A shape-driven reentrant jamming transition in confluent monolayers of synthetic cell-mimics.

Many critical biological processes, like wound healing, require densely packed cell monolayers/tissues to transition from a jammed solid-like to a fluid-like state. Although numerical studies anticipate changes in the cell shape alone can lead to unjamming, experimental support for this prediction is not definitive because, in living systems, fluidization due to density changes cannot be ruled out. Additionally, a cell's ability to modulate its motility only compounds difficulties since even in assemblies of rigid active particles, changing the nature of self-propulsion has non-trivial effects on the dynamics. Here, we design and assemble a monolayer of synthetic cell-mimics and examine their collective behaviour. By systematically increasing the persistence time of self-propulsion, we discovered a cell shape-driven, density-independent, re-entrant jamming transition. Notably, we observed cell shape and shape variability were mutually constrained in the confluent limit and followed the same universal scaling as that observed in confluent epithelia. Dynamical heterogeneities, however, did not conform to this scaling, with the fast cells showing suppressed shape variability, which our simulations revealed is due to a transient confinement effect of these cells by their slower neighbors. Our experiments unequivocally establish a morphodynamic link, demonstrating that geometric constraints alone can dictate epithelial jamming/unjamming.

Harnessing Viscoelasticity to Suppress Irreversibility Buildup in a Colloidal Stirling Engine.

Typically, the rate at which a heat engine can produce useful work is constrained by the buildup of irreversibility with increasing operating speed. Here, using a recently developed reservoir engineering technique, we designed and quantified the performance of a colloidal Stirling engine operating in a viscoelastic bath. While the bath acts like a viscous fluid in the quasistatic limit, and the engine's performance agrees with equilibrium predictions, on reducing the cycle time to the bath's structural relaxation time, the increasingly elastic response of the bath aids suppress the buildup of irreversibility. We show that the elastic energy stored during the isothermal compression step of the Stirling cycle facilitates quick equilibration in the isothermal expansion step. This results in equilibriumlike efficiencies even for cycle times shorter than the equilibration time of the colloidal particle.

Overcoming power-efficiency tradeoff in a micro heat engine by engineered system-bath interactions.

All real heat engines, be it conventional macro engines or colloidal and atomic micro engines, inevitably tradeoff efficiency in their pursuit to maximize power. This basic postulate of finite-time thermodynamics has been the bane of all engine design for over two centuries and all optimal protocols implemented hitherto could at best minimize only the loss in the efficiency. The absence of a protocol that allows engines to overcome this limitation has prompted theoretical studies to suggest universality of the postulate in both passive and active engines. Here, we experimentally overcome the power-efficiency tradeoff in a colloidal Stirling engine by selectively reducing relaxation times over only the isochoric processes using system bath interactions generated by electrophoretic noise. Our approach opens a window of cycle times where the tradeoff is reversed and enables the engine to surpass even their quasistatic efficiency. Our strategies finally cut loose engine design from fundamental restrictions and pave way for the development of more efficient and powerful engines and devices.

Intermediate-range order governs dynamics in dense colloidal liquids.

The conventional wisdom is that liquids are completely disordered and lack nontrivial structure beyond nearest-neighbor distances. Recent observations have upended this view and demonstrated that the microstructure in liquids is surprisingly rich and plays a critical role in numerous physical, biological, and industrial processes. However, approaches to uncover this structure are either system-specific or yield results that are not physically intuitive. Here, through single-particle resolved three-dimensional confocal microscope imaging and the use of a recently introduced four-point correlation function, we show that bidisperse colloidal liquids have a highly nontrivial structure comprising alternating layers with icosahedral and dodecahedral order, which extends well beyond nearest-neighbor distances and grows with supercooling. By quantifying the dynamics of the system on the particle level, we establish that it is this intermediate-range order, and not the short-range order, which has a one-to-one correlation with dynamical heterogeneities, a property directly related to the relaxation dynamics of glassy liquids. Our experimental findings provide a direct and much sought-after link between the structure and dynamics of liquids and pave the way for probing the consequences of this intermediate-range order in other liquid state processes.

Hierarchical Colloidal Self-Assembly on Lattice-Mismatched Moiré Patterns.

Extending atomic epitaxy concepts to colloidal systems for realizing functional surface structures has recently piqued scientific interest. Akin to the growth of ordered metal clusters on graphene moiré, spatially ordered colloidal crystals have been realized on soft lithographically fabricated moiré patterns. In addition to moiré periodicity, lattice misfit strain can bring about a further level of hierarchy in colloidal self-assembly, although its role in self-organization remains unexplored. Here, we demonstrate the self-organized growth of micrometer-sized colloidal pyramid arrays with lateral order extending over millimeter length scales on lattice-mismatched moiré patterns. By probing the film growth dynamics with single-particle resolution, we uncovered the interplay between lattice misfit strain and topographically varying surface potential within the moiré unit cell, which significantly alters the nucleation process. We also show that the structural organization of colloids within moiré regions primarily depends on the moiré angle, and by tuning it, multiple levels of hierarchy can be achieved.

Synergistic action in colloidal heat engines coupled by non-conservative flows.

Colloidal heat engines are model systems to analyze mechanisms of transduction of heat to work at the mesoscale. While engines developed hitherto were realized using conservative potentials and operated in isolation, biological micromotors - their real counterparts - seldom perform under such simplifications. Here, we examine thermodynamics beyond such idealizations by constructing a pair of engines from two colloidal microspheres in optical traps at close separation. We demonstrate that at such proximity, non-conservative scattering forces that were hitherto neglected affect the particle motion. Hydrodynamics generated while dissipating these are hindered by the microsphere in the adjacent trap and energy that was otherwise rejected into the medium gets reused. Thus, despite being in contact with the same reservoir, the particles are driven out of equilibrium and can exchange energy, allowing cooperative behavior. Leveraging this in a manner analogous to microswimmers and active Brownian particles that utilize such flows to enhance propulsion, we construct two colloidal engines in close proximity. To estimate thermodynamic quantities, we develop a minimal model that is appropriate in the asymptotic limit and is similar to active Brownian particles. While complete theoretical frameworks to understand such scenarios remain to be developed, results based on our model demonstrate the intuitive idea that a pair of Stirling engines at close proximity outperform those that are well separated. Although these results explore the simplest case of two Stirling engines, the concepts unraveled could aid in designing larger collections akin to biological systems.

Direct Measurements of Surface Strain-Mediated Lateral Interactions between Adsorbates in Colloidal Heteroepitaxy.

Surface strain can alter the dynamics of adsorbates, and often, the adsorbates themselves induce and interact via their surface strain fields. In epitaxy, such strain-mediated effects get further compounded when a misfit strain exists due to lattice mismatch between the growing film and substrate. Here, we carry out particle-resolved imaging of heteroepitaxial growth of multilayer colloidal films where the particles interact via a short-range attraction. Surprisingly, although the misfit strain relaxed systematically with film thickness, the adcolloid diffusivity was nonmonotonic. We show that this nonmonotonicity stems from the competition between the spatial extent of self-induced in-layer strain and the short interaction range. Importantly, we provide direct evidence for long-ranged strain-mediated interactions between adsorbates and show that it alters the growing film's morphology.

Observation of two-step melting on a sphere.

Melting in two-dimensional flat space is typically two-step and via the hexatic phase. How melting proceeds on a curved surface, however, is not known. Topology mandates that crystalline particle assemblies on these surfaces harbor a finite density of defects, which itself can be ordered, like the icosahedral ordering of 5-coordinated disclination defects on a sphere. Thus, melting even on a sphere, the simplest closed surface, involves the loss of both crystalline and defect order. Probing the interplay of these two forms of order, however, requires a system in which melting can be performed in situ, and this has not been achieved hitherto. Here, by tuning interparticle interactions in situ, we report an observation of an intermediate hexatic phase during the melting of colloidal crystals on a sphere. Remarkably, we observed a precipitous drop in icosahedral defect order in the hexatic phase where the shear modulus is expected to vanish. Furthermore, unlike in flat space, where disorder can fundamentally alter the nature of the melting process, on the sphere, we observed the signature characteristics of ideal melting. Our findings have profound implications for understanding, for instance, the self-assembly and maturation dynamics of viral capsids and also phase transitions on curved surfaces.

Structural origin of excitations in a colloidal glass-former.

Despite decades of intense research, whether the transformation of supercooled liquids into glass is a kinetic phenomenon or a thermodynamic phase transition remains unknown. Here, we analyzed optical microscopy experiments on 2D binary colloidal glass-forming liquids and investigated the structural links of a prominent kinetic theory of glass transition. We examined a possible structural origin for localized excitations, which are building blocks of the dynamical facilitation theory-a purely kinetic approach for the glass transition. To accomplish this, we utilize machine learning methods to identify a structural order parameter termed "softness" that has been found to be correlated with reorganization events in supercooled liquids. Both excitations and softness qualitatively capture the dynamical slowdown on approaching the glass transition and motivated us to explore spatial and temporal correlations between them. Our results show that excitations predominantly occur in regions with high softness and the appearance of these high softness regions precedes excitations, thus suggesting a causal connection between them. Thus, unifying dynamical and thermodynamical theories into a single structure-based framework may provide a route to understand the glass transition.

Motile Topological Defects Hinder Dynamical Arrest in Dense Liquids of Active Ellipsoids.

Recent numerical studies have identified the persistence time of active motion as a critical parameter governing glassy dynamics in dense active matter. Here we studied dynamics in liquids of granular active ellipsoids with tunable persistence and velocity. We show that increasing the persistence time at moderate supercooling is equivalent to increasing the strength of attraction in equilibrium liquids and results in reentrant dynamics not just in the translational degrees of freedom, as anticipated, but also in the orientational ones. However, at high densities, motile topological defects, unique to active liquids of elongated particles, hindered dynamical arrest. Most remarkably, for the highest activity, we observed intermittent dynamics due to the jamming-unjamming of these defects for the first time.

Tuning the performance of a micrometer-sized Stirling engine through reservoir engineering.

Colloidal heat engines are paradigmatic models to understand the conversion of heat into work in a noisy environment - a domain where biological and synthetic nano/micro machines function. While the operation of these engines across thermal baths is well-understood, how they function across baths with noise statistics that is non-Gaussian and also lacks memory, the simplest departure from the thermal case, remains unclear. Here we quantified the performance of a colloidal Stirling engine operating between an engineered memoryless non-Gaussian bath and a Gaussian one. In the quasistatic limit, the non-Gaussian engine functioned like a thermal one as predicted by theory. On increasing the operating speed, due to the nature of noise statistics, the onset of irreversibility for the non-Gaussian engine preceded its thermal counterpart and thus shifted the operating speed at which power is maximum. The performance of nano/micro machines can be tuned by altering only the nature of reservoir noise statistics.

Emergent stereoselective interactions and self-recognition in polar chiral active ellipsoids.

In many active matter systems, particle trajectories have a well-defined handedness or chirality. Whether such chiral activity can introduce stereoselective interactions between particles is not known. Here, we developed a strategy to tune the nature of chiral activity of three-dimensionally printed granular ellipsoids without altering their shape or size. In vertically agitated monolayers of these particles, we observed two types of dimers form depending on the chirality of the pairing monomers. Heterochiral dimers moved collectively as a single achiral active unit, while homochiral ones formed a translationally immobile spinner. In active racemic mixtures, the former was more abundant than the latter, indicating that interactions were stereoselective. Through dimer lifetime measurements, we further provide evidence for chiral self-recognition in mixtures of particles with different chiral activities. We lastly show that, at fixed particle number density, changing the net chirality of a dense active liquid fundamentally alters the nature of collective relaxation.

Cooperatively rearranging regions change shape near the mode-coupling crossover for colloidal liquids on a sphere.

The structure and dynamics of liquids on curved surfaces are often studied through the lens of frustration-based approaches to the glass transition. Competing glass transition theories, however, remain largely untested on such surfaces and moreover, studies hitherto have been entirely theoretical/numerical. Here we carry out single particle-resolved imaging of dynamics of bi-disperse colloidal liquids confined to the surface of a sphere. We find that mode-coupling theory well captures the slowing down of dynamics in the moderate to deeply supercooled regime. Strikingly, the morphology of cooperatively rearranging regions changed from string-like to compact near the mode-coupling crossover-a prediction unique to the random first-order theory of glasses. Further, we find that in the limit of strong curvature, Mermin-Wagner long-wavelength fluctuations are irrelevant and liquids on a sphere behave like three-dimensional liquids. A comparative evaluation of competing mechanisms is thus an essential step towards uncovering the true nature of the glass transition.

Role of particle orientational order during shear thickening in suspensions of colloidal rods.

Rheology of dense anisotropic colloidal suspensions often exhibits unsteady flow at constant imposed shear stress and/or shear rate. Using simultaneous high-resolution confocal microscopy and rheology, we find that the temporal behavior arises due to a strong coupling between shear flow and particle orientation. At smaller applied stresses, the orientation of rods fluctuates around the flow direction. A transition to an intermittent disordered state is observed at higher stresses when the angle between the flow and the rod orientation reaches a critical value. This disordered state is associated with transient drop in shear rate and an increase in viscosity. Simultaneous visualization of boundary stresses and orientation shows that the disordered regions lead to heterogeneous stresses and positive normal forces at the boundary, indicating the formation of systems spanning disordered particle contact networks.

Cooperative particle rearrangements facilitate the self-organized growth of colloidal crystal arrays on strain-relief patterns.

Strain-relief pattern formation in heteroepitaxy is well understood for particles with long-range attraction and is a routinely exploited organizational principle for atoms and molecules. However, for particles with short-range attraction such as colloids and nanoparticles, which form brittle assemblies, the mechanism(s) of strain-relief is not known. Here, we found that for colloids with short-range attraction, monolayer films on substrates with square symmetry could accommodate large compressive misfit strains through locally dewetted hexagonally ordered stripes. Unexpectedly, over a window of compressive strains, cooperative particle rearrangements first resulted in a periodic strain-relief pattern, which then guided the growth of laterally ordered defect-free colloidal crystals. Particle-resolved imaging of monomer dynamics on strained substrates also helped uncover cooperative kinetic pathways for surface transport. These processes, which substantially influenced the film morphology, have remained unobserved in atomic heteroepitaxy studies hitherto. Leaning on our findings, we developed a heteroepitaxy approach for fabricating hierarchically ordered surface structures.

Long-wavelength fluctuations and anomalous dynamics in 2-dimensional liquids.

In 2-dimensional systems at finite temperature, long-wavelength Mermin-Wagner fluctuations prevent the existence of translational long-range order. Their dynamical signature, which is the divergence of the vibrational amplitude with the system size, also affects disordered solids, and it washes out the transient solid-like response generally exhibited by liquids cooled below their melting temperatures. Through a combined numerical and experimental investigation, here we show that long-wavelength fluctuations are also relevant at high temperature, where the liquid dynamics do not reveal a transient solid-like response. In this regime, these fluctuations induce an unusual but ubiquitous decoupling between long-time diffusion coefficient D and structural relaxation time τ, where [Formula: see text], with [Formula: see text] Long-wavelength fluctuations have a negligible influence on the relaxation dynamics only at extremely high temperatures in molecular liquids or at extremely low densities in colloidal systems.

Strength of Mechanical Memories is Maximal at the Yield Point of a Soft Glass.

We show experimentally that both single and multiple mechanical memories can be encoded in an amorphous bubble raft, a prototypical soft glass, subject to an oscillatory strain. In line with recent numerical results, we find that multiple memories can be formed sans external noise. By systematically investigating memory formation for a range of training strain amplitudes spanning yield, we find clear signatures of memory even beyond yielding. Most strikingly, the extent to which the system recollects memory is largest for training amplitudes near the yield strain and is a direct consequence of the spatial extent over which the system reorganizes during the encoding process. Our study further suggests that the evolution of force networks on training plays a decisive role in memory formation in jammed packings.

Measurements of growing surface tension of amorphous-amorphous interfaces on approaching the colloidal glass transition.

There is mounting evidence indicating that relaxation dynamics in liquids approaching their glass transition not only become increasingly cooperative, but the relaxing regions also become more compact in shape. Of the many theories of the glass transition, only the random first-order theory-a thermodynamic framework-anticipates the surface tension of relaxing regions to play a role in deciding both their size and morphology. However, owing to the amorphous nature of the relaxing regions, even the identification of their interfaces has not been possible in experiments hitherto. Here, we devise a method to directly quantify the dynamics of amorphous-amorphous interfaces in bulk supercooled colloidal liquids. Our procedure also helped unveil a non-monotonic evolution in dynamical correlations with supercooling in bulk liquids. We measure the surface tension of the interfaces and show that it increases rapidly across the mode-coupling area fraction. Our experiments support a thermodynamic origin of the glass transition.

Site-specific colloidal crystal nucleation by template-enhanced particle transport.

The monomer surface mobility is the single most important parameter that decides the nucleation density and morphology of islands during thin-film growth. During template-assisted surface growth in particular, low surface mobilities can prevent monomers from reaching target sites and this results in a partial to complete loss of nucleation control. Whereas in atomic systems a broad range of surface mobilities can be readily accessed, for colloids, owing to their large size, this window is substantially narrow and therefore imposes severe restrictions in extending template-assisted growth techniques to steer their self-assembly. Here, we circumvented this fundamental limitation by designing templates with spatially varying feature sizes, in this case moiré patterns, which in the presence of short-range depletion attraction presented surface energy gradients for the diffusing colloids. The templates serve a dual purpose: first, directing the particles to target sites by enhancing their surface mean-free paths and second, dictating the size and symmetry of the growing crystallites. Using optical microscopy, we directly followed the nucleation and growth kinetics of colloidal islands on these surfaces at the single-particle level. We demonstrate nucleation control, with high fidelity, in a regime that has remained unaccessed in theoretical, numerical, and experimental studies on atoms and molecules as well. Our findings pave the way for fabricating nontrivial surface architectures composed of complex colloids and nanoparticles as well.

Localized Excitations and the Morphology of Cooperatively Rearranging Regions in a Colloidal Glass-Forming Liquid.

We develop a scheme based on a real space microscopic analysis of particle dynamics to ascertain the relevance of dynamical facilitation as a mechanism of structural relaxation in glass-forming liquids. By analyzing the spatial organization of localized excitations within clusters of mobile particles in a colloidal glass former and examining their partitioning into shell-like and corelike regions, we establish the existence of a crossover from a facilitation-dominated regime at low area fractions to a collective activated hopping-dominated one close to the glass transition. This crossover occurs in the vicinity of the area fraction at which the peak of the mobility transfer function exhibits a maximum and the morphology of cooperatively rearranging regions changes from stringlike to a compact form. Collectively, our findings suggest that dynamical facilitation is dominated by collective hopping close to the glass transition, thereby constituting a crucial step towards identifying the correct theoretical scenario for glass formation.