid and the B12 molecules interact with each other via π-π interactions. All results obtained at temperatures above 75 °C confirm the formation of a single, homogeneously mixed phase with freely mobile B12 molecules.

Self-assembly of imidazolium-based rodlike ionic liquid crystals: transition from lamellar to micellar organization.

By using aryl-amination chemistry, a series of rodlike 1-phenyl-1H-imidazole-based liquid crystals (LCs) and related imidazolium-based ionic liquid crystals (ILCs) has been prepared. The number and length of the C-terminal chains (at the noncharged end of the rodlike core) and the length of the N-terminal chain (on the imidazolium unit in the ILCs) were modified and the influence of these structural parameters on the mode of self-assembly in LC phases was investigated by polarizing microscopy, differential scanning calorimetry, and X-ray diffraction. For the single-chain imidazole derivatives nematic phases (N) and bilayer SmA2 phases were found, but upon increasing the number of alkyl chains the LC phases were lost. For the related imidazolium salts LC phases were preserved upon increasing the number and length of the C-terminal chains and in this series it leads to the phase sequence SmA-columnar (Col)-micellar cubic (CubI /Pm3n). Elongation of the N-terminal chain gives the reversed sequence. Short N-terminal chains prefer an end-to-end packing of the mesogens in which these chains are separated from the C-terminal chains. Elongation of the N-terminal chain leads to a mixing of N- and C-terminal chains, which is accompanied by complete intercalation of the aromatic cores. In the smectic phases this gives rise to a transition from bilayer (SmA2) to monolayer smectic (SmA) phases. For the columnar and cubic phases the segregated end-to-end packing leads to core-shell aggregates. In this case, elongation of the N-terminal chains distorts core-shell formation and removes CubI and Col phases in favor of single-layer SmA phases. Hence, by tailoring the length of the N-terminal chain, a crossover from taper-shaped to polycatenar LC tectons was achieved, which provides a powerful tool for control of self-assembly in ILCs.

Controlling the Miscibility of X-Shaped Bolapolyphiles in Lipid Membranes by Varying the Chemical Structure and Size of the Polyphile Polar Headgroup.

Bolaamphiphiles are well-known naturally occurring structures that can increase the thermal and mechanical stability of the phospholipid membrane by incorporation in a transmembrane manner. Modifications of bolaamphiphiles to introduce particular structural elements such as a conjugated aromatic backbone and lateral side chains in the hydrophobic region lead to bolapolyphiles (BPs). We investigated the ability of BPs to form lyotropic phases in water. The BPs had an identical backbone and side chains, but different headgroup structures, leading to different abilities to act as hydrogen bond donors and acceptors. BPs with hydrophilic headgroups capable of acting as hydrogen bond donors as well as acceptors did not form lyotropic phases and were insoluble in water, independent of whether the polar groups were small or large. The extended lipophilic core structure and the multiple intermolecular hydrogen bonds between the headgroups prevented the formation of well-hydrated lyotropic aggregates. A BP with two large hydrophilic headgroups of several ethylene oxide moieties terminated by methyl groups formed sheet- and vesicle-like aggregates in water. These headgroups act only as hydrogen bond acceptors and cannot form hydrogen bonds in the absence of water. The miscibility of BPs with vesicles of 1,2-dipalmitoyl- sn-glycero-3-phosphocholine (DPPC) in water and the resulting aggregate structures were also investigated. For BPs with headgroups acting as donors and acceptors of hydrogen bonds, macroscopic phase separation occurred in the mixed membranes, and two different membrane domains, a DPPC-rich one containing only little polyphile and a BP-rich one containing varying amounts of lipid, were formed. For headgroups without the ability to act as hydrogen bond donors, small BP aggregates were formed that were homogeneously distributed over the membrane. The lateral organization of BPs in lipid membranes can thus be controlled by the nature of the BP headgroup.

Effects of Lateral and Terminal Chains of X-Shaped Bolapolyphiles with Oligo(phenylene ethynylene) Cores on Self-Assembly Behaviour. Part 1: Transition between Amphiphilic and Polyphilic Self-Assembly in the Bulk.

Polyphilic self-assembly leads to compartmentalization of space and development of complex structures in soft matter on different length scales, reaching from the morphologies of block copolymers to the liquid crystalline (LC) phases of small molecules. Whereas block copolymers are known to form membranes and interact with phospholipid bilayers, liquid crystals have been less investigated in this respect. Here, series of bolapolyphilic X-shaped molecules were synthesized and investigated with respect to the effect of molecular structural parameters on the formation of LC phases (part 1), and on domain formation in phospholipid bilayer membranes (part 2). The investigated bolapolyphiles are based on a rod-like π-conjugated oligo(phenylene ethynylene) (OPE) core with two glycerol groups being either directly attached or separated by additional ethylene oxide (EO) units to both ends. The X-shape is provided by two lateral alkyl chains attached at opposite sides of the OPE core, being either linear, branched, or semiperfluorinated. In this report, the focus is on the transition from polyphilic (triphilic or tetraphilic) to binary amphiphilic self-assembly. Polyphilic self-assembly, i.e., segregation of all three or four incorporated units into separate nano-compartments, leads to the formation of hexagonal columnar LC phases, representing triangular honeycombs. A continuous transition from the well-defined triangular honeycomb structures to simple hexagonal columnar phases, dominated by the arrangement of polar columns on a hexagonal lattice in a mixed continuum formed by the lipophilic chains and the OPE rods, i.e., to amphiphilic self-assembly, was observed by reducing the length and volume of the lateral alkyl chains. A similar transition was found upon increasing the length of the EO units involved in the polar groups. If the lateral alkyl chains are enlarged or replaced by semiperfluorinated chains, then the segregation of lateral chains and rod-like cores is retained, even for enlarged polar groups, i.e., the transition from polyphilic to amphiphilic self-assembly is suppressed.

Effects of Lateral and Terminal Chains of X-Shaped Bolapolyphiles with Oligo(phenylene ethynylene) Cores on Self-Assembly Behavior. Part 2: Domain Formation by Self-Assembly in Lipid Bilayer Membranes.

Supramolecular self-assembly of membrane constituents within a phospholipid bilayer creates complex functional platforms in biological cells that operate in intracellular signaling, trafficking and membrane remodeling. Synthetic polyphilic compounds of macromolecular or small size can be incorporated into artificial phospholipid bilayers. Featuring three or four moieties of different philicities, they reach beyond ordinary amphiphilicity and open up avenues to new functions and interaction concepts. Here, we have incorporated a series of X-shaped bolapolyphiles into DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) bilayers of giant unilamellar vesicles. The bolapolyphiles consist of a rod-like oligo(phenylene ethynylene) (OPE) core, hydrophilic glycerol-based headgroups with or without oligo(ethylene oxide) expansions at both ends and two lateral alkyl chains attached near the center of the OPE core. In the absence of DPPC and water, the compounds showed thermotropic liquid-crystalline behavior with a transition between polyphilic and amphiphilic assembly (see part 1 in this issue). In DPPC membranes, various trends in the domain morphologies were observed upon structure variations, which entailed branched alkyl chains of various sizes, alkyl chain semiperfluorination and size expansion of the headgroups. Observed effects on domain morphology are interpreted in the context of the bulk behavior (part 1) and of a model that was previously developed based on spectroscopic and physicochemical data.