Alexander J. Wagner

Influence of Monolayer-Monolayer Coupling on the Phase Behavior of a Fluid Lipid Bilayer

We suggest a minimal model for the coupling of the lateral phase behavior in an asymmetric lipid membrane across its two monolayers. Our model employs one single order parameter for each monolayer leaflet, namely its composition. Regular solution theory on the mean-field level is used to describe the free energy in each individual leaflet. Coupling between monolayers entails an energy penalty for any local compositional differences across the membrane. We calculate and analyze the phase behavior of this model. It predicts a range of possible scenarios. A monolayer with a propensity for phase separation is able to induce phase separation in the apposed monolayer. Conversely, a monolayer without this propensity is able to prevent phase separation in the apposed monolayer. If there is phase separation in the membrane, it may lead to either complete or partial registration of the monolayer domains across the membrane. The latter case which corresponds to a three-phase coexistence is only found below a critical coupling strength. We calculate that critical coupling strength. Above the critical coupling strength, the membrane adopts a uniform compositional difference between its two monolayers everywhere in the membrane, implying phase coexistence between only two phases and thus perfect spatial registration of all domains on the apposed membrane leafs. We use the lattice Boltzmann simulation method to also study the morphologies that form during phase separation within the three-phase coexistence region. Generally, domains in one monolayer diffuse but remain fully enclosed within domains in the other monolayer.

Thermodynamic consistency of liquid-gas lattice Boltzmann simulations.

Lattice Boltzmann simulations have been very successful in simulating liquid-gas and other multiphase fluid systems. However, the underlying second-order analysis of the equation of motion has long been known to be insufficient to consistently derive the fourth-order terms that are necessary to represent an extended interface. These same terms are also responsible for thermodynamic consistency--i.e., to obtain a true equilibrium solution with both a constant chemical potential and a constant pressure. In this article we present an equilibrium analysis of nonideal lattice Boltzmann methods of sufficient order to identify those higher-order terms that lead to a lack of thermodynamic consistency. We then introduce a thermodynamically consistent forcing method.

Survey of morphologies formed in the wake of an enslaved phase-separation front in two dimensions

A phase-separation front will leave in its wake a phase-separated morphology that differs markedly from homogeneous phase-separation morphologies. For a purely diffusive system such a front, moving with constant velocity, will generate very regular, nonequilibrium structures. We present here a numerical study of these fronts using a lattice Boltzmann method. In two dimensions these structures are regular stripes or droplet arrays. In general the kind and orientation of the selected morphology and the size of the domains depends on the speed of the front as well as the composition of the material overtaken by the phase-separation front. We present a survey of morphologies as a function of these two parameters. We show that the resulting morphologies are initial condition dependent. We then examine which of the potential morphologies is the most stable. An analytical analysis for symmetrical compositions predicts the transition point from orthogonal to parallel stripes.

Symmetric free-energy-based multicomponent lattice Boltzmann method.

We present a lattice Boltzmann algorithm based on an underlying free energy that allows the simulation of the dynamics of a multicomponent system with an arbitrary number of components. The thermodynamic properties, such as the chemical potential of each component and the pressure of the overall system, are incorporated in the model. We derived a symmetrical convection diffusion equation for each component as well as the Navier Stokes equation and continuity equation for the overall system. The algorithm was verified through simulations of binary and ternary systems. The equilibrium concentrations of components of binary and ternary systems simulated with our algorithm agree well with theoretical expectations.

Electrostatic interactions across a charged lipid bilayer

We present theoretical work in which the degree of electrostatic coupling across a charged lipid bilayer in aqueous solution is analyzed on the basis of nonlinear Poisson–Boltzmann theory. In particular, we consider the electrostatic interaction of a single, large macroion with the two apposed leaflets of an oppositely charged lipid bilayer where the macroion is allowed to optimize its distance to the membrane. Three regimes are identified: a weak and a high macroion charge regime, separated by a regime of close macroion–membrane contact for intermediate charge densities. The corresponding free energies are used to estimate the degree of electrostatic coupling in a lamellar cationic lipid–DNA complex. That is, we calculate to what extent the one-dimensional DNA arrays in a sandwich-like lipoplex interact across the cationic membranes. We find that, in spite of the low dielectric constant inside a lipid membranes, there can be a significant electrostatic contribution to the experimentally observed cross-bilayer orientational ordering of the DNA arrays. Our approximate analytical model is complemented and supported by numerical calculations of the electrostatic potentials and free energies of the lamellar lipoplex geometry. To this end, we solve the nonlinear Poisson–Boltzmann equation within a unit cell of the lamellar lipoplex using a new lattice Boltzmann method.

Role of inertia in two-dimensional deformation and breakdown of a droplet.

We investigate by lattice Boltzmann methods the effect of inertia on the deformation and breakdown of stability of a two-dimensional fluid droplet surrounded by fluid of equal viscosity (in a confined geometry) whose shear rate is increased very slowly. We give evidence that in two dimensions inertia is necessary for the loss of stability, so that at zero Reynolds number there is always a stable stationary droplet shape. We identify two different routes to breakdown, via two-lobed and three-lobed structures and give evidence for a sharp transition between these routes as parameters are varied.

Enslaved phase-separation fronts in one-dimensional binary mixtures.

Phase-separation fronts leave in their wakes morphologies that are substantially different from the morphologies formed in homogeneous phase separation. In this paper we focus on fronts in binary mixtures that are enslaved phase-separation fronts, i.e., fronts that follow in the wake of a control-parameter front. In the one-dimensional case, which is the focus of this paper, the formed morphology is deceptively simple: alternating domains of a regular size. However, determining the size of these domains as a function of the front speed and other system parameters is a nontrivial problem. We present an analytical solution for the case where no material is deposited ahead of the front and numerical solutions and scaling arguments for more general cases. Through these enslaved phase-separation fronts large domains can be formed that are practically unattainable in homogeneous one-dimensional phase separation.

Pinning of domains for fluid–fluid phase separation in lipid bilayers with asymmetric dynamics

We propose a physical mechanism for the arrest of domain coarsening in a system of two apposed two-dimensional binary fluids. The two fluids are subject to a dynamic asymmetry: strong friction with the environment allows domains in one fluid layer (the “bottom” fluid) to grow only diffusively, whereas hydrodynamic flow leads to initially faster growth in the apposed fluid (the “top” layer). The two fluids are energetically coupled so that domains of similar type interact favorably across the two fluids. Using lattice Boltzmann simulations we observe that at a certain length scale, which is independent of the coarsening state in the bottom layer, domain growth in the top layer comes to an arrest. A phenomenological model suggests the pinning of domains across the two fluids to cause the arrest in domain growth. The pinning results from the interplay between line tension and domain coupling strength across the two fluids. We apply our model to a lipid bilayer for which we calculate the length scale of the dynamically arrested domains in the top layer. We find domain extensions of about or somewhat larger than 20 nm. Potential applications of our pinning model are to mixed lipid bilayers that tend to phase separate and are subject to a dynamic asymmetry; these include model membranes on a solid support and lipid rafts in the plasma membrane.

Fluctuating lattice Boltzmann method for the diffusion equation

We derive a fluctuating lattice Boltzmann method for the diffusion equation. The derivation removes several shortcomings of previous derivations for fluctuating lattice Boltzmann methods for hydrodynamic systems. The comparative simplicity of this diffusive system highlights the basic features of this first exact derivation of a fluctuating lattice Boltzmann method.

Lattice gas with molecular dynamics collision operator

We introduce a lattice gas implementation that is based on coarse-graining a molecular dynamics (MD) simulation. Such a lattice gas is similar to standard lattice gases, but its collision operator is informed by an underlying MD simulation. This can be considered an optimal lattice gas implementation because it allows for the representation of any system that can be simulated with MD. We show here that equilibrium behavior of the popular lattice Boltzmann algorithm is consistent with this optimal lattice gas. This comparison allows us to make a more accurate identification of the expressions for temperature and pressure in lattice Boltzmann simulations, which turn out to be related not only to the physical temperature and pressure but also to the lattice discretization. We show that for any spatial discretization, we need to choose a particular temporal discretization to recover the lattice Boltzmann equilibrium.