Effects of counterion fluctuations in a polyelectrolyte brush

We investigate the effect of counterion fluctuations in a single polyelectrolyte brush in the absence of added salt by systematically expanding the counterion free energy about Poisson-Boltzmann mean-field theory. We find that for strongly charged brushes, there is a collapse regime in which the brush height decreases with increasing charge on the polyelectrolyte chains. The transition to this collapsed regime is similar to the liquid-gas transition, which has a first-order line terminating at a critical point. We find that, for monovalent counterions, the transition is discontinuous in theta solvent, while for multivalent counterions, the transition is generally continuous. For collapsed brushes, the brush height is not independent of grafting density as it is for osmotic brushes, but scales linear with it.Received: 26 November 2003, Published online: 11 May 2004PACS: 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling - 61.20.Qg Structure of associated liquids: electrolytes, molten salts, etc.     

Macroions in salty water with multivalent ions: giant inversion of charge

Screening of a strongly charged macroion by oppositely charged colloidal particles, micelles, or short polyelectrolytes is considered. Because of strong lateral repulsion such multivalent counterions form a strongly correlated liquid at the surface of the macroion. This liquid provides correlation-induced attraction of multivalent counterions to the macroion surface. As a result even a moderate concentration of multivalent counterions in the solution inverts the sign of the net macroion charge. We show that at high concentration of monovalent salt the absolute value of inverted charge can be larger than the bare one. This giant inversion of charge can be observed in electrophoresis.     

Strong attraction between charged spheres due to metastable ionized states

We report a mechanism which can lead to long-range attractions between like-charged spherical macroions, stemming from the existence of metastable ionized states. We show that the ground state of a single highly charged colloid plus a few excess counterions is overcharged. For the case of two highly charged macroions in their neutralizing divalent counterion solution we demonstrate that, in the regime of strong Coulomb coupling, the counterion clouds are very likely to be unevenly distributed, leading to one overcharged and one undercharged macroion. This long-living metastable configuration in turn leads to a long-range Coulomb attraction.     

Direct observation of counterion organization in F-actin polyelectrolyte bundles

Attractions between like-charged polyelectrolytes have been observed in a variety of systems (W.M. Gelbart, R.F. Bruinsma, P.A. Pincus, V.A. Parsegian, Phys. Today 53, September issue, 38 (2000)). Recent biological examples include DNA, filamentous viruses, and F-actin. Theoretical investigations on idealized systems indicate that counterion correlations play a central role, but no experiments that specifically probe such correlations have been performed. Using synchrotron X-ray diffraction, we have directly observed the organization of multivalent ions on cytoskeletal filamentous actin (a well-defined biological polyelectrolyte) and found an unanticipated symmetry-breaking collective counterion mechanism for generating attractions. Surprisingly, the counterions do not form a lattice that simply follows actins helical symmetry; rather, the counterions organize into frozen ripples parallel to the actin filaments and form structures reminiscent of charge density waves. Moreover, these 1D counterion charge density waves form a coupled mode with twist deformations of the oppositely charged actin filaments. This counterion organization is not sensitive to thermal fluctuations in temperature range accessible to protein-based polyelectrolyte systems. Moreover, the counterion density waves are pinned to the spatial periodicity of charges on the actin filament even if the global filament charge density is varied, indicating the importance of charge periodicity on the polyelectrolyte substrate.     

Simple model for attraction between like-charged polyions

We present a simple model for the possible mechanism of appearance of attraction between like charged polyions inside a polyelectrolyte solution. The attraction is found to be short ranged, and exists only in the presence of multivalent counterions. It is produced by the correlations in layers of condensed counterions surrounding each polyion and is only weakly temperature dependent. We find the attraction to be maximum at zero temperature and dimish as the temperature is raised. The attraction is only possible if the number of condensed counterions exceeds the threshold, , where is the valence of counterions and Z is the polyion charge. Received 10 March 1999 and Received in final form 20 April 1999     

带电聚合电介质表面吸附理论研究

应用聚合电介质吸附的定标理论,根据介质和表面电介质常数的比率,考虑多化合价吸附电介质之间强相关性作用,我们提出一种表面排斥电荷的近似定标理论方法,根据这种方法把电介质表面吸附层的相图分为本质上不同的两大类。从相图可知：当表面电荷密度低（或体带相反电荷离子密度高）,这时表面和体带相反电荷离子密度几乎相同;一旦表面电荷密度足够高,就使带相反电荷的离子在表面上浓缩。据此,可确定在这个区域内,低化合价聚合电介质形成一个相关的多链状态,当化合价足够高时,由于近邻链之间的更强排斥增强,使状态转变成单链。     

带电聚合电介质表面吸附理论研究

摘要：应用聚合电介质吸附的定标理论,根据介质和表面电介质常数的比率,考虑多化合价吸附电介质之间强相关性作用,我们提出一种表面排斥电荷的近似定标理论方法,根据这种方法把电介质表面吸附层的相图分为本质上不同的两大类。从相图可知：当表面电荷密度低（或体带相反电荷离子密度高）,这时表面和体带相反电荷离子密度几乎相同;一旦表面电荷密度足够高,就使带相反电荷的离子在表面上浓缩。据此,可确定在这个区域内,低化合价聚合电介质形成一个相关的多链状态,当化合价足够高时,由于近邻链之间的更强排斥增强,使状态转变成单链。     

Ion multivalence and like-charge polyelectrolyte attraction

It is known empirically that multivalent ions generate attractions between like-charged polyelectrolytes, with different valence requirements for different systems. How multivalent must an ion be before it can condense a given polyelectrolyte? Using charge-tunable M13 virus rods and a family of artificial homologous "dumbbell" divalent ions of different sizes, we have constructed a multivalent ion-polyelectrolyte phase diagram, and find an experimentally motivated general criterion for like-charged attraction based on the ion valence, ion size, and the Gouy-Chapman length.     

Attraction of like-charged macroions in the strong-coupling limit

Like-charged macroions attract each other as a result of strong electrostatic correlations in the presence of multivalent counterions or at low temperatures. We investigate the effective electrostatic interaction between i) two like-charged rods and ii) two like-charged spheres using the recently introduced strong-coupling theory, which becomes asymptotically exact in the limit of large coupling parameter (i.e. for large counterion valency, low temperature, or high surface charge density on macroions). In contrast to previous applications of the strong-coupling theory, we deal with curved surfaces and an additional parameter, referred to as Manning parameter, is introduced, which measures the ratio between the radius of curvature of macroions to the Gouy-Chapman length. This parameter, together with the size of the confining box enclosing the two macroions and their neutralizing counterions, controls the counterion-condensation process that directly affects the effective interactions. For sufficiently large Manning parameters (weakly-curved surfaces), we find a strong long-ranged attraction between two macroions that form a closely-packed bound state with small surface-to-surface separation of the order of the counterion diameter in agreement with recent simulations results. For small Manning parameters (highly-curved surfaces), on the other hand, the equilibrium separation increases and the macroions unbind from each other as the confinement volume increases to infinity. This occurs via a continuous universal unbinding transition for two charged rods at a threshold Manning parameter of , while the transition is strongly discontinuous for spheres because of a pronounced potential barrier at intermediate distances. Unlike the cylindrical case, the attractive forces between spheres disappear slowly for increasing confinement volume due to the complete de-condensation of counterions. Scaling arguments suggest that for moderate values of coupling parameter, strong-coupling predictions remain valid for sufficiently small surface-to-surface separations.Received: 20 August 2003, Published online: 2 March 2004PACS: 87.15.-v Biomolecules: structure and physical properties - 82.70.Dd Colloids - 87.15.Nn Properties of solutions; aggregation and crystallization of macromolecules     

Binding of similarly charged plates with counterions only

Similarly and highly charged plates in the presence of multivalent counterions attract each other and form electrostatically bound states. Using Monte-Carlo simulations, we obtain the interplate pressure in the global parameter space. The equilibrium plate separation, where the pressure changes from attractive to repulsive, exhibits a novel unbinding transition. A systematic and asymptotically exact strong-coupling field theory yields the bound state from a competition between counterion entropy and electrostatic attraction, in agreement with simple scaling arguments and simulations.     

Reentrant condensation of proteins in solution induced by multivalent counterions

Negatively charged globular proteins in solution undergo a condensation upon adding trivalent counterions between two critical concentrations C and C, C 相似文献   

Scaling Theory of Strongly Charged Cylindrical Polyelectrolyte Brushes

Scaling theory of charged cylindrical polyelectrolyte brushes is developed. The dependence of brush thickness on the grafting density, charge fraction, and chain length is analyzed. A full phase diagram is established. Characteristics and boundaries between different regimes of cylindrical polyelectrolyte brushes are summarized. Special attentions are paid to electrostatic interaction induced stiffening and counterion condensation effects. If the Bjerrum length of the solution is larger than the Kuhn length of the polyelectrolyte chains, counterion condensation occurs in the strongly charged polyelectrolyte brushes. On the contrary, the electrostatic interaction stretches the strongly charged grafted polyelectrolyte chains to their contour length.     

Salt-induced collapse and reexpansion of highly charged flexible polyelectrolytes

We study the salt-dependent conformations of dilute flexible polyelectrolytes in solution via computer simulations. Low concentrations of multivalent salt induce the known conformational collapse of individual polyelectrolyte chains, but as the salt concentration is increased further this is followed by a reexpansion. We explicitly demonstrate that multivalent counterions can overcompensate the bare charge of the chain in the reexpansion regime. Both the degree of reexpansion and the occurrence of overcharging sensitively depend on ion size. Our findings are relevant for a wide range of salt-induced complexation phenomena.     

Effects of ionic strength and charge annealing in star-branched polyelectrolytes

We have developed a scaling theory that describes the conformations of weak star-branched polyelectrolytes in dilute solutions. The dependences of the overall star size on the number of branches and on the ionic strength of the solution (tuned by the addition of low molecular weight salt) are analyzed. The intrinsic structure of the polyelectrolyte stars in salt-free and salt-added solutions is discussed in terms of concentration and elastic blobs. In contrast to neutral stars, the swollen corona of the polyelectrolyte star consists of blobs which are not closely packed. We have shown that the size of star polyelectrolytes is less sensitive to the variation in the ionic strength than the size of linear polyelectrolytes. The effects of the ionization-recombination balance in the star polyelectrolyte were taken into account. For polyelectrolytes with small ionization constant, the size of the star depends nonmonotonically on the number of branches and on the ionic strength of the solution due to recombination of counterions with charged monomers. Received: 10 November 1997 / Revised: 16 February 1998 / Accepted: 1st April 1998     

Fluctuation-induced forces in and out of equilibrium

In a fluctuating medium of quantum, thermal, or non-thermal origin, an interaction is induced between external objects that modify the fluctuations. These interactions can appear in a vast variety of systems, leading to a plethora of interesting phenomena. Notable examples of these include: (1) like-charge attraction in the presence of multivalent counterions, (2) Ludwig-Soret effect in charged colloids, (3) mass renormalization of moving defects in a phononic background and moving metallic objects in EM quantum vacuum, and (4) dissipation due to motion-induced radiation. The fluctuationinduced forces are statistical in nature, and this could make their measurement very difficult, because the actual value of the force might deviate most of the time from the predicted average value.     

A counterion condensation theory for the relaxation,rise, and frequency dependence of the parallel polarization of rodlike polyelectrolytes

We calculate the relaxation, rise, and frequency dependence of the parallel polarization of counterions condensed on rodlike polyelectrolytes and charged colloids. Emphasis is placed on an effective counterion mobility along the rod as strongly influenced by electrostatic interactions.     

Counterion distribution in a spherical charged sparse brush

The counterion distribution within a spherical polyelectrolyte sparse brush was measured by small-angle X-ray scattering using contrast variation with different counterions by means of ion dialysis. The brush was made by self-association of charged diblock copolymers. Thanks to the contrast variation method, we were able to separate the signal due to the monomers and the signal due to the counterions. At a small length scale, it is demonstrated that the system behaves as independent charged rods whose counterion distribution follows the Poisson-Boltzmann model. Received 14 February 2001 and Received in final form 2 May 2001     

Dynamical clustering of counterions on flexible polyelectrolytes

Molecular dynamics simulations are used to study the spatiotemporal dynamics of charge fluctuations around a polyelectrolyte molecule at charge densities above and below the classic counterion condensation threshold. Surprisingly, the counterions form weakly interacting clusters which exhibit slowly decaying short range orientational order. Local charge fluctuations create energy fluctuations at the order of k_(B)T that is sufficient to affect the polyelectrolyte interaction with an approaching ligand molecule. The predictions of the classical theory appear to be appropriate only over much longer time scales.     

Counterions at highly charged interfaces: from one plate to like-charge attraction

We present an analytical approach for similarly and highly charged planar interfaces in the presence of counterions. The procedure is physically transparent and based on an exact low temperature expansion around the ground state formed by the two-dimensional Wigner crystal of counterions. The one plate problem is worked out, together with the two plates situation. Unlike previous approaches, the expansion is free of divergences, and is shown to be in excellent agreement with available data of Monte?Carlo simulations under strong Coulombic couplings. In the two plates case, the present results shed light on the like-charge attraction regime.     

Simulations of counterions at charged plates

Using Monte Carlo simulations, we study the counterion distribution close to planar charged walls in two geometries: i) when only one charged wall is present and the counterions are confined to one half-space, and ii) when the counterions are confined between two equally charged walls. In both cases the surface charge is smeared out and the dielectric constant is the same everywhere. We obtain the counterion density profile and compare it with both the Poisson-Boltzmann theory (asymptotically exact in the limit of weak coupling, i.e. low surface charge, high temperature and low counterion valence) and the strong-coupling theory (valid in the opposite limit of high surface charge, low temperature and high counterion valence) and with previously calculated correction terms to both theories for different values of the coupling parameter, thereby establishing the domain of validity of the asymptotic limits. Gaussian corrections to the leading Poisson-Boltzmann behavior (obtained via a systematic loop expansion) in general perform quite poorly: At coupling strengths low enough so that the Gaussian (or one-loop) correction does describe the numerical deviations from the Poisson-Boltzmann result correctly, the leading Poisson-Boltzmann term by itself matches the data within high accuracy. This reflects the slow convergence of the loop expansion. For a single charged plane, the counterion pair correlation function indicates a behavioral change from a three-dimensional, weakly correlated counterion distribution (at low coupling) to a two-dimensional, strongly correlated counterion distribution (at high coupling), which is paralleled by the specific-heat capacity which displays a rounded hump at intermediate coupling strengths. For the case of counterions confined between two equally charged walls, we analyze the inter-wall pressure and establish the complete phase diagram, featuring attraction between the walls for large enough coupling strength and at intermediate wall separation. Depending on the thermodynamic ensemble, the phase diagram exhibits a discontinuous transition where the inter-wall distance jumps to infinity (in the absence of a chemical potential coupling to the inter-wall distance, as for charged lamellae in excess solvent) or a critical point where two coexisting states with different inter-wall distance become indistinguishable (in the presence of a chemical potential, as for charged lamellae with a finite fixed solvent fraction). The attractive pressure decays with the inter-wall distance as an inverse cube, similar to analytic predictions, although the amplitude differs by an order of magnitude from previous theoretical results. Finally, we discuss in detail our simulation methods and compare the finite-size scaling behavior of different boundary conditions (periodic, minimal image and open). Received 6 November 2001