Dielectrophoresis of nanocolloids: A molecular dynamics study

Dielectrophoresis (DEP), the motion of polarizable particles in non-uniform electric fields, has become an important tool for the transport, separation, and characterization of microparticles in biomedical and nanoelectronics research. In this article we present, to our knowledge, the first molecular dynamics simulations of DEP of nanometer-sized colloidal particles. We introduce a simplified model for a polarizable nanoparticle, consisting of a large charged macroion and oppositely charged microions, in an explicit solvent. The model is then used to study DEP motion of the particle at different combinations of temperature and electric field strength. In accord with linear response theory, the particle drift velocities are shown to be proportional to the DEP force. Analysis of the colloid DEP mobility shows a clear time dependence, demonstrating the variation of friction under non-equilibrium. The time dependence of the mobility further results in an apparent weak variation of the DEP displacements with temperature.     

Charge relaxation in polyampholytes of various statistics

We discuss theoretically the relaxation of charge fluctuations in polyampholyte solutions. It has been shown previously by some of us (J. Wittmer et al. Europhys. Lett. 24, 263 (1993)) that the charge distribution along the polyampholyte backbone has a dramatic influence on the polarization energy and hence on the solubility. Here it is demonstrated that a similar effect exists for the charge relaxation. The charge relaxation mechanism qualitatively depends on the statistics: for alternating polyampholytes the relaxation is mainly due to local dipole inversion and is not primarily driven by electrostatic interactions, whereas for random polyampholytes it is driven by electrostatic interactions. Intermediate statistics (with short-ranged (exponential) correlations) appear as a combination of these two limiting cases: short-wavelength modes are insensitive to the loss of correlations along the backbone, whereas long-wavelength modes correspond to a random statistics with renormalized charges. The relaxation of the dielectric constant is also calculated. Received: 20 December 2002 / Accepted: 13 March 2003 / Published online: 24 April 2003 RID="a" ID="a"e-mail: johner@ics.u-strasbg.fr     

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     

Globules of annealed amphiphilic copolymers: Surface structure and interactions

A mean-field theory of globules of random amphiphilic copolymers in selective solvents is developed for the case of an annealed copolymer sequence: each unit can be in one of two states, H (insoluble) or P (soluble or less insoluble). The study is focussed on the regime when H and P units tend to form long blocks, and when P units dominate in the dilute phase, but are rare in the globule core. A first-order coil-to-globule transition is predicted at some T = T _cg. The globule core density at the transition point increases as the affinity of P units to the solvent, ˜, is increased. Two collapse transitions, coil → “loose” globule and “loose” globule → “dense” globule, are predicted if ˜ is high enough and P units are marginally soluble or weakly insoluble. H and P concentration profiles near the globule surface are obtained and analyzed in detail. It is shown that the surface excess of P units rises as ˜ is increased. The surface tension decreases in parallel. Considering the interaction between close enough surfaces of two globules, we show that they always attract each other at a complete equilibrium. It is pointed out, however, that such equilibrium may be difficult to reach, so that partially equilibrium structures (defined by the condition that a chain forming one globule does not penetrate into the core of the other globule) are relevant. It is shown that at such partial equilibrium the interaction is repulsive, so the globules may be stabilized from aggregation. The strongest repulsion is predicted at the coil-to-globule transition point T _cg: the repulsion force decreases with the distance between the surfaces according to a power law. In the general case (apart from T _cg) the force vs. distance decay becomes exponential; the decay length ξ diverges as T → T _cg. The developed theory explains certain anomalous properties observed for globules of amphiphilic homopolymers.     

Excluded-volume polymer-induced depletion interaction between parallel flat plates

The interaction between two parallel plates due to non-adsorbing polymer chains with excluded volume is calculated using the adsorption method. The adsorption is calculated from the profile of the polymer segment concentration between the plates, which is obtained from the product function of the concentration profile near a single wall, involving the correlation length. The renormalization group theory provides expressions for the osmotic pressure and consequently for the osmotic compressibility, chemical potential and correlation length of a polymer solution. Both the local polymer concentration profiles as well as the minimum of the interaction potential between the plates agree with recently published self-avoiding random walk computer simulations. Received 9 August 2001     

Shape transformations of protein-like copolymer globules

Shapes of globules formed by amphiphilic multi-block-copolymers in a selective solvent are considered theoretically. We focus on copolymers consisting mostly of insoluble H-units forming large core surrounded by a shell of soluble P-blocks. It is shown that the globule becomes non-spherical when the effective shell tension is low enough. The resultant shape depends on the shell bending energy: it is prolate if this energy is larger than the elastic energy of the core, and oblate in the opposite case. The central result is the prediction of the formation of a surface pattern of fingers accompanying or even preempting the shape transition mentioned above. We elucidate and discuss the following finger morphologies: 1) nearly spherical knob; 2) a necklace of spherical beads extending away from the surface; 3) mostly cylindrical fingers; 4) large thorn-like fingers. The first 3 morphologies develop at equilibrium as the shell area increases (or, equivalently, the shell tension decreases). Considering the relevant kinetical aspects we show that formation of fingers is a nucleation and growth process, and that the energy of their equilibrium nucleation is likely to be high. Therefore, the finger formation may be delayed, and may actually occur in the regime where the plain spherical surface is metastable. It is the last morphology (thorn-like fingers) that characterizes the metastable regimes when the finger formation is controlled by a high activation energy. The universal features of the above predictions inviting experimental tests are discussed.     

Scaling concepts for polymer brushes and their test with computer simulation

After a brief review of the scaling concepts for static and dynamic properties of polymer brushes in good solvents and Theta solvents, the Monte Carlo evidence is discussed. It is shown that under typical conditions the diameter of the last blob is of the order of 10-20% of the brush height, and therefore pronounced deviations from the self-consistent field predictions occur. In bad solvents, lateral microphase separation occurs leading to an irregular pattern of “dimples”. Particularly interesting is the response of brushes to shear deformation, and the interaction between two interpenetrating brushes. Recent attempts to understand the resulting shear forces via molecular-dynamics simulations are briefly described, and an outlook on related experiments is given. Dedicated to Prof. H.E. Stanley on the occasion of his 60th birthday Received 11 March 2002 and Received in final form 3 June 2002     

Stratification of foam films made from polyelectrolyte solutions

Studies of thin liquid films, made from semidilute polyelectrolyte solutions, are presented. The disjoining pressure variation with film thickness exhibits oscillations, corresponding to film stratification. The oscillations become sharper as the polymer concentration c increases, and disappear when salt is added. The period of the oscillations scales as c ^-1/2. The observed stratification is related to the polymer network and the size of the steps to the mesh size ξ. Received 25 April 2000 and Received in final form 3 October 2000     

Dynamical properties of the slithering-snake algorithm: A numerical test of the activated-reptation hypothesis

Correlations in the motion of reptating polymers in a melt are investigated by means of Monte Carlo simulations of the three-dimensional slithering-snake version of the bond-fluctuation model. Surprisingly, the slithering-snake dynamics becomes inconsistent with classical reptation predictions at high chain overlap (created either by chain length N or by the volume fraction φ of occupied lattice sites), where the relaxation times increase much faster than expected. This is due to the anomalous curvilinear diffusion in a finite time window whose upper bound (N) is set by the density of chain ends φ/N. Density fluctuations created by passing chain ends allow a reference polymer to break out of the local cage of immobile obstacles created by neighboring chains. The dynamics of dense solutions of “snakes” at t ≪ is identical to that of a benchmark system where all chains but one are frozen. We demonstrate that the subdiffusive dynamical regime is caused by the slow creeping of a chain out of its correlation hole. Our results are in good qualitative agreement with the activated-reptation scheme proposed recently by Semenov and Rubinstein (Eur. Phys. J. B, 1 (1998) 87). Additionally, we briefly comment on the relevance of local relaxation pathways within a slithering-snake scheme. Our preliminary results suggest that a judicious choice of the ratio of local to slithering-snake moves is crucial to equilibrate a melt of long chains efficiently. Received: 18 December 2002 / Accepted: 3 April 2003 / Published online: 12 May 2003 RID="a" ID="a"e-mail: jwittmer@dpm.univ-lyon1.fr RID="b" ID="b"Current address: University of Illinois at Urbana-Champaign.     

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.     

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     

Adsorption of a semiflexible wormlike chain

Adsorption of ideal polymers with stiff backbone onto a flat surface is considered theoretically. Both scaling approach and quantitative theory are developed. We predict a self-similar monomer concentration profile c(x) ∼ x ^-4/3 near the surface (when the distance to the surface x is much smaller than the chain persistence length l /2). The typical conformation of a weakly adsorbed chain can be viewed as a sequence of alternating flat (2-dimensional) trains of wormlike short loops (flat blobs) and coil-like (3-dimensional) loops forming a triple-layer structure: contact layer (x < Δ) of adsorbed fragments virtually laid on the surface, proximal layer (Δ < x < l) of flat blobs, and more dilute distal corona layer (x > l). Here Δ defines the range of monomer/surface attraction, Δ ≪ l. The adsorption transition is continuous. However, its relative width is small (T ^* is the adsorption temperature, ΔT is the relevant temperature interval): ∼ , i.e. a discontinuous transition in the limit Δ/l↦ 0. Received 10 October 2002 and Received in final form 22 November 2002 RID="a" ID="a"Permanent address: Physics Department, Moscow State University, Moscow 119992, Russia. e-mail: semenov@polly.phys.msu.ru     

The timescale of spinodal dewetting at a polymer/polymer interface

We investigate the dynamics of spinodal dewetting in liquid-liquid polymer systems. Dewetting of poly(methyl-methacrylate) (PMMA) thin films on polystyrene (PS) “substrates” is followed in situ using neutron reflectivity. By following the development of roughness at the PS/PMMA interface and the PMMA surface we extract characteristic growth times for the dewetting process. These characteristic growth times are measured as a function of the molecular weight of the two polymers. By also carrying out experiments in the regime where the dynamics are independent of the PS molecular weight, we are able to use dewetting to probe the scaling of the PMMA thin film viscosity with temperature and molecular weight. We find that this scaling reflects bulk behaviour. However, absolute values are low compared to bulk viscosities, which we suggest may be due in part to slippage at the polymer/polymer interface. Received 25 June 2001 and Received in final form 5 December 2001     

Confinement-induced differences between dielectric normal modes and segmental modes of an ion-conducting polymer

Dielectric measurement in the range 0.1 Hz to 1 MHz were used to study the motions of polymers and ions in an ion-conducting polymer, polypropylene oxide containing small quantities (on the order of 1%) of lithium ions (LiClO₄), confined as a sandwich of uniform thickness between parallel insulating mica surfaces. In the dielectric loss spectrum, we observed three peaks; they originated from the normal mode of the polymer, segmental mode of the polymer, and ion motions. With decreasing film thickness, the peak frequencies corresponding to the normal mode and ion motion shifted to lower frequencies, indicating retardation due to confinement above 30 nm. This was accompanied by diminished intensity of the dielectric normal-mode relaxation, suggesting that confinement diminished the fluctuations of the end-to-end vector of the chain dipole in the direction between the confining surfaces. On the contrary, the segmental mode was not affected at that thickness. Finally, significant retardation of the segmental mode was observed only for the thinnest film (14 nm). The different dynamical modes of the polymer (segmental and slowest normal modes) respond with different thickness and temperature dependence to confinement. Received 31 August 2001 and Received in final form 30 October 2001     

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     

Nematic ordering in anisotropic elastomers: Effect of frozen anisotropy

Nematic ordering in anisotropic non-Gaussian elastomers is considered theoretically using mean field approximation. We focus on the effect of anisotropy during network cross-linking on the system elasticity and, in particular, on the so-called soft deformation mode. As the main result, we calculate the dependence of the elastomer free energy on the angle between the axis of “frozen” anisotropy and the nematic director. The dependence of the isotropic-nematic transition point on the orientational field acting on the monomers during the cross-linking process is also calculated. Received: 5 November 1997 / Revised and Accepted: 29 June 1998     

Gels at interfaces

We discuss the adsorption of polymer gels on flat surfaces. Even in cases of complete wetting where the spreading power S is positive and where an equivalent liquid would spread, the elastic stresses due to the gel deformation upon adsorption oppose the spreading. The competition between elasticity characterized by the bulk shear modulus G and capillarity characterized by the spreading power S defines a typical length scale ℓ = S/G for the deformation in the gel. For loose gels ℓ can be of the order of 1 μm. Macroscopic gels larger than ℓ deform only at their edges over a region of size ℓ. Microscopic gels smaller than ℓ show a finite deformation despite the elastic stresses. The elastic stresses limit the spreading of the polymer, but solvent can be sucked out of a swollen gel by wetting the surface. The thin solvent film can extend rather far from the gel edge and carry solvent. We calculate the kinetics of the solvent film formation and of the solvent transfer from a more swollen gel to a less swollen gel. Received 16 July 2001     

Phase behavior of a suspension of hard spherocylinders plus ideal polymer chains

We study isotropic-isotropic and isotropic-nematic phase transitions of fluid mixtures containing hard spherocylinders (HSC) and added non-adsorbing ideal polymer chains using scaled particle theory (SPT). First, we investigate isotropic-nematic (I -N phase coexistence using SPT in the absence of polymer. We compare the results obtained using a Gaussian form of the orientational distribution function (ODF) to minimize the free energy versus minimizing numerically. We find that formal numerical minimization gives results that are much closer to computer simulation results. In order to describe mixtures of HSC plus ideal chains we studied the depletion of ideal chains around a HSC. We analyze the density profiles of ideal chains near a hard cylinder and find the depletion thickness δ is a function of the ratio of the polymer's radius of gyration R_g and the cylinder radius R_c. Our results are compared with a common approximation in which the depletion thickness is taken equal to the radius of gyration of the polymer chain. We incorporate the correct depletion thickness into SPT and find that for R _g/R _c < 1.56 using ideal chains gives phase transitions at smaller polymer concentrations, whereas for R _g/R _c > 1.56 , which is a common experimental situation, the phase transitions are found at larger polymer concentrations with respect to δ = R _g . The differences are significant, especially for R _g ≫ R _c , so we can conclude it is essential to take into account the properties of ideal polymer chains and the resulting depletion near a cylinder. Finally, we present phase diagrams for rod-polymer mixtures which could be realized under experimental conditions.     

Glassy effects in the swelling/collapse dynamics of homogeneous polymers

We investigate, using numerical simulations and analytical arguments, a simple one-dimensional model for the swelling or the collapse of a closed polymer chain of size N, representing the dynamical evolution of a polymer in a Θ-solvent that is rapidly changed into a good solvent (swelling) or a bad solvent (collapse). In the case of swelling, the density profile for intermediate times is parabolic and expands in space as t ^1/3, as predicted by a Flory-like continuum theory. The dynamics slows down after a time ∝N ² when the chain becomes stretched, and the polymer gets stuck in metastable “zig-zag” configurations, from which it escapes through thermal activation. The size of the polymer in the final stages is found to grow as . In the case of collapse, the chain very quickly (after a time of order unity) breaks up into clusters of monomers (“pearls”). The evolution of the chain then proceeds through a slow growth of the size of these metastable clusters, again evolving as the logarithm of time. We enumerate the total number of metastable states as a function of the extension of the chain, and deduce from this computation that the radius of the chain should decrease as 1/ln(ln t). We compute the total number of metastable states with a given value of the energy, and find that the complexity is non-zero for arbitrary low energies. We also obtain the distribution of cluster sizes, that we compare to simple “cut-in-two” coalescence models. Finally, we determine the aging properties of the dynamical structure. The subaging behaviour that we find is attributed to the tail of the distribution at small cluster sizes, corresponding to anomalously “fast” clusters (as compared to the average). We argue that this mechanism for subaging might hold in other slowly coarsening systems. Received 23 October 2000