We reconsider the isothermal equation of state (EOS) for linear homopolymers in good solvents, $p=p(c,T)$, which relates the osmotic pressure $p$ of polymers with the bulk concentration $c$ and the temperature $T$. The classical scaling theory predicts the EOS in dilute and semidilute regimes. We suggest a generalized EOS that extends the universal behavior of polymer solutions up to the highly concentrated state and confirm it by molecular dynamics simulations and available experimental data. Our conjecture implies that properties of polymer chains dominate the EOS in the presence of many-body interactions. Our theoretical approach is based on a viral expansion in terms of concentration blobs leading to a superposition of two power laws in the regime of concentrated solutions.

A key ingredient within theories focusing on the rheology of entangled polymers is the way how the topological constraints of an entangled chain are lifted by unconstrained segments, i.e., how the constraining tube is dilated. This important question has been addressed by directly measuring the tube diameter $d$ at the scale of the tube by neutron spin echo spectroscopy. The tube diameter $d$ and plateau modulus $G_N^0$ of highly entangled polyethylene oxide (PEO) chains of volume fraction $c$ that are diluted by low molecular PEO show a concentration dependence $d\propto c^{a/2}$ and $G_N^0\propto c^{1+a}$ with an exponent $a$ close to $4/3$. This result allows the clear discrimination between different theoretical models that predict $4/3$ or other values between 1 and 2 and provides an important ingredient to tube model theories.

Molecular exchange processes are important equilibration and transport mechanisms in both synthetic and biological self-assembled systems such as micelles, vesicles, and membranes. Still, these processes are not entirely understood, in particular the effect of crystallinity and the interplay between cooperative melting processes and chain exchange. Here we focus on a set of simple polymer micelles formed by binary mixtures of poly(ethylene oxide)-mono-$n$-alkyl-ethers (${\mathrm{C}}_n\text{−}\mathrm{PEO}5$) which allows the melting point to be tuned over a wide range. We show that the melting transition is cooperative in the confined 4–5 nm micellar core, whereas the exchange process is widely decoupled and unimeric in nature. As confirmed by differential scanning calorimetry, the total activation energy for ejecting a molecule out of the micellar core below the melting point is the sum of the enthalpy of fusion and the corresponding activation energy in the melt state. This suggests that a “local, single-chain melting process” preludes the molecular diffusion out of the micelle during chain exchange.

The dynamics of an active walker in a harmonic potential is studied experimentally, numerically, and theoretically. At odds with usual models of self-propelled particles, we identify two dynamical states for which the particle condensates at a finite distance from the trap center. In the first state, also found in other systems, the particle points radially outward from the trap, while diffusing along the azimuthal direction. In the second state, the particle performs circular orbits around the center of the trap. We show that self-alignment, taking the form of a torque coupling the particle orientation and velocity, is responsible for the emergence of this second dynamical state. The transition between the two states is controlled by the persistence of the particle orientation. At low inertia, the transition is continuous. For large inertia, the transition is discontinuous and a coexistence regime with intermittent dynamics develops. The two states survive in the overdamped limit or when the particle is confined by a curved hard wall.

A long cylindrical cavity through a soft solid forms a soft microfluidic channel, or models a vascular capillary. We observe experimentally that, when such a channel bears a pressurized fluid, it first dilates homogeneously, but then becomes unstable to a peristaltic elastic instability. We combine theory and numerics to fully characterize the instability in a channel with initial radius $a$ through an incompressible bulk neo-Hookean solid with shear modulus $\mu$. We show instability occurs supercritically with wavelength $12.278\dots a$ when the cavity pressure exceeds $2.052\dots \mu$. In finite solids, the wavelength for peristalsis lengthens, with peristalsis ultimately being replaced by a long-wavelength bulging instability in thin-walled cylinders. Peristalsis persists in Gent strain-stiffening materials, provided the material can sustain extension by more than a factor of 6. Although naively a pressure driven failure mode of soft channels, the instability also offers a route to fabricate periodically undulating channels, producing, e.g., waveguides with photonic or phononic stop bands.

Asymmetric segregation of key proteins at cell division—be it a beneficial or deleterious protein—is ubiquitous in unicellular organisms and often considered as an evolved trait to increase fitness in a stressed environment. Here, we provide a general framework to describe the evolutionary origin of this asymmetric segregation. We compute the population fitness as a function of the protein segregation asymmetry $a$, and show that the value of $a$ which optimizes the population growth manifests a phase transition between symmetric and asymmetric partitioning phases. Surprisingly, the nature of phase transition is different for the case of beneficial proteins as opposed to deleterious proteins: a smooth (second order) transition from purely symmetric to asymmetric segregation is found in the former, while a sharp transition occurs in the latter. Our study elucidates the optimization problem faced by evolution in the context of protein segregation, and motivates further investigation of asymmetric protein segregation in biological systems.

We study the cyclization and relaxation dynamics of ideal as well as interacting polymers as a function of chain length $N$. For the cyclization time ${\tau }_{\mathrm{cyc}}$ of ideal chains we recover the known scaling ${\tau }_{\mathrm{cyc}}\sim N^2$ for different backbone models, for a self-avoiding slightly collapsed chain we obtain from Langevin simulations and scaling theory a modified scaling ${\tau }_{\mathrm{cyc}}\sim N^{5/3}$. The cyclization and relaxation dynamics of a finite-length collapsed chain scale differently; this unexpected dynamic multiscale behavior is rationalized by the crossover between swollen and collapsed chain behavior.

Nuclear magnetic resonance measurements of rotational and translational molecular dynamics are applied to characterize the nanoscale dynamic heterogeneity of a physically cross-linked solvent-polymer system above and below the glass transition temperature. Measured rotational dynamics identify domains associated with regions of solidlike and liquidlike dynamics. Translational dynamics provide quantitative length and timescales of nanoscale heterogeneity due to polymer network cross-link density. Mean squared displacement measurements of the solvent provide microrheological characterization of the system and indicate glasslike caging dynamics both above and below the glass transition temperature.

Rare earths, which are fundamental components of modern technologies, are often extracted from aqueous solutions using surfactants at oil-water interfaces. Heavier lanthanides are more easily extracted, even though all lanthanides are chemically very similar. Using x-ray fluorescence measurements and theoretical arguments, we show that there is a sharp bulk-concentration-dependent transition in the interfacial adsorption of cations from aqueous solutions containing ${\mathrm{Er}}^{3+}$ or ${\mathrm{Nd}}^{3+}$ in contact with a floating monolayer. The threshold bulk concentration of erbium ($Z=68$) is an order of magnitude lower than that of neodymium ($Z=60$), and erbium is preferentially adsorbed when the solution contains both ions. This implies that elemental selectivity during separation originates at the surfactant interface. Electrostatic effects arising from the interface dielectric mismatch, ionic correlations, and sizes of the ions explain the sharp adsorption curve and selectivity.

Symmetries are ubiquitous in network systems and have profound impacts on the observable dynamics. At the most fundamental level, many synchronization patterns are induced by underlying network symmetry, and a high degree of symmetry is believed to enhance the stability of identical synchronization. Yet, here we show that the synchronizability of almost any symmetry cluster in a network of identical nodes can be enhanced precisely by breaking its structural symmetry. This counterintuitive effect holds for generic node dynamics and arbitrary network structure and is, moreover, robust against noise and imperfections typical of real systems, which we demonstrate by implementing a state-of-the-art optoelectronic experiment. These results lead to new possibilities for the topological control of synchronization patterns, which we substantiate by presenting an algorithm that optimizes the structure of individual clusters under various constraints.

We find that the coupled interactions between protein and water polarization fluctuations play a dominant role in driving the configuration space random walk of solvated proteins. We perform atomistic molecular dynamics simulations on five proteins. Owing to a very low dielectric constant of protein, its dipolar groups experience forces from water along with local forces due to protein atoms. Energy fluctuations reveal a pronounced anticorrelation between protein and water contributions. The protein energy spectrum shows bimodal $1/f$ noise, which can be attributed to the influence of water on the dynamics of protein.

There is now growing evidence of the emergence and biological functionality of liquid crystal features, including nematic order and topological defects, in cellular tissues. However, how such features that intrinsically rely on particle elongation emerge in monolayers of cells with isotropic shapes is an outstanding question. In this Letter, we present a minimal model of cellular monolayers based on cell deformation and force transmission at the cell-cell interface that explains the formation of topological defects and captures the flow-field and stress patterns around them. By including mechanical properties at the individual cell level, we further show that the instability that drives the formation of topological defects, and leads to active turbulence, emerges from a feedback between shape deformation and active driving. The model allows us to suggest new explanations for experimental observations in tissue mechanics, and to propose designs for future experiments.

Sequence-dependent DNA conformation and flexibility play a fundamental role in the specificity of DNA-protein interactions. Here we quantify the DNA crookedness: a sequence-dependent deformation of DNA that consists of periodic bends of the base pair centers chain. Using extensive $100\mu \mathrm{s}$-long, all-atom molecular dynamics simulations, we found that DNA crookedness and its associated flexibility are bijective, which unveils a one-to-one relation between DNA structure and dynamics. This allowed us to build a predictive model to compute the stretch moduli of different DNA sequences from solely their structure. Sequences with very little crookedness show extremely high stretching stiffness and have been previously shown to form unstable nucleosomes and promote gene expression. Interestingly, the crookedness can be tailored by epigenetic modifications, known to affect gene expression. Our results rationalize the idea that the DNA sequence is not only a chemical code, but also a physical one that allows finely regulating its mechanical properties and, possibly, its 3D arrangement inside the cell.

The newborn mammalian cranial vault consists of five flat bones that are joined together along their edges by soft fibrous tissues called sutures. Early fusion of these sutures leads to a medical condition known as craniosynostosis. The mechanobiology of normal and craniosynostotic skull growth is not well understood. In a series of previous studies, we characterized and modeled radial expansion of normal and craniosynostotic (Crouzon) mice. Here, we describe a new modeling algorithm to simulate bone formation at the sutures in normal and craniosynostotic mice. Our results demonstrate that our modeling approach is capable of predicting the observed ex vivo pattern of bone formation at the sutures in the aforementioned mice. The same approach can be used to model different calvarial reconstruction in children with craniosynostosis to assist in the management of this complex condition.

The physics underlying hydrophobicity at macroscopic and microscopic levels is fundamentally distinct. However, experimentally quantifying the length scale dependence of hydrophobicity is challenging. Here we show that the size-dependent hydrophobic free energy of a collapsed polymer nanosphere can be continuously monitored from its single-molecule force-extension curve using a novel theoretical framework. The hydrophobic free energy shows a change from cubic to square dependence of the radius of the polymer nanosphere at a radius of $\sim 1\mathrm{nm}$—this is consistent with Lum-Chandler-Weeks theory and simulations. We can also observe a large variation of the hydrophobic free energy of each polymer nanosphere implying the heterogeneity of the self-assembled structures and/or the fluctuation of the water-polymer interface. We expect that our approach can be used to address many fundamental questions about hydrophobic hydration, which are otherwise inaccessible by ensemble measurements.

Using a dynamic variant of the Vicsek model, we show that the emergence of disorder from an orderly moving human crowd is a nonequilibrium first-order phase transition. We also show that this transition can be reversed by modifying the dynamics of a few agents, deemed as game changers. Surprisingly, the optimal placement of these game changers is found to be in regions of maximum local crowd speed. The presence of such game changers is effective owing to the discontinuous nature of the underlying phase transition. Thus our generic approach provides strategies to (i) delay crowd crush and (ii) design safe evacuation procedures, two aspects that are of paramount importance in maintaining safety of mass gatherings of people.

The transition between shear-flowing and shear-arrested states of frictional granular matter is studied using constant-stress discrete element simulations. By subjecting a dilute system of frictional grains to a constant external shear stress and pressure, friction-dependent critical shear stress and density are clearly identified with both exhibiting a crossover between low and high friction. The critical shear stress bifurcates two nonequilibrium steady states: (i) steady state shear flow characterized by a constant deformation rate, and (ii) shear arrest characterized by temporally decaying creep to a statically stable state. The onset of arrest below critical shear stress occurs at a time $t_c$ that exhibits a heavy-tailed distribution, whose mean and variance diverge as a power law at the critical shear stress with a friction-dependent exponent that also exhibits a crossover between low and high friction. These observations indicate that granular arrest near critical shear stress is highly unpredictable and is strongly influenced by interparticle friction.

Degradation processes in living systems often take place gradually by front propagation. An important context of such processes is loss of biological productivity in drylands or desertification. Using a dryland-vegetation model, we analyze the stability and dynamics of desertification fronts, identify linear and nonlinear front instabilities, and highlight the significance of these instabilities in inducing self-recovery. The results are based on the derivation and analysis of a universal amplitude equation for pattern-forming living systems for which nonuniform instabilities cannot emerge from the nonviable (zero) state. The results may therefore be applicable to other contexts of animate matter where degradation processes occur by front propagation.