Polyelectrolyte chains in poor solvent. A variational description of necklace formation

We study the properties of polyelectrolyte chains under different solvent conditions, using a variational technique. The free energy and the conformational properties of a polyelectrolyte chain are studied by minimizing the free energy F_N, depending on N(N - 1)/2 trial probabilities that characterize the conformation of the chain. The Gaussian approximation is considered for a ring of length 2⁴ < N < 2⁸ and for an open chain of length 50 < N < 200 in poor- and theta-solvent conditions, including a Coulomb repulsion between the monomers. In theta-solvent conditions the blob size is measured and found in agreement with scaling theory, including charge depletion effects, expected for the case of an open chain. In poor-solvent conditions, a globule instability, driven by electrostatic repulsion, is observed. We notice also inhomogeneous behavior of the monomer-monomer correlation function, reminiscence of necklace formation in poor-solvent polyelectrolyte solutions. A global phase diagram in terms of solvent quality and inverse Bjerrum length is presented. Received 7 June 2001 and Received in final form 17 October 2001     

The electrostatic persistence length of polymers beyond the OSF limit

We use large-scale Monte Carlo simulations to test scaling theories for the electrostatic persistence length l _e of isolated, uniformly charged polymers with Debye-Hückel intrachain interactions in the limit where the screening length κ^-1 exceeds the intrinsic persistence length of the chains. Our simulations cover a significantly larger part of the parameter space than previous studies. We observe no significant deviations from the prediction l _e∝κ^-2 by Khokhlov and Khachaturian which is based on applying the Odijk-Skolnick-Fixman theories of electrostatic bending rigidity and electrostatically excluded volume to the stretched de Gennes-Pincus-Velasco-Brochard polyelectrolyte blob chain. A linear or sublinear dependence of the persistence length on the screening length can be ruled out. We show that previous results pointing into this direction are due to a combination of excluded-volume and finite chain length effects. The paper emphasizes the role of scaling arguments in the development of useful representations for experimental and simulation data. Received 12 February 2002     

Radial distribution function of rod-like polyelectrolytes

We study the effect of electrostatic interactions on the distribution function of the end-to-end distance of a single polyelectrolyte chain in the rod-like limit. The extent to which the radial distribution function of a polyelectrolyte is reproduced by that of a wormlike chain with an adjusted effective persistence length is investigated. Strong evidence is found for a universal scaling formula connecting the effective persistence length of a polyelectrolyte with the strength of the electrostatic interaction and the Debye screening length. Received 4 March 2002 and Received in final form 1 July 2002 RID="a" ID="a"e-mail: jrudnick@physics.ucla.edu     

Stretching DNA: Role of electrostatic interactions

The effect of electrostatic interactions on the stretching of DNA is investigated using a simple worm like chain model. In the limit of small force there are large conformational fluctuations which are treated using a self-consistent variational approach. For small values of the external force f, we find the extension scales as where is the Debye screening length. In the limit of large force the electrostatic effects can be accounted for within the semiflexible chain model of DNA by assuming that only small excursions from rod-like conformations are possible. In this regime the extension approaches the contour length as where f is the magnitude of the external force. The theory is used to analyze experiments that have measured the extension of double-stranded DNA subject to tension at various salt concentrations. The theory reproduces nearly quantitatively the elastic response of DNA at small and large values of f and for all concentration of the monovalent counterions. The limitations of the theory are also pointed out. Received 13 October 1998 and Received in final form 9 June 1999     

Adsorption of polymer chains by disordered traps

We study the adsorption cross-over of ideal polymer chains in an environment of disordered traps. Starting from the assumption of an optimal cluster size of traps (optimal fluctuation method) we derive a general scaling form of the free energy function for arbitrary spatial dimensions. For small concentrations of traps we find a cross-over from localized (adsorbed) behavior to delocalized behavior depending on the chain's length and on the depth of the traps; this is connected with the non-monotonic behavior of the chain's extension. In terms of the free energy of the chain this cross-over resembles a first order transition scenario, the chain gets localized at many traps at once. Received 18 November 1998     

Phase behaviour of a dispersion of charge-stabilised colloidal spheres with added non-adsorbing interacting polymer chains

We present a theory for the phase behaviour of mixtures of charge-stabilised colloidal spheres plus interacting polymer chains in good and θ -solvents within the framework of free-volume theory. We use simple but accurate combination rules for the depletion thickness around a colloidal particle and for the osmotic pressure up to the semi-dilute concentration regime. Hence, we obtain expressions for the free energy for mixtures of charged colloidal particles and non-adsorbing interacting polymers. From that, we calculate the phase behaviour, and discuss its topology in dependence on the competition between the charge-induced repulsion and the polymer-induced attraction. The homogeneous mixture of colloids and polymers becomes more stabilised against demixing when increasing the electrostatic repulsion. This charge-induced stabilisation is strongest for small polymer-to-colloid size ratios and is more pronounced for charged colloids mixed with polymers in a good solvent than for polymers in a θ -solvent. For the weakly charged regime we find that the phase diagram becomes salt-concentration-independent in the protein limit for charged colloids plus polymers in a θ -solvent. The liquid window, i.e., the concentration regimes where a colloidal liquid exists, is narrowed down upon increasing the charge-induced repulsion. Also this effect is more pronounced when charged colloids are mixed with polymer chains in a good solvent. In summary, we demonstrate that the solvent quality significantly influences the phase behaviour of mixtures of charged colloids plus non-adsorbing polymers if the range of the screened electrostatic repulsion becomes of the order of the range of the depletion-induced attraction.     

Persistence length for a model semirigid polyelectrolyte as seen by small angle neutron scattering: a relevant variation of the lower bound with ionic strength

In a SANS experiment, we have directly determined for the first time the conformation of hyaluronan, a model semirigid polyelectrolyte. At high ionic strength, this is completely possible, where the scattered intensity crosses over (when decreasing q) from a q(-1) rod variation to a q(-2) and, where fitting to the "wormlike" chain model gives the backbone, intrinsic, persistence length: L0 = 86.5 A. At low ionic strength, we can safely check that the measured persistence length appears increased by at least the amount predicted by Odijk for the electrostatic contribution, L(e) (approximately kappa(-2), square of the Debye screening length). However, the intensity at the lowest q is not only due to the single chain, since it crosses over from a q(-1) to a q(-4) variation, characteristic of polymer associations.     

Molecular-dynamics simulation of a glassy polymer melt: Incoherent scattering function

We present simulation results for a model polymer melt, consisting of short, nonentangled chains, in the supercooled state. The analysis focuses on the monomer dynamics, which is monitored by the incoherent intermediate scattering function. The scattering function is recorded over six decades in time and for many different wave-vectors which range from the size of a chain to about three times the maximum position of the static structure factor. The lowest temperatures studied are slightly above , the critical temperature of mode-coupling theory (MCT), where was determined from a quantitative analysis of the - and -relaxations. We find evidence for the space-time factorization theorem in the -relaxation regime, and for the time-temperature superposition principle in the -regime, if the temperature is not too close to . The wave-vector (q-) dependence of the nonergodicity parameter, of the critical amplitude, and the -relaxation time are in qualitative agreement with calculations for hard spheres. For q larger than the maximum of the structure factor the -relaxation time already agrees fairly well with the asymptotic MCT-prediction . The behavior of the relaxation time at small q can be rationalized by the validity of the Gaussian approximation and the value of the Kohlrausch stretching exponent, as suggested in neutron-scattering experiments. Received 30 October 1998     

Adsorption of polyelectrolytes at an oppositely charged surface

We develop a scaling theory of polyelectrolyte adsorption at an oppositely charged surface. At low surface charge densities, the thickness of the adsorbed layer is determined by the balance between electrostatic attraction to the charged surface and chain entropy. At high surface charge densities, it is determined by the balance between electrostatic attraction and short-range monomer-monomer repulsion. These different stabilizing mechanisms result in the nonmonotonic dependence of the layer thickness on the surface charge density.     

Adsorption of a polyampholyte on a charged spherical particle

We develop a scaling theory for a single polyampholyte chain adsorbed on a charged spherical particle in a theta-solvent. Adsorption of a polyampholyte molecule is due to its polarization in the electrostatic field of the particle. For large particles with sizes exceeding the thickness of the adsorbed layer, the conformations of the chain are similar to the one found for polyampholyte adsorption on charged planar surface. However, an adsorbed polyampholyte chain forms a self-similar flower-like structure near the particles with sizes smaller than its Gaussian size. These self-similar structures result from the balance of the polarization energy of loops and the excluded volume interactions between monomers. The structure of an adsorbed polyampholyte in the flower-like conformation is similar to that of a neutral star polymer. Received 3 March 2000 and Received in final form 5 July 2000     

Weak violation of universality for polyelectrolyte chains: Variational theory and simulations

A variational approach is considered to calculate the free energy and the conformational properties of a polyelectrolyte chain in d dimensions. We consider in detail the case of pure Coulombic interactions between the monomers, when screening is not present, in order to compute the end-to-end distance and the asymptotic properties of the chain as a function of the polymer chain length N. We find R≃N ^ν(log N)^γ, where ν = and λ is the exponent which characterizes the long-range interaction U∝ 1/r ^λ. The exponent γ is shown to be non-universal, depending on the strength of the Coulomb interaction. We check our findings by a direct numerical minimization of the variational energy for chains of increasing size 2⁴ < N < 2¹⁵. The electrostatic blob picture, expected for small enough values of the interaction strength, is quantitatively described by the variational approach. We perform a Monte Carlo simulation for chains of length 2⁴ < N < 2¹⁰. The non-universal behavior of the exponent γ previously derived within the variational method is also confirmed by the simulation results. Non-universal behavior is found for a polyelectrolyte chain in d = 3 dimension. Particular attention is devoted to the homopolymer chain problem, when short-range contact interactions are present. Received 8 August 2000 and Received in final form 19 December 2000     

Static and dynamic properties of polymer brush with topological ring structures: Molecular dynamic simulation

By defining a topological constraint value(rn),the static and dynamic properties of a polymer brush composed of moderate or short chains with different topological ring structures are studied using molecular dynamics simulation,and a comparison with those of linear polymer brush is also made.For the center-of-mass height of the ring polymer brush scaled by chain length h~N~v,there is no significant difference of exponent from that of a linear brush in the small topological constraint regime.However,as the topological constraint becomes stronger,one obtains a smaller exponent.It is found that there exists a master scaling power law of the total stretching energy scaled by chain length N for moderate chain length regime,F_(ene)~Np~v,for ring polymer brushes,but with a larger exponent v than 5/6,indicating an influence of topological constraint to the dynamic properties of the system.A topological invariant of free energy scaled by(c)~(5/4) is found.     

Small-angle X-ray scattering from salt-free solutions of star-branched polyelectrolytes

The dispersion state of sodium-sulphonated polystyrene ( NaPSS) star-branched polyelectrolytes was investigated in salt-free aqueous solutions, by use of the small-angle X-ray scattering technique. With respect to polystyrene (PS) star-branched polymers of identical functionality, the ordering phenomenon occurring in the neighborhood of the overlap concentration c^* is reinforced and observed in a larger range of concentrations. Moreover, the degree of order is no longer maximum at c^* and is improved as the concentration decreases. The dispersion state is then mainly controlled by the electrostatic interaction. A crystalline order should therefore be achieved with stars of lower functionality, provided the electrostatic interaction is added to the osmotic repulsion. On the other hand, unusual scattering patterns are measured for aqueous solutions of NaPSS star polyelectrolytes. Indeed, a diffuse scattering is revealed at high angles, in addition to the regular diffraction rings related to preferred interstar distances. It is similar to the broad scattering peak produced by semidilute solutions of NaPSS linear polyelectrolytes and associated to the electrostatic correlation hole within the isotropic model. In the dilute regime (c < c ^*), it is just an intramolecular characteristic and represents the electrostatic repulsion between arms belonging to the same star. In the semidilute regime (c > c ^*), it also reflects the electrostatic repulsion between arms of distinct stars. So, as the concentration increases, it is mainly caused by the interpenetration of NaPSS stars. Such an observation is in agreement with the composite structure earlier proposed by Daoud and Cotton for star semidilute solutions. For c > c ^*, NaPSS star aqueous solutions can therefore be pictured as effective stars immersed in a matrix formed by the overlap of the arm ends. With respect to the dilute regime, the effective stars are smaller; the higher the concentration the smaller the size. Received 14 May 1999 and Received in final form 15 March 2000     

Variational theory for a single polyelectrolyte chain revisited

We reconsider the electrostatic contribution to the persistence length, , of a single, infinitely long-charged polymer in the presence of screening. A Gaussian variational method is employed, taking as the only variational parameter. For weakly charged and flexible chains, crumpling occurs at small length scales because conformational fluctuations overcome electrostatic repulsion. The electrostatic persistence length depends on the square of the screening length, , as first argued by Khokhlov and Khachaturian by applying the Odijk-Skolnick-Fixman (OSF) theory to a string of crumpled blobs. We compare our approach to previous theoretical works (including variational formulations) and show that the result found by several authors comes from the improper use of a cutoff at small length scales. For highly charged and stiff chains, crumpling does not occur; here we recover the OSF result and validate the perturbative calculation for slightly bent rods.PACS: 36.20.-r Macromolecules and polymer molecules - 82.70.-y Disperse systems; complex fluids - 87.15.-v Biomolecules: structure and physical properties     

Anomalous viscosity exponent in a discretized model for a chain diffusion in one dimension

We present a one-dimensional Monte Carlo simulation for the diffusion motion of a chain of N beads. We found that the scaling exponent for the viscosity can be smaller or greater than 3. This anomalous behavior cannot be attributed to the diffusivity scaling or the length fluctuations but is due to the chain dynamics details during diffusion in which the end beads play the key role. The viscosity exponent 3 and its expected relation with the diffusivity exponent are recovered in the asymptotic regime (N ↦∞). Received 24 September 2001 and Received in final form 28 January 2002     

Ionic distribution and polymer conformation, near phase separation, in sodium polyacrylate/divalent cations mixtures: small angle X-ray and neutron scattering

Anomalous small angle X-ray scattering experiments show that before demixion in sodium polyacrylate/cobalt and sodium polyacrylate/calcium mixtures all the divalent counterions are in the close vicinity of the polyacrylate chain. The present results are consistent with previous UV/VIS spectroscopy, which have shown that all cobalt ions are chemically associated with acrylate groups. The chemical association dehydrates the acrylate monomers. However, the hydrophobicity of the complexed monomers is not strong enough to induce a collapse of the polymer chain at small spatial scale before the demixion. Indeed, the scattered intensity (X-ray and neutron scattering) decreases with the scattering vector q as q^-x with for q > 0.1 nm ^-1 which indicates that the local conformation of the chain is Gaussian. Received 21 January 1999     

Scattering from solutions of star polymers

We study the scattering intensity of dilute and semi-dilute solutions of star polymers. The star conformation is described by a model introduced by Daoud and Cotton. In this model, a single star is regarded as a spherical region of a semi-dilute polymer solution with a local, position dependent screening length. For high enough concentrations, the outer sections of the arms overlap and build a semi-dilute solution (a sea of blobs) where the inner parts of the actual stars are embedded. The scattering function is evaluated following a method introduced by Auvray and de Gennes. In the dilute regime there are three regions in the scattering function: the Guinier region (low wave vectors, ) from where the radius of the star can be extracted; the intermediate region () that carries the signature of the form factor of a star with f arms: ; and a high wavevector zone () where the local swollen structure of the polymers gives rise to the usual q ^-5/3 decay. In the semi-dilute regime the different stars interact strongly, and the scattered intensity acquires two new features: a liquid peak that develops at a reciprocal position corresponding to the star-star distances; and a new large wavevector contribution of the form q ^-5/3 originating from the sea of blobs. Received: 3 September 1997 / Revised: 13 January 1988 / Accepted: 31 March 1998     

Log-periodic oscillations for biased diffusion of a polymer chain in a porous medium

A coarse-grained off-lattice bead-spring model is used to reveal the complex dynamics of a polymer chain in a quenched porous medium in the presence of an external field B. The behavior of the mean square displacement (MSD) of the center chain bead and that of the center of mass of the chain as a function of time is studied at different values of the barrier concentration C, the field strength B and the chain length N. In a field, important information on the way in which chains move between obstacles and overcome them is gained from the MSD vs. time analysis in the directions parallel and perpendicular to the flow. Instead of a steady approach to uniform drift-like motion at low C, for sufficiently strong field B we observe logarithmic oscillations in the effective exponents describing the time dependence of the MSD along and perpendicular to field. A common nature of this phenomenon with oscillatory behavior, observed earlier for biased diffusion of tracers on random lattices, is suggested. Received 7 August 1998