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Geometric frustration is recognized to generate complex morphologies in self-assembling particulate and molecular systems. In bulk states, frustration drives structured arrays of topological defects. In the dilute limit, these systems have been shown to form a novel state of self-limiting assembly, in which the equilibrium size of multiparticle domains are finite and well defined. In this article we employ Monte Carlo simulations of a recently developed 2D lattice model of geometrically frustrated assembly [Hackney et al., Phys. Rev. X 13, 041010 (2023)] to study the phase transitions between the self-limiting and defect bulk phase driven by two distinct mechanisms: (1) increasing concentration and (2) decreasing temperature or frustration. The first transition is mediated by a concentration-driven percolation transition of self-limiting, wormlike domains into an intermediate heterogeneous network mesophase, which gradually fills in at high concentration to form a quasiuniform defect bulk state. We find that the percolation threshold is weakly dependent on frustration and shifts to higher concentration as frustration is increased, but depends strongly on the ratio of cohesion to elastic stiffness in the model. The second transition takes place between self-limiting assembly at high-temperature or frustration and phase separation into a condensed bulk state at low temperature or frustration. We consider the competing influences that translational and conformational entropy have on the critical temperature or frustration and show that the self-limiting phase is stabilized at higher frustrations and temperatures than previously expected. Taken together, this understanding of the transition pathways from self-limiting to bulk defect phases of frustrated assembly allows us to map the phase behavior of this 2D minimal model over the full range of concentration. 

Bottom-up self-assembly is a powerful approach to engineering at small scales. Special strategies are needed to formulate components that assemble into predetermined shapes with precise sizes. 

Understanding the mechanisms that dictate the localization of cytoskeletal filaments is crucial for elucidating cell shape regulation in prokaryotes. The actin homolog MreB plays a pivotal role in maintaining the shape of many rod-shaped bacteria such as Escherichia coli by directing cell-wall synthesis according to local curvature cues. However, the basis of MreB’s curvature-dependent localization has remained elusive. Here, we develop a biophysical model for the energetics of a filament binding to a surface that integrates the complex interplay between filament twist and bending and the two-dimensional surface geometry. Our model predicts that the spatial localization of a filament like MreB with substantial intrinsic twist is governed by both the mean and Gaussian curvatures of the cell envelope, which strongly covary in rod-shaped cells. Using molecular dynamics simulations to estimate the mechanical properties of MreB filaments, we show that their thermodynamic preference for regions with lower mean and Gaussian curvatures matches experimental observations for physiologically relevant filament lengths of ~50 nm. We find that the experimentally measured statistical curvature preference is maintained in the absence of filament motion and after a cycle of depolymerization, repolymerization, and membrane rebinding, indicating that equilibrium energetics can explain MreB localization. These findings provide critical insights into the physical principles underlying cytoskeletal filament localization and suggest design principles for synthetic shape-sensing nanomaterials. 

Programmable self-assembly has recently enabled the creation of complex structures through precise control of the interparticle interactions and the particle geometries. Targeting ever more structurally complex, dynamic, and functional assemblies necessitates going beyond the design of the structure itself, to the measurement and control of the local flexibility of the intersubunit connections and its impact on the collective mechanics of the entire assembly. In this study, we demonstrate a method to infer the mechanical properties of multisubunit assemblies using cryogenic electron microscopy (cryo-EM) and RELION’s multi-body refinement. Specifically, we analyze the fluctuations of pairs of DNA-origami subunits that self-assemble into tubules. By measuring the fluctuations of dimers using cryo-EM, we extract mechanical properties such as the bending modulus and interparticle spring constant. These properties are then applied to elastic models to predict assembly outcomes, which align well with experimental observations. This approach not only provides a deeper understanding of nanoparticle mechanics but also opens pathways to refining subunit designs to achieve precise assembly behavior. This methodology could have broader applications in the study of nanomaterials, including protein assemblies, where understanding the interplay of mechanical properties and subunit geometry is essential for controlling complex self-assembled structures. 

We study the effect of geometric frustration on dilational mechanical metamaterial membranes. While shape frustrated elastic plates can only accommodate nonzero Gaussian curvature up to size scales that ultimately vanish with their elastic thickness, we show that frustrated metamembranes accumulate hyperbolic curvatures up to mesoscopic length scales that are ultimately independent of the size of their microscopic constituents. A continuum elastic theory and discrete numerical model describe the size-dependent shape and internal stresses of axisymmetric, trumpetlike frustrated metamembranes, revealing a nontrivial crossover to a much weaker power-law growth in elastic strain energy with size than in frustrated elastic membranes. We study a consequence of this for the self-limiting assembly thermodynamics of frustrated trumpets, showing a severalfold increase in the size range of self-limitation of metamembranes relative to elastic membranes. 

We study the ground state thermodynamics of a model class of geometrically frustrated assemblies, known as warped-jigsaw particles. While it is known that frustration in soft matter assemblies has the ability to propagate up to mesoscopic, multi-particle size scales, notably through the selection of the self-limiting domain, little is understood about how the symmetry of shape-misfit at the particle scale influences emergent morphologies at the mesoscale. Here we show that polarity in the shape-misfit of warped-jigsaw puzzles manifests at a larger scale in the morphology and thermodynamics of the ground-state assembly of self-limiting domains. We use a combination of continuum theory and discrete particle simulations to show that the polar misfit gives rise to two mesoscopically distinct polar, self-limiting ribbon domains. Thermodynamic selection between the two ribbon morphologies is controlled by a combination of the binding anisotropy along distinct neighbor directions and the orientation of polar shape-misfit. These predictions are valuable as design features for ongoing efforts to program self-limiting assemblies through the synthesis of intentionally frustrated particles, further suggesting a generic classification of frustrated assembly behavior in terms of the relative symmetries of shape-misfit and the underlying long-range inter-particle order it frustrates. 

In geometrically frustrated assemblies local intersubunit misfits propagate to intra-assembly strain gradients, giving rise to anomalous self-limiting assembly thermodynamics. Here we use theory and coarse-grained simulation to study a recently developed class of “curvamer” particles, flexible shell-like particles that exhibit self-limiting assembly due to the build up of curvature deformation in cohesive stacks. To address a generic, yet poorly understood aspect of frustrated assembly, we introduce a model of curvamer assembly that incorporates both intraparticle shape deformation as well as compliance of interparticle cohesive gaps, an effect we can attribute to a finite range of attraction between particles. We show that the ratio of intraparticle (bending elasticity) to interparticle stiffness not only controls the regimes of self-limitation but also the nature of frustration propagation through curvamer stacks. We find a transition from uniformly bound, curvature-focusing stacks at small size to gap opened, uniformly curved stacks at large size is controlled by a dimensionless measure of inter- versus intracurvamer stiffness. The finite range of interparticle attraction determines the range of cohesion in stacks that are self-limiting, a prediction which is in strong agreement with numerical studies of our coarse-grained colloidal model. These predictions provide critical guidance for experimental realizations of frustrated particle systems designed to exhibit self-limitation at especially large multiparticle scales.