Using a combination of small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), we document the composition-dependent morphologies of 39 new poly(lactide-block-1,4-butadiene-block-lactide) (LBL) block polymers, comprising a broad dispersity B segment (Mn = 4.5–17.7 kg/mol; Đ = Mw/Mn = 1.72–1.88) and narrow dispersity L end blocks (Mn = 0.6–15.3 kg/mol; Đ = 1.10–1.21) with volume fractions 0.26 ≤ fB ≤ 0.95. A subset of these samples undergo melt self-assembly into cylindrical, lamellar, and apparently bicontinuous morphologies. By assessing the states of order and disorder in these triblock polymer melts using temperature-dependent SAXS, we find that broad B segment dispersity increases the minimum segregation strength χN ≳ 27 required for LBL triblock self-assembly relative to the self-consistent mean-field theory prediction χN ≥ 17.9 for narrow dispersity analogues. While B segment dispersity has previously been shown to thermodynamically stabilize the self-assembled morphologies of low χ/high N ABA triblocks, the present study indicates that broad B block dispersity in related high χ/low N systems destabilizes the microphase-separated melt. These observations are rationalized in terms of recent theories that suggest that broad segmental dispersity substantially enhances fluctuation effects at low N, thus disfavoring melt segregation.

Nanoporous proton-transporting media are critical components in fuel cells and other electrochemical devices, yet general molecular design criteria for new materials with enhanced performance remain obscure. Aqueous lyotropic liquid crystals (LLCs) comprise a platform for detailed studies of the molecular-level features governing proton transport in monodisperse, water-filled nanopores lined with well-defined chemical functionalities. We report new alkylsulfonic acid LLCs that exhibit H+ conductivities as high as σ = 380 mS/cm at 80 °C, which rival those of more acidic, perfluorinated polymers, thus demonstrating that the acidity of the pore functionality is not the sole determinant of proton transport. Direct experimental comparisons of LLCs with convex and concave nanopores of similar dimensions indicate that H+ conductivities therein sensitively depend on the hydration state of the acid functionalities and the pore curvature. These experiments suggest that judicious manipulation of pore curvature provides a new means for optimizing the activities of proton-exchange membranes and nanoporous solid acid catalysts.

The development of high capacity anodes and high voltage cathodes for advanced lithium-ion batteries motivates the search for new polymer electrolytes that exhibit superior electrochemical stabilities and high ionic conductivities. We report a convenient, three-step synthesis of lithium bis(non-8-enyl-malonato)borate (LiBNMB) as a α,ω-diene monomer, which undergoes thermally initiated thiol–ene crosslinking polymerizations in propylene carbonate to yield gel polymer electrolytes with high lithium ion concentrations (∼0.9 M). By conducting these crosslinking polymerizations using mixtures of di- and tri-thiols and LiBNMB with [thiol] : [ene] = 1 : 1, we synthesized a series of gel networks with dynamic elastic moduli ranging from G′ = 40–79 kPa that increase monotonically with trifunctional crosslinker content. While ionic conductivities for these polymer gels measured by electrochemical impedance spectroscopy at 22 °C are σ = 0.82–2.5 × 10−6 S cm−1, we show that the conductivity of propylene carbonate-solvated lithium ions though the bulk of these gel electrolytes is 8.5 × 10−5 S cm−1 independent of crosslinker density. However, the conductivities of the gel interfaces depend sensitively on crosslinker content, suggesting the importance of segmental rearrangement dynamics at the electrode interface in limiting the rate of ion motion. Thus, the design of highly conductive polymer electrolytes for advanced batteries demands careful design of both the internal and interfacial properties of these new materials.

Supramolecular self-assembly enables access to designer soft materials that typically exhibit high-symmetry packing arrangements, which optimize the interactions between their mesoscopic constituents over multiple length scales. We report the discovery of an ionic small molecule surfactant that undergoes water-induced self-assembly into spherical micelles, which pack into a previously unknown, low-symmetry lyotropic liquid crystalline Frank–Kasper σ phase. Small-angle X-ray scattering studies reveal that this complex phase is characterized by a gigantic tetragonal unit cell, in which 30 sub-2-nm quasispherical micelles of five discrete sizes are arranged into a tetrahedral close packing, with exceptional translational order over length scales exceeding 100 nm. Varying the relative concentrations of water and surfactant in these lyotropic phases also triggers formation of the related Frank–Kasper A15 sphere packing as well as a common body-centered cubic structure. Molecular dynamics simulations reveal that the symmetry breaking that drives the formation of the σ and A15 phases arises from minimization of local deviations in surfactant headgroup and counterion solvation to maintain a nearly spherical counterion atmosphere around each micelle, while maximizing counterion-mediated electrostatic cohesion among the ensemble of charged particles.

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. These experiments demonstrate that the position of the linker directly impacts the maximum counterion–headgroup hydration capacity and the extent of counterion–headgroup association, all of which contribute to the aqueous lyotropic double gyroid network phase stability. Thus, judicious selection of the linker position in ionic gemini surfactants provides a new molecular design tool for manipulating LLC network phase stability.

We report a reactive polymer platform for the rapid discovery of strongly segregated diblock polymers that microphase separate into well-defined morphologies with sub-5 nm features. Our strategy employs reactive poly(styrene-block-2-vinyl-4,4-dimethylazlactone) (SV) polymers with low degrees of polymerization (N), in which the V blocks undergo selective and quantitative reactions with functional primary amines, to identify new poly(acrylamides) that are highly immiscible with poly(styrene) and induce block polymer self-assembly. Using a combination of optical birefringence and small-angle X-ray scattering (SAXS), we characterize a library of 17 block polymers produced by amine functionalization of four parent SV diblocks synthesized by sequential RAFT polymerizations. We demonstrate that V block functionalization with hydroxy- and methoxy-functional amines yields diblocks that order into lamellar mesophases with half-pitches as small as 3.8 nm. Thus, this azlactone-based reactive molecular platform enables combinatorial generation of polymer libraries with diverse side chain structures that may be rapidly screened to identify new high χ/low N systems for self-assembly at ever decreasing length scales.

We report synthetic six-tailed mimics of the bacterial glycolipid Lipid A that trigger changes in the internal ordering of water-dispersed liquid crystal (LC) microdroplets at ultralow (picogram-per-milliliter) concentrations. These molecules represent the first class of synthetic amphiphiles to mimic the ability of Lipid A and bacterial endotoxins to trigger optical responses in LC droplets at these ultralow concentrations. This behavior stands in contrast to all previously reported synthetic surfactants and lipids, which require near-complete monolayer coverage at the LC droplet surface to trigger ordering transitions. Surface-pressure measurements and SAXS experiments reveal these six-tailed synthetic amphiphiles to mimic key aspects of the self-assembly of Lipid A at aqueous interfaces and in solution. These and other results suggest that these amphiphiles trigger orientational transitions at ultralow concentrations through a unique mechanism that is similar to that of Lipid A and involves formation of inverted self-associated nanostructures at topological defects in the LC droplets.