Unexpected role of linker position on ammonium gemini surfactant lyotropic gyroid phase stability.

Arising from the water-driven self-assembly of amphiphiles over generally narrow temperature and composition phase windows, aqueous lyotropic liquid crystal (LLC) network phases are useful in applications as therapeutic delivery vehicles and templates for mesoporous material syntheses. While a clear set of amphiphile design rules that enables access to these intricate three-dimensional structures has yet to emerge, recent work indicates that bis(ammonium), bis(phosphonium), and dicarboxylate gemini ("twin tail") surfactants enable enhanced access to LLC network phases such as the double gyroid (G). In order to better understand the scope of this amphiphile design strategy, we investigated the synthesis and aqueous LLC self-assembly behaviors of a homologous series of quaternary gemini bis(ammonium) dichloride surfactants, in which we varied the position of the hydrophobic linker that connects the constituent single tail surfactants.

High-resolution structures of a heterochiral coiled coil.

Interactions between polypeptide chains containing amino acid residues with opposite absolute configurations have long been a source of interest and speculation, but there is very little structural information for such heterochiral associations. The need to address this lacuna has grown in recent years because of increasing interest in the use of peptides generated from d amino acids (d peptides) as specific ligands for natural proteins, e.g.

Linker Length-Dependent Control of Gemini Surfactant Aqueous Lyotropic Gyroid Phase Stability.

Network-phase lyotropic liquid crystals (LLCs) derived from the water-directed self-assembly of small molecule amphiphiles comprise a useful class of soft nanomaterials, with wide-ranging applications in structural biology and membrane science. However, few known surfactants enable access to these mesophases over wide temperature and amphiphile concentration phase windows. Recent studies have demonstrated that gemini ("twin tail") dicarboxylate surfactants, in which alkyl carboxylates are covalently linked near the headgroups by a hydrophobic bridge, exhibit increased propensities to form double gyroid network phase LLCs.

Reply to the 'Comment on "Discovery of a tetracontinuous, aqueous lyotropic network phase with unusual 3D-hexagonal symmetry"' by G. Schröder-Turk, M. Fischer and S. Hyde.

A new calculation by Fischer et al. suggests that the 3etc network phase with 3D-hexagonal symmetry (space group #193: P63/mcm) may be a generic structure adopted by self-assembling soft materials, thereby broadening the context for our recent report of its spontaneous formation in lyotropic liquid crystals. The experimental observation of the 3etc phase further validates previous theoretical models used to predict its stability, provocatively suggesting that other polycontinuous network phases predicted by these methods may be discovered in the future.

Discovery of a tetracontinuous, aqueous lyotropic network phase with unusual 3D-hexagonal symmetry.

Network phase aqueous lyotropic liquid crystals (LLCs) are technologically useful materials with myriad applications in chemistry, biology, and materials science, which stem from their structurally periodic aqueous and hydrophobic nanodomains (∼0.7-5.0 nm in diameter) that are lined with well-defined chemical functionalities.

Unusually stable aqueous lyotropic gyroid phases from gemini dicarboxylate surfactants.

Aqueous lyotropic liquid crystal (LLC) assemblies with bicontinuous cubic morphologies (Q-phases) have shown promise in applications ranging from selective chemical separations to ion transporting media, yet universal design criteria for amphiphiles that adopt these unique structures remain elusive. Recent reports have demonstrated that cationic gemini surfactants exhibit a tendency to form bicontinuous cubic LLCs as compared to single-tail amphiphiles; however, the universality of this surfactant design motif in stabilizing Q-phases remains untested. Herein, we report the modular synthesis of a new class of anionic gemini surfactants derived from aliphatic carboxylic acids and demonstrate their unexpectedly strong propensity to form gyroid LLC phases with unprecedented stability between 25 and 100 °C over amphiphile concentration windows up to 20 wt % wide.