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1.
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 相似文献
2.
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 相似文献
3.
We investigate the drift of an end-labeled telehelic polymer chain in a frozen disordered medium under the action of a constant
force applied to the one end of the macromolecule by means of an off-lattice bead spring Monte Carlo model. The length of
the polymers N is varied in the range 8 < N < 128, and the obstacle concentration in the medium C is varied from zero up to the percolation threshold C≈ 0.75. For field intensities below a C-dependent critical field strength B
c, where jamming effects become dominant, we find that the conformational properties of the drifting chains can be interpreted
as described by a scaling theory based on Pincus blobs. The variation of drag velocity with C in this interval of field intensities is qualitatively described by the law of Mackie-Meares. The threshold field intensity
B
c itself is found to decrease linearly with C.
Received 20 August 2001 and Received in final form 19 November 2001 相似文献
4.
G. Migliorini V.G. Rostiashvili T.A. Vilgis 《The European Physical Journal B - Condensed Matter and Complex Systems》2003,33(1):61-73
The Langevin dynamics of a self-interacting chain embedded in a quenched random medium is investigated by making use of the
generating functional method and one-loop (Hartree) approximation. We have shown how this intrinsic disorder causes different
dynamical regimes. Namely, within the Rouse characteristic time interval the anomalous diffusion shows up. The corresponding
subdiffusional dynamical exponents have been explicitly calculated and thoroughly discussed. For the larger time interval
the disorder drives the center of mass of the chain to a trap or frozen state provided that the Harris parameter, (Δ/b
d)N
2 - νd≥1, where Δ is a disorder strength, b is a Kuhnian segment length, N is a chain length and ν is the Flory exponent. We have derived the general equation for the non-ergodicity function f (p) which characterizes the amplitude of frozen Rouse modes with an index p = 2πj/N. The numerical solution of this equation has been implemented and shown that the different Rouse modes freeze up at the same
critical disorder strength Δ
c ∼ N
- γ where the exponent γ ≈ 0.25 and does not depend from the solvent quality.
Received 17 December 2002 Published online 23 May 2003
RID="a"
ID="a"e-mail: vilgis@mpip-mainz.mpg.de 相似文献
5.
Mattioni L Wittmer JP Baschnagel J Barrat JL Luijten E 《The European physical journal. E, Soft matter》2003,10(4):369-385
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. 相似文献
6.
N. Lee D. Thirumalai 《The European Physical Journal B - Condensed Matter and Complex Systems》1999,12(4):599-605
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 相似文献
7.
The static structure factor (S(q)) of dispersions and gels of disk-like mineral colloids (Laponite) was investigated using time- and ensemble-averaged light
scattering. The evolution of S(q) in time after increasing the ionic strength of well-dispersed Laponite suspensions shows that Laponite aggregates and forms
fractal clusters. The structure of the aggregates does not depend on the ionic strength, but the rate of growth increases
very strongly with the ionic strength. At concentrations below about 3 g/l (0.12% v/v) the aggregates sediment while at higher
concentrations space-filling gels are formed. The gels are homogeneous on length scales larger than the correlation length
which decreases strongly with decreasing ionic strength and increasing concentration. However, the local structure is the
same, independent of the concentration and the ionic strength.
Received 6 August 2000 and Received in final form 16 March 2001 相似文献
8.
R.R. Netz H. Orland 《The European Physical Journal B - Condensed Matter and Complex Systems》1999,8(1):81-98
Variational methods are applied to a single polyelectrolyte chain. The polymer is modeled as a Gaussian chain with screened
electrostatic repulsion between all monomers. As a variational Hamiltonian, the most general Gaussian kernel, including the
possibility of a classical or mean polymer path, is employed. The resulting self-consistent equations are systematically solved
both for large and small monomer-monomer separations along the chain. In the absence of screening, the polymer is stretched
on average. It is described by a straight classical path with Gaussian fluctuations around it. If the electrostatic repulsion
is screened, the polymer is isotropically swollen for large separations, and for small separations the polymer correlation
function is calculated as an analytic expansion in terms of the monomer-monomer separation along the chain. The electrostatic
persistence length and the electrostatic blobsize are inferred from the crossover between distinct scaling ranges. We perform
a global analysis of the scaling behavior as a function of the screening length and electrostatic interaction strength , where is the Bjerrum length and A is the distance of charges along the polymer chain. We find three different scaling regimes. i) A Gaussian-persistent regime with Gaussian behavior at small, persistent behavior at intermediate, and isotropically swollen behavior at large length
scales. This regime occurs for weakly charged polymers and only for intermediate values of the screening length. The electrostatic
persistence length is defined as the crossover length between the persistent and the asymptotically swollen behavior and is given by and thus disagrees with previous (restricted) variational treatments which predict a linear dependence on the screening length
.ii) A Gaussian regime with Gaussian behavior at small and isotropically swollen behavior at large length scales. This regime occurs for weakly
charged polymers and/or strong screening, and the electrostatic repulsion between monomers only leads to subfluent corrections
to Gaussian scaling at small separations. The concept of a persistence length is without meaning in this regime. iii) A persistent regime , where the chain resembles a stretched rod on intermediate and small scales. Here the persistence length is given by the
original Odijk prediction, , if the overstretching of the chain is avoided. We also investigate the effects of a finite polymer length and of an additional
excluded-volume interaction, which modify the resultant scaling behavior. Applications to experiments and computer simulations
are discussed.
Received 24 December 1997 相似文献
9.
M. Baiesi E. Orlandini A.L. Stella 《The European Physical Journal B - Condensed Matter and Complex Systems》2002,28(4):467-473
The linking number (topological entanglement) and the writhe (geometrical entanglement) of a model of circular double stranded
DNA undergoing a thermal denaturation transition are investigated by Monte Carlo simulations. By allowing the linking number
to fluctuate freely in equilibrium we see that the linking probability undergoes an abrupt variation (first-order) at the
denaturation transition, and stays close to 1 in the whole native phase. The average linking number is almost zero in the
denatured phase and grows as the square root of the chain length, N, in the native phase. The writhe of the two strands grows as in both phases.
Received 8 May 2002 Published online 13 August 2002 相似文献
10.
Spherical polyelectrolyte block copolymer micelles: Structural change in presence of monovalent salt
Muller F Guenoun P Delsanti M Demé B Auvray L Yang J Mays JW 《The European physical journal. E, Soft matter》2004,15(4):465-472
Spherical polyelectrolyte block copolymer micelles were investigated as a function of added NaCl salt concentration using Small-Angle Neutron Scattering (SANS) and Light Scattering (LS). The micelles are formed by the self-association of charged-neutral copolymers made of a long deuterated polyelectrolyte moiety (NaPSSd)251 and a short hydrophobic moiety (PEP)52. In presence of salt, the core shape and the aggregation number of the micelles are not affected. The hydrodynamic radius of the micelle is found to be identical to the radius of the whole micelle deduced from neutron scattering and thus the hydrodynamic radius is a valid measure of the corona thickness. At the lowest salt concentrations investigated the thickness of the corona, Rs, remains essentially constant and a contraction is observed above an added-salt concentration cs of 2×10-2 M where this crossover concentration corresponds to the average ionic strength of the free counterions in the corona. The contraction takes place while maintaining a rod-like behavior of the chains at short scale and obeys to: Rs cs-0.18. The exponent 0.18 suggests an electrostatic persistence length proportional to the Debye screening length. 相似文献
11.
Monte Carlo simulations are used to study the non-uniform equilibrium charge distribution along a single annealed polyelectrolyte
chain under θ solvent conditions and with added salt. Within a range of the order of the Debye length charge accumulates at
chain ends while a slight charge depletion appears in the central part of the chain. The simulation results are compared with
theoretical predictions recently given by Castelnovo et al. In the parameter range where the theory can be applied we find almost perfect quantitative agreement.
Received 7 March 2002 and Received in final form 28 May 2002 相似文献
12.
Equilibrium structures of planar polyelectrolyte brushes formed by grafted chains carrying charges of opposite sign are examined
by employing mean-field lattice theory. Two brushes of different architecture are considered: one formed by grafted diblock
copolymers with oppositely charged blocks and the other being a mixed brush composed of oppositely charged homopolymers. The
systems display nontrivial intrinsically inhomogeneous brush structures originating from the chain connectivity and the electrostatic
interaction among the segments. In addition, a coexistence of stretched and coiled chains inside the brush is observed. The
influence of the charges of the blocks, the relative length of the oppositely charged blocks, and the ionic strength of the
solution on the brush inhomogeneity and structural differences between the two types of brushes are discussed.
Received 14 March 2001 and Received in final form 18 June 2001 相似文献
13.
F. Muller P. Fontaine M. Delsanti L. Belloni J. Yang Y.J. Chen J.W. Mays P. Lesieur M. Tirrell P. Guenoun 《The European physical journal. E, Soft matter》2001,6(2):109-115
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 相似文献
14.
O.V. Borisov F. Hakem T.A. Vilgis J.-F. Joanny A. Johner 《The European physical journal. E, Soft matter》2001,6(1):37-47
We present a scaling theory for the adsorption of a weakly charged polyelectrolyte chain in a poor solvent onto an oppositely
charged surface. Depending on the fraction of charged monomers and on the solvent quality for uncharged monomers, the globule
in the bulk of the solution has either a spherical conformation or a necklace structure. At sufficiently high surface charge
density, a chain in the globular conformation adsorbs in a flat pancake conformation due to the Coulombic attraction to the
oppositely charged surface. Different adsorption regimes are predicted depending on two screening lengths (the Debye screening
length monitored by the salt concentration and the Gouy-Chapman length monitored by the surface charge density), on the degree
of ionization of the polymer and on the solvent strength. At low bulk ionic strength, an increase in the surface charge density
may induce a transition from an adsorbed necklace structure to a uniform pancake due to the enhanced screening of the intra-chain
Coulombic repulsion by the counterions localized near the surface.
Received 12 April 2001 相似文献
15.
G. Migliorini V.G. Rostiashvili T.A. Vilgis 《The European physical journal. E, Soft matter》2001,4(4):475-487
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 相似文献
16.
Semenov AN 《The European physical journal. E, Soft matter》2002,9(4):353-363
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 相似文献
17.
Ngai KL 《The European physical journal. E, Soft matter》2002,8(2):225-235
Large increases of mobility of local segmental relaxation observed in polymer films as the film thickness is decreased, as
evidenced by decreases of the glass temperature, are not found for relaxation mechanisms that have longer length scales including
the Rouse relaxation modes and the diffusion of entire polymer chains. We show that the coupling model predictions, when extended
to consider polymer thin films, are consistent with a large increase of the mobility of the local segmental motions and the
lack of such a change for the Rouse modes and the diffusion of entire polymer chains. There are two effects that can reduce
the coupling parameter of the local segmental relaxation in thin films. One is the chain orientation that is induced parallel
to the surface when the film thickness h becomes smaller than the end-to-end distance of the chains and the other is a finite-size effect when h is no longer large compared to the cooperative length scale. Extremely thin ( ≈ 1.5 nm) films obtained by intercalating a
polymer into layered silicates have thickness significantly less than the cooperative length scale near the bulk polymer glass
transition temperature. As a result, the coupling parameter of the local segmental relaxation in such thin films is reduced
almost to zero. With this plausible assumption, we show the coupling model can explain quantitatively the large decrease of
the local segmental relaxation time found experimentally.
Received 1 August 2001 and Received in final form 1 December 2001 相似文献
18.
G. Migliorini N. Lee V. Rostiashvili T.A. Vilgis 《The European physical journal. E, Soft matter》2001,6(3):259-270
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 FN, 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 相似文献
19.
We studied the formation of actin scaffolds in giant vesicles of dimyristoylphosphatidylcholine (DMPC). Polymerization of
actin was induced at low ionic strength through ionophore-mediated influx of Mg2+ (2 mM). The spatial organization of the filamentous actin was visualized by confocal and epifluorescence microscopy as a
function of the filaments length and membrane composition, by including various amounts of cholesterol or lipids with neutral
and positively charged polyethyleneglycol headgroups (PEG lipopolymers). In vesicles of pure DMPC, the newly polymerized actin
adsorbs to the membrane and forms a thin shell. In the presence of 2.5 mol% lipopolymers or of cholesterol at a molar fraction
x = 0.37, formation of a thin adsorbed film is impeded. A fuzzy cortex is predominantly formed in vesicles of diameter d smaller than the filament persistence length ( d ⩽ 15μm) while for larger vesicles a homogeneous network formation is favoured in the bulk of the vesicle. The fuzzy-cortex
formation is interpreted as a consequence of the reduction of the bending energy if the actin filaments accumulate close to
the vesicle wall.
Received: 17 January 2002 / Accepted: 21 March 2003 / Published online: 24 April 2003
RID="a"
ID="a"e-mail: Laurent_Limozin@ph.tum.de 相似文献
20.
Single- and double-stranded DNA and many biological and synthetic polyelectrolytes undergo two structural transitions upon
increasing the concentration of multivalent salt or molecules. First, the expanded-stretched chains in low monovalent salt
solutions collapse into nearly neutral compact structures when the density of multivalent salt approaches that of the monomers.
With further addition of multivalent salt the chains redissolve acquiring expanded-coiled conformations. We study the redissolution
transition using a two-state model (F.J. Solis, M. Olvera de la Cruz, J. Chem. Phys. 112, 2030 (2000)). The redissolution occurs when there is a high degree of screening of the electrostatic interactions between
monomers, thus reducing the energy of the expanded state. The transition is determined by the chemical potential of the multivalent
ions in the solution, μ and the inverse screening length, κ. The transition point also depends on the charge distribution
along the chain but is nearly independent of the molecular weight and degree of flexibility of the polyelectrolytes. We generate
a diagram of μversusκ2 where we find two regions of expanded conformations, one with charged chains and the other with overcharged (inverted charge)
chains, separated by a collapsed nearly neutral conformation region. The collapse and redissolution transitions occur when
the trajectory of the properties of the salt crosses the boundaries between these regions. We find that in most cases the
redissolution occurs within the same expanded branch from which the chain precipitates.
Received 15 May 2000 and Received in final form 28 June 2000 相似文献