Thermal and non-thermal fluctuations in active polar gels

We discuss general features of noise and fluctuations in active polar gels close to and away from equilibrium. We use the single-component hydrodynamic theory of active polar gels built by Kruse and coworkers to describe the cytoskeleton in cells. Close to equilibrium, we calculate the response function of the gel to external fields and introduce Langevin forces in the constitutive equations with correlation functions respecting the fluctuation-dissipation theorem. We then discuss the breakage of the fluctuation-dissipation theorem due to an external field such as the activity of the motors. Active gels away from equilibrium are considered at the scaling level. As an example of application of the theory, we calculate the density correlation function (the dynamic structure factor) of a compressible active polar gel and discuss possible instabilities.     

Self-oscillations in chemoresponsive gels: a theoretical approach

Some gels can swell or shrink in function of the concentration of the solutes contained in the solvent. We develop and discuss an algorithm based on Stefan-Maxwell equations to study the dynamics of a sphere of chemoresponsive gel immersed in a medium kept far from equilibrium. We show that the coupling of the reaction with these volume changes creates some feedback that can lead to chemomechanical instabilities. As a result, a reaction that is not oscillatory in homogeneous conditions or in a nonresponsive gel can induce self-oscillations of volume and concentrations in a responsive gel. We also show that chemical oscillations related to long range activation can be strongly modified in such gels, even when the changes of volume are small.     

The kinetic spin-1 Blume-Capel model with Glauber dynamic

We study the dynamic phase transitions (DPT), within a mean-field approach, in the kinetic spin-1 Blume-Capel model by using the Glauber-type stochastic dynamics. The nature of the transition is characterized by investigating the behavior of the thermal variation of the dynamic order parameter and the Lyapunov exponent. The phase diagram is constructed in the temperatures (T) and single-ion anisotropy amplitude (D) plane. Our results predict first-order transitions at low temperature and large anisotropy strengths, which correspond in the phase diagram to the existence of a nonequilibrium tricritical point (TCP). We compare our results with the equilibrium phase diagram.     

Generic phase diagram of active polar films

We study theoretically the phase diagram of compressible active polar gels such as the actin network of eukaryotic cells. Using generalized hydrodynamics equations, we perform a linear stability analysis of the uniform states in the case of an infinite bidimensional active gel to obtain the dynamic phase diagram of active polar films. We predict, in particular, modulated flowing phases and a macroscopic phase separation at high activity. This qualitatively accounts for experimental observations of various active systems, such as actomyosin gels, microtubules and kinesins in vitro solutions, or swimming bacterial colonies.     

Critical voltages and blocking stresses in nematic gels

We present a model of the dynamics of director rotation in nematic gels under combined electro-mechanical loading. Focusing on a model specimen, we describe the critical voltages that must be exceeded to achieve director reorientation, and the blocking stresses that prevent alignment of the nematic director with the applied electric field. The corresponding phase diagram shows that the dynamic thresholds defined above are different from those predicted on the sole basis of energetics. Multistep loading programs are used to explore the energy landscape of our model specimen, showing the existence of multiple local minima under the same voltage and applied stress. This leads us to conclude that hysteresis should be expected in the electro-mechanical response of nematic gels.     

Static and time-dependent properties of polymer gels around the volume phase transition

Recent progress in the study of the volume phase transition of polymer gels is reviewed. The phenomenological theories of swelling equilibrium and phase transition of gels are summarized, and some basic experimental results on poly-N-isopropylacrylamide (NIPA) gels are compared with the prediction from these theories. Special attention is paid to the elastic properties of the gel network near the volume phase transition. The effect of external stresses on the swelling and the phase transition is analyzed. Some anomalous and unique characteristics revealed in NIPA gels such as shape- and size-dependent swelling and phase transition properties, curious phase coexistence, and domain structure are presented. Experimental results on some time-dependent phenomena such as phase separation, spinodal decomposition, and pattern formation are also presented and discussed. Some problems inherent to gels from biological bodies are briefly discussed.     

Magnetic resonance elastography and diffusion-weighted imaging of the sol/gel phase transition in agarose

The dynamics of the sol/gel phase transition in agarose was analyzed with magnetic resonance elastography (MRE) and diffusion-weighted imaging, providing complementary information on a microstructural as well as on a macroscopic spatial scale. In thermal equilibrium, the diffusion coefficient of agarose is linearly correlated with temperature, independent of the sol/gel phase transition. In larger agarose samples, the transition from the sol to the gel state was characterized by a complex position and temperature dependency of both MRE shear wave patterns and apparent diffusion coefficients (ADC). The position dependency of the temperature was experimentally found to be qualitatively similar to the behavior of the ADC maps. The dynamics of the temperature could be described with a simplified model that described the heat exchange between sol and gel compartments. The experiments supported the approach to derive temperature maps from the ADC maps by a linear relationship. The spatially resolved dynamics of the temperature maps were therefore employed to determine the elasticities. For this reason, experimental MRE data were simulated using a model of coupled harmonic oscillators. The calculated images agreed well with the experimentally observed MRE wave patterns.     

Static and dynamic heterogeneities in a model for irreversible gelation

We study the structure and the dynamics in the formation of irreversible gels by means of molecular dynamics simulation of a model system where the gelation transition is due to the random percolation of permanent bonds between neighboring particles. We analyze the heterogeneities of the dynamics in terms of the fluctuations of the self-intermediate scattering functions: in the sol phase close to the percolation threshold, we find that this dynamic susceptibility increases with the time until it reaches a plateau. At the gelation threshold this plateau scales as a function of the wave vector k as k(eta-2), with eta being related to the decay of the percolation pair connectedness function. At the lowest wave vector, approaching the gelation threshold it diverges with the same exponent gamma as the mean cluster size. These findings suggest an alternative way of measuring critical exponents in a system undergoing chemical gelation.     

Equilibrium cluster phases and low-density arrested disordered states: the role of short-range attraction and long-range repulsion

We study a model in which particles interact with short-ranged attractive and long-ranged repulsive interactions, in an attempt to model the equilibrium cluster phase recently discovered in sterically stabilized colloidal systems in the presence of depletion interactions. At low packing fractions, particles form stable equilibrium clusters which act as building blocks of a cluster fluid. We study the possibility that cluster fluids generate a low-density disordered arrested phase, a gel, via a glass transition driven by the repulsive interaction. In this model the gel formation is formally described with the same physics of the glass formation.     

Mri measurements of T1, T2 and D for gels undergoing volume phase transition

Gels consist of crosslinked polymer network swollen in solvent. The network of flexible long-chain molecules traps the liquid medium they are immersed in. Some gels undergo abrupt volume change, a phase transition process, by swelling-shrinking in response to external stimuli changes in solvent composition, temperature, pH, electric field, etc. We report that during volume phase transition changes of NMR longitudinal relaxation time T(1), NMR transverse relaxation time T(2), and diffusion coefficient D of the PMMA gel, and D of the NIPA gel. We describe how the gels were synthesized and the reason of using the snapshot FLASH imaging sequence to measure T(1), T(2), and D. Since T(1), T(2) and D maps have identical field of view and data are extracted from identical areas from their respective maps, these values can be correlated quantitatively on a pixel-by-pixel basis. Thus a complete set of NMR parameters is measured in-situ: the gels are in their natural state, immersed in the liquid, during the phase transition. The results of spectroscopic method agree with that of snapshot FLASH imaging method. For the PMMA gel T(1), T(2) and D decrease when gels undergo volume phase transition between deuterated acetone concentration of 30% and 40%. At its contracted state, T(1) is reduced to a little less than one order of magnitude, T(2) over two orders of magnitude, and D over one order of magnitude, smaller from values of PMMA gel at the swollen state. At an elevated temperature of 54 degrees C the thermosensitive NIPA gel is at a contracted state, with its D reduced to almost one order of magnitude smaller from that of the swollen NIPA at room temperature.     

Dynamical phase diagram of the random field Ising model

The stationary states of the random-field Ising model are determined through the master equation approach, where the contact with the heat bath is simulated by the Glauber stochastic dynamics. The phase diagram of the model is constructed from the stationary values of the magnetization as a function of temperature and field amplitude. The continuous phase transitions coincide with the equilibrium ones, while the first-order transitions occur at fields larger than the corresponding values at equilibrium. The difference between the fields at the limit of stability of the ordered phase and that of the equilibrium is maximum at zero temperature and vanishes at the tricritical point. We also find the mean field time auto-correlation function at the stationary states of the model. Received: 4 June 1997 / Revised: 5 August 1997 / Accepted: 10 November 1997     

A non-equilibrium Ising model of turbulence

We introduce a model of interacting lattices at different resolutions driven by the two-dimensional Ising dynamics with a nearest-neighbor interaction. We study this model both with tools borrowed from equilibrium statistical mechanics as well as non-equilibrium thermodynamics. Our findings show that this model keeps the signature of the equilibrium phase transition. The critical temperature of the equilibrium models corresponds to the state maximizing the entropy and delimits two out-of-equilibrium regimes, one satisfying the Onsager relations for systems close to equilibrium and one resembling convective turbulent states. Since the model preserves the entropy and energy fluxes in the scale space, it seems a good candidate for parametric studies of out-of-equilibrium turbulent systems.     

Thermo-sensitive N-n-propylacrylamide gels

Thermo-sensitive gels were prepared by irradiating aqueous solutions of poly(N-n-propylacrylamide) (NNPA) and its copolymers with acrylic acid (AA) with γ-rays from a ⁶⁰Co source. The equilibrium swelling volume of the gel in water was determined as a function of temperature. NNPA gel showed a discontinuous and reversible volume phase transition. The transition temperature and the volume change at the transition decreased with irradiation time. The transition temperature was approximately 12°C lower than that of poly(N-isopropylacrylamide) gel. A discontinuous volume transition was also observed in the copolymer gels of NNPA and AA. The dependence of the transition temperature on the concentration of carboxyl groups revealed a marked difference depending on whether they were protonated or dissociated. For gels having side groups of COONa, the transition temperature rose and the volume change at the transition was elevated as the COONa concentration increased. In contrast, an increase in the COOH concentration resulted in a decrease in the transition temperature. These results are discussed in terms of an equation of state constructed based on scaling theory.     

Interplay between spinodal decomposition and glass formation in proteins exhibiting short-range attractions

We investigate the competition between spinodal decomposition and dynamical arrest using aqueous solutions of the globular protein lysozyme as a model system for colloids with short-range attractions. We show that quenches below a temperature Ta lead to gel formation as a result of a local arrest of the protein-dense phase during spinodal decomposition. The rheological properties of these gels allow us to use centrifugation experiments to determine the local densities of both phases and to precisely locate the gel boundary and the attractive glass line close to and within the unstable region of the phase diagram.     

Phase transition in polymer gels due to local heating by illumination of light

The volume phase transition in gels induced by visible light and its related properties are presented, the mechanism of which is based on local heating of a polymer network by illumination of light. The gels consist of a covalently cross-linked copolymer network of thermosensitive N-isopropylacrylamide and a chromophore. Without light illumination, the gel volume changes sharply, but continuously at approximately 34°C when the temperature is varied. At a fixed temperature of an appropriate value, a discontinuous volume transition is observed when the light intensity is gradually changed. The phase transitions can be understood in terms of the temperature increment at the immediate vicinity of polymer chains due to the local heating via light absorption and subsequent thermal dissipation of light by the chromophore. The results can be qualitatively described by the Flory-Huggins mean-field equation of state of gels. In order to make clear the mechanism of the light-induced phase transition in the present system, we measured the light transmitting properties and the swelling as well as shrinking kinetics. These preliminary results are described semi-qualitatively by making use of a simple phenomenological model.     

Equilibrium swelling and mesoscopic structure of a diblock copolymer gel in a selective solvent

Our previous analytic model [A.I. Victorov, C.J. Radke, J.M. Prausnitz. Molec. Phys., 100, 2277 (2002)] of a block-copolymer gel swollen in selective solvent was obtained from self–consistent field theory in the strong–segregation approximation; it takes into account the structure of the gel on the mesoscopic scale but is restricted to the case where the solvent–selective polymer subchains are located in the inner (minority) domains. In this work, the model is generalized to include swollen outer domains. The dependence of the equilibrium microdomain size on solvent uptake has been established. We calculate equilibrium swelling and determine relative stabilities for gels of different morphologies. Predicted equilibrium profiles of polymer segments are compared with computer simulation. Based on the average–solvent–fraction approximation, results obtained for an athermal solvent are very close to those from equilibrium profiles. Attention is given to the effect of partial restrictions in self–assembly of polymer chains on microdomain spacing and on equilibrium swelling.     

Non-equilibrium behavior at a liquid-gas critical point

Second-order phase transitions in a non-equilibrium liquid-gas model with reversible mode couplings, i.e., model H for binary-fluid critical dynamics, are studied using dynamic field theory and the renormalization group. The system is driven out of equilibrium either by considering different values for the noise strengths in the Langevin equations describing the evolution of the dynamic variables (effectively placing these at different temperatures), or more generally by allowing for anisotropic noise strengths, i.e., by constraining the dynamics to be at different temperatures in d _|| - and d _⊥-dimensional subspaces, respectively. In the first, isotropic case, we find one infrared-stable and one unstable renormalization group fixed point. At the stable fixed point, detailed balance is dynamically restored, with the two noise strengths becoming asymptotically equal. The ensuing critical behavior is that of the standard equilibrium model H. At the novel unstable fixed point, the temperature ratio for the dynamic variables is renormalized to infinity, resulting in an effective decoupling between the two modes. We compute the critical exponents at this new fixed point to one-loop order. For model H with spatially anisotropic noise, we observe a critical softening only in the d _⊥-dimensional sector in wave vector space with lower noise temperature. The ensuing effective two-temperature model H does not have any stable fixed point in any physical dimension, at least to one-loop order. We obtain formal expressions for the novel critical exponents in a double expansion about the upper critical dimension d _c = 4 - d _|| and with respect to d _|| , i.e., about the equilibrium theory. Received 4 April 2002 Published online 13 August 2002     

Spreading of liquid drops on Agar gels

We study the spreading of pure water drops or water drops with surfactine (surfactant produced by bacteria Bacillus Subtilis) on gels (Agar/Water gel). We find that, surprisingly, the drops do not spread indefinitely, but remain in a state of partial wetting. Eventually the liquid diffuses into the gel on a time scale short with respect to evaporation times. The drops containing surfactant show a complex dynamics: at first the spreading velocity decreases, until the front stops and starts receding at about constant velocity. Concurrently, a second front detaches from the rim of the drop if the agar concentration is sufficiently low, and continues to move outwards.     

Fracture of a biopolymer gel as a viscoplastic disentanglement process

We present an extensive experimental study of mode-I, steady, slow crack dynamics in gelatin gels. Taking advantage of the sensitivity of the elastic stiffness to gel composition and history we confirm and extend the model for fracture of physical hydrogels which we proposed in a previous paper (Nature Mater. 5, 552 (2006)), which attributes decohesion to the viscoplastic pull-out of the network-constituting chains. So, we propose that, in contrast with chemically cross-linked ones, reversible gels fracture without chain scission.     

Polyelectrolyte gels in poor solvent: Elastic moduli

We study theoretically using scaling arguments the behavior of polyelectrolyte gels in poor solvents. Following the classical picture of Katchalsky, our approach is based on single-chain elasticity but it accounts for the recently proposed pearl necklace structure of polyelectrolytes in poor solvents. The elasticity both of gels at swelling equilibrium and of partially swollen gels is studied when parameters such as the ionic strength or the fraction of charged monomers are varied. Our theory could be useful to interpret recent experiments performed in Strasbourg that show that if identical gel samples are swollen to the same extent at different pH the sample with the highest charge has the lowest shear modulus. Received 7 April 2000