Re-entrant melting as a design principle for DNA-coated colloids

Angioletti‐Uberti, Stefano; Mognetti, Bortolo Matteo; Frenkel, Daan

doi:10.1038/nmat3314

Cited by 108 publications

(157 citation statements)

References 27 publications

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“…Although this selective interaction is a result of the complex structure of the proteins, research on functionalized colloids unveils unprecedented possibilities of synthesizing particles with tunable interactions. Recently, experimental works on coated colloids have brought the real possibility of having species with selective interactions by grafting highly specific singlestranded DNA (ssDNA) (47)(48)(49)(50)(51)(52)(53)(54).…”

Section: Resultsmentioning

confidence: 99%

Arrested demixing opens route to bigels

Varrato

Michele

Belushkin

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

107

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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 ...

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Section: Resultsmentioning

confidence: 99%

Arrested demixing opens route to bigels

Varrato

Michele

Belushkin

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

107

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“…A key feature of our approach is that it separates the functions of the grafted strands, which encode the interaction matrix, and the W. B. Rogers, V. N. Manoharan, Science 347: 639 (2015) free displacing strands, which control the temperature dependence of the interaction matrix. Other competitive binding schemes have been proposed (28,29,30), but none result in independent control of the temperature-dependent phase transitions and the symmetry of the equilibrium phases. This independent control, which is crucial to fully program self-assembly, could make it possible to assemble complex materials in multiple stages.…”

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confidence: 99%

Programming colloidal phase transitions with DNA strand displacement

Rogers

Manoharan

2015

Science

193

197

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DNA-grafted nanoparticles have been called “programmable atom-equivalents”: Like atoms, they form three-dimensional crystals, but unlike atoms, the particles themselves carry information (the sequences of the grafted strands) that can be used to “program” the equilibrium crystal structures. We show that the programmability of these colloids can be generalized to the full temperature-dependent phase diagram, not just the crystal structures themselves. We add information to the buffer in the form of soluble DNA strands designed to compete with the grafted strands through strand displacement. Using only two displacement reactions, we program phase behavior not found in atomic systems or other DNA-grafted colloids, including arbitrarily wide gas-solid coexistence, reentrant melting, and even reversible transitions between distinct crystal phases.

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“…The problem of describing the melting transition into a fluid state [2][3][4][5][6][7][8][9] is complicated in amorphous solids by the difficulties inherent in describing the elasticity down to the atomistic level (where the thermal fluctuations take place). It is well known that the standard (Born-Huang) lattice-dynamic theory of elastic constants, and also its later developments [10], breaks down on the microscopic scale.…”

mentioning

confidence: 99%

Disorder-Assisted Melting and the Glass Transition in Amorphous Solids

2013

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The mechanical response of solids depends on temperature because the way atoms and molecules respond collectively to deformation is affected at various levels by thermal motion. This is a fundamental problem of solid state science and plays a crucial role in metallurgy, aerospace engineering, energy. In glasses the vanishing of rigidity upon increasing temperature is the reverse process of the glass transition. It remains poorly understood due to the disorder leading to nontrivial (nonaffine) components in the atomic displacements. Our theory explains the basic mechanism of the melting transition of amorphous (disordered) solids in terms of the lattice energy lost to this nonaffine motion, compared to which thermal vibrations turn out to play only a negligible role. It predicts the square-root vanishing of the shear modulus G ∼ √ Tc − T at criticality observed in the most recent numerical simulation study. The theory is also in good agreement with classic data on melting of amorphous polymers (for which no alternative theory can be found in the literature) and offers new opportunities in materials science.PACS numbers: 81.05. Lg, 64.70.pj, 61.43.Fs The phenomenon of the transition of a supercooled liquid into an amorphous solid has been studied extensively and many theories have been proposed in the past, starting with the Gibbs-DiMarzio theory [1]. All these theories focus on the fluid to solid aspect, coming to this glass transition from the liquid side (supercooling). However, it is only one facet of the problem. For the reverse process, i.e. the melting of the amorphous solid into a liquid, no established theories are available.The problem of describing the melting transition into a fluid state [2-9] is complicated in amorphous solids by the difficulties inherent in describing the elasticity down to the atomistic level (where the thermal fluctuations take place). It is well known that the standard (Born-Huang) lattice-dynamic theory of elastic constants, and also its later developments [10], breaks down on the microscopic scale. The reason is that its basic assumption, that the macroscopic deformation is affine and thus can be downscaled to the atomistic level, does not hold [11]. Atomic displacements in amorphous solids are in fact strongly nonaffine [11][12][13][14], a phenomenon illustrated in Fig. 1. Nonaffinity is caused by the lattice disorder: the forces transmitted to every atom by its bonded neighbors upon deformation do not balance, and the resulting non-zero force can only be equilibrated by an additional nonaffine displacement, which adds to the affine motion dictated by the macroscopic strain.Recently, it has been shown [15] that nonaffinity could play a role in the melting of model amorphous solids, although the basic interplay between nonaffinity, thermal expansion, and thermal vibrations remains unclear. With a number of other models of the glass transition, such as mode-coupling theories, there is also an issue when they rely on liquid-state theory for relating the stress tensor to local ...

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Re-entrant melting as a design principle for DNA-coated colloids

Cited by 108 publications

References 27 publications

Arrested demixing opens route to bigels

Arrested demixing opens route to bigels

Programming colloidal phase transitions with DNA strand displacement

Disorder-Assisted Melting and the Glass Transition in Amorphous Solids

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