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Register a new userTransport in polymer membranes beyond linear response: Controlling permselectivity by the driving force
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In the popular solution-diffusion picture, the membrane permeability is defined as the product of the partition ratio and the diffusivity of penetrating solutes inside the membrane in the linear response regime, i.e., in equilibrium. However, of practical importance is the penetrants flux across the membrane driven by external forces. Here, we study nonequilibrium membrane permeation orchestrated by a uniform external driving field using molecular computer simulations and continuum (Smoluchowski) theory in the stationary state. In the simulations, we explicitly resolve the penetrants transport across a finite monomer-resolved polymer network, addressing one-component penetrant systems and mixtures. We introduce and discuss possible definitions of nonequilibrium, force-dependent permeability, representing `system and `membrane permeability. In particular, we present for the first time a definition of the differential permeability response to the force. We demonstrate that the latter turns out to be significantly nonlinear for low-permeable systems, leading to a high amount of selectiveness in permeability, called `permselectivity, and is tunable by the driving force. Our continuum-level analytical solutions exhibit remarkable qualitative agreement with the penetrant- and polymer-resolved simulations, thereby allowing us to characterize the underlying mechanism of permeabilities and steady-state transport beyond the linear response level.
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We propose a `phase diagram for particulate systems that interact via purely repulsive contact forces, such as granular media and colloidal suspensions. We identify and characterize two distinct classes of behavior as a function of the input kinetic energy per degree of freedom $T_0$ and packing fraction deviation above and below jamming onset $Delta phi=phi - phi_J$ using numerical simulations of purely repulsive frictionless disks. Iso-coordinated solids (ICS) only occur above jamming for $Delta phi > Delta phi_c(T_0)$; they possess average coordination number equal to the isostatic value ($< z> = z_{rm iso}$) required for mechanically stable packings. ICS display harmonic vibrational response, where the density of vibrational modes from the Fourier transform of the velocity autocorrelation function is a set of sharp peaks at eigenfrequencies $omega_k^d$ of the dynamical matrix evaluated at $T_0=0$. Hypo-coordinated solids (HCS) occur both above and below jamming onset within the region defined by $Delta phi > Delta phi^*_-(T_0)$, $Delta phi < Delta phi^*_+(T_0)$, and $Delta phi > Delta phi_{cb}(T_0)$. In this region, the network of interparticle contacts fluctuates with $< z> approx z_{rm iso}/2$, but cage-breaking particle rearrangements do not occur. The HCS vibrational response is nonharmonic, {it i.e} the density of vibrational modes $D(omega)$ is not a collection of sharp peaks at $omega_k^d$, and its precise form depends on the measurement method. For $Delta phi > Delta phi_{cb}(T_0)$ and $Delta phi < Delta phi^*_{-}(T_0)$, the system behaves as a hard-particle liquid.
For a wide range of modern soft functional materials the selective transport of sub-nanometer-sized molecules (`penetrants) through a stimuli-responsive polymeric membrane is key to the desired function. In this study, we investigate the diffusion properties of penetrants ranging from non-polar to polar molecules and ions in a matrix of collapsed Poly(N-isopropylacrylamide) (PNIPAM) polymers in water by means of extensive molecular dynamics simulations. We find that the water distributes heterogeneously in fractal-like cluster structures embedded in the nanometer-sized voids of the polymer matrix. The nano-clustered water acts as an important player in the penetrant diffusion, which proceeds via a hopping mechanism through `wet transition states: the penetrants hop from one void to another via transient water channels opened by rare but decisive polymer fluctuations. The diffusivities of the studied penetrants extend over almost five orders of magnitude and thus enable a formulation of an analytical scaling relation with a clear non-Stokesian, exponential dependence of the diffusion coefficient on the penetrants radius for the uncharged penetrants. Charged penetrants (ions) behave differently as they get captured in large isolated water clusters. Finally, we find large energetic activation barriers for hopping, which significantly depend on the hydration state and thereby challenge available transport theories.
We study the driven translocation of polymers under time-dependent driving forces using $N$-particle Langevin dynamics simulations. We consider the force to be either sinusoidally oscillating in time or dichotomic noise with exponential correlation time, to mimic both plausible experimental setups and naturally occurring biological conditions. In addition, we consider both the case of purely repulsive polymer-pore interactions and the case with additional attractive polymer-pore interactions, typically occurring inside biological pores. We find that the nature of the interaction fundamentally affects the translocation dynamics. For the non-attractive pore, the translocation time crosses over to a fast translocation regime as the frequency of the driving force decreases. In the attractive pore case, because of a free energy well induced inside the pore, the translocation time can be a minimum at the optimal frequency of the force, the so-called resonant activation. In the latter case, we examine the effect of various physical parameters on the resonant activation, and explain our observations using simple theoretical arguments.
The uptake and sorption of charged molecules by responsive polymer membranes and hydrogels in aqueous solutions is of key importance for the development of soft functional materials. Here we investigate the partitioning of simple monoatomic (Na$^+$, K$^+$, Cs$^+$, Cl$^-$, I$^-$) and one molecular ion (4-nitrophenolate; NP$^-$) within a dense, electroneutral poly($N$-isopropylacrylamide) membrane using explicit-water molecular dynamics simulations. Inside the predominantly hydrophobic environment water distributes in a network of polydisperse water nanoclusters. The average cluster size determines the mean electrostatic self-energy of the simple ions, which preferably reside deeply inside them; we therefore find substantially larger partition ratios $Ksimeq>$10$^{-1}$ than expected from a simple Born picture using a uniform dielectric constant. Despite their irregular shapes we observe that the water clusters possess a universal negative electrostatic potential with respect to their surrounding, as is known for aqueous liquid-vapor interfaces. This potential, which we find concealed in cases of symmetric monoatomic salts, can dramatically impact the transfer free energies of larger charged molecules because of their weak hydration and increased affinity to interfaces. Consequently, and in stark contrast to the simple ions, the molecular ion NP$^-$ can have a partition ratio much larger than unity, $Ksimeq>$10-30 (depending on the cation type) or even $10^3$ in excess of monovalent salt, which explains recent observations of enhanced reaction kinetics of NP$^-$ reduction catalyzed within dense polymer networks. These results also suggest that ionizing a molecule can even enhance the partitioning in a collapsed, rather hydrophobic gel, which strongly challenges the traditional simplistic reasoning.
The complex interplay between the various attractive and repulsive forces that mediate between biological membranes governs an astounding array of biological functions: cell adhesion, membrane fusion, self-assembly, binding-unbinding transition among others. In this work, the entropic repulsive force between membranes---which originates due to thermally excited fluctuations---is critically reexamined both analytically and through systematic Monte Carlo simulations. A recent work by Freund cite {Freund13} has questioned the validity of a well-accepted result derived by Helfrich cite{Helfrich78}. We find that, in agreement with Freund, for small inter-membrane separations ($d$), the entropic pressure scales as $psim 1/d $, in contrast to Helfrichs result: $psim 1/d^3$. For intermediate separations, our calculations agree with that of Helfrich and finally, for large inter-membrane separations, we observe an exponentially decaying behavior.
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