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Synthetic LAPONITE®-clay particles with platelet-like shape display strong aging when dispersed in aqueous solutions, preventing the latter from reaching their natural liquid-crystalline equilibrium state. Here we introduce a facile method that successfully prevents this aging behaviour and enables accessing the systems' liquid-crystal and crystalline phases. We graft the comb-like polymer PLL-PEG (poly(l-lysine)-g-poly(ethylene glycol)) onto the clay surfaces from solution, thereby screening the negative surface charges and thus ensuring steric stabilisation. We show zeta-sizer and rheology measurements, respectively, confirming complete steric coating and that aging of dilute samples is completely suppressed even after a year. Using evaporation as a means to concentrate the particles, we observe various liquid crystalline textures under a polarized optical microscope (POM). Upon sequential spreading and drying, we are also able to obtain transparent films with hierarchical architecture.

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., SCOPUS: ar.j, info:eu-repo/semantics/published

DNA plays a special role in polymer science not just because of the highly selective recognition of complementary single DNA strands but also because bacteria can express DNA chains that are very long yet perfectly monodisperse. The latter reason makes long DNA mols. widely used as model systems in polymer science. Here, we report the unusual self-assembly that takes place in systems of colloids coated with very long double-stranded DNA. In particular, we find that colloids coated with such long DNA can assemble into unique "floating" cryst. monolayers. Floating colloidal structures have potentially interesting applications as such ordered structures can be assembled in one location and then deposited somewhere else. This would open the way to the assembly of multi-component, layered colloidal crystals.

Examined the effects of a TV documentary about the safety of the Sellafield nuclear reprocessing plant in the Northwest of England on public attitudes. In a study of 805 respondents (average age 47.8 yrs) to questionnaires from 4 districts in the Southwest of England, the attitudes and beliefs of these Ss were assessed both before and after the documentary about Sellafield. Results indicate a significant attitude change in a more antinuclear direction.

Traditionally it has been difficult to study the porous structure of dense colloidal gels and (macro) molecular transport through them simply because of the difference in refractive index between the colloid material and the continuous fluid phase surrounding it, rendering the samples opaque even at low colloidal volume fractions. Here, we demonstrate a novel colloidal gel that can be refractive index-matched in aqueous solutions owing to the low refractive index of fluorinated latex (FL)-particles (n = 1.37). Synthesizing them from heptafluorobutyl methacrylate using emulsion polymerization, we demonstrate that they can be functionalized with short DNA sequences via a dense brush-layer of polystyrene-b-poly(ethylene oxide) block-copolymers (PS-PEO). The block-copolymer, holding an azide group at the free PEO end, was grafted to the latex particle utilizing a swelling-deswelling method. Subsequently, DNA was covalently attached to the azide-end of the block copolymer via a strain-promoted alkyne-azide click reaction. For comparison, we present a structural study of single gels made of FL-particles only and composite gels made of a percolating FL-colloid gel coated with polystyrene (PS) colloids. Further we demonstrate that the diffusivity of tracer colloids dispersed deep inside a refractive index matched FL-colloidal gel can be measured as function of the local confinement using Dynamic Differential Microscopy (DDM).

Fluorinated latex particles were synthesized and functionalized with single stranded-DNA, facilitating controlled aggregation into porous gel networks; these can be studied deep into the bulk phase due to refractive-index matching., Traditionally it has been difficult to study the porous structure of dense colloidal gels and (macro) molecular transport through them simply because of the difference in refractive index between the colloid material and the continuous fluid phase surrounding it, rendering the samples opaque even at low colloidal volume fractions. Here, we demonstrate a novel colloidal gel that can be refractive index-matched in aqueous solutions owing to the low refractive index of fluorinated latex (FL)-particles (n = 1.37). Synthesizing them from heptafluorobutyl methacrylate using emulsion polymerization, we demonstrate that they can be functionalized with short DNA sequences via a dense brush-layer of polystyrene-b-poly(ethylene oxide) block-copolymers (PS-PEO). The block-copolymer, holding an azide group at the free PEO end, was grafted to the latex particle utilizing a swelling–deswelling method. Subsequently, DNA was covalently attached to the azide-end of the block copolymer via a strain-promoted alkyne–azide click reaction. For comparison, we present a structural study of single gels made of FL-particles only and composite gels made of a percolating FL-colloid gel coated with polystyrene (PS) colloids. Further we demonstrate that the diffusivity of tracer colloids dispersed deep inside a refractive index matched FL-colloidal gel can be measured as function of the local confinement using Dynamic Differential Microscopy (DDM).

© 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.