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Coupling between chemical fuel consumption and phase separation can lead to condensation at a nonequilibrium steady state, resulting in phase behaviors that are not described by equilibrium thermodynamics. Theoretical models of such “chemically driven fluids” typically invoke near-equilibrium approximations at small length scales. However, because dissipation occurs due to both molecular-scale chemical reactions and mesoscale diffusive transport, it has remained unclear which properties of phase-separated reaction–diffusion systems can be assumed to be at an effective equilibrium. Here, we use microscopic simulations to show that mesoscopic fluxes are dependent on nonequilibrium fluctuations at phase-separated interfaces. We further develop a first-principles theory to predict nonequilibrium coexistence curves, localization of mesoscopic fluxes near phase-separated interfaces, and droplet size-scaling relations in good agreement with simulations. Our findings highlight the central role of interfacial properties in governing nonequilibrium condensation and have broad implications for droplet nucleation, coarsening, and size control in chemically driven fluids. 

Nearly thirty years after its inception, the field of DNA-programmed colloidal self-assembly has begun to realize its initial promise. In this review, we summarize recent developments in designing effective interactions and understanding the dynamic self-assembly pathways of DNA-coated nanoparticles and microparticles, as well as how these advances have propelled tremendous progress in crystal engineering. We also highlight exciting new directions showing that new classes of subunits combining nanoparticles with DNA origami can be used to engineer novel multicomponent assemblies, including structures with self-limiting, finite sizes. We conclude by providing an outlook on how recent theoretical advances focusing on the kinetics of self-assembly could usher in new materials-design opportunities, like the possibility of retrieving multiple distinct target structures from a single suspension or accessing new classes of materials that are stabilized by energy dissipation, mimicking self-assembly in living systems. 

Nonspecific interactions between DNA-coated colloidal particles play a critical role in determining the stabilities of competing crystal polymorphs. 

Phase-separated biomolecular condensates containing proteins and RNAs can assemble into higher-order structures by forming thermodynamically stable interfaces between immiscible phases. Using a minimal model of a protein/RNA interaction network, we demonstrate how a “shared” protein species that partitions into both phases of a multiphase condensate can function as a tunable surfactant that modulates the interfacial properties. We use Monte Carlo simulations and free-energy calculations to identify conditions under which a low concentration of this shared species is sufficient to trigger a wetting transition. We also describe a numerical approach based on classical density functional theory to predict concentration profiles and surface tensions directly from the model protein/RNA interaction network. Finally, we show that the wetting phase diagrams that emerge from our calculations can be understood in terms of a simple model of selective adsorption to a fluctuating interface. Our work shows how a low-concentration protein species might function as a biological switch for regulating multiphase condensate morphologies. Published by the American Physical Society2024 

Chemically driven fluids can demix to form condensed droplets that exhibit phase behaviors not observed at equilibrium. In particular, nonequilibrium interfacial properties can emerge when the chemical reactions are driven differentially between the interior and exterior of the phase-separated droplets. Here, we use a minimal model to study changes in the interfacial tension between coexisting phases away from equilibrium. Simulations of both droplet nucleation and interface roughness indicate that the nonequilibrium interfacial tension can either be increased or decreased relative to its equilibrium value, depending on whether the driven chemical reactions are accelerated or decelerated within the droplets. Finally, we show that these observations can be understood using a predictive theory based on an effective thermodynamic equilibrium.