Controlling the topology of structures self-assembled from a set of heterogeneous building blocks is highly desirable for many applications, but is poorly understood theoretically. Here we show that the thermodynamic theory of self-assembly involves an inevitable divergence in chemical potential. The divergence and its detailed structure are controlled by the spectrum of the transfer matrix, which summarizes all of self-assembly design degrees of freedom. By analyzing the transfer matrix, we map out the phase boundary between the designable structures and the unstructured aggregates, driven by the level of cross-talk.
Jamming describes a transition from a flowing or liquid state to a solid or rigid state in a loose assembly of particles such as grains or bubbles. In contrast, clogging describes the ceasing of the flow of particulate matter through a bottleneck. It is not clear how to distinguish jamming from clogging, nor is it known whether they are distinct phenomena or fundamentally the same. We examine an assembly of disks moving through a random obstacle array and identify a transition from clogging to jamming behavior as the disk density increases. The clogging transition has characteristics of an abs…
We demonstrate scaffolding of plasmonic nanoparticles by topological defects induced by colloidal microspheres to match their surface boundary conditions with a uniform far-field alignment in a liquid crystal host. Displacing energetically costly liquid crystal regions of reduced order, anisotropic nanoparticles with concave or convex shapes not only stably localize in defects but also self-orient with respect to the microsphere surface. Using laser tweezers, we manipulate the ensuing nanoparticle-microsphere colloidal dimers, probing the strength of elastic binding and demonstrating self-asse…
Topological defect engineering enables size and shape control in self-assembly
Université Paris-Saclay（巴黎萨克雷大学）；CNRS（法国国家科学研究中心）；LPTMS（理论物理实验室）；Max Planck Institute for the Physics of Complex Systems（马克斯·普朗克复杂系统物理研究所）；Technical University of Munich（慕尼黑工业大学）；Max Planck School Matter to Life（马克斯·普朗克生命物质学院）；Aix Marseille Université（艾克斯-马赛大学）；CINAM（中子与磁学中心）；Turing Center for Living Systems（图灵生命系统中心）；PMMH（物理化学与分子宏观结构实验室）；ESPCI Paris（巴黎高等物理化工学院）；PSL University（巴黎文理研究大学）；Sorbonne Université（索邦大学）
We exploit the long-ranged elastic fields inherent to confined nematic liquid crystals to assemble colloidal particles trapped at the liquid crystal interface into reconfigurable structures with complex symmetries and packings. Spherical colloids with homeotropic anchoring trapped at the interface between air and the nematic liquid crystal 5CB create quadrupolar distortions in the director field causing particles to repel and consequently form close-packed assemblies with a triangular habit. Here we report on complex, open structures organized via interactions with defects in the bulk. Specifi…
Motivated by observations of heterogeneous domain structure on the surface of cells, we consider a minimal model to describe the dynamics of phase separation on the surface of a spherical particle. Finite-size effects on the curved particle surface lead to the formation of long-lived, metastable states for which the density is distributed in patches over the particle surface. We study the time evolution and stability of these states as a function of both the particle size and the thermodynamic parameters. Finally, by connecting our findings with studies of patchy particles, we consider the imp…
A heterogeneous and dilute suspension of catalytically active colloids is studied as a non-equilibrium analogue of ionic systems, which has the remarkable feature of action-reaction symmetry breaking. Symmetrically coated colloids are found to join up to form self-assembled molecules that could be inert or have spontaneous activity in the form of net translational velocity and spin depending on their symmetry properties and their constituents. The type of activity can be adjusted by changing the surface chemistry and ambient variables that control the surface reactions and the phoretic drift.
Understanding how topological constraints affect the dynamics of polymers in solution is at the basis of any polymer theory and it is particularly needed for melts of rings. These polymers fold as crumpled and space-filling objects and, yet, they display a large number of topological constraints. To understand their role, here we systematically probe the response of solutions of rings at various densities to "random pinning" perturbations. We show that these perturbations trigger non-Gaussian and heterogeneous dynamics, eventually leading to non-ergodic and glassy behaviours. We then derive un…
Chirality frustrates and shapes the assembly of flexible filaments in rope-like, twisted bundles and fibers by introducing gradients of both filament shape (i.e. curvature) and packing throughout the structure. Previous models of chiral filament bundle formation have shown that this frustration gives rise to several distinct morphological responses, including self-limiting bundle widths, anisotropic domain (tape-like) formation and topological defects in the lateral inter-filament order. In this paper, we employ a combination of continuum elasticity theory and discrete filament bundle simulati…
Many structural properties of conventional passive materials are known to arise from the symmetries of their microscopic constituents. By contrast, it is largely unclear how the interplay between cell shape and self-propulsion controls the meso- and macroscale behavior of active matter. Here, we analyze large-scale simulations of homo- and heterogeneous self-propelled particle systems to identify generic effects of broken particle symmetry on collective motion. We find that even small violations of fore-aft symmetry lead to fundamentally different collective behaviors, which may facilitate dem…
We examine emergent properties of 2D supramolecular networks, using enumeration of configurations formed by interacting dominoes on square lattices as a simple model system. Possible ground states are identified using a convex hull construction in the interaction parameters for nearest-neighbour bonds. We demonstrate how this construction can be used to design interaction parameters which lead to networks with specific properties, including chirality and highly degenerate ground states. We then introduce kinetics as simple local rearrangements. By partitioning the configuration space into smal…
Self-assembly is one of the crucial mechanisms allowing to design multifunctional materials. Soft hybrid materials contain components of different nature and exhibit competitive interactions which drive self-organisation into structures of a particular function. Here we demonstrate a novel type of a magnetic hybrid material where the molecular tilt can be manipulated through a delicate balance between the topologically-assisted colloidal self-assembly of \rev{magnetic nanoparticles} and the anisotropic molecular interactions in a liquid crystal matrix.
Controlling the assembly of polyelectrolytes and surfactant at liquid-liquid interfaces offers new ways to fabricate soft materials with specific physical properties. However, little is known of the relationships between the kinetics of interfacial assembly, structural and rheological properties of such interfaces. We studied the kinetics at water-oil interface of the assembly of a positively charged biopolymer, chitosan, with an anionic fatty acid using a multi-scale approach. The growth kinetics of the membrane was followed by interfacial rheometry and space- and time- resolved dynamic light…
Biomolecular condensates self-assemble when proteins and nucleic acids spontaneously demix to form droplets within the crowded intracellular milieu. This simple mechanism underlies the formation of a wide variety of membraneless compartments in living cells. To understand how multiple condensates with distinct compositions can self-assemble in such a heterogeneous system, we study a minimal model in which we can "program" the pairwise interactions among hundreds of species. We show that the number of distinct condensates that can be reliably assembled grows superlinearly with the number of spe…
Self-assembly is ubiquitous in nature, particularly in biology, where it underlies the formation of protein quaternary structure and protein aggregation. Quaternary structure assembles deterministically and performs a wide range of important functions in the cell, whereas protein aggregation is the hallmark of a number of diseases and represents a non-deterministic self-assembly process. Here we build on previous work on a lattice model of deterministic self-assembly to investigate non-deterministic self-assembly of single lattice tiles and mixtures of two tiles at varying relative concentrati…
As the beneficial effects of curcumin have often been reported to be limited to its small concentrations, we have undertaken a study to find the aggregation properties of curcumin in water by varying the number of monomers. Our molecular dynamics simulation results show that the equilibrated structure is always an aggregated state with remarkable structural rearrangements as we vary the number of curcumin monomers from 4 to 16 monomers. We find that curcumin monomers form clusters in a very definite pattern where they tend to aggregate both in parallel and anti-parallel orientation of the phen…
Soft materials can self-assemble into highly structured phases which replicate at the mesoscopic scale the symmetry of atomic crystals. As such, they offer an unparalleled platform to design mesostructured materials for light and sound. Here, we present a bottom-up approach based on self-assembly to engineer three-dimensional photonic and phononic crystals with topologically protected Weyl points. In addition to angular and frequency selectivity of their bulk optical response, Weyl materials are endowed with topological surface states, which allows for the existence of one-way channels even in…
We measure the defect density as a function of time at different temperatures in simulations of a two dimensional system of interacting particles. Just above the solid to liquid transition temperature, the power spectrum of the defect fluctuations shows a 1/f signature, which crosses over to a white noise signature at higher temperatures. When 1/f noise is present, the 5-7 defects predominately form string like structures, and the particle trajectories show a 1D correlated motion that follows the defect strings. At higher temperatures this heterogeneous motion is lost. We demonstrate this hete…
Curvature-guided topology and self-assembly in chiral nematics and liquid-crystal colloids
University of Colorado Boulder（科罗拉多大学博尔德分校）；University of Colorado, Boulder（科罗拉多大学博尔德分校）；National Renewable Energy Laboratory（国家可再生能源实验室）；Hiroshima University（广岛大学）；Universidade de Lisboa（里斯本大学）
This perspective will overview an emerging paradigm for self-organized soft materials, {\it geometrically-frustrated assemblies}, where interactions between self-assembling elements (e.g. particles, macromolecules, proteins) favor local packing motifs that are incompatible with uniform global order in the assembly. This classification applies to a broad range of material assemblies including self-twisting protein filament bundles, amyloid fibers, chiral smectics and membranes, particle-coated droplets, curved protein shells and phase-separated lipid vesicles. In assemblies, geometric frustrati…
The field of complex self-assembly is moving toward the design of multi-particle structures consisting of thousands of distinct building blocks. To exploit the potential benefits of structures with such `addressable complexity,' we need to understand the factors that optimize the yield and the kinetics of self-assembly. Here we use a simple theoretical method to explain the key features responsible for the unexpected success of DNA-brick experiments, which are currently the only demonstration of reliable self-assembly with such a large number of components. Simulations confirm that our theory …
Inspired by the synchronized beating of cilia, we show that the collective dynamics of hair-like fibers in a meniscus during fast drainage enables their self-organization into multiple topologies including complex shape inversions. By draining liquid from triangular-base hair bundles, we demonstrate their transformations into concave hexagons, rounded triangles, circles and inverted triangles. These topologically distinct shapes are quenched collective mode shapes of the beating hair each corresponding to specific drainage rates of the liquid, and cyclic shape re-transformations can be simply …
Despite their considerable practical and biological applications, the link between molecular properties, assembly conditions and self-organized structure in confined polymer solutions remains elusive. Here, we explore the lyotropic nematic ordering of semi-flexible chains in spherical confinement for multiple contour lengths across a wide regime of concentrations. We uncover an original crossover from two distinct quadrupolar states, both characterized by regular tetrahedral patterns of surface topological defects, to either longitudinal, latitudinal or spontaneously-twisted bipolar structures…
We simulate a model of repulsively interacting colloids on a commensurate two-dimensional triangular pinning substrate where the amount of heterogeneous motion that appears at melting can be controlled systematically by turning off a fraction of the pinning sites. We correlate the amount of heterogeneous motion with the average topological defect number, time dependent defect fluctuations, colloid diffusion, and the form of the van Hove correlation function. When the pinning sites are all off or all on, the melting occurs in a single step. When a fraction of the sites are turned off, the melti…
Functionalizing colloids with reactive DNA linkers is a versatile way of programming self-assembly. DNA selectivity provides direct control over colloid-colloid interactions allowing the engineering of structures such as complex crystals or gels. However, self-assembly of localized and finite structures remains an open problem with many potential applications. In this work, we present a system in which functionalized surfaces initiate a cascade reaction between linkers leading to self-assembly of crystals with a controllable number of layers. Specifically, we consider colloidal particles funct…
We have developed Norland Optical Adhesive (NOA) flow focusing devices, making use of the excellent solvent compatibility and surface properties of NOA to generate micron scale oil-in-water emulsions with polydispersities as low as 5%. While current work on microfluidic oil-in-water emulsification largely concerns the production of droplets with sizes on the order of 10s of micrometres, large enough that Brownian motion is negligible, our NOA devices can produce droplets with radii ranging from 2 μm to 12 μm. To demonstrate the utility of these emulsions as colloidal model systems we produce f…
Combining topology and plasmonics paradigms in nanocolloidal systems may enable new means of pre-engineering desired composite material properties. Here we design and realize orientationally ordered assemblies of noble metal nanoparticles with genus-one topology and unusual long-range ordering mediated by their interactions with the surrounding nematic fluid host. Facile electric switching of these composites is reminiscent to that of pristine liquid crystals (LCs), but provides a means of reconfiguring the nanoparticle assembly and thus also the ensuing composite medium's optical properties. …
We present a novel, self-consistent and robust theoretical model to investigate elastic interactions between topological defects in liquid crystal shells. Accounting for the non-concentric nature of the shell in a simple manner, we are able to successfully and accurately explain and predict the positions of the defects, most relevant in the context of colloidal self-assembly. We calibrate and test our model on existing experimental data, and extend it to all newly observed defects configurations in chiral nematic shells. We perform new experiments to check further and confirm the validity of t…
We introduce topological methods for quantifying spatially heterogeneous dynamics, and use these tools to analyze particle-tracking data for a quasi-two-dimensional granular system of air-fluidized beads on approach to jamming. In particular we define two overlap order parameters, which quantify the correlation between particle configurations at different times, based on a Voronoi construction and the persistence in the resulting cells and nearest neighbors. Temporal fluctuations in the decay of the persistent area and bond order parameters define two alternative dynamic four-point susceptibil…
Steady structures originating from dynamic self-assembly have begun to show their advantages in new generation materials, and pose challenges to equilibrium self-assembly. In view of the important role of confinement in self-assembly, here, we propose a new type of confinement leading to dynamic steady structures, which opens a new window for the conventional confinement. In our model, we consider the self-assembly of ellipsoids in 2D circular confinement via the boundary performing periodically stretching and contracting oscillation. Langevin dynamics simulations reveal the achievement of non…
Colloidal particles in polymer solutions and functionalized nanoparticles often exhibit short-range attraction coupled with long-range repulsion (SALR) leading to the spontaneous formation of symmetric patterns. Chiral nanostructures formed by thin film of SALR particles have not been reported yet. In this study, we observe striking topological transitions from a symmetric pattern of concentric rings to a chiral structure of a spiral shape, when the system is in hexagonal confinement. We find that the spiral formation can be induced either by breaking the system symmetry with a wedge, or by me…
Monopole-like electrostatic interactions are ubiquitous in biology and condensed matter, but they are often screened by counter-ions and cannot be switched from attractive to repulsive. In colloidal science, where the prime goal is to develop colloidal particles that mimic and exceed the diversity and length-scales of atomic and molecular assembly, electrostatically charged particles cannot change the sign of their surface charge or transform from monopoles to higher-order multipoles. In liquid-crystal colloids, elastic interactions between particles arise to minimize the free energy associate…
