The critical Casimir force (CF) is observed in thin wetting films of a binary liquid mixture close to the liquid/vapor coexistence. X-ray reflectivity shows thickness (L) enhancement near the bulk consolute point. The extracted Casimir amplitude Delta(+-)=3+/-1 agrees with the theoretical universal value for the antisymmetric 3D Ising films. The onset of CF in the one-phase region occurs at L/xi approximately 5 regardless of whether the bulk correlation length xi is varied with temperature or composition. The shape of the Casimir scaling function depends monotonically on the dimensionality.

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The assembly of individual molecules into hierarchical structures is a promising strategy for developing three-dimensional materials with properties arising from interaction between the individual building blocks. Virus capsids are elegant examples of biomolecular nanostructures, which are themselves hierarchically assembled from a limited number of protein subunits. Here we demonstrate the bio-inspired modular construction of materials with two levels of hierarchy; the formation of catalytically active individual virus-like particles (VLPs) through directed self-assembly of capsid subunits with enzyme encapsulation, and the assembly of these VLP building blocks into three-dimensional arrays. The structure of the assembled arrays was successfully altered from an amorphous aggregate to an ordered structure, with a face-centered cubic lattice, by modifying the exterior surface of the VLP without changing its overall morphology, to modulate interparticle interactions. The assembly behavior and resultant lattice structure was a consequence of interparticle interaction between exterior surfaces of individual particles, and thus independent of the enzyme cargos encapsulated within the VLPs. These superlattice materials, composed of two populations of enzyme packaged VLP modules, retained the coupled catalytic activity in a two-step reaction for isobutanol synthesis. This study demonstrates a significant step toward the bottom-up fabrication of functional superlattice materials using a self-assembly process across multiple length scales, and exhibits properties and function that arise from the interaction between individual building blocks.

Piezoelectric polymers hold great potential for various electromechanical applications, but only show low performance, with |d33 | < 30 pC/N. We prepare a highly piezoelectric polymer (d33 = −62 pC/N) based on a biaxially oriented poly(vinylidene fluoride) (BOPVDF, crystallinity = 0.52). After unidirectional poling, macroscopically aligned samples with pure β crystals are achieved, which show a high spontaneous polarization (Ps) of 140 mC/m2. Given the theoretical limit of Ps,β = 188 mC/m2 for the neat β crystal, the high Ps cannot be explained by the crystalline-amorphous two-phase model (i.e., Ps,β = 270 mC/m2). Instead, we deduce that a significant amount (at least 0.25) of an oriented amorphous fraction (OAF) must be present between these two phases. Experimental data suggest that the mobile OAF resulted in the negative and high d33 for the poled BOPVDF. The plausibility of this conclusion is supported by molecular dynamics simulations.

This study unveils a new tetracene derivative that forms dense, upright monolayers on the surface of aluminum oxide. These monolayers spontaneously self-organize into the active layer in nanoscale field-effect transistor devices when aluminum oxide is used as the dielectric layer. This method gives high yields of working devices that have source-drain distances that are less than 60 nm, thereby providing a method to electrically probe the monolayer assemblies formed from approximately 10 zeptomoles of material (approximately 104 molecules). Moreover, this study delineates a new avenue for research in thin-film organic transistors where the active molecules are linked to the dielectric surface to form a monolayer transistor.

Interfacial polarization due to space charges enhances electrical insulation and thus breakdown strength for multilayer polymer films.

DNA-driven assembly of nanoscale objects has emerged as a powerful platform for the creation of materials by design via self-assembly. Recent years have seen much progress in the experimental realization of this approach for three-dimensional systems. In contrast, two-dimensional (2D) programmable nanoparticle (NP) systems are not well explored, in part due to the difficulties in creating such systems. Here we demonstrate the use of charged liquid interfaces for the assembly and reorganization of 2D systems of DNA-coated NPs. The absorption of DNA-coated NPs to the surface is controlled by the interaction between a positively charged lipid layer and the negatively charged DNA shells of particles. At the same time, interparticle interactions are switchable, from electrostatic repulsion between DNA shells to attraction driven by DNA complementarity, by increasing ionic strength. Using in situ surface X-ray scattering methods and ex situ electron microscopy, we reveal the corresponding structural transformation of the NP monolayer, from a hexagonally ordered 2D lattice to string-like clusters and finally to a weakly ordered network of DNA cross-linked particles. Moreover, we demonstrate that the ability to regulate 2D morphology yields control of the interfacial rheological properties of the NP membrane: from viscous to elastic. Theoretical modeling suggests that the structural adaptivity of interparticle DNA linkages plays a crucial role in the observed 2D transformation of DNA-NP systems at liquid interfaces.

The microscopic structure of Langmuir films of derivatized gold nanoparticles has been studied as a function of area/particle on the water surface. The molecules (AuSHDA) consist of gold particles of mean core diameter D∼22 Å that have been stabilized by attachment of carboxylic acid terminated alkylthiols, HS–(CH2)15–COOH. Compression of the film results in a broad plateau of finite pressure in the surface pressure versus area/particle isotherm that is consistent with a first-order monolayer/bilayer transition. X-ray specular reflectivity (XR) and grazing incidence diffraction show that when first spread at large area/particle, AuSHDA particles aggregate two dimensionally to form hexagonally packed monolayer domains at a nearest-neighbor distance of a=34 Å. The lateral positional correlations associated with the two-dimensional (2D) hexagonal order are of short range and extend over only a few interparticle distances; this appears to be a result of the polydispersity in particle size. Subsequent compression of the film increases the surface coverage by the monolayer but has little effect on the interparticle distance in the close-packed domains. The XR and off-specular diffuse scattering (XOSDS) results near the onset of the monolayer/bilayer coexistence plateau are consistent with complete surface coverage by a laterally homogeneous monolayer of AuSHDA particles. On the high-density side of the plateau, the electron-density profile extracted from XR clearly shows the formation of a bilayer in which the newly formed second layer on top is slightly less dense than the first layer. In contrast to the case of the homogeneous monolayer, the XOSDS intensities observed from the bilayer are higher than the prediction based on the capillary wave model and the assumption of homogeneity, indicating the presence of lateral density inhomogeneities in the bilayer. According to the results of Bragg rod measurements, the 2D hexagonal order in the two layers of the bilayer are only partially correlated.