Orthotropic organization of a cellulose nanocrystal suspension realized via the combined action of frontal ultrafiltration and ultrasound as revealed by in situ SAXS.

Hypothesis: Rodlike cellulose nanocrystals (CNCs) exhibit significant potential as building blocks for creating uniform, sustainable materials. However, a critical hurdle lies in the need to enhance existing or devise novel processing that provides improved control over the alignment and arrangement of CNCs across a wide spatial range. Specifically, the challenge is to achieve orthotropic organization in a single-step processing, which entails creating non-uniform CNC orientations to generate spatial variations in anisotropy.

Bonded straight and helical flagellar filaments form ultra-low-density glasses.

We study how the three-dimensional shape of rigid filaments determines the microscopic dynamics and macroscopic rheology of entangled semidilute Brownian suspensions. To control the filament shape we use bacterial flagella, which are microns-long helical or straight filaments assembled from flagellin monomers. We compare the dynamics of straight rods, helical filaments, and shape-diblock copolymers composed of seamlessly joined straight and helical segments.

Correction: Interpenetration of fractal clusters drives elasticity in colloidal gels formed upon flow cessation.

Correction for 'Interpenetration of fractal clusters drives elasticity in colloidal gels formed upon flow cessation' by Noémie Dagès , , 2022, , 6645-6659, https://doi.org/10.1039/D2SM00481J.

Interpenetration of fractal clusters drives elasticity in colloidal gels formed upon flow cessation.

Colloidal gels are out-of-equilibrium soft solids composed of attractive Brownian particles that form a space-spanning network at low volume fractions. The elastic properties of these systems result from the network microstructure, which is very sensitive to shear history. Here, we take advantage of such sensitivity to tune the viscoelastic properties of a colloidal gel made of carbon black nanoparticles.

Light-Controlled Aggregation and Gelation of Viologen-Based Coordination Polymers.

Ditopic bis-(triazole/pyridine)viologens are bidentate ligands that self-assemble into coordination polymers. In such photo-responsive materials, light irradiation initiates photo-induced electron transfer to generate π-radicals that can self-associate to form π-dimers. This leads to a cascade of events: processes at the supramolecular scale associated with mechanical and structural transition at the macroscopic scale.

Colloidal transport in bacteria suspensions: from bacteria collision to anomalous and enhanced diffusion.

Swimming microorganisms interact and alter the dynamics of Brownian particles and tend to modify their transport properties. In particular, dilute colloids coupled to a bath of swimming cells generically display enhanced diffusion on long time scales. This transport dynamics stems from a subtle interplay between the active and passive particles that still resists our understanding despite decades of intense research.

Force-Induced Formation of Twisted Chiral Ribbons.

We demonstrate that an achiral stretching force transforms disk-shaped colloidal membranes composed of chiral rods into twisted ribbons with handedness opposite the preferred twist of the rods. Using an experimental technique that enforces torque-free boundary conditions we simultaneously measure the force-extension curve and the ribbon shape. An effective theory that accounts for the membrane bending energy and uses geometric properties of the edge to model the internal liquid crystalline degrees of freedom explains both the measured force-extension curve and the force-induced twisted shape.

Equation of state of colloidal membranes.

In the presence of a non-adsorbing polymer, monodisperse rod-like colloids assemble into one-rod-length thick liquid-like monolayers, called colloidal membranes. The density of the rods within a colloidal membrane is determined by a balance between the osmotic pressure exerted by the enveloping polymer suspension and the repulsion between the colloidal rods. We developed a microfluidic device for continuously observing an isolated membrane while dynamically controlling the osmotic pressure of the polymer suspension.

Irreversible hardening of a colloidal gel under shear: The smart response of natural rubber latex gels.

Natural rubber is obtained by processing natural rubber latex, a liquid colloidal suspension that rapidly gels after exudation from the tree. We prepared such gels by acidification, in a large range of particle volume fractions, and investigated their rheological properties. We show that natural rubber latex gels exhibit a unique behavior of irreversible strain hardening: when subjected to a large enough strain, the elastic modulus increases irreversibly.

Redox-Induced Molecular Metamorphism Promoting a Sol/Gel Phase Transition in a Viologen-Based Coordination Polymer.

We have developed a strategy enabling control over the organization of ditopic molecular tectons within a palladium-based self-assembled system. The key electron-responsive sub-unit is a viologen-based mechanical hinge that can toggle under electric stimulation between a folded and a stretched position, the driving force of the folding motion being the π-dimerisation of the electrogenerated viologen cation radicals. The title ditopic tecton features two planar, N2-type, triazole/pyridine-based bidentate binding units, providing the tecton with the ability to chelate two palladium ions both in its folded and in its elongated conformations.

Direct Liquid to Crystal Transition in a Quasi-Two-Dimensional Colloidal Membrane.

Using synchrotron-based small-angle X-ray scattering, we study rigid fd viruses assembled into isolated monolayers from mixtures with a nonabsorbing polymer, which acts as an osmotic agent. As the polymer concentration increases, we observe a direct liquid to crystal transition, without an intermediate hexatic phase, in contrast with many other similar systems, such as concentrated DNA phases or packings of surfactant micelles. We tentatively attribute this effect to the difference in stiffness.

Filamentous phages as building blocks for reconfigurable and hierarchical self-assembly.

Filamentous bacteriophages such as fd-like viruses are monodisperse rod-like colloids that have well defined properties of diameter, length, rigidity, charge and chirality. Engineering these viruses leads to a library of colloidal rods, which can be used as building blocks for reconfigurable and hierarchical self-assembly. Their condensation in an aqueous solution with additive polymers, which act as depletants to induce attraction between the rods, leads to a myriad of fluid-like micronic structures ranging from isotropic/nematic droplets, colloid membranes, achiral membrane seeds, twisted ribbons, π-wall, pores, colloidal skyrmions, Möbius anchors, scallop membranes to membrane rafts.

Achiral symmetry breaking and positive Gaussian modulus lead to scalloped colloidal membranes.

In the presence of a nonadsorbing polymer, monodisperse rod-like particles assemble into colloidal membranes, which are one-rod-length-thick liquid-like monolayers of aligned rods. Unlike 3D edgeless bilayer vesicles, colloidal monolayer membranes form open structures with an exposed edge, thus presenting an opportunity to study elasticity of fluid sheets. Membranes assembled from single-component chiral rods form flat disks with uniform edge twist.

Predicting and assessing rupture in protein gels under oscillatory shear.

Soft materials may break irreversibly upon applying sufficiently large shear oscillations, a process whose physical mechanism remains largely elusive. In this work, the rupture of protein gels made of sodium caseinate under an oscillatory stress is shown to occur in an abrupt, brittle-like manner. Upon increasing the stress amplitude, the build-up of harmonic modes in the strain response can be rescaled for all gel concentrations.

Multiple yielding processes in a colloidal gel under large amplitude oscillatory stress.

Fatigue refers to the changes in material properties caused by repeatedly applied loads. It has been widely studied for, e.g.

Condensation and dissolution of nematic droplets in dispersions of colloidal rods with thermo-sensitive depletants.

Nematic droplets are droplets composed of elongated molecules that tend to point in the same direction but do not have any positional order. Such droplets are well known to adopt a spindle shape called tactoid. How such droplets condensate or melt and how the orientational symmetry is broken remains however unclear.

Hierarchical wrinkling in a confined permeable biogel.

Confined thin surfaces may wrinkle as a result of the growth of excess material. Elasticity or gravity usually sets the wavelength. We explore new selection mechanisms based on hydrodynamics.

Imprintable membranes from incomplete chiral coalescence.

Coalescence is an essential phenomenon that governs the equilibrium behaviour in a variety of systems from intercellular transport to planetary formation. In this report, we study coalescence pathways of circularly shaped two-dimensional colloidal membranes, which are one rod-length-thick liquid-like monolayers of aligned rods. The chirality of the constituent rods leads to three atypical coalescence pathways that are not found in other simple or complex fluids.

Unexpected decoupling of stretching and bending modes in protein gels.

We show that gels formed by arrested spinodal decomposition of protein solutions exhibit elastic properties in two distinct frequency domains, both elastic moduli exhibiting a remarkably strong dependence on volume fraction. Considering the large difference between the protein size and the characteristic length of the network we model the gels as porous media and show that the high and low frequency elastic moduli can be respectively attributed to stretching and bending modes. The unexpected decoupling of the two modes in the frequency domain is attributed to the length scale involved: while stretching mainly relates to the relative displacement of two particles, bending involves the deformation of a strand with a thickness of the order of a thousand particle diameters.

New routes to food gels and glasses.

We describe the possibility to create solid-like protein samples whose structural and mechanical properties can be varied and tailored over an extremely large range in a very controlled way through an arrested spinodal decomposition process. We use aqueous lysozyme solutions as a model globular protein system. A combination of video microscopy, small-angle neutron and X-ray scattering and reverse Monte Carlo modeling is used to characterize the structure of the bicontinuous network with two coexisting phases of a dilute protein solution and a glassy or arrested dense protein backbone at all relevant length scales.

Reconfigurable self-assembly through chiral control of interfacial tension.

From determining the optical properties of simple molecular crystals to establishing the preferred handedness in highly complex vertebrates, molecular chirality profoundly influences the structural, mechanical and optical properties of both synthetic and biological matter on macroscopic length scales. In soft materials such as amphiphilic lipids and liquid crystals, the competition between local chiral interactions and global constraints imposed by the geometry of the self-assembled structures leads to frustration and the assembly of unique materials. An example of particular interest is smectic liquid crystals, where the two-dimensional layered geometry cannot support twist and chirality is consequently expelled to the edges in a manner analogous to the expulsion of a magnetic field from superconductors.

A closer look at arrested spinodal decomposition in protein solutions.

Concentrated aqueous solutions of the protein lysozyme undergo a liquid-solid transition upon a temperature quench into the unstable spinodal region below a characteristic arrest temperature of T(f) = 15 °C. We use video microscopy and ultra-small angle light scattering in order to investigate the arrested structures as a function of initial concentration, quench temperature and rate of the temperature quench. We find that the solid-like samples show all the features of a bicontinuous network that is formed through an arrested spinodal decomposition process.

Influence of boundary conditions on yielding in a soft glassy material.

The yielding behavior of a sheared Laponite suspension is investigated within a 1 mm gap under two different boundary conditions. No-slip conditions, ensured by using rough walls, lead to shear localization as already reported in various soft glassy materials. When apparent wall slip is allowed using a smooth geometry, the sample breaks up into macroscopic solid pieces that get slowly eroded by the surrounding fluidized material up to the point where the whole sample is fluid.