Colloidal particles with directional interactions are key in the realization of new colloidal materials with possibly unconventional phase behaviors. Here we exploit DNA self-assembly to produce bulk quantities of "DNA stars" with three or four sticky terminals, mimicking molecules with controlled limited valence. Solutions of such molecules exhibit a consolution curve with an upper critical point, whose temperature and concentration decrease with the valence. Upon approaching the critical point from high temperature, the intensity of the scattered light diverges with a power law, whereas the intensity time autocorrelation functions show a surprising two-step relaxation, somehow reminiscent of glassy materials. The slow relaxation time exhibits an Arrhenius behavior with no signs of criticality, demonstrating a unique scenario where the critical slowing down of the concentration fluctuations is subordinate to the large lifetime of the DNA bonds, with relevant analogies to critical dynamics in polymer solutions. The combination of equilibrium and dynamic behavior of DNA nanostars demonstrates the potential of DNA molecules in diversifying the pathways toward collective properties and selfassembled materials, beyond the range of phenomena accessible with ordinary molecular fluids.DNA nanotechnology | limited valence colloids | critical behavior I n recent years, a strong effort has been devoted to introduce a new generation of micro-and nanocolloids interacting via strongly anisotropic forces. Anisotropic interactions can simply arise from a nonspherical particle shape or from more sophisticated physical and/or chemical patterning of the particle surface (1-7). An alternative strategy to produce complex nanoparticles is to exploit the self-assembly of DNA oligomers. The rational design of the DNA sequences enables guiding the association of multiple DNA strands into a rich variety of nanosized objects, such as geometrical figures, hollow capsules, and nanomachines, as well as more complex meso-and macroscopic structures (8-13). The selectivity of DNA binding can also be exploited to control the mutual interactions between the structures (14, 15), whereas the spontaneous assembly of DNA sequences enables producing large ensembles of particles. These properties make DNA a powerful tool to explore fundamental phenomena of soft matter and statistical physics, as indicated by previous studies of liquid-crystalline ordering and phase separations in solutions of short DNA oligomers (16-18). Here we exploit DNA self-assembly to experimentally address the phase behavior of particles interacting with specific valence, strength, and selectivity.Colloidal particles with controlled valence are the next step toward the realization of new colloidal materials and phases dependent on the presence of a small number of bonds (1-7). Theoretical and numerical studies (19) predict that a solution of low-valence particles should exhibit phase coexistence-the colloidal analog of the vapor-liquid coexistence in simple liquidsbut only at v...
Kinetic arrest in colloidal dispersions with isotropic attractive interactions usually occurs through the destabilization of the homogeneous phase and the formation of a non-equilibrium network of jammed particles. Theory and simulations predict that a different route to gelation should become available when the valence of each colloidal particle is suitably reduced. Under these conditions, gelation should be achievable through a reversible sequence of equilibrium states. Here we report the reversible dynamic arrest of a dispersion of DNA-based nanoparticles with anisotropic interactions and a coordination number equal to four. As the temperature is decreased, the relaxation time for density fluctuations slows down by about five orders of magnitude, following an Arrhenius scaling in the entire experimentally accessible temperature window. The system is in thermodynamic equilibrium at all temperatures. Gelation in our system mimics the dynamic arrest of networking atomic strong glass formers such as silica, for which it could thus provide a suitable colloidal model.
We assessed the effects of repeated hydropeaking over five consecutive days on the zoobenthic community by manipulating discharge in five experimental flumes directly fed by an Alpine stream. Treatment consisted of two different hydropeaking intensities which increased discharge two‐ and threefold from baseflow and lasted for 5 h each day. The resulting sudden changes in flow directly affected benthic invertebrates through the induction of catastrophic drift as a direct response to high (hydropeaking) flow conditions, and of behavioural drift in the low, baseflow conditions (at the conclusion of each hydropeaking event) for some taxa. We observed: an initial strong peak in catastrophic drift within the first 3 min of increased discharge, followed by a decreased drift rate throughout the following hours of the experiment; a strong response in the first day of the simulation, with successive days having substantially decreased drift; taxa‐specific responses over the short and long‐time scales: least‐resistant taxa (i.e. Baetis spp.) were removed via the initial catastrophic drift, while more resistant taxa began to behaviourally drift later in each hydropeak (i.e. Simuliidae). Peaks in drift rates corresponded to the initial removal of CPOM which, during low flows, provided habitat and food resource for a high number of individuals and taxa. Quantification of drift responses over time scales larger than the single hydropeaking event underlines the relevance of the typical intermittency and repetition frequency as a stress factor for benthic communities, and that the response to hydropeaking is closely related to the time elapsed since the last perturbation. Copyright © 2015 John Wiley & Sons, Ltd.
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