Control of nanomaterial self-assembly in ultrasonically levitated droplets

We demonstrate that acoustic trapping can be used to levitate and manipulate droplets of soft matter, in particular, lyotropic mesophases formed from selfassembly of different surfactants and lipids, which can be analyzed in a contact-less manner by X-ray scattering in a controlled gas-phase environment. On the macroscopic length scale, the dimensions and the orientation of the particle are shaped by the ultrasonic field, while on the microscopic length scale the nanostructure can be controlled by varying the humidity of the atmosphere around the droplet. We demonstrate levitation and in situ phase transitions of micellar, hexagonal, bicontinuous cubic, and lamellar phases. The technique opens up a wide range of new experimental approaches of fundamental importance for environmental, biological, and chemical research

Following in Real Time the Two-Step Assembly of Nanoparticles into Mesocrystals in Levitating Drops

Mesocrystals composed of crystallographically aligned nanocrystals are present in biominerals and assembled materials which show strongly directional properties of importance for mechanical protection and functional devices. Mesocrystals are commonly formed by complex biomineralization processes and can also be generated by assembly of anisotropic nanocrystals. Here, we follow the evaporation-induced assembly of maghemite nanocubes into mesocrystals in real time in levitating drops. Analysis of time-resolved small-angle X-ray scattering data and ex situ scanning electron microscopy together with interparticle potential calculations show that the substrate-free, particle-mediated crystallization process proceeds in two stages involving the formation and rapid transformation of a dense, structurally disordered phase into ordered mesocrystals. Controlling and tailoring the particle-mediated formation of mesocrystals could be utilized to assemble designed nanoparticles into new materials with unique functions

Unraveling the Structural Puzzle of the Giant Glutenin PolymerAn Interplay between Protein Polymerization, Nanomorphology, and Functional Properties in Bioplastic Films

A combination of genotype, cultivation environment, and protein separation procedure was used to modify the nanoscale morphology, polymerization, and chemical structure of glutenin proteins from wheat. A low-polymerized glutenin starting material was the key to protein–protein interactions mainly via SS cross-links during film formation, resulting in extended β-sheet structures and propensity toward the formation of nanoscale morphologies at molecular level. The properties of glutenin bioplastic films were enhanced by the selection of a genotype with a high number of cysteine residues in its chemical structure and cultivation environment with a short grain maturation period, both contributing positively to gluten strength. Thus, a combination of factors affected the structure of glutenins in bioplastic films by forming crystalline β-sheets and propensity toward the ordered nanostructures, thereby resulting in functional properties with high strength, stiffness, and extensibility

Formation of Inverse Topology Lyotropic Phases in Dioleoylphosphatidylcholine/Oleic Acid and Dioleoylphosphatidylethanolamine/Oleic Acid Binary Mixtures

The addition of saturated fatty acids (FA) to phosphatidylcholine lipids (PC) that have saturated acyl chains has been shown to promote the formation of lyotropic liquid-crystalline phases with negative mean curvature. PC/FA mixtures may exhibit inverse bicontinuous cubic phases (<i>Im</i>3<i>m</i>, <i>Pn</i>3<i>m</i>) or inverse topology hexagonal phases (H_II), depending on the length of the acyl chains/fatty acid. Here we report a detailed study of the phase behavior of binary mixtures of dioleoylphosphatidylcholine (DOPC)/oleic acid (OA) and dioleoylphosphatidylethanolamine (DOPE)/oleic acid at limiting hydration, constructed using small-angle X-ray diffraction (SAXD) data. The phase diagrams of both systems show a succession of phases with increasing negative mean curvature with increasing OA content. At high OA concentrations, we have observed the occurrence of an inverse micellar <i>Fd</i>3<i>m</i> phase in both systems. Hitherto, this phase had not been reported for phosphatidylethanolamine/fatty acid mixtures, and as such it highlights an additional route through which fatty acids may increase the propensity of bilayer lipid membranes to curve. We also propose a method that uses the temperature dependence of the lattice parameters of the H_II phases to estimate the spontaneous radii of curvature (<i>R</i>₀) of the binary mixtures and of the component lipids. Using this method, we calculated the <i>R</i>₀ values of the complexes comprising one phospholipid molecule and two fatty acid molecules, which have been postulated to drive the formation of inverse phases in PL/FA mixtures. These are −1.8 nm (±0.4 nm) for DOPC­(OA)₂ and −1.1 nm (±0.1 nm) for DOPE­(OA)₂. <i>R</i>₀ values estimated in this way allow the quantification of the contribution that different lipid species make to membrane curvature elastic properties and hence of their effect on the function of membrane-bound proteins

Following in Real Time the Two-Step Assembly of Nanoparticles into Mesocrystals in Levitating Drops

Mesocrystals composed of crystallographically aligned nanocrystals are present in biominerals and assembled materials which show strongly directional properties of importance for mechanical protection and functional devices. Mesocrystals are commonly formed by complex biomineralization processes and can also be generated by assembly of anisotropic nanocrystals. Here, we follow the evaporation-induced assembly of maghemite nanocubes into mesocrystals in real time in levitating drops. Analysis of time-resolved small-angle X-ray scattering data and ex situ scanning electron microscopy together with interparticle potential calculations show that the substrate-free, particle-mediated crystallization process proceeds in two stages involving the formation and rapid transformation of a dense, structurally disordered phase into ordered mesocrystals. Controlling and tailoring the particle-mediated formation of mesocrystals could be utilized to assemble designed nanoparticles into new materials with unique functions

Experimental Confirmation of Transformation Pathways between Inverse Double Diamond and Gyroid Cubic Phases

A macroscopically oriented double diamond inverse bicontinuous cubic phase (Q_II^D) of the lipid glycerol monooleate is reversibly converted into a gyroid phase (Q_II^G). The initial Q_II^D phase is prepared in the form of a film coating the inside of a capillary, deposited under flow, which produces a sample uniaxially oriented with a ⟨110⟩ axis parallel to the symmetry axis of the sample. A transformation is induced by replacing the water within the capillary tube with a solution of poly­(ethylene glycol), which draws water out of the Q_II^D sample by osmotic stress. This converts the Q_II^D phase into a Q_II^G phase with two coexisting orientations, with the ⟨100⟩ and ⟨111⟩ axes parallel to the symmetry axis, as demonstrated by small-angle X-ray scattering. The process can then be reversed, to recover the initial orientation of Q_II^D phase. The epitaxial relation between the two oriented mesophases is consistent with topology-preserving geometric pathways that have previously been hypothesized for the transformation. Furthermore, this has implications for the production of macroscopically oriented Q_II^G phases, in particular with applications as nanomaterial templates

Experimental Confirmation of Transformation Pathways between Inverse Double Diamond and Gyroid Cubic Phases

A macroscopically oriented double diamond inverse bicontinuous cubic phase (Q_II^D) of the lipid glycerol monooleate is reversibly converted into a gyroid phase (Q_II^G). The initial Q_II^D phase is prepared in the form of a film coating the inside of a capillary, deposited under flow, which produces a sample uniaxially oriented with a ⟨110⟩ axis parallel to the symmetry axis of the sample. A transformation is induced by replacing the water within the capillary tube with a solution of poly­(ethylene glycol), which draws water out of the Q_II^D sample by osmotic stress. This converts the Q_II^D phase into a Q_II^G phase with two coexisting orientations, with the ⟨100⟩ and ⟨111⟩ axes parallel to the symmetry axis, as demonstrated by small-angle X-ray scattering. The process can then be reversed, to recover the initial orientation of Q_II^D phase. The epitaxial relation between the two oriented mesophases is consistent with topology-preserving geometric pathways that have previously been hypothesized for the transformation. Furthermore, this has implications for the production of macroscopically oriented Q_II^G phases, in particular with applications as nanomaterial templates

Effect of Clay Surface Charge on the Emerging Properties of Polystyrene–Organoclay Nanocomposites

A series of polystyrene–clay nanocomposites, based on two natural clay types (Na–Montmorillonite and Hectorite) and two synthetic clays (Laponite and Li–Fluorohectorite), were prepared via in situ intercalative polymerization after surface modification with an organic ammonium cation (CTAB). The structural characteristics of the organically modified clays as well as the nanocomposites were investigated by means of wide-angle X-ray scattering (WAXS), and the thermal properties were studied with TGA. In the organically modified clays, the silicate interlayer spacing increases, and the magnitude seems to be directly correlated with the amount of clay surface charge. In the nanocomposites, polymer intercalation is also observed, but partial exfoliation is present, modifying significantly the morphology of the material. The degree of dispersion of the clay platelets, as well as the resulting properties of the nanocomposites, were found again to be systematically, and almost linearly, correlated with the intrinsic surface charge of the clays, which varied between 44 and 120 meq/100 g. Increased dispersion was seen in the nanocomposites made from clays with low surface charge, here Hectorite and Laponite, suggesting that these can be suitable alternatives to the more employed Montmorillonite for enhancement of thermal properties. The thermal stability was found to be better for the nanocomposites than for the pure polystyrene

Oxygen-Controlled Phase Segregation in Poly(<i>N</i>‑isopropylacrylamide)/Laponite Nanocomposite Hydrogels

The combination of nanoparticles and polymers into nanocomposite gels has been shown to be a promising route to creating soft materials with new or improved properties. In the present work, we have made use of Laponite nanoparticles in combination with a poly­(<i>N</i>-isopropylacrylamide) (PNIPAAM) polymer and describe a phenomenon taking place during the polymerization and gelling of this system. The presence of small amounts of oxygen in the process induces two distinctly separated phases, one polymer-rich and one polymer-deficient water–clay phase. Complex interactions among clay, oxygen, and the polymer are found to govern the behavior of these phases. It is also observed that the initial clay concentration can be used to control the volume fraction of the polymer-deficient phase directly. The dynamics of the phase boundary is found to be dependent on water penetration and in general to exhibit non-Fickian behavior. An approach using video recording to monitor hydrogel swelling is also presented, and its advantages are addressed