Development of Structural Complexity by Liquid‐Crystal Self‐assembly

Tschierske, Carsten

doi:10.1002/anie.201300872

Cited by 523 publications

(415 citation statements)

References 599 publications

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“…Not only the Meier-Saupe type interactions (reduction of excluded volume) and attractive -, respectively C-H--interactions between the rod-like units 32,[41][42][43] , but also the strong segregation of these rigid units from the flexible alkyl chains (rigid-flexible incompatibility) [22][23] should contribute to this effect. Simultaneously, as two sides of the molecule are shielded by the lateral alkyl chains, the possible modes of packing are restricted, mainly leaving the option of a linear side-by-side stacking in ribbons (strings).…”

Section: Discussionmentioning

confidence: 99%

Temperature-Dependent In-Plane Structure Formation of an X-Shaped Bolapolyphile within Lipid Bilayers

et al. 2015

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The polyphilic compound B12 is an X-shaped molecule with stiff aromatic core, flexible aliphatic side chains and hydrophilic end groups. Forming a thermotropic triangular honeycomb phase in the bulk between 177 °C 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.

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Section: Discussionmentioning

confidence: 99%

Temperature-Dependent In-Plane Structure Formation of an X-Shaped Bolapolyphile within Lipid Bilayers

et al. 2015

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“…Despite the fact that a great number of LC molecules are often not ideal calamitics and have bulky substitutients near the lateral and terminal atoms, 31 we have tried to choose for our investigation such model compounds which satisfied the requirement of rod-like configuration. First, we performed the molecular modeling (see Experimental) for the structure with heterocyclic 2,5-dihydroimidazole core spirofused with cyclohexane moiety possessing 4-(aroyloxy)phenyl substituent on the C4 position.…”

Section: Resultsmentioning

confidence: 99%

New spirocyclic nitroxides of 2,5-dihydroimidazole series flanked by two mesogenic fragments

Zaytseva¹,

Shernyukov²,

Genaev³

et al. 2014

Arkivoc

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N/C-Hydroxylated spirofused derivatives of 2,5-dihydroimidazole which were synthesized by condensation of 4-(4-hydroxyphenyl)cyclohexanone with aryl hydroxylaminoalkyl ketones in the presence of ammonia were determined to be trans-ee-isomers of 1,4-cyclohexane framework by NMR spectroscopy. Oxidation of the cyclic hydroxylamino moiety followed by acylation of the phenolic hydroxyl group with 4-alkyloxybenzoic acid chlorides led to the corresponding spirocyclic nitroxides bearing two mesogenic fragments.

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“…These flexible lateral chains cause a frustration of the layer-like organization for steric reasons (Figure 1a,b). Moreover, the flexible chains are more or less incompatible with the rigid rod-like cores, thus tending to organize in distinct compartments, and therefore, these molecules are considered as bolapolyphiles [14][15][16][17]. The bulk self-assembly of these compounds is complex, and a huge variety of distinct LC phases can be observed, as shown in Figure 1.…”

Section: Methodsmentioning

confidence: 99%

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

Poppe

Ebert

et al. 2017

Polymers

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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.

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Development of Structural Complexity by Liquid‐Crystal Self‐assembly

Cited by 523 publications

References 599 publications

Temperature-Dependent In-Plane Structure Formation of an X-Shaped Bolapolyphile within Lipid Bilayers

Temperature-Dependent In-Plane Structure Formation of an X-Shaped Bolapolyphile within Lipid Bilayers

New spirocyclic nitroxides of 2,5-dihydroimidazole series flanked by two mesogenic fragments

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

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