Engineering the glass structure of a discotic liquid crystal by multiple kinetic arrests.

X-ray scattering has been used to characterize the columnar packing and the π stacking in a glass-forming discotic liquid crystal. In the equilibrium liquid state, the intensities of the scattering peaks for π stacking and columnar packing are proportional to each other, indicating concurrent development of the two orders. Upon cooling into the glassy state, the π-π distance shows a kinetic arrest with a change in the thermal expansion coefficient (TEC) from 321 to 109 ppm/K, while the intercolumnar spacing exhibits a constant TEC of 113 ppm/K.

Using 4D STEM to Probe Mesoscale Order in Molecular Glass Films Prepared by Physical Vapor Deposition.

Physical vapor deposition can be used to prepare highly stable organic glass systems where the molecules show orientational and translational ordering at the nanoscale. We have used low-dose four-dimensional scanning transmission electron microscopy (4D STEM), enabled by a fast direct electron detector, to map columnar order in glassy samples of a discotic mesogen using a 2 nm probe. Both vapor-deposited and liquid-cooled glassy films show domains of similar orientation, but their size varies from tens to hundreds of nanometers, depending on processing.

3D Printing Graphene Oxide Soft Robotics.

We propose a universal strategy to 3D printing the graphene oxide (GO) complex structure with GO highly aligned and densely compacted, by the combination of direct ink writing and constrained drying. The constraints not only allow the generation of a huge capillary force accompanied by water evaporation at nanoscale, which induces the high compaction and alignment of GO, but also limit the shrinkage of the extruded filaments only along the wall thickness direction, therefore, successfully maintaining the uniformity of the structure at macroscale. We discover that the shrinkage stress gradually increased during the drying process, with the maximum exceeding ∼0.

Nanosheet-Stabilized Emulsions: Near-Minimum Loading and Surface Energy Design of Conductive Networks.

Here, we develop a framework for assembly, understanding, and application of functional emulsions stabilized by few-layer pristine two-dimensional (2D) nanosheets. Liquid-exfoliated graphene and MoS are demonstrated to stabilize emulsions at ultralow nanosheet volume fractions, approaching the minimum loading achievable with 2D materials. These nanosheet-stabilized emulsions allow controlled droplet deposition free from the coffee ring effect to facilitate single-droplet devices from minute quantities of material or assembly into large-area films with high network conductivity.

Short-wave and near infrared π-conjugated polymers hosted in a biocompatible microemulsion: a pioneering approach for photoacoustic contrast agents.

In the present study a biocompatible oil-in-water (O/W) microemulsion was developed carrying short-wave infrared (SWIR) π-conjugated polymers and possessing photoacoustic properties for the first time. SWIR and NIR absorbing conjugated polymers were accomplished to be dissolved in a Food & Drug Administration (FDA) approved natural oil limonene, to formulate an O/W microemulsion using biocompatible surfactants (Span80, Labrasol®). Detailed structural characterization in the absence and presence of the polymers was performed by means of dynamic light scattering (DLS), small-angle X-ray scattering (SAXS) and electron paramagnetic resonance (EPR) spectroscopy.

Liquid Crystal-Mediated 3D Printing Process to Fabricate Nano-Ordered Layered Structures.

The emergence of three-dimensional (3D) printing promises a disruption in the design and on-demand fabrication of smart structures in applications ranging from functional devices to human organs. However, the scale at which 3D printing excels is within macro- and microlevels and principally lacks the spatial ordering of building blocks at nanolevels, which is vital for most multifunctional devices. Herein, we employ liquid crystal (LC) inks to bridge the gap between the nano- and microscales in a single-step 3D printing.

Highly confined stacks of graphene oxide sheets in water.

Since the discovery of graphene oxide (GO), the most accessible of the precursors of graphene, this material has been widely studied for applications in science and technology. In this work, we describe a procedure to obtain GO dispersions in water at high concentrations, these highly dehydrated dispersions being in addition fully redispersible by dilution. With the availability of such concentrated samples, it was possible to investigate the structure of hydrated GO sheets in a previously unexplored range of concentrations, and to evidence a structural phase transition.

Surfactant films in lyotropic lamellar (and related) phases: Fluctuations and interactions.

The analogy between soap films thinning under border capillary suction and lamellar stacks of surfactant bilayers dehydrated by osmotic stress is explored, in particular in the highly dehydrated limit where the soap film becomes a Newton black film. The nature of short-range repulsive interactions between surfactant-covered interfaces and acting across water channels in both cases will be discussed.

Superflexibility of graphene oxide.

Graphene oxide (GO), the main precursor of graphene-based materials made by solution processing, is known to be very stiff. Indeed, it has a Young's modulus comparable to steel, on the order of 300 GPa. Despite its very high stiffness, we show here that GO is superflexible.

Water activity in lamellar stacks of lipid bilayers: "Hydration forces" revisited.

Water activity and its relationship with interactions stabilising lamellar stacks of mixed lipid bilayers in their fluid state are investigated by means of osmotic pressure measurements coupled with small-angle X-ray scattering. The (electrically neutral) bilayers are composed of a mixture in various proportions of lecithin, a zwitterionic phospholipid, and Simulsol, a non-ionic cosurfactant with an ethoxylated polar head. For highly dehydrated samples the osmotic pressure profile always exhibits the "classical" exponential decay as hydration increases but, depending on Simulsol to lecithin ratio, it becomes either of the "bound" or "unbound" types for more water-swollen systems.

Stabilising lamellar stacks of lipid bilayers with soft confinement and steric effects.

Structure and interactions stabilising the lamellar stack of mixed lipid bilayers in their fluid state are investigated by means of small-angle X-ray scattering. The (electrically neutral) bilayers are composed of a mixtures of lecithin, a zwitterionic phospholipid, and Simulsol, a non-ionic cosurfactant with an ethoxylated polar head. The soft confinement of the bilayer hydrophilic components is varied by changing hydration and bilayer composition, as well as the length of the cosurfactant polar head.

Multiscale electrochemistry of hydrogels embedding conductive nanotubes.

The local functionalities of biocompatible objects can be characterized under conditions similar to the operating ones, using scanning electrochemical microscopy (SECM). In the case of alginate beads entrapping carbon nanotubes (CNTs), SECM allows evidencing of the local conductivity, organization, and communication between the CNTs. It shows that the CNT network is active enough to allow long range charge evacuation, enabling the use of alginate/CNT beads as soft 3D electrodes.

How polymers lose memory with age.

Uniquely in the world of materials, polymers deformed at high temperature and subsequently quenched at low temperature, memorize the temperature at which they have been processed. Polymers can even memorize multiple temperatures. This temperature memory is reflected by a maximum of residual stress restored at the temperature of initial processing.

From Brittle to Pliant Viscoelastic Materials with Solid State Linear Polyphosphonium - Carboxylate Assemblies.

A polystyrenylphosphonium polymer was synthesized and complexed with various carboxylic acid derivatives to form new solid-state polyelectrolyte-surfactant assemblies. The properties of these ionic materials were highly dependent on the nature of the anion and included a brittle material, a rubbery ball that bounces, or a sticky fiber. The values for the equilibrium modulus, storage modulus, and loss modulus were dependent on the composition of the carboxylic acid and the number of electrostatic interactions.

Anisotropic Brownian motion in ordered phases of DNA fragments.

Using Fluorescence Recovery After Photobleaching, we investigate the Brownian motion of DNA rod-like fragments in two distinct anisotropic phases with a local nematic symmetry. The height of the measurement volume ensures the averaging of the anisotropy of the in-plane diffusive motion parallel or perpendicular to the local nematic director in aligned domains. Still, as shown in using a model specifically designed to handle such a situation and predicting a non-Gaussian shape for the bleached spot as fluorescence recovery proceeds, the two distinct diffusion coefficients of the DNA particles can be retrieved from data analysis.

Dynamics in the smectic phase of stiff viral rods.

We report on the dynamics in colloidal suspensions of stiff viral rods, called fd-Y21M. This mutant filamentous virus exhibits a persistence length 3.5 times larger than the wild-type fd-wt.

Sensitivity of carbon nanotubes to the storage of stress in polymers.

Residual stress in polymers arises from the freezing of unstable molecular conformations. Residual stress is critical because its relaxation can cause shrinkage, defects, and fractures of polymer materials. The storage of stress is purposely enhanced to develop shape memory materials.

Effect of onion-type multilamellar liposomes on Trametes versicolor laccase activity and stability.

Trametes versicolor laccase was encapsulated into onion-type, lipid-based multilamellar vesicles (MLVs). When encapsulated, laccase was isolated from the assay medium but was still active once freed from its capsule. The encapsulation efficiency was larger than 65% at 25 °C and 37 °C and decreased to 55% by introducing 140 mM NaCl into the buffered medium (pH = 4.

Photonic control of surface anchoring on solid colloids dispersed in liquid crystals.

The anchoring of liquid-crystal (LC) mesogens to the surfaces of colloids is an important factor in determining intercolloidal interactions and the symmetry of the ensuing colloidal assembly in nematic colloids. The dynamic control of surface anchoring could therefore provide a handle to tune the colloidal organization and resulting properties in these systems. In this article, we report our results on the study of thermotropic nematic LC (E7) dispersions of silica and glass microcolloids bearing photosensitive surface azobenzene groups.

Wavelength-dependent emission enhancement through the design of active plasmonic nanoantennas.

Owing to the competition between the radiative and non-radiative decay channels occurring in plasmonic assemblies, we show here how to conceive a long pass emission filter and actually design it. We report the synthesis of gold@silica nanoparticles grafted with dye molecules. The control of the thickness of the silica shell allows us to tune the distance between the metal core and the dye molecules.

Supramolecular polymorphism of DNA in non-cationic Lα lipid phases.

The structure of a complex between hydrated DNA and a non-cationic lipid is studied, including its phase diagram. The complex is spontaneously formed by adding DNA fragments (ca. 150 base pairs in length) to non-cationic lipids and water.

Graphene solutions.

Thermodynamics drive the spontaneous dissolution of a graphite intercalation compound (GIC) KC(8) in NMP to form stable solutions. Reduction potential of graphene is measured at +22 mV vs. SCE.

Production of magnetic multilamellar liposomes as highly T2-efficient MRI contrast agents.

Unlabelled: Lipid-based multilamellar vesicles loaded with aminosilane-modified maghemite nanoparticles (a-MNPs), also called magnetonions (MO), were analyzed for their magnetic resonance imaging (MRI) contrast agent properties. They were shown to be better T(2)-MRI contrast agents than commercial contrast agents and other reported liposome-based contrast agents as shown by their higher value of relaxivity ratio (r(2)/r(1) = 17), although a lower magnetic field intensity was used (0.2 T).