Membranes are widely used for separation processes in applications such as water desalination, batteries and dialysis, and are crucial in key sectors of our economy and society1. The majority of technologically exploited membranes are based on solid polymers and function as passive barriers, whose transport characteristics are governed by their chemical composition and nanostructure. Although such membranes are ubiquitous, it has proved challenging to maximize selectivity and permeability independently, leading to trade-offs between these pertinent characteristics2. Self-assembled biological membranes, in which barrier and transport functions are decoupled3,4, provide the inspiration to address this problem5,6. Here we introduce a self-assembly strategy that uses the interface of an aqueous two-phase system to template and stabilize molecularly thin (approximately 35 nm) biomimetic block copolymer bilayers of scalable area that can exceed 10 cm2 without defects. These membranes are self-healing, and their barrier function against the passage of ions (specific resistance of approximately 1 MΩ cm2) approaches that of phospholipid membranes. The fluidity of these membranes enables straightforward functionalization with molecular carriers that shuttle potassium ions down a concentration gradient with exquisite selectivity over sodium ions. This ion selectivity enables the generation of electric power from equimolar solutions of NaCl and KCl in devices that mimic the electric organ of electric rays.
Multilamella polymer crystals are grown from the melt for the first time, in molecular dynamics simulations of a united-monomer model, with in excess of 1500000 united-monomers. Two-component systems comprised of equal weight fractions of 2000 united-monomer long chains and 200 united-monomer short chains are considered, with varying numbers of short butyl branches placed along the long chains. Utilizing two different cooling protocols, continuous-cooling and self-seeding, drastically different multilamella structures are revealed, which depend heavily on the branch content and crystallization protocol used. By self-seeding, well-aligned multilamella crystals are grown, which more clearly reveal the subtle alterations an increasing number of branches create on the size and shape of the crystallites in the early stages of spherulite formation. Under continuous cooling, this observation is almost completely obscured. At maximum thickness, chain portions as long as 100 united-monomers (200 carbons) are extended inside the crystalline lamella.
Condensed matter textbooks teach us that melting cannot be continuous and indeed experience, including with polymers and other long-chain compounds, tells us that it is a strongly first-order transition. However, here we report nearly continuous melting of monolayers of ultralong n-alkane C390H782 on graphite, observed by AFM and reproduced by mean-field theory and MD simulation. On heating, the crystal-melt interface moves steadily and reversibly from chain ends inward. Remarkably, the final melting point is 80 K above that of the bulk, and equilibrium crystallinity decreases continuously from ~100% to <50% prior to final melting. We show that the similarity in melting behavior of polymers and non-polymers is coincidental. In the bulk, the intermediate melting stages of long-chain crystals are forbidden by steric overcrowding at the crystal-liquid interface. However, there is no crowding in a monolayer as chain segments can escape to the third dimension.
Fan-shaped molecules with aromatic head-groups and two or more flexible pendant chains often self-assemble into columns that form columnar liquid crystals by packing on a 2d lattice. Such dendrons or minidendrons are essential building blocks in a large number of synthetic self-assembled systems and organic device materials. Here we report a new type of phase transition that occurs between two hexagonal columnar phases, Colh1 and Colh2, of Na-salt of 3,4,5-tris-dodecyloxy benzoic acid. Interestingly, the transition does not change the symmetry, which is p6mm in both phases, but on heating it involves a quantised drop in the number of molecules n in the cross-section of a column. The drop is from 4 to 3.5, with a further continuous decrease toward n = 3 as temperature increases further above Tc. The finding is based on evidence from X-ray diffraction. Using a transfer matrix formulation for the interactions within a column, with small additional mean field terms, we describe quantitatively the observed changes in terms of intermolecular forces responsible for the formation of supramolecular columns. The driving force behind temperature-induced molecular ejection from the columns is the increase in conformational disorder and the consequent lateral expansion of the alkyl chains. The asymmetry of the transition is due to the local order between 4-molecule discs giving extra stability to purely n = 4 columns.
