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Ziebert 2009 PRE Preprint

Ziebert 2009 PRE Preprint

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Effective zero-thickness model for a conductive membrane driven by an electric field
Falko Ziebert
1
, Martin Z. Bazant
2
, and David Lacoste
1
1
Laboratoire de Physico-Chimie Th´eorique - UMR CNRS Gulliver 7083,ESPCI, 10 rue Vauquelin, F-75231 Paris, France and 
2
Department of Chemical Engineering and Department of Mathematics,Massachusetts Institute of Technology, Cambridge, MA 02139, USA
(Dated: October 21, 2009)The behavior of a conductive membrane in a static (DC) electric field is investigated theoretically.An effective zero-thickness model is constructed based on a Robin-type boundary condition for theelectric potential at the membrane, originally developed for electrochemical systems. Within sucha framework, corrections to the elastic moduli of the membrane are obtained, which arise fromcharge accumulation in the Debye layers due to capacitive effects and electric currents through themembrane and can lead to an undulation instability of the membrane. The fluid flow surroundingthe membrane is also calculated, which clarifies issues regarding these flows sharing many similaritieswith flows produced by induced charge electro-osmosis (ICEO). Non-equilibrium steady states of the membrane and of the fluid can be effectively described by this method. It is both simpler,due to the zero thickness approximation which is widely used in the literature on fluid membranes,and more general than previous approaches. The predictions of this model are compared to recentexperiments on supported membranes in an electric field.
PACS numbers: 87.16.-b, 82.39.Wj, 05.70.Np
I. INTRODUCTION
Bilayer membranes formed from phospholipidmolecules are an essential component of the membranesof cells. The mechanical properties of equilibriummembranes are characterized by two elastic moduli, thesurface tension and the curvature modulus [1], whichtypically depend on the electrostatic properties of themembranes [2]. Understanding how these propertiesare modified when the membrane is driven out of equilibrium is a problem of considerable importance tothe physics of living cells. A membrane can be drivenout of equilibrium in many ways, for instance by ionconcentration gradients or electric fields, either appliedexternally or generated internally.The external application of electric fields on lipid filmsis used to produce artificial vesicles (by electroformation),as well as to create holes in the membrane (by electro-poration) [3]. Both processes are important for biotech-nological applications, they are widely used experimen-tally although they are still rather poorly understood.The generation of ion concentration gradients by inter-nal means is controlled in biological cells by membrane-bound ion pumps and channels, which play key roles inmany areas of biology [4].The non-equilibrium fluctuations of membranes in-cluding ion channels and pumps were first analyzed inRefs. [5, 6] by means of an hydrodynamic theory. Arti-ficially made active membranes inspired by these ideaswere then studied experimentally [7–9]. Several theo-retical studies followed, mainly motivated by the ques-tion of how to model non-equilibrium effects producedby protein conformation changes [10–13]. One limitationof existing active membrane models is that they do notdescribe electrostatic effects associated with ion trans-port in details. In previous papers by our group [14, 15],we have addressed this limitation by studying a theo-retical model for a membrane with a finite conductiv-ity transverse to the membrane plane (due for instanceto ion channels or pumps) using electrokinetic equations[16–19]. Our work complements Ref. [20], where the cor-rection to the elastic moduli of a membrane in a DCelectric field were calculated using an approach purelybased on electrostatics (no currents). It is also inspiredby Ref. [21] were a similar problem was considered us-ing electrokinetic equations. In contrast to these studies,our approach focuses on the non-equilibrium case, wherefurther corrections to the elastic moduli arise due to cur-rents through the membrane.In particular, a negative correction to the surface ten-sion arises due to capacitive effects, also called Lippmantension [22]. This negative tension leads to instabili-ties as can be understood from the high-salt limit [23].This lowering of the tension due to electrostatic or elec-trokinetic effects has been observed experimentally withsupported membranes subjected to an AC electric field[24] and in active membranes [9]. The resulting flowfields around the membrane are interpreted within theframework of ’induced charge electro-osmosis(ICEO)[19, 25, 26]. Similar flows within vesicles subject toAC electric fields have been observed experimentally andstudied theoretically [27–29]. These references describethe response of lipid vesicles to alternating fields in vari-ous medium conditions and report a rich panel of possiblebehaviors, which are found experimentally and throughtheoretical modeling.This paper extends previous work [14, 15], by provid-ing an effective zero-thickness membrane model that con-tains both capacitive effects and ionic currents. In a firstattempt [14], a zero-thickness membrane model has beenproposed with the boundary condition (BC) of zero elec-
 
2tric field at the membrane. Although the shape of thepotential was acceptable, the charge distribution had thewrong sign and the elastic moduli were orders of magni-tude too small. A model with finite membrane thicknessand dielectric constant has thus been considered in Ref.[15], leading to correct signs of the charge distributionand correct orders of magnitude of the elastic moduli.However, this model needed approximations and finallynumerical evaluations. In view of this, we present herean improved zero-thickness model, by using the more re-alistic BC of a dielectric interface sustaining Faradaiccurrents [30]. Although this Robin-type BC has beenintroduced in Ref. [15], its consequences were not devel-opped. In particular this model leads to simple analyticalexpressions for the corrections to the elastic constants of the membrane. The model clearly captures both non-equilibrium effects due to ion currents and equilibriumeffects, of capacitive nature. We also calculate the flowfield around the membrane, which has in fact the oppositesign as compared to the one of [15] for the zero-thicknesscase and is thus similar to standard ICEO flow fields.The effective zero-thickness model for a DC-field drivenconductive membrane is simple enough to be the startingpoint of more refined further studies.The work is organized as follows: in section II we de-scribe the equations for the charges in the electrolyte.A special emphasis is put on the boundary conditionswhich is the crucial point here. Then the base state so-lution corresponding to a flat membrane is calculated insection III. In section IV we calculate the leading or-der contributions to the electric and ion density fieldsfor a spatially modulated membrane height and analyzethe corresponding hydrodynamic flows around the mem-brane. Using the boundary conditions for the stress ten-sor at the membrane (which includes Maxwell and hydro-dynamic stresses), we calculate in section V the growthrate of membrane fluctuations. In section VI, our resultsare discussed and compared to previous calculations andto related experiments.
II. MODEL EQUATIONS
We consider a steady (DC) current driven by a voltage
 
between two electrodes at a fixed distance
, appliedto an initially flat membrane located initially at
= 0.The membrane is embedded in an electrolyte of mono-valent ions with densities
+
and
. The membranehas channels for both ion species but is itself neutral (nofixed charges at the membrane). The channels/pumpsare assumed to be homogeneously distributed in themembrane and enter only in the effective conductance
, as introduced below. For the effect of non-uniformdistributions of channels/pumps in membranes we referto Refs. [11, 31]. A point in the membrane is charac-terized by its Monge representation (valid in the limitof small undulations) by introducing a height function
(
r
), where
r
is a two-dimensional in-plane vector.In the electrolyte, the governing equation for the elec-tric potential
is Poisson’s equation
∂ 
2
=
1
(

+

.
(1)Here
is the elementary charge and
is the dielectricconstant of the electrolyte. For the sake of simplicity,we assume a symmetric 1 : 1 electrolyte, so that far awayfrom the membrane
+
=
=
. We also assume thatthe total system is electrically neutral.The densities of the ion species are assumed to obeythe Poisson-Nernst-Planck equations for a dilute solution
∂ 
±
+
∂ 
 
±
= 0
,
(2)with ionic current densities
 
±
=
∂ 
±
±
 ∂ 
,
(3)where
 
is the thermal energy. We have assumedthat both ion types have the same diffusion coefficient
, and neglected various corrections for concentrated so-lutions [32]. We consider a steady state situation anduse the Debye-H¨uckel approximation by linearizing theconcentrations
±
=
+

±
, leading to
∂ 
2
=
(

+

,
(4)
∂ 
∂ 

+

 ∂ 
= 0
,
(5)
∂ 
∂ 

+

 ∂ 
= 0
.
(6)For symmetric binary electrolytes, it is useful to intro-duce
half 
of the charge density [30, 33],
=

+

2
,
(7)as well as the average concentration of the two ionicspecies,
=

+
+

2
. The latter quantity turns outnot to be a relevant variable in the following since it isdecoupled from the field at small applied voltages [33].Moreover, since we have considered a steady state and asymmetric situation, there is no net particle current. Wealso define
 
=
+
 
2=
∂ 
+
2
 
,
(8)which represents half of the electric current density, andwe arrive at the equations
∂ 
2
=
2
,
(9)
∂ 
2
+
2
 ∂ 
2
= 0
.
(10)Insertion of Eq. (9) into Eq. (10) leads to
(
∂ 
2
2
= 0
,
(11)
 
3where
2
=2
2

 
(12)and
1
=
is the Debye length that defines the char-acteristic length scale for charge relaxation in the elec-trolyte.
A. Boundary conditions
At the electrodes located at
=
±
2
, we externallyimpose the voltage leading to
=
±
2
=
±
 
2
.
(13)This BC is oversimplified for real electrodes, since itneglects interfacial polarization across the double layerspassing Faradaic currents [30, 34], which makes the volt-age imposed across the electrolyte, outside the doublelayers, different from the applied voltage. Since we focuson the membrane dynamics, however, electrode polariza-tion is inconsequential, and the voltage
 
in the modelsimply serves as a means to apply a steady DC current,which could be directly measured or imposed in exper-iments testing our theory. We assume in the followingthat the distance between the electrodes is much largerthen the Debye length
=
1
. In that case, thebulk electrolyte is quasi-neutral,
+
=
=
, withnegligible charge density (compared to the total salt con-centration),
=
±
2
= 0
.
(14)Since the conductivity of a quasi-neutral electrolyte isconstant, the applied uniform current is equivalent to anapplied electric field far from the membrane.As we will see, the BC at the membrane is crucial torecover the correct physical behavior. In the simple zero-thickness model proposed in Ref. [14] the Neumann BC
∂ 
=0
= 0
,
(15)was used for the potential, corresponding to a vanishingelectric field at the membrane. Thus the dielectric mis-match between the electrolyte and the membrane wasaccounted for only approximatively. When compared tothe full finite thickness calculation, the agreement waspoor. To address this issue, a more general Robin-typeBC was introduced [15]
∂ 
=0+
=
∂ 
=0
=
(0
+
)
(0
)
.
(16)where
=
(17)is a length scale that contains the effective membranethickness
and the ratio of the dielectric constant of theelectrolyte,
, and of the membrane,
. This BC (withone side held at constant potential) was originally devel-oped for electrodes sustaining Faradaic current [30, 34–36] or charging capacitively [19, 33]. In that context theanalog of our membrane is a Stern monolayer of solventmolecules or a thin dielectric coating, such as a nativeoxide, on a metallic surface, and
is denoted
 
.The modified boundary condition (16) introduces anew dimensionless parameter [30],
 
=

=
=

/
=
 
 
(18)which plays a central role in our analysis below. For ablocking or “ideally polarizable” surface, which does notpass normal current and only allows capacitive chargingof the double layer, this parameter controls the relativeimportance of the capacitance of the surface (here, themembrane)
 
=
/
compared to that of the diffusepart of of the double layer,
 
=

. The BC (16) thenimplies that these capacitances are effectively coupled inseries in an equivalent-circuit representation of the dou-ble layer [33]. For a surface sustaining normal current,either by electron-transfer reactions at an electrode orby ionic flux through a membrane, the situation is morecomplicated. It can be shown that the same electrostaticBC (16) remains valid for a thin dielectric layer, as longas it has zero total free charge [32], which is typical formembranes containing a high density of fixed countercharge. However, the same parameter
 
no longer playsthe role of a capacitance ratio. Instead, it controls the ef-fect of diffuse charge on the normal current, the so-called“Frumkin correction” to reaction kinetics in electrochem-istry, reviewed in Ref. [34]. Two distinct regimes werefirst identified in Ref. [30] in the context of electrolyticcells and recently extended to galvanic cells [34]: (i) the“Helmholtz limit”
 
1, where most of the doublelayer voltage is dropped across the surface or membraneand the diffuse-layer has no effect on the current, and (ii)the “Gouy-Chapman limit”
 
1 where the diffuse layercarries all of the voltage and thus determines the current.In the Helmholtz limit, the Robin BC (16) reduces to theNeumann BC (15) used in Ref. [15], so that paper ana-lyzed the limit where the diffuse charge is small and haslittle effect on the current. In this paper we consider thegeneral case of finite
 
.
III. BASE STATE
The base state of the problem is a flat membrane.The electric field, assumed to be perfectly aligned in
-direction, is then perpendicular to the membrane. Thesystem is completely characterized by the electrostaticpotential
0
(
) (or by the field
 
0
(
) =
 
0
(
) =
∂ 
0
),by the steady-state ion distribution
0
(
), as well as by

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