Liquid-like State Research Articles

A self-organizing robotic aggregate using solid and liquid-like collective states.

Designing robotic systems that can change their physical form factor as well as their compliance to adapt to environmental constraints remains a major conceptual and technical challenge. To address this, we introduce the Granulobot, a modular system that blurs the distinction between soft, modular, and swarm robotics. The system consists of gear-like units that each contain a single actuator such that units can self-assemble into larger, granular aggregates using magnetic coupling. These aggregates can reconfigure dynamically and also split into subsystems that might later recombine. Aggregates can self-organize into collective states with solid- and liquid-like properties, thus displaying widely differing compliance. These states can be perturbed locally via actuators or externally via mechanical feedback from the environment to produce adaptive shape-shifting in a decentralized manner. This, in turn, can generate locomotion strategies adapted to different conditions. Aggregates can move over obstacles without using external sensors or coordinates to maintain a steady gait over different surfaces without electronic communication among units. The modular design highlights a physical, morphological form of control that advances the development of resilient robotic systems with the ability to morph and adapt to different functions and conditions.

Motion and teleportation of polar bubbles in low-dimensional ferroelectrics

Electric bubbles are sub-10nm spherical vortices of electric dipoles that can spontaneously form in ultra-thin ferroelectrics. While the static properties of electric bubbles are well established, little to nothing is known about the dynamics of these particle-like structures. Here, we reveal pathways to realizing both the spontaneous and controlled dynamics of electric bubbles in ultra-thin Pb(Zr0.4Ti0.6)O3 films. In low screening conditions, we find that electric bubbles exhibit thermally-driven chaotic motion giving rise to a liquid-like state. In the high screening regime, we show that bubbles remain static but can be continuously displaced by a local electric field. Additionally, we predict and experimentally demonstrate the possibility of bubble teleportation - a process wherein a bubble is transferred to a new location via a single electric field pulse of a PFM tip. Finally, we attribute the discovered phenomena to the hierarchical structure of the energy landscape.

A platform to induce and mature biomolecular condensates using chemicals and light.

Biomolecular condensates are membraneless compartments that impart spatial and temporal organization to cells. Condensates can undergo maturation, transitioning from dynamic liquid-like states into solid-like states associated with neurodegenerative diseases, including amyotrophic lateral sclerosis (ALS) and Huntington's disease. Despite their important roles, many aspects of condensate biology remain incompletely understood, requiring tools for acutely manipulating condensate-relevant processes within cells. Here we used the BCL6 BTB domain and its ligands BI-3802 and BI-3812 to create a chemical genetic platform, BTBolig, allowing inducible condensate formation and dissolution. We also developed optogenetic and chemical methods for controlled induction of condensate maturation, where we surprisingly observed recruitment of chaperones into the condensate core and formation of dynamic biphasic condensates. Our work provides insights into the interaction of condensates with proteostasis pathways and introduces a suite of chemical-genetic approaches to probe the role of biomolecular condensates in health and disease.

Recognition of supercritical CO2 liquid-like and gas-like molecules based on deep neural network

So far, it is still controversial about how to divide the liquid-like and gas-like states boundary and Widom delta, since the deviation of boundaries determined by different thermodynamic criteria increases significantly when away from the critical point. For this reason, a superior method that does not rely on thermodynamic criteria to define the boundary line between liquid-like and gas-like states needs to be proposed urgently and the recent extensive use of deep neural networks in molecular dynamics simulation provides a feasible choice. The present work attempts to determine a novel phase state boundary and Widom delta of supercritical CO2 from extracting the microstructure features of subcritical vapor and liquid states in equilibrium by deep neural network coupled with molecular dynamics simulation. In addition, visualization of simulated systems containing distinct liquid-like molecule ratio πLL of supercritical CO2 is also presented as well as the radial distribution function at different states. The results show that the novel boundary is located in the middle of the Widom lines constructed by multiple thermodynamic criteria. The lower boundary T- of the novel Widom delta agrees well with the theoretical boundary constructed by pseudo-boiling theory when it is close to the critical point but starts to deviate when it is far away from the critical point, while the upper boundary T+ of that is opposite. More importantly, the novel boundary and Widom delta constructed have no pressure upper limit compared to those constructed by thermodynamic criteria, only depending on πLL, which means that the novel boundary and Widom delta can extend to the supercritical deep region. Further, the visualization and radial distribution function of simulated systems of supercritical CO2 at different states provide the persistence of a liquid-like and a gas-like transition. The work conducted here can present novel microscopic insight into supercritical phase transition and provide another available alternative to define the Widom line.

Signatures of a Majorana-Fermi surface in the Kitaev magnet Ag3LiIr2O6

Detecting Majorana fermions in experimental realizations of the Kitaev honeycomb model is often complicated by non-trivial interactions inherent to potential spin liquid candidates. In this work, we identify several distinct thermodynamic signatures of massive, itinerant Majorana fermions within the well-established analytical paradigm of Landau-Fermi liquid theory. We find a qualitative and quantitative agreement between the salient features of our Landau-Majorana liquid theory and the Kitaev spin liquid candidate Ag3LiIr2O6. Our study presents strong evidence for a Fermi liquid-like ground state in the fundamental excitations of a honeycomb iridate, and opens new experimental avenues to detect itinerant Majorana fermions in condensed matter systems.

Quantum criticality at cryogenic melting of polar bubble lattices

Quantum fluctuations (QFs) caused by zero-point phonon vibrations (ZPPVs) are known to prevent the occurrence of polar phases in bulk incipient ferroelectrics down to 0 K. On the other hand, little is known about the effects of QFs on the recently discovered topological patterns in ferroelectric nanostructures. Here, by using an atomistic effective Hamiltonian within classical Monte Carlo (CMC) and path integral quantum Monte Carlo (PI-QMC), we unveil how QFs affect the topology of several dipolar phases in ultrathin Pb(Zr0.4Ti0.6)O3 (PZT) films. In particular, our PI-QMC simulations show that the ZPPVs do not suppress polar patterns but rather stabilize the labyrinth, bimeron and bubble phases within a wider range of bias field magnitudes. Moreover, we reveal that quantum fluctuations induce a quantum critical point (QCP) separating a hexagonal bubble lattice from a liquid-like state characterized by spontaneous motion, creation and annihilation of polar bubbles at cryogenic temperatures. Finally, we show that the discovered quantum melting is associated with anomalous physical response, as, e.g., demonstrated by a negative longitudinal piezoelectric coefficient.

Solid-to-liquid phase transition in the dissolution of cytosolic misfolded-protein aggregates

Accumulation of protein aggregates is a hallmark of cellular aging and degenerative disorders. This could result from either increased protein misfolding and aggregation or impaired dissolution of aggregates formed under stress, the latter of which is poorly understood. In this study, we employed quantitative live-cell imaging to investigate the dynamic process of protein disaggregation in yeast. We show that protein aggregates formed upon heat stress are solid condensates, but after stress attenuation these protein aggregates first transition into a liquid-like state during their dissolution. This solid-to-liquid phase transition (SLPT) accompanies the reduction in aggregate number due to the fusion of the liquid condensates. The chaperone activity of Hsp104, a Clp/HSP100 family chaperone, is required for both SLPT and subsequent dispersal of the liquid condensates. Sse1, a yeast HSP110 chaperone, also facilitates SLPT. These results illuminate an unexpected mechanistic framework of cellular control over protein disaggregation upon stress attenuation.

Inorganic Nanoparticles Embedded in Polydimethylsiloxane Nanodroplets.

To stabilize and transport them through complex systems, nanoparticles are often encapsulated in polymeric nanocarriers, which are tailored to specific environments. For example, a hydrophilic polymer capsule maintains the circulation and stability of nanoparticles in aqueous environments. A more highly designed nanocarrier might have a hydrophobic core and a hydrophilic shell to allow the transport of hydrophobic nanoparticles and pharmaceuticals through physiological media. Polydimethylsiloxane, PDMS, is a hydrophobic material in a liquid-like state at room temperature. The preparation of stable, aqueous dispersions of PDMS droplets in water is problematic due to the intense mismatch in surface energies between PDMS and water. The present work describes the encapsulation of hydrophobic metal and metal oxide nanoparticles within PDMS nanodroplets using flash nanoprecipitation. The PDMS is terminated by amino groups, and the nanodroplet is capped with a layer of poly(styrenesulfonate), forming a glassy outer shell. The hydrophobic nanoparticles nucleate PDMS droplet formation, decreasing the droplet size. The resulting nanocomposite nanodroplets are stable in aqueous salt solutions without the use of surfactants. The hierarchical structuring, elucidated with small-angle X-ray scattering, offers a new platform for the isolation and transport of hydrophobic molecules and nanoparticles through aqueous systems.

Chemorheology of a Si/Al > 3 Alkali Activated Metakaolin Paste through Parallel Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA).

Although geopolymers, as structural materials, should have superior engineering properties than traditional cementitious materials, they often need to improve their final characteristics' reproducibility due to the need for more control of the complex silico-aluminate decomposition and polymerisation stages. Thermosetting of a reactive geopolymeric paste involves tetrahedral Silicate and Aluminate precursor condensation into polyfunctional oligomers of progressively higher molecular weight, transforming the initial liquid into a gel and a structural solid. Viscosity and gelation control become particularly critical when the geopolymer is processed with 3D printing additive technology. Its physical state modification kinetics should match the flow and setting characteristics required by the deposition process. The reaction kinetics and the elastic and viscous characteristics preceding gelation and hardening have been investigated for an alkali-activated Metakaolin/Sodium Silicate-Sodium Hydroxide paste with a Si/Al ratio > 3. A chemoreological approach has been extended to these inorganic polymerisable systems, as already utilised for organic thermosetting polymers. Differential scanning calorimetry and Oscillatory DMA were carried out to monitor the advancement of the polymerisation reaction and the associated variations of the rheological viscoelastic properties. Dynamic thermal scans were run at 1 °C/min and a frequency of 10 Hz for the dynamic mechanical tests. The observed kinetics of polymerisation and variations of the elastic and viscous components of the complex viscosities and shear moduli are described in terms of polycondensation of linear and branched chains of oligomeric macromolecules of increasing complexity and molecular weight up to gelation (Gel1) and cross-linking of the gelled macrostructure (Gel2) and final glassy state. Geopolymerization can be allocated into two main behavioural zones: a viscoelastic liquid paste below 32.5% of reaction advancement and a viscoelastic solid above. Initial complex viscosities range from 2.3 ± 0.9 × 10-5 MPa*s to 6.8 ± 0.9 × 10-2 in the liquid-like state and from 1.9 ± 0.1 MPa to 9.6 ± 2.1 × 102 MPa in the solid-like state.

Depressurization of CO2 in a pipe: Effect of initial state on non-equilibrium two-phase flow

It is key in several industrial applications to accurately describe rapid depressurization of liquid and dense phase states. Examples include refrigeration systems, nuclear reactor cooling and CO2 capture and storage (CCS). It is expected that large-scale CO2 pipeline transportation must be deployed as a vital part of reaching net zero emissions by 2050. During rapid depressurization of liquid-like CO2, boiling will in many cases occur out of equilibrium, at a lower pressure than the local saturation pressure. Capturing the non-equilibrium effects is necessary to predict outflow rates and the resulting pressure and temperature inside the pipe. In the present work, we quantify the non-equilibrium effects by studying a series of CO2 pipe depressurization experiments from liquid-like states at initial temperatures from 10°C to 40°C. We compare the experimental results to predictions of the homogeneous equilibrium model (HEM) and a homogeneous relaxation-type non-equilibrium model (HRM*) where the mass-transfer rate from liquid to gas is tuned by a relaxation time. The relaxation time was found to decrease for increasing temperatures, and it was observed to be approximately 60 times longer for the coldest experiment than for the warmest one.

Analysis of Dynamical Peculiarities in Nanoalloys at Subsystems Level: Dynamical Degrees of Freedom, Temperature Differences and the Chameleon Effect.

A novel analysis of the dynamical behavior of nanoalloy systems, as represented by model Ni/Al 13-atom clusters, over a broad range of energies that cover the stage-wise transition of the systems from their solidlike to liquidlike state is presented. Conceptually, the analysis is rooted in partitioning the systems into judiciously chosen subsystems and characterizing the latter in terms of subsystem-specific dynamical descriptors that includedynamical degrees of freedom,root-mean-square bond-length fluctuation, andelement-specific subsystem temperature. The analysis reveals a host of new intriguing peculiarities in the dynamical behavior of the Ni/Al 13-mers, among which are what we call thechameleon effectand the difference in the temperatures of the Ni and Al subsystems at high energies, a difference that strongly depends on the cluster composition and also changes with energy. These do not have an analog in pure Ni13and Al13and are explained in terms of the coupled effects of the difference between the masses of the Ni and Al atoms (the mass effect) and of the difference in the anharmonicity of the overall interaction potential as experienced by the Ni and Al subsystems of the clusters (the potential effect).

Theoretical and experimental investigation on nonlinear dynamic of grain-beam system

We experimentally investigated the system of a simply supported beam immersed in a granular medium, which displays jump and new peaks in its amplitude-frequency curve under harmonic excitation. The relationship between the macroscopic nonlinear response and microscopic state of the granular medium was studied using the discrete element method. Using the dynamic modulus and vibrational density of states as indicators, we show that the granular medium changes from a solid-like to liquid-like state when the frequency increases to approach the jumping point. Considering the similarity between this system and acoustic metamaterial beams, an equivalent theoretical model was established for the former. Numerical results of the theoretical model were consistent with the experimental ones. It was revealed that the new peak and jump phenomena were caused by negative equivalent mass, negative equivalent stiffness of the granular medium and abrupt change in the additional stiffness cause by the jamming transition. This theoretical model is useful for studying the nonlinear dynamic characteristics of this coupled grain-beam system.

DYRK3 enables secretory trafficking by maintaining the liquid-like state of ER exit sites

The dual-specificity kinase DYRK3 controls the formation and dissolution of multiple biomolecular condensates, regulating processes including stress recovery and mitotic progression. Here, we report that DYRK3 functionally interacts with proteins associated with endoplasmic reticulum (ER) exit sites (ERESs) and that inhibition of DYRK3 perturbs the organization of the ERES-Golgi interface and secretory trafficking. DYRK3-mediated regulation of ERES depends on the N-terminal intrinsically disordered region (IDR) of the peripheral membrane protein SEC16A, which co-phase separates with ERES components to form liquid-like condensates on the surface of the ER. By modulating the liquid-like properties of ERES, we show that their physical state is essential for functional cargo trafficking through the early secretory pathway. Our findings support a mechanism whereby phosphorylation by DYRK3 and its reversal by serine-threonine phosphatases regulate the material properties of ERES to create a favorable physicochemical environment for directional membrane traffic in eukaryotic cells.

A novel SATB1 protein isoform with different biophysical properties.

Intra-thymic T cell development is coordinated by the regulatory actions of SATB1 genome organizer. In this report, we show that SATB1 is involved in the regulation of transcription and splicing, both of which displayed deregulation in Satb1 knockout murine thymocytes. More importantly, we characterized a novel SATB1 protein isoform and described its distinct biophysical behavior, implicating potential functional differences compared to the commonly studied isoform. SATB1 utilized its prion-like domains to transition through liquid-like states to aggregated structures. This behavior was dependent on protein concentration as well as phosphorylation and interaction with nuclear RNA. Notably, the long SATB1 isoform was more prone to aggregate following phase separation. Thus, the tight regulation of SATB1 isoforms expression levels alongside with protein post-translational modifications, are imperative for SATB1's mode of action in T cell development. Our data indicate that deregulation of these processes may also be linked to disorders such as cancer.

Hydrodynamic coupling melts acoustically levitated crystalline rafts

Going beyond the manipulation of individual particles, first steps have recently been undertaken with acoustic levitation in air to investigate the collective dynamical properties of many-body systems self-assembled within the levitation plane. However, these assemblies have been limited to two-dimensional, close-packed rafts where forces due to scattered sound pull particles into direct frictional contact. Here, we overcome this restriction using particles small enough that the viscosity of air establishes a repulsive streaming flow at close range. By tuning the particle size relative to the characteristic length scale for viscous streaming, we control the interplay between attractive and repulsive forces and show how particles can be assembled into monolayer lattices with tunable spacing. While the strength of the levitating sound field does not affect the particles' steady-state separation, it controls the emergence of spontaneous excitations that can drive particle rearrangements in an effectively dissipationless, underdamped environment. Under the action of these excitations, a quiescent particle lattice transitions from a predominantly crystalline structure to a two-dimensional liquid-like state. We find that this transition is characterized by dynamic heterogeneity and intermittency, involving cooperative particle movements that remove the timescale associated with caging for the crystalline lattice. These results shed light on the nature of athermal excitations and instabilities that can arise from strong hydrodynamic coupling among interacting particles.

Liquid-Like States in Micelle-Forming Diblock Copolymer Melts.

Large cell self-consistent field theory (SCFT) solutions for a neat, micelle-forming diblock copolymer melt, initialized using the structure of a Lennard-Jones fluid, reveal the existence of a vast number of liquid-like states, with free energies of order 10-3 kBT per chain higher than the body-centered cubic (bcc) state near the order-disorder transition (ODT). Computation of the structure factor for these liquids at temperatures below the ODT indicates that their intermicellar distance is slightly swollen compared to bcc. In addition to providing a mean-field picture of the disordered micellar state, the number of liquid-like states and their near-degeneracy with the equilibrium bcc morphology suggest that self-assembly of micelle-forming diblock copolymers navigates a rugged free energy landscape with many local minima. This picture provides a basis for the anomalously slow ordering kinetics of particle-forming diblock copolymer melts observed in experiments.

Dark quantum droplets and solitary waves in beyond-mean-field Bose-Einstein condensate mixtures

Quantum liquidlike states of matter have been realized in an ongoing series of experiments with ultracold Bose gases. Using a combination of analytical and numerical methods we identify the specific criteria for the existence of dark solitons in beyond-mean-field binary condensates, revealing how these excitations exist for both repulsive and attractive interactions, the latter leading to dark quantum droplets with properties intermediate between a dark soliton and a quantum droplet. The phenomenology of these excitations is explored within the full parameter space of the model, revealing a spatial profile of the excitation that differs significantly from the Zakharov-Shabat soliton, leading to a negative effective mass that is enhanced in the presence of the quantum fluctuations. Finally the dynamics of pairs of the excitations are explored, showing nonintegrable dynamics and dark soliton bound states in the attractive regime.

Phosphorylation sites are evolutionary checkpoints against liquid–solid transition in protein condensates

Assemblies of multivalent RNA-binding protein fused in sarcoma (FUS) can exist in the functional liquid-like state as well as less dynamic and potentially toxic amyloid- and hydrogel-like states. How could then cells form liquid-like condensates while avoiding their transformation to amyloids? Here, we show how posttranslational phosphorylation can provide a "handle" that prevents liquid-solid transition of intracellular condensates containing FUS. Using residue-specific coarse-grained simulations, for 85 different mammalian FUS sequences, we show how the number of phosphorylation sites and their spatial arrangement affect intracluster dynamics preventing conversion to amyloids. All atom simulations further confirm that phosphorylation can effectively reduce the β-sheet propensity in amyloid-prone fragments of FUS. A detailed evolutionary analysis shows that mammalian FUS PLDs are enriched in amyloid-prone stretches compared to control neutrally evolved sequences, suggesting that mammalian FUS proteins evolved to self-assemble. However, in stark contrast to proteins that do not phase-separate for their function, mammalian sequences have phosphosites in close proximity to these amyloid-prone regions. These results suggest that evolution uses amyloid-prone sequences in prion-like domains to enhance phase separation of condensate proteins while enriching phosphorylation sites in close proximity to safeguard against liquid-solid transitions.

A change in biophysical properties accompanies heterochromatin formation in mouse embryos.

The majority of our genome is composed of repeated DNA sequences that assemble into heterochromatin, a highly compacted structure that constrains their mutational potential. How heterochromatin forms during development and how its structure is maintained are not fully understood. Here, we show that mouse heterochromatin phase-separates after fertilization, during the earliest stages of mammalian embryogenesis. Using high-resolution quantitative imaging and molecular biology approaches, we show that pericentromeric heterochromatin displays properties consistent with a liquid-like state at the two-cell stage, which change at the four-cell stage, when chromocenters mature and heterochromatin becomes silent. Disrupting the condensates results in altered transcript levels of pericentromeric heterochromatin, suggesting a functional role for phase separation in heterochromatin function. Thus, our work shows that mouse heterochromatin forms membrane-less compartments with biophysical properties that change during development and provides new insights into the self-organization of chromatin domains during mammalian embryogenesis.

Insights into the CO2 Capture Characteristics within the Hierarchical Pores of Carbon Nanospheres Using Small-Angle Neutron Scattering.

Understanding adsorption processes at the molecular level has transformed the discovery of engineered materials for maximizing gas storage capacity and kinetics in adsorption-based carbon capture applications. In this work, we studied the molecular mechanism of gas (CO2, H2, methane, and ethane) adsorption inside an interconnected porous network of carbon. This was achieved by synthesizing novel macro-meso-microporous carbon (M3C) nanospheres with interconnected pore structures. The M3Cs showed a CO2 capture capacity of 5.3 mmol/g at atmospheric CO2 pressure, with excellent kinetics. This was due to fast CO2 adsorption within the interconnected hierarchical macro-meso-microporous M3C. In situ small-angle neutron scattering (SANS) under various CO2 pressures indicated that the macro- and mesopores of M3C enable fast diffusion of CO2 molecules inside the micropores, where adsorbed CO2 molecules densify into a liquid-like state. This strong densification of CO2 molecules causes fast CO2 diffusion in the macro- and mesopores of M3C, restarting the adsorption cycle for fresh CO2 molecules until all pores are completely filled. Notably, M3C also showed good capture capacities for hydrogen and various hydrocarbons, with excellent selectivity toward ethane over methane.