Layering, freezing and re-entrant melting of hard spheres in soft confinement

Confinement can have a dramatic effect on the behavior of all sorts of particulate systems and it therefore is an important phenomenon in many different areas of physics and technology. Here, we investigate the role played by the softness of the confining potential. Using grand canonical Monte Carlo simulations, we determine the phase diagram of three-dimensional hard spheres that in one dimension are constrained to a plane by a harmonic potential. The phase behavior depends strongly on the density and on the stiffness of the harmonic confinement. Whilst we find the familiar sequence of confined hexagonal and square-symmetric packings, we do not observe any of the usual intervening ordered phases. Instead, the system phase separates under strong confinement, or forms a layered re-entrant liquid phase under weaker confinement. It is plausible that this behavior is due to the larger positional freedom in a soft confining potential and to the contribution that the confinement energy makes to the total free energy. The fact that specific structures can be induced or suppressed by simply changing the confinement conditions (e.g. in a dielectrophoretic trap) is important for applications that involve self-assembled structures of colloidal particles.Comment: 5 pages, 5 figure

Structural and Linear Elastic Properties of DNA Hydrogels by Coarse-Grained Simulation

© 2019 American Chemical Society. We introduce a coarse-grained numerical model that represents a generic DNA hydrogel consisting of Y-shaped building blocks. Each building block comprises three double-stranded DNA arms with single-stranded DNA sticky ends, mimicked by chains of beads and patchy particles, respectively, to allow for an accurate representation of both the basic geometry of the building blocks and the interactions between complementary units. We demonstrate that our coarse-grained model reproduces the correct melting behavior between the complementary ends of the Y-shapes, and their self-assembly into a percolating network. Structural analysis of this network reveals three-dimensional features consistent with a uniform distribution of inter-building-block dihedral angles. When applying an oscillatory shear strain to the percolating system, we show that the system exhibits a linear elastic response when fully connected. We finally discuss to what extent the system's elastic modulus may be controlled by simple changes to the building block complementarity. Our model offers a computationally tractable approach to predicting the structural and mechanical properties of DNA hydrogels made of different types of building blocks

Associations between authoritative parenting and the sun exposure and sun protective behaviours of adolescents and their friends.

addresses: School of Psychology, Washington Singer Laboratories, University of Exeter, Exeter EX44QG, UK. [email protected]: Comparative Study; Journal Article; Research Support, Non-U.S. Gov'tThis is a postprint of an article published in Psychology and Health, 2011, Vol. 26, Issue 5, pp. 549 – 565 © 2011 copyright Taylor & Francis. Psychology and Health is available online at: http://www.tandfonline.com/toc/gpsh20/currentAssociations between the sun exposure and sun protective behaviours of adolescents and their friends were examined along with the role played by authoritative parenting and other family and peer socialisation factors. Four hundred and two adolescents (198 males, 204 females) participated in the research. It was found that these adolescents and their friends shared similar sun exposure and sun protective behaviours and had similar parenting backgrounds. Parental authoritativeness was positively associated with the use of sun protection, even after the effects of other familial and peer variables were controlled, but not with the time spent sunbathing which was associated with friends' behaviours. The theoretical and practical implications of these findings are discussed

Volume and porosity thermal regulation in lipid mesophases by coupling mobile ligands to soft membranes

Short DNA linkers are increasingly being exploited for driving specific self-assembly of Brownian objects. DNA-functionalised 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.Funding was provided by the Ernest Oppenheimer Fund and Emmanuel College Cambridge (L.D.M.), EPSRC Programme Grant CAPITALS number EP/J017566/1 (L.P., J.K., P.C. and L.D.M.) and the Winton Fund for Physics of Sustainability (E.E.).This article was originally published in Nature Communications (L Parolini, BM Mognetti, J Kotar, E Eiser, P Cicuta, L Di Michele, Nature Communications 2015, 6, 5948

Oscillatory rheology of dense, athermal suspensions of nearly hard spheres below the jamming point

The viscosity of a dense suspension has contributions from hydrodynamics and particle interactions, both of which depend upon the flow-induced arrangement of particles into fragile structures. Here, we study the response of nearly hard sphere suspensions to oscillatory shear using simulations and experiments in the athermal, non-inertial limit. Three distinct regimes are observed as a function of the strain amplitude γ0. For γ0 10(1), the microstructure becomes well-established at the beginning of each shear cycle and the rheology is quasi-Newtonian: the shear stress varies with the rate, but flow-induced structures lead to non-zero normal stresses. At intermediate γ0, particle-particle contacts break and reform across entire oscillatory cycles, and we probe a non-linear regime that reveals the fragility of the material. Guided by these features, we further show that oscillatory shear may serve as a diagnostic tool to isolate specific stress contributions in dense suspensions, and more generally in those materials whose rheology has contributions with both hydrodynamic and non-hydrodynamic origin

Fluctuation-dissipation theorem in an aging colloidal glass

We provide a direct experimental test of the Stokes-Einstein relation as a special case of the fluctuation-dissipation theorem (FDT) in an aging colloidal glass. The use of combined active and passive microrheology allows us to independently measure both the correlation and response functions in this non-equilibrium situation. Contrary to previous reports, we find no deviations from the FDT over several decades in frequency (1 Hz-10 kHz) and for all aging times. In addition, we find two distinct viscoelastic contributions in the aging glass, including a nearly elastic response at low frequencies that grows during aging. This is the clearest change in material properties of the system with aging.Comment: 5 pages,4 figure

Transparent Films Made of Highly Scattering Particles

Today, colloids are widely employed in various products from creams and coatings to electronics. The ability to control their chemical, optical, or electronic features by controlling their size and shape explains why these materials are so widely preferred. Nevertheless, altering some of these properties may also lead to some undesired side effects, one of which is an increase in optical scattering upon concentration. Here, we address this strong scattering issue in films made of binary colloidal suspensions. In particular, we focus on raspberry-type polymeric particles made of a spherical polystyrene core decorated by small hemispherical domains of acrylate with an overall positive charge, which display an unusual stability against aggregation in aqueous solutions. Their solid films display a brilliant red color due to Bragg scattering but appear completely white on account of strong scattering otherwise. To suppress the scattering and induce transparency, we prepared films by hybridizing them with oppositely charged PS particles with a size similar to that of the bumps on the raspberries. We report that the smaller PS particles prevent raspberry particle aggregation in solid films and suppress scattering by decreasing the spatial variation of the refractive index inside the film. We believe that the results presented here provide a simple strategy to suppress strong scattering of larger particles to be used in optical coatings