Short DNA linkers are increasingly being exploited for driving-specific self-assembly of Brownian objects. DNA-functionalized colloids can assemble into ordered or amorphous materials with tailored morphology. Recently, the same approach has been applied to compliant units, including emulsion droplets and lipid vesicles. The liquid structure of these substrates introduces new degrees of freedom: the tethers can diffuse and rearrange, radically changing the physics of the interactions. Unlike droplets, vesicles are extremely deformable and DNA-mediated adhesion causes significant shape adjustments. We investigate experimentally the thermal response of pairs and networks of DNA-tethered liposomes and observe two intriguing and possibly useful collective properties: negative thermal expansion and tuneable porosity of the liposome networks. A model providing a thorough understanding of this unexpected phenomenon is developed, explaining the emergent properties out of the interplay between the temperature-dependent deformability of the vesicles and the DNA-mediated adhesive forces.

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Equilibrium self-assembly relies on the relaxation of disordered mixtures of building blocks towards an ordered ground state. The main drawback of this traditional approach lies in the kinetic traps that often interrupt the progression of the system towards equilibrium and lead to the formation of arrested phases. The latest techniques to control colloidal interactions open up the possibility of exploiting the tendency to dynamically arrest in order to construct amorphous materials with a specific morphology and local separation between multiple components. Here we propose strategies to direct the gelation of two-component colloidal mixtures by sequentially activating selective interactions. We investigate morphological changes in the structure of the arrested phases both by means of molecular dynamics simulations and experimentally by using DNA-coated colloids. Our approach can be exploited to assemble multicomponent mesoporous materials with possible applications in hybrid photovoltaics, photonics and drug delivery.

SignificanceWhile widely known as the molecule of life, DNA is also an amazing building block at the nanoscale, since it allows us to design and program the structure and dynamics of functional nanomaterials. We exploit the programmability of DNA to achieve control over the rheology of self-assembled hydrogels, which have elastic or viscous behavior (similar to that of slime) that is finely regulated by temperature. Using microrheology to investigate the mechanical properties of DNA hydrogels at the microlength scale, we map the viscoelastic response over a broad range of frequencies and temperatures. The deep understanding in the fundamental physics provides a way to design DNA-based materials with precise control over the structure stability and rigidity at molecular level.

We studied the spontaneous emulsification and droplet growth mechanism in trans-anethol/water/ethanol solutions, also known as the beverage ouzo, using dynamic light scattering spectroscopy. This simple ternary mixture is a generic example of a system that forms microemulsions spontaneously when brought into the two-phase region. The volume fraction of the dispersed phase was found to profoundly affect the growth rates of the droplets, which is a new finding that has not been predicted by the Lifshitz-Slyozov-Wagner theory. Time-dependent measurements show that the droplet growth is governed by Ostwald ripening (OR), and no coalescence was observed. Furthermore, the OR rates increase with increasing oil concentration at low alcohol content. We attribute this behavior to enhanced droplet-droplet interactions. At high ethanol concentrations, we found that the measured rates decreased as the oil concentration increased. The OR growth mechanism completely correlates with changes in droplet size. The kinetics of droplet growth shows that the ripening has a saturation limit at a droplet radius of about 1.5 mum. Thus, formed emulsions remain stable for months.

In this article we review the latest achievements in understanding and controlling DNA-mediated interactions between colloidal particles. We report the results of experiments, theoretical studies and computer simulations designed to investigate interactions and aggregation/melting behaviour of DNA-functionalized colloids. The unprecedented insight into the physical effects influencing the interactions and their relation with the tunable parameters of the grafted DNA has resulted in innovative DNA coatings, which are expected to solve the decennial issues encountered in the self assembly of DNA-coated colloids.

Understanding and, ultimately, controlling the properties of amorphous materials is one of the key goals of material science. Among the different amorphous structures, a very important role is played by colloidal gels. It has been only recently understood that colloidal gels are the result of the interplay between phase separation and arrest. When short-ranged attractive colloids are quenched into the phase-separating region, density fluctuations are arrested and this results in ramified amorphous space-spanning structures that are capable of sustaining mechanical stress. We present a mechanism of aggregation through arrested demixing in binary colloidal mixtures, which leads to the formation of a yet unexplored class of materials--bigels. This material is obtained by tuning interspecies interactions. Using a computer model, we investigate the phase behavior and the structural properties of these bigels. We show the topological similarities and the geometrical differences between these binary, interpenetrating, arrested structures and their well-known monodisperse counterparts, colloidal gels. Our findings are supported by confocal microscopy experiments performed on mixtures of DNA-coated colloids. The mechanism of bigel formation is a generalization of arrested phase separation and is therefore universal.spinodal decomposition | DNA-coated colloids | programmable interactions | amorphous self-assembly T he properties of a self-assembled material are ultimately controlled by the interactions among its building blocks and by the conditions in which they are prepared. It is by tuning these two properties that different structures can be obtained. Shortranged attractive colloidal systems, for example, can form crystals, two glasses of different origin, or gels. The latter have great technological importance. Colloidal gels find applications in synthetic colloid porous materials (1, 2), functionalization of surfaces and films production (3, 4), ceramics processing (5, 6), protein assemblies (7, 8), food science (9, 10), and soft matter (11, 12). Although they have been known for some time (13,14), it has only recently been understood that the colloidal gels arise as a result of arrested phase separation (15-18).The gels are characterized by a ramified amorphous spacespanning structure that is capable of sustaining mechanical stress. The colloidal density plays a crucial role in the aggregation and therefore in the resulting structure. At low densities, irreversible aggregation leads to fractal gels. At intermediate densities more compact porous structures are observed, whereas a homogeneous glass emerges when the solute occupies more than 50% of the volume (11,10,14,19).It has been proven that when colloidal particles are quenched into the gas-liquid phase separation region, gelation occurs as a consequence of dynamic arrest that interferes with phase separation (15, 18). After the quench, the system is thermodynamically unstable and strong density fluctuations set in, favoring the separation of the fluid into two ...