Fragility in glassy liquids: A structural approach based on machine learning.

The rapid rise of viscosity or relaxation time upon supercooling is a universal hallmark of glassy liquids. The temperature dependence of viscosity, however, is quite nonuniversal for glassy liquids and is characterized by the system's "fragility," with liquids with nearly Arrhenius temperature-dependent relaxation times referred to as strong liquids and those with super-Arrhenius behavior referred to as fragile liquids. What makes some liquids strong and others fragile is still not well understood. Here, we explore this question in a family of harmonic spheres that range from extremely strong to extremely fragile, using "softness," a structural order parameter identified by machine learning to be highly correlated with dynamical rearrangements. We use a support vector machine to identify softness as the same linear combination of structural quantities across the entire family of liquids studied. We then use softness to identify the factors controlling fragility.

Quantifying the link between local structure and cellular rearrangements using information in models of biological tissues.

Machine learning techniques have been used to quantify the relationship between local structural features and variations in local dynamical activity in disordered glass-forming materials. To date these methods have been applied to an array of standard (Arrhenius and super-Arrhenius) glass formers, where work on "soft spots" indicates a connection between the linear vibrational response of a configuration and the energy barriers to non-linear deformations. Here we study the Voronoi model, which takes its inspiration from dense epithelial monolayers and which displays anomalous, sub-Arrhenius scaling of its dynamical relaxation time with decreasing temperature. Despite these differences, we find that the likelihood of rearrangements can nevertheless vary by several orders of magnitude within the model tissue and extract a local structural quantity, "softness," that accurately predicts the temperature dependence of the relaxation time. We use an information-theoretic measure to quantify the extent to which softness determines impending topological rearrangements; we find that softness captures nearly all of the information about rearrangements that is obtainable from structure, and that this information is large in the solid phase of the model and decreases rapidly as state variables are varied into the fluid phase.

Glass Transition in Supercooled Liquids with Medium-Range Crystalline Order.

The origin of the rapid dynamical slowdown in glass forming liquids in the growth of static length scales, possibly associated with identifiable structural ordering, is a much debated issue. Growth of medium range crystalline order (MRCO) has been observed in various model systems to be associated with glassy behavior. Such observations raise the question of whether molecular mechanisms for the glass transition in liquids with and without MRCO are the same. In this study we perform extensive molecular dynamics simulations of a number of glass forming liquids and show that the static and dynamic properties of glasses with MRCO are different from those of other glass forming liquids with no predominant local order. We also resolve an important issue regarding the so-called point-to-set method for determining static length scales, and demonstrate it to be a robust method for determining static correlation lengths in glass formers.

Possible universal relation between short time ß-relaxation and long time α-relaxation in glass-forming liquids.

Relaxation processes in supercooled liquids are known to exhibit interesting complex behavior. One of the hallmarks of this relaxation process observed in the measured auto correlation function is the occurrence of multiple steps of relaxations. The shorter time relaxation is known as the ß-relaxation which is believed to be due to the motion of particles in the cage formed by their neighbors. The longer time relaxation is called the α-relaxation. The time scales of these two relaxations processes dramatically separate out with supercooling. In spite of decades of research, it is still not clearly known how these relaxation processes are related to each other. In this work, we show that there is a possible universal relation between short time ß-relaxation and long time α-relaxation. We also show that the proposed relation can be rationalized within random first order transition theory of glass transition if power law relation is assumed between static and dynamic length scales.

Block Analysis for the Calculation of Dynamic and Static Length Scales in Glass-Forming Liquids.

We present block analysis, an efficient method of performing finite-size scaling for obtaining the length scale of dynamic heterogeneity and the point-to-set length scale for generic glass-forming liquids. This method involves considering blocks of varying sizes embedded in a system of a fixed (large) size. The length scale associated with dynamic heterogeneity is obtained from a finite-size scaling analysis of the dependence of the four-point dynamic susceptibility on the block size. The block size dependence of the variance of the α relaxation time yields the static point-to-set length scale. The values of the obtained length scales agree quantitatively with those obtained from other conventional methods. This method provides an efficient experimental tool for studying the growth of length scales in systems such as colloidal glasses for which performing finite-size scaling by carrying out experiments for varying system sizes may not be feasible.

Minimal vertex model explains how the amnioserosa avoids fluidization during Drosophila dorsal closure.

Dorsal closure is a process that occurs during embryogenesis of Drosophila melanogaster . During dorsal closure, the amnioserosa (AS), a one-cell thick epithelial tissue that fills the dorsal opening, shrinks as the lateral epidermis sheets converge and eventually merge. During this process, the aspect ratio of amnioserosa cells increases markedly. The standard 2-dimensional vertex model, which successfully describes tissue sheet mechanics in multiple contexts, would in this case predict that the tissue should fluidize via cell neighbor changes. Surprisingly, however, the amnioserosa remains an elastic solid with no such events. We here present a minimal extension to the vertex model that explains how the amnioserosa can achieve this unexpected behavior. We show that continuous shrinkage of the preferred cell perimeter and cell perimeter polydispersity lead to the retention of the solid state of the amnioserosa. Our model accurately captures measured cell shape and orientation changes and predicts non-monotonic junction tension that we confirm with laser ablation experiments. Significance Statement: During embryogenesis, cells in tissues can undergo significant shape changes. Many epithelial tissues fluidize, i.e. cells exchange neighbors, when the average cell aspect ratio increases above a threshold value, consistent with the standard vertex model. During dorsal closure in Drosophila melanogaster , however, the amnioserosa tissue remains solid even as the average cell aspect ratio increases well above threshold. We introduce perimeter polydispersity and allow the preferred cell perimeters, usually held fixed in vertex models, to decrease linearly with time as seen experimentally. With these extensions to the standard vertex model, we capture experimental observations quantitatively. Our results demonstrate that vertex models can describe the behavior of the amnioserosa in dorsal closure by allowing normally fixed parameters to vary with time.

Minimal vertex model explains how the amnioserosa avoids fluidization during Drosophila dorsal closure.

Dorsal closure is a process that occurs during embryogenesis of Drosophila melanogaster. During dorsal closure, the amnioserosa (AS), a one-cell thick epithelial tissue that fills the dorsal opening, shrinks as the lateral epidermis sheets converge and eventually merge. During this process, the aspect ratio of amnioserosa cells increases markedly. The standard 2-dimensional vertex model, which successfully describes tissue sheet mechanics in multiple contexts, would in this case predict that the tissue should fluidize via cell neighbor changes. Surprisingly, however, the amnioserosa remains an elastic solid with no such events. We here present a minimal extension to the vertex model that explains how the amnioserosa can achieve this unexpected behavior. We show that continuous shrink-age of the preferred cell perimeter and cell perimeter polydispersity lead to the retention of the solid state of the amnioserosa. Our model accurately captures measured cell shape and orientation changes and predicts non-monotonic junction tension that we confirm with laser ablation experiments.

Understanding Slow and Heterogeneous Dynamics in Model Supercooled Glass-Forming Liquids.

Glasses are ubiquitous in nature. Many common items such as ketchups, cosmetic products, toothpaste, etc. and metallic glasses are examples of such glassy materials whose dynamical and rheological properties matter in our daily life. The dynamics of these glass-forming systems are known to be very sluggish and heterogeneous, but a detailed understanding of the origin of such slowing down is still lacking. Slow heterogeneous dynamics occur in a wide variety of systems at scales ranging from microscopic to macroscopic. Polymeric liquids, granular material, such as powder and sand, gels, and foams and also metallic alloys show such complex glassy dynamics at appropriate conditions. Recently, the existence of dynamical heterogeneity has also been found in biological systems starting from collective cell migration in a monolayer of cells to embryonic morphogenesis, cancer invasion, and wound healing. Extensive research in the past decade or so lead to the understanding that there are growing dynamic and static correlation lengths associated with the observed dynamical heterogeneity and rapid rise in viscosity. In this review, we have highlighted the recent developments on measuring these correlation lengths in glass-forming liquids and their possible implications in the physics of the glass transition.

Non-Gaussianity of the van Hove function and dynamic-heterogeneity length scale.

Non-Gaussian nature of the probability distribution of particles' displacements in the supercooled temperature regime in glass-forming liquids are believed to be one of the major hallmarks of glass transition. It has already been established that this probability distribution, which is also known as the van Hove function, shows universal exponential tail. The origin of such an exponential tail in the distribution function is attributed to the hopping motion of particles observed in the supercooled regime. The non-Gaussian nature can also be explained if one assumes that the system has heterogeneous dynamics in space and time. Thus exponential tail is the manifestation of dynamic heterogeneity. In this work we directly show that non-Gaussianity of the distribution of particles' displacements occur over the dynamic heterogeneity length scale and the dynamical behavior course grained over this length scale becomes homogeneous. We study the non-Gaussianity of the van Hove function by systematically coarse graining at different length scales and extract the length scale of dynamic heterogeneity at which the shape of the van Hove function crosses over from non-Gaussian to Gaussian. The obtained dynamic heterogeneity scale is found to be in very good agreement with the scale obtained from other conventional methods.

How Does a Hydrophobic Macromolecule Respond to a Mixed Osmolyte Environment?

The role of the protecting osmolyte trimethyl N-oxide (TMAO) in counteracting the denaturing effect of urea on a protein is quite well established. However, the mechanistic role of osmolytes on the hydrophobic interaction underlying protein folding is a topic of contention and is emerging as a key area of biophysical interest. Although recent experiments and computer simulations have established that an individual aqueous solution of TMAO and urea respectively stabilizes and destabilizes the collapsed conformation of a hydrophobic polymer, it remains to be explored how a mixed aqueous solution of protecting and denaturing osmolytes influences the conformations of the polymer. In order to bridge the gap, we have simulated the conformational behavior of both a model hydrophobic polymer and a synthetic polymer polystyrene in an aqueous mixture of TMAO and urea. Intriguingly, our free energy based simulations on both of the systems show that, even though a pure aqueous solution of TMAO stabilizes the collapsed or globular conformation of the hydrophobic polymer, addition of TMAO to an aqueous solution of urea further destabilizes the collapsed conformation of the hydrophobic polymer. We also observe that the extent of destabilization in a mixed osmolyte solution is relatively higher than that in pure aqueous urea solution. The reinforcement of the denaturation effect of the hydrophobic macromolecule in a mixed osmolyte solution is in stark contrast to the well-known counteracting role of TMAO in proteins under denaturing condition of urea. In both model and realistic systems, our results show that, in a mixed aqueous solution, a greater number of cosolutes preferentially bind to the extended conformation of the polymer relative to that in the collapsed conformation, thereby complying with the Tanford-Wyman preferential solvation theory disfavoring the collapsed conformation. The results are robust across a range of osmolyte concentrations and multiple cosolute force fields. Our findings unequivocally imply that the action of mixed osmolyte solution on hydrophobic polymer is significantly distinct from that of proteins.