Thomas Gibaud

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. Here we demonstrate a consequence of this geometric frustration that leads to a new design principle for the assembly of chiral molecules. Using a model system of colloidal membranes, we show that molecular chirality can control the interfacial tension, an important property of multi-component mixtures. This suggests an analogy between chiral twist, which is expelled to the edges of two-dimensional membranes, and amphiphilic surfactants, which are expelled to oil–water interfaces. As with surfactants, chiral control of interfacial tension drives the formation of many polymorphic assemblages such as twisted ribbons with linear and circular topologies, starfish membranes, and double and triple helices. Tuning molecular chirality in situ allows dynamical control of line tension, which powers polymorphic transitions between various chiral structures. These findings outline a general strategy for the assembly of reconfigurable chiral materials that can easily be moved, stretched, attached to one another and transformed between multiple conformational states, thus allowing precise assembly and nanosculpting of highly dynamical and designable materials with complex topologies.

Interplay between Spinodal Decomposition and Glass Formation in Proteins Exhibiting Short-Range Attractions

We investigate the competition between spinodal decomposition and dynamical arrest using aqueous solutions of the globular protein lysozyme as a model system for colloids with short-range attractions. We show that quenches below a temperature Ta lead to gel formation as a result of a local arrest of the protein-dense phase during spinodal decomposition. The rheological properties of these gels allow us to use centrifugation experiments to determine the local densities of both phases and to precisely locate the gel boundary and the attractive glass line close to and within the unstable region of the phase diagram.

A simple patchy colloid model for the phase behavior of lysozyme dispersions

We propose a minimal model for spherical proteins with aeolotopic pair interactions to describe the equilibrium phase behavior of lysozyme. The repulsive screened Coulomb interactions between the particles are taken into account assuming that the net charges are smeared out homogeneously over the spherical protein surfaces. We incorporate attractive surface patches, with the interactions between patches on different spheres modeled by an attractive Yukawa potential. The parameters entering the attractive Yukawa potential part are determined using information on the experimentally accessed gas-liquid-like critical point. The Helmholtz free energy of the fluid and solid phases is calculated using second-order thermodynamic perturbation theory. Our predictions for the solubility curve are in fair agreement with experimental data. In addition, we present new experimental data for the gas-liquid coexistence curves at various salt concentrations and compare these with our model calculations. In agreement with earlier findings, we observe that the strength and the range of the attractive potential part only weakly depend on the salt content.

Heterogeneous yielding dynamics in a colloidal gel

Attractive colloidal gels display a solid-to-fluid transition as shear stresses above the yield stress are applied. This shear-induced transition is involved in virtually any application of colloidal gels. It is also crucial for controlling material properties. Still, the yielding transition is far from understood, mainly because rheological measurements are spatially averaged over the whole sample. We use high-frequency ultrasound during creep and oscillatory shear experiments to observe the local dynamics of opaque attractive colloidal gels. The transition proceeds from the cell walls and heterogeneously fluidizes the whole sample with a characteristic time that exponentially decreases with the applied stress. The present results reveal the importance of activated processes for the gel dynamics and raise a number of open questions in the attempt to better understand the yielding transition.

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. We determine the correlation length ξ and demonstrate that ξ exhibits a temperature dependence that closely follows the critical scaling expected for density fluctuations during the early stages of spinodal decomposition. These findings are in agreement with an arrest scenario based on a state diagram where the arrest or gel line extends far into the unstable region below the spinodal line. Arrest then occurs when during the early stage of spinodal decomposition the volume fraction φ(2) of the dense phase intersects the dynamical arrest threshold φ(2,Glass), upon which phase separation gets pinned into a space-spanning gel network with a characteristic length ξ.

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. Such a drastic effect of boundary conditions on yielding suggests the existence of some macroscopic characteristic length that could be connected to cooperativity effects in jammed materials under shear.

Shear-induced fragmentation of laponite suspensions

Simultaneous rheological and velocity profile measurements are performed in a smooth Couette geometry on laponite suspensions seeded with glass microspheres and undergoing the shear-induced solid-to-fluid (or yielding) transition. Under these slippery boundary conditions, a rich temporal behaviour is uncovered, in which shear localization is observed at short times, which rapidly gives way to a highly heterogeneous flow, characterized by intermittent switching from plug-like flow to linear velocity profiles. Such a temporal behaviour is linked to the fragmentation of the initially solid sample into blocks separated by fluidized regions. These solid pieces get progressively eroded over timescales ranging from a few minutes to several hours depending on the applied shear rate . The steady-state is characterized by a homogeneous flow with almost negligible wall slip. The characteristic timescale for erosion is shown to diverge below some critical shear rate * and to scale as ( − *)−n with n ≃ 2 above *. A tentative model for erosion is discussed together with open questions raised by the present results.

Hierarchical organization of chiral rafts in colloidal membranes

Liquid–liquid phase separation is ubiquitous in suspensions of nanoparticles, proteins and colloids. It has an important role in gel formation, protein crystallization and perhaps even as an organizing principle in cellular biology. With a few notable exceptions, liquid–liquid phase separation in bulk proceeds through the continuous coalescence of droplets until the system undergoes complete phase separation. But when colloids, nanoparticles or proteins are confined to interfaces, surfaces or membranes, their interactions differ fundamentally from those mediated by isotropic solvents, and this results in significantly more complex phase behaviour. Here we show that liquid–liquid phase separation in monolayer membranes composed of two dissimilar chiral colloidal rods gives rise to thermodynamically stable rafts that constantly exchange monomeric rods with the background reservoir to maintain a self-limited size. We visualize and manipulate rafts to quantify their assembly kinetics and to show that membrane distortions arising from the rods’ chirality lead to long-range repulsive raft–raft interactions. Rafts assemble into cluster crystals at high densities, but they can also form bonds to yield higher-order structures. Taken together, our observations demonstrate a robust membrane-based pathway for the assembly of monodisperse membrane clusters that is complementary to existing methods for colloid assembly in bulk suspensions. They also reveal that chiral inclusions in membranes can acquire long-range repulsive interactions, which might more generally have a role in stabilizing assemblages of finite size.

Time dependence in large amplitude oscillatory shear: A rheo-ultrasonic study of fatigue dynamics in a colloidal gel

We report on the response of a yield stress material, namely, a colloidal gel made of attractive carbon black particles, submitted to large amplitude oscillatory shear stress (LAOStress) in a Couette geometry. At a constant stress amplitude well below its apparent yield stress, the gel displays fatigue and progressively turns from an elastic solid to a viscous fluid. The time-resolved analysis of the strain response, of the Fourier components, and of Lissajous plots allows one to define two different timescales τw<τf associated with the yielding and fluidization of the gel. Coupling rheology to ultrasonic imaging further leads to a local picture of the LAOStress response in which the gel first fails at the walls at τw and then undergoes a slow heterogeneous fluidization involving solid–fluid coexistence until the whole sample is fluid at τf. Spatial heterogeneities are observed in both the gradient and vorticity directions and suggest a fragmentation of the initially solidlike gel into macroscopic domains...

Entropic forces stabilize diverse emergent structures in colloidal membranes

The depletion interaction mediated by non-adsorbing polymers promotes condensation and assembly of repulsive colloidal particles into diverse higher-order structures and materials. One example, with particularly rich emergent behaviors, is the formation of two-dimensional colloidal membranes from a suspension of filamentous fd viruses, which act as rods with effective repulsive interactions, and dextran, which acts as a condensing, depletion-inducing agent. Colloidal membranes exhibit chiral twist even when the constituent virus mixture lacks macroscopic chirality, change from a circular shape to a striking starfish shape upon changing the chirality of constituent rods, and partially coalesce via domain walls through which the viruses twist by 180°. We formulate an entropically-motivated theory that can quantitatively explain these experimental structures and measurements, both previously published and newly performed, over a wide range of experimental conditions. Our results elucidate how entropy alone, manifested through the viruses as Frank elastic energy and through the depletants as an effective surface tension, drives the formation and behavior of these diverse structures. Our generalizable principles propose the existence of analogous effects in molecular membranes and can be exploited in the design of reconfigurable colloidal structures.