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Here we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: "flattened chains" which lie flat on the solid and are densely packed, and "loosely adsorbed polymer chains" which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesion testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer-adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as "connector molecules", bridging the free chains and substrate surface and improving the interfacial adhesion. These findings not only shed light on the structure-property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.

Crystal orientation in semi-crystalline polymers tends to enhance their performance, such as increased yield strength and modulus, along the orientation direction. Zone annealing (ZA) orients the crystal lamellae through a sharp temperature gradient that effectively directs the crystal growth, but the sweep rate (VZA) of this gradient significantly impacts the extent of crystal orientation. Here, we demonstrate rotational zone annealing (RZA) as an efficient method to elucidate the influence of VZA on the crystal morphology of thin films in a single experiment using isotactic poly(1-butene), PB-1, as a model semi-crystalline polymer. These RZA results are confirmed using standard, serial linear ZA to tune the structure from an almost unidirectional oriented morphology to weakly oriented spherulites. The overall crystallinity is only modestly changed in comparison to isothermal crystallization (maximum of 55% from ZA vs. 48% for isothermal crystallization). However, the average grain size increases and the spherulites become anisotropic from ZA. Due to these structural changes, the Young's modulus of the oriented films, both parallel and perpendicular to the spherulite orientation direction, is significantly increased by ZA. The modulus does become anisotropic after ZA due to the directionality in the crystal structure, with more than a threefold increase in the modulus parallel to the orientation direction for the highest oriented film in comparison to the modulus from isothermal crystallization. RZA enables rapid identification of conditions to maximize orientation of crystals in thin polymer films, which could find utility in determining conditions to improve crystallinity and performance in organic electronics.

An energy dissipation mechanism during deformation is required to impart toughness to hydrogels. Here we describe how in situ small angle X-ray scattering (SAXS) provides insight into possible energy dissipation mechanisms for a tough hydrogel based on an amphiphilic copolymer where nanoscale associations of the hydrophobic moieties act as effective crosslinks. The mechanical properties of the hydrogels are intimately coupled with the nanostructure that provides reversible crosslinks and evolves during deformation. As the extension rate increases, more mechanical energy is dissipated from rearrangements of the crosslinks. The scattering is consistent with hopping of hydrophobes between the nanoscale aggregates as the primary rearrangement mechanism. This rearrangement changes the network conformation that leads to non-affine deformation, where the change in the nanostructure dimension from SAXS is less than 15% of the total macroscopic strain. These nanostructure changes are rate dependent and correlated with the relaxation time of the hydrogel. At low strain rate (0.15% s-1), no significant change of the nanostructure was observed, whereas at higher strain rates (1.5% s-1 and 8.4% s-1) significant nanostructure anisotropy occurred during extension. These differences are attributed to the ability for the network chains to rearrange on the time scale of the deformation; when the characteristic time for extension is longer than the average segmental relaxation time, no significant change in nanostructure occurs on uniaxial extension. These results illustrate the importance of strain rate in the mechanical characterization and consideration of relaxation time in the design of tough hydrogels with reversible crosslinks.

Correction for ‘Shear-induced polydomain structures of nematic lyotropic chromonic liquid crystal disodium cromoglycate’ by Hend Baza et al., Soft Matter, 2020, 16, 8565–8576.

We report an experimental demonstration of a strategy for inducing two-dimensional (2D) crystallization of charged nanoparticles on oppositely charged fluid interfaces. This strategy aims to maximize the interfacial adsorption of nanoparticles, and hence their lateral packing density, by utilizing a combination of weakly charged particles and a high surface charge density on the planar interface. In order to test this approach, we investigated the assembly of cowpea mosaic virus (CPMV) on positively charged lipid monolayers at the aqueous solution surface, by means of in situ X-ray scattering measurements at the liquid-vapor interface. The assembly was studied as a function of the solution pH, which was used to vary the charge on CPMV, and of the mole fraction of the cationic lipid in the binary lipid monolayer, which set the interface charge density. The 2D crystallization of CPMV occurred in a narrow pH range just above the particle's isoelectric point, where the particle charge was weakly negative, and only when the cationic-lipid fraction in the monolayer exceeded a threshold. The observed 2D crystals exhibited nearly the same packing density as the densest lattice plane within the known 3D crystals of CPMV. The above electrostatic approach of maximizing interfacial adsorption may provide an efficient route to the crystallization of nanoparticles at aqueous interfaces.

We investigate two-dimensional (2D) assembly of the icosahedral turnip yellow mosaic virus (TYMV) under cationic lipid monolayers at the aqueous solution–vapor interface. The 2D crystallization of TYMV has been achieved by enhancing electrostatically induced interfacial adsorption, an approach recently demonstrated for another virus. In situ X-ray scattering reveals two close-packed 2D crystalline phases of TYMV that are distinct from the previously reported hexagonal and centered square (√2 × √2) arrays of TYMV. One of the newly observed phases arises from either a dimeric double-square (2 × 1) or tetrameric square (2 × 2) unit cell. The other is a rhombic crystal with a lattice angle of 80°. The two observed crystal phases are substantially less dense (by over 10%) than a 2D lattice of TYMV could be according to its known size and shape, indicating that local anisotropic interparticle interactions play a key role in stabilizing these crystals. TYMV's anisotropy attributes and numerical analysis of 2D arrays of virus-shaped particles are used to derive a model for the rhombic crystal in which the particle orientation is consistent with the electrostatic lipid–TYMV attraction and the interparticle contacts exhibit steric complementarity. The interplay between particle anisotropy and packing is contrasted between the rhombic crystal model and the square (√2 × √2) crystal. This study highlights how the high symmetry and subtle asphericity of icosahedral particles enrich the variety and complexity of ordered 2D structures that can be generated through self-assembly.

The two-dimensional (2D) assembly of the protein streptavidin on a biotin-bearing lipid monolayer was studied as a function of the surface density of biotin, a protein-binding ligand, by means of in situ X-ray scattering and optical Brewster angle microscopy measurements at the liquid–vapor interface. Although this model system has been studied extensively, the relationship between the surface biotin density and the adsorption, 2D phase behavior, and binding state of streptavidin has yet to be determined quantitatively. The observed equilibrium phase behavior provides direct structural evidence that the 2D crystallization of the lipid-bound streptavidin occurs as a density-driven first-order phase transition. The minimum biotin density required for the 2D crystallization of streptavidin is found to be remarkably close to the density of the ligand-binding sites in the protein crystal. Moreover, both above and below this transition, the observed biotin-density dependence of protein adsorption is well described by the binding of biotin-bearing lipids at both of the two available sites per streptavidin molecule. These results imply that even in the low-density noncrystalline phase, the bound proteins share a common, fixed orientation relative to the surface normal, and that the 2D crystallization occurs when the lateral protein density reaches 50–70% of the 2D crystal density. This study demonstrates that in addition to a well-defined molecular orientation, high lateral packing density is essential to the 2D crystallization of proteins.

We created two-dimensional (2D) assemblies of tobacco mosaic viruses (TMVs) and characterized their structures using Atomic Force Microscopy (AFM) and X-ray scattering. The TMVs were adsorbed on an oppositely charged, fluid lipid monolayer supported by a solid substrate and submerged in a buffer solution. The lipid monolayer confined the viral particles within a plane, while providing them with lateral mobility so that overall the TMV assembly behaved like a 2D liquid. We controlled the inter-particle interaction by adjusting the chemical condition in the buffer to induce ordered TMV assemblies. We found that the presence of the lipid layer was essential for forming ordered TMV assemblies. Packed TMV assemblies formed on the lipid layer, with an average inter-particle spacing of 42 nm. By introducing Ca2+ ions into the buffer solution, we were able to improve the in-plane order within the TMV assemblies and reduce the average inter-particle spacing to 20 nm, compared to the TMV diameter of 18 nm. Quantitative analysis of the X-ray scattering data shows that the structural order within the TMV assemblies prepared under a Ca2+-free buffer solution is consistent with purely repulsive, electrostatic inter-particle interaction. In contrast, the structural order within Ca2+-induced TMV assemblies is consistent with the behavior of a fluid of sticky rods, implying the presence of a strong attraction between TMVs. In addition to the screening of Coulomb repulsion, this behavior is likely the result of counterion-induced as well as membrane-mediated attractions.