Local vs. cooperative: Unraveling glass transition mechanisms with SEER.

Which phenomenon slows down the dynamics in supercooled liquids and turns them into glasses is a long-standing question of condensed matter. Most popular theories posit that as the temperature decreases, many events must occur in a coordinated fashion on a growing length scale for relaxation to occur. Instead, other approaches consider that local barriers associated with the elementary rearrangement of a few particles or "excitations" govern the dynamics. To resolve this conundrum, our central result is to introduce an algorithm, Systematic Excitation ExtRaction, which can systematically extract hundreds of excitations and their energy from any given configuration. We also provide a measurement of the activation energy, characterizing the liquid dynamics, based on fast quenching and reheating. We use these two methods in a popular liquid model of polydisperse particles. Such polydisperse models are known to capture the hallmarks of the glass transition and can be equilibrated efficiently up to millisecond time scales. The analysis reveals that cooperative effects do not control the fragility of such liquids: the change of energy of local barriers determines the change of activation energy. More generally, these methods can now be used to measure the degree of cooperativity of any liquid model.

Heterogeneous attenuation of sound waves in three-dimensional amorphous solids.

Sound waves are attenuated as they propagate in amorphous materials. We investigate the mechanism driving sound attenuation in the Rayleigh scattering regime by resolving the dynamics of an excited phonon in time and space via numerical simulations. We find sound attenuation is spatiotemporally heterogeneous. It starts in localized regions, which identify soft regions within the material and correlate with low-frequency vibrational modes. As time progresses, the regions where sound is primarily attenuated invade the system via an apparent diffusive process.

The Role of Receptor Uniformity in Multivalent Binding.

Multivalency is prevalent in various biological systems and applications due to the superselectivity that arises from the cooperativity of multivalent binding. Traditionally, it was thought that weaker individual binding would improve the selectivity in multivalent targeting. Here, using analytical mean field theory and Monte Carlo simulations, we discover that, for receptors that are highly uniformly distributed, the highest selectivity occurs at an intermediate binding energy and can be significantly greater than the weak binding limit. This is caused by an exponential relationship between the bound fraction and receptor concentration, which is influenced by both the strength and combinatorial entropy of binding. Our findings not only provide new guidelines for the rational design of biosensors using multivalent nanoparticles but also introduce a new perspective in understanding biological processes involving multivalency.

Mismatched ligand density enables ordered assembly of mixed-dimensional, cross-species materials.

The ordered coassembly of mixed-dimensional species-such as zero-dimensional (0D) nanocrystals and 2D microscale nanosheets-is commonly deemed impracticable, as phase separation almost invariably occurs. Here, by manipulating the ligand grafting density, we achieve ordered coassembly of 0D nanocrystals and 2D nanosheets under standard solvent evaporation conditions, resulting in macroscopic, freestanding hybrid-dimensional superlattices with both out-of-plane and in-plane order. The key to suppressing the notorious phase separation lies in hydrophobizing nanosheets with molecular ligands identical to those of nanocrystals but having substantially lower grafting density. The mismatched ligand density endows the two mixed-dimensional components with a molecular recognition-like capability, driving the spontaneous organization of densely capped nanocrystals at the interlayers of sparsely grafted nanosheets. Theoretical calculations reveal that the intercalation of nanocrystals can substantially reduce the short-range repulsions of ligand-grafted nanosheets and is therefore energetically favorable, while subsequent ligand-ligand van der Waals attractions induce the in-plane order and kinetically stabilize the laminate superlattice structure.

Hidden Order Beyond Hyperuniformity in Critical Absorbing States.

Disordered hyperuniformity is a description of hidden correlations in point distributions revealed by an anomalous suppression in fluctuations of local density at various coarse-graining length scales. In the absorbing phase of models exhibiting an active-absorbing state transition, this suppression extends up to a hyperuniform length scale that diverges at the critical point. Here, we demonstrate the existence of additional many-body correlations beyond hyperuniformity. These correlations are hidden in the higher moments of the probability distribution of the local density and extend up to a longer length scale with a faster divergence than the hyperuniform length on approaching the critical point. Our results suggest that a hidden order beyond hyperuniformity may generically be present in complex disordered systems.

Entropy-controlled cross-linking in linker-mediated vitrimers.

Recently developed linker-mediated vitrimers based on metathesis of dioxaborolanes with various commercially available polymers have shown both good processability and outstanding performance, such as mechanical, thermal, and chemical resistance, suggesting new ways of processing cross-linked polymers in industry, of which the design principle remains unknown [M. Röttger et al., Science 356, 62-65 (2017)]. Here we formulate a theoretical framework to elucidate the phase behavior of the linker-mediated vitrimers, in which entropy plays a governing role. We find that, with increasing the linker concentration, vitrimers undergo a reentrant gel-sol transition, which explains a recent experiment [S. Wu, H. Yang, S. Huang, Q. Chen, Macromolecules 53, 1180-1190 (2020)]. More intriguingly, at the low temperature limit, the linker concentration still determines the cross-linking degree of the vitrimers, which originates from the competition between the conformational entropy of polymers and the translational entropy of linkers. Our theoretical predictions agree quantitatively with computer simulations, and offer guidelines in understanding and controlling the properties of this newly developed vitrimer system.

Reverse Janssen Effect in Narrow Granular Columns.

When grains are added to a cylinder, the weight at the bottom is smaller than the total weight of the column, which is partially supported by the lateral walls through frictional interactions with the grains. This is known as the Janssen effect. Via a combined experimental and numerical investigation, here we demonstrate a reverse Jansen effect whereby the fraction of the weight supported by the base overcomes one. We characterize the dependence of this phenomenon on the various control parameters involved, rationalize the physical process causing the emergence of the compressional frictional forces responsible for the anomaly, and introduce a model to reproduce our findings. Contrary to prior assumptions, our results demonstrate that the constitutive relation on a material element can depend on the applied stress.

Hexatic phase in a model of active biological tissues.

In many biological processes, such as wound healing, cell tissues undergo an epithelial-to-mesenchymal transition, which is a transition from a more rigid to a more fluid state. Here, we investigate the solid/fluid transition of cell tissues within the framework of the self-propelled Voronoi model, which accounts for the deformability of the cells, for their many-body interactions, and for their polarized motility. The transition is controlled by two parameters, respectively accounting for the strength of the self-propelling force of the cells, and for the mechanical rigidity of the cells. We find the melting transition to occur via a continuous solid-hexatic transition followed by a continuous hexatic-liquid transition, as in the Kosterlitz, Thouless, Halperin, Nelson, and Young scenario. This finding indicates that the hexatic phase may have an unexpected biological relevance.

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.

Oscillatory Instabilities in Frictional Granular Matter.

Frictional granular matter is shown to be fundamentally different in its plastic responses to external strains from generic glasses and amorphous solids without friction. While regular glasses exhibit plastic instabilities due to the vanishing of a real eigenvalue of the Hessian matrix, frictional granular materials can exhibit a previously unnoticed additional mechanism for instabilities, i.e., the appearance of a pair of complex eigenvalues leading to oscillatory exponential growth of perturbations that are tamed by dynamical nonlinearities. This fundamental difference appears crucial for the understanding of plasticity and failure in frictional granular materials. The possible relevance to earthquake physics is discussed.

Rattler-induced aging dynamics in jammed granular systems.

Granular materials jam when developing a network of contact forces able to resist the applied stresses. Through numerical simulations of the dynamics of the jamming process, we show that the jamming transition does not occur when the kinetic energy vanishes. Rather, as the system jams, the kinetic energy becomes dominated by rattler particles, which scatter within their cages. The relaxation of the kinetic energy in the jammed configuration exhibits a double power-law decay, which we interpret in terms of the interplay between backbone and rattler particles.

Universal behaviour of the glass and the jamming transitions in finite dimensions for hard spheres.

We investigate the glass and the jamming transitions of hard spheres in finite dimensions d, through a revised cell theory, that combines the free volume and the Random First Order Theory (RFOT). Recent results show that in infinite dimension the ideal glass transition and jamming transitions are distinct, while based on our theory we argue that they indeed coincide for finite d. As a consequence, jamming results into a percolation transition described by RFOT, with a static length diverging with exponent ν = 2/d, which we verify through finite size scaling, and standard critical exponents α = 0, ß = 0 and γ = 2 independent on d.

Cage Size and Jump Precursors in Glass-Forming Liquids: Experiment and Simulations.

Glassy dynamics is intermittent, as particles suddenly jump out of the cage formed by their neighbors, and heterogeneous, as these jumps are not uniformly distributed across the system. Relating these features of the dynamics to the diverse local environments explored by the particles is essential to rationalize the relaxation process. Here we investigate this issue characterizing the local environment of a particle with the amplitude of its short time vibrational motion, as determined by segmenting in cages and jumps the particle trajectories. Both simulations of supercooled liquids and experiments on colloidal suspensions show that particles in large cages are likely to jump after a small time-lag, and that, on average, the cage enlarges shortly before the particle jumps. At large time-lags, the cage has essentially a constant size, which is smaller for longer-lasting cages. Finally, we clarify how this coupling between cage size and duration controls the average behavior and opens the way to a better understanding of the relaxation process in glass-forming liquids.

Effective antibodies immobilization and functionalized nanoparticles in a quartz-crystal microbalance-based immunosensor for the detection of parathion.

BACKGROUND: Biosensor-based detection provides a rapid and low-cost alternative to conventional analytical methods for revealing the presence of the contaminants in water as well as solid matrices. Although important to be detected, small analytes (few hundreds of Daltons) are an issue in biosensing since the signal they induce in the transducer, and specifically in a Quartz-Crystal Microbalance, is undetectable. A pesticide like parathion (M = 292 Da) is a typical example of contaminant for which a signal amplification procedure is desirable. METHODS/FINDINGS: The ballasting of the analyte by gold nanoparticles has been already applied to heavy target as proteins or bacteria to improve the limit of detection. In this paper, we extend the application of such a method to small analytes by showing that once the working surface of a Quartz-Crystal Microbalance (QCM) has been properly functionalized, a limit of detection lower than 1 ppb is reached for parathion. The effective surface functionalization is achieved by immobilizing antibodies upright oriented on the QCM gold surface by a simple photochemical technique (Photonic Immobilization Technique, PIT) based on the UV irradiation of the antibodies, whereas a simple protocol provided by the manufacturer is applied to functionalize the gold nanoparticles. Thus, in a non-competitive approach, the small analyte is made detectable by weighing it down through a "sandwich protocol" with a second antibody tethered to heavy gold nanoparticles. The immunosensor has been proved to be effective against the parathion while showing no cross reaction when a mixture of compounds very similar to parathion is analyzed. CONCLUSION/SIGNIFICANCE: The immunosensor described in this paper can be easily applied to any small molecule for which polyclonal antibodies are available since both the functionalization procedure of the QCM probe surface and gold nanoparticle can be applied to any IgG, thereby making our device of general application in terms of target analyte.

Escape rate and diffusion of a Stochastically Driven particle.

The dynamical properties of a tracer repeatedly colliding with heat bath particles can be described within a Langevin framework provided that the tracer is more massive than the bath particles, and that the collisions are frequent. Here we consider the escape of a particle from a potential well, and the diffusion coefficient in a periodic potential, without making these assumptions. We have thus investigated the dynamical properties of a Stochastically Driven particle that moves under the influence of the confining potential in between successive collisions with the heat bath. In the overdamped limit, both the escape rate and the diffusion coefficient coincide with those of a Langevin particle. Conversely, in the underdamped limit the two dynamics have a different temperature dependence. In particular, at low temperature the Stochastically Driven particle has a smaller escape rate, but a larger diffusion coefficient.

Emergence of linear elasticity from the atomistic description of matter.

We investigate the emergence of the continuum elastic limit from the atomistic description of matter at zero temperature considering how locally defined elastic quantities depend on the coarse graining length scale. Results obtained numerically investigating different model systems are rationalized in a unifying picture according to which the continuum elastic limit emerges through a process determined by two system properties, the degree of disorder, and a length scale associated to the transverse low-frequency vibrational modes. The degree of disorder controls the emergence of long-range local shear stress and shear strain correlations, while the length scale influences the amplitude of the fluctuations of the local elastic constants close to the jamming transition.

Simple and Flexible Model for Laser-Driven Antibody-Gold Surface Interactions: Functionalization and Sensing.

Interactions between biomolecules and between substrates and biomolecules is a crucial issue in physics and applications to topics such as biotechnology and organic electronics. The efficiency of bio- and mechanical sensors, of organic electronics systems, and of a number of other devices critically depends on how molecules are deposited on a surface so that these acquire specific functions. Here, we tackle this vast problem by developing a coarse grained model of biomolecules having a recognition function, such as antibodies, capable to quantitatively describe in a simple manner essential phenomena: antigen-antibody and antibody substrate interactions. The model is experimentally tested to reproduce the results of a benchmark case, such as (1) gold surface functionalization with antibodies and (2) antibody-antigen immune-recognition function. The agreement between experiments and model prediction is excellent, thus unveiling the mechanism for antibody immobilization onto metals at the nanoscale in various functionalization schemes. These results shed light on the geometrical packing properties of the deposited molecules, and may open the way to a novel coarse-grained based approach to describe other processes where molecular packing is a key issue with applications in a huge number of fields from nano- to biosciences.

Connecting short and long time dynamics in hard-sphere-like colloidal glasses.

Glass-forming materials are characterized by an intermittent motion at the microscopic scale. Particles spend most of their time rattling within the cages formed by their neighbors, and seldom jump to a different cage. In molecular glass formers the temperature dependence of the jump features, such as the average caging time and jump length, characterizes the relaxation processes and allows for a short-time prediction of the diffusivity. Here we experimentally investigate the cage-jump motion of a two-dimensional hard-sphere-like colloidal suspension, where the volume fraction is the relevant parameter controlling the slowing down of the dynamics. We characterize the volume fraction dependence of the cage-jump features and show that, as in molecular systems, they allow for a short time prediction of the diffusivity.

The first jamming crossover: geometric and mechanical features.

The jamming transition characterizes athermal systems of particles interacting via finite range repulsive potentials, and occurs on increasing the density when particles cannot avoid making contacts with those of their first coordination shell. We have recently shown [M. Pica Ciamarra and P. Sollich, e-print arXiv:1209.3334] that the same systems are also characterized by a series of jamming crossovers. These occur at higher volume fractions as particles are forced to make contact with those of subsequent coordination shells. At finite temperature, the crossovers give rise to dynamic and thermodynamic density anomalies, including a diffusivity anomaly and a negative thermal expansion coefficient. Density anomalies may therefore be related to structural changes occurring at the jamming crossovers. Here we elucidate these structural changes, investigating the evolution of the structure and of the mechanical properties of a jammed system as its volume fraction varies from the jamming transition to and beyond the first jamming crossover. We show that the first jamming crossover occurs at a well defined volume fraction, and that it induces a rearrangement of the force network causing a softening of the system. It also causes qualitative changes in the normal mode density of states and the spatial properties of the normal mode vectors.

High-order jamming crossovers and density anomalies.

We demonstrate that particles interacting via core-softened potentials exhibit a series of successive density anomalies upon isothermal compression, leading to oscillations in the diffusivity and thermal expansion coefficient, with the latter reaching negative values. These finite-temperature density anomalies are then shown to correspond to zero-temperature high-order jamming crossovers. These occur when particles are forced to come into contact with neighbours in successive coordination shells upon increasing the density. The crossovers induce anomalous behavior of the bulk modulus, which oscillates with density. We rationalize the dependence of these crossovers on the softness of the interaction potential, and relate the jamming crossovers and the anomalous diffusivity via the properties of the vibrational spectrum.