Emmanuel Stiakakis

Asymmetric caging in soft colloidal mixtures

The long-standing observations that different amorphous materials exhibit a pronounced enhancement of viscosity and eventually vitrify on compression or cooling continue to fascinate and challenge scientists, on the ground of their physical origin and practical implications. Glass formation is a generic phenomenon, observed in physically quite distinct systems that encompass hard and soft particles. It is believed that a common underlying scenario, namely cage formation, drives dynamical arrest, especially at high concentrations. Here, we identify a novel, asymmetric glassy state in soft colloidal mixtures, which is characterized by strongly anisotropically distorted cages, bearing similarities to those of hard-sphere glasses under shear. The anisotropy is induced by the presence of soft additives. This phenomenon seems to be generic to soft colloids and its origins lie in the penetrability of the constituent particles. The resulting phase diagram for mixtures of soft particles is clearly distinct from that of hard-sphere mixtures and brings forward a rich variety of vitrified states that delineate an ergodic lake in the parameter space spanned by the size ratio between the two components and by the concentration of the additives. Thus, a new route opens for the rational design of soft particles with desired tunable rheological properties.

Osmotic shrinkage in star/linear polymer mixtures

Abstract.Multiarm star polymers were used as model grafted colloidal particles with long hairs, to study their size variation due to osmotic forces arising from added linear homopolymers of smaller size. This is the origin of the depletion phenomenon that has been exploited in the past as a means to melt soft colloidal glasses by adding linear chains and analyzed using dynamic light scattering experiments and an effective interactions analysis yielding the depletion potential. Shrinkage is a generic phenomenon for hairy particles, which affects macroscopic properties and state transitions at high concentrations. In this work we present a small-angle neutron scattering study of star/linear polymer mixtures with different size ratios (varying the linear polymer molar mass) and confirm the depletion picture, i.e., osmotic star shrinkage. Moreover, we find that as the linear/star polymer size ratio increases for the same effective linear volume fraction ( c/c*with c*the overlapping concentration), the star shrinkage is reduced whereas the onset of shrinkage appears to take place at higher linear polymer volume fractions. A theoretical description of the force balance on a star polymer in solution, accounting for the classic Flory contributions, i.e. elastic and excluded volume, as well as the osmotic force due to the linear chains, accurately predicts the experimental findings of reduced star size as a function of linear polymer concentration. This is done in a parameter-free fashion, in which the size of the cavity created by the star, and from which the chains are excluded, is related to the radius of the former from first principles.

Smectic phase in suspensions of gapped DNA duplexes

Smectic ordering in aqueous solutions of monodisperse stiff double-stranded DNA fragments is known not to occur, despite the fact that these systems exhibit both chiral nematic and columnar mesophases. Here, we show, unambiguously, that a smectic-A type of phase is formed by increasing the DNAs flexibility through the introduction of an unpaired single-stranded DNA spacer in the middle of each duplex. This is unusual for a lyotropic system, where flexibility typically destabilizes the smectic phase. We also report on simulations suggesting that the gapped duplexes (resembling chain-sticks) attain a folded conformation in the smectic layers, and argue that this layer structure, which we designate as smectic-fA phase, is thermodynamically stabilized by both entropic and energetic contributions to the systems free energy. Our results demonstrate that DNA as a building block offers an exquisitely tunable means to engineer a potentially rich assortment of lyotropic liquid crystals.

Probing glassy states in binary mixtures of soft interpenetrable colloids

We present experimental evidence confirming the recently established rich dynamic state diagram of asymmetric binary mixtures of soft colloidal spheres. These mixtures consist of glassy suspensions of large star polymers to which different small stars are added at varying concentrations. Using rheology and dynamic light scattering measurements along with a simple phenomenological analysis, we show the existence of re-entrance and multiple glassy states, which exhibit distinct features. Cooperative diffusion, as a probe for star arm interpenetration, is proven to be sensitive to the formation of the liquid pockets which signal the melting of the large-star-glass upon addition of small stars. These results provide ample opportunities for tailoring the properties of soft colloidal glasses.