Comparison of experimental and theoretical persistence length of some polyelectrolytes at various ionic strengths

Tricot, Michel

doi:10.1021/ma00139a010

Cited by 178 publications

(133 citation statements)

References 12 publications

(15 reference statements)

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“…In addition, there is a number of recent theories which fall into neither of the two classes outlined above [14,15,16,17,18]. While there is a growing consensus among theoreticians that the OSFKK result is asymptotically correct [19,20,21], experiments [22,23,24,25,26] as well as computer simulations [27,28,29] have consistently provided evidence for a comparatively weak κ-dependence of the electrostatic presistence length.…”

Section: Introductionmentioning

confidence: 99%

The electrostatic persistence length of polymers beyond the OSF limit

2002

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Abstract. We use large scale Monte Carlo simulations to test scaling theories for the electrostatic persistence length le 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 le ∝ κ −2 by Khokhlov and Khachaturian which is based on applying the Odijk-Skolnick-Fixman theory 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 argue that previous numerical results pointing into this direction are probably 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.PACS. 6 4.60.-i -3 6.20.-r -8 7.15.By

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Section: Introductionmentioning

confidence: 99%

The electrostatic persistence length of polymers beyond the OSF limit

2002

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“…Persistence length of polyelectrolytes varies with solution ionic strength, 21 due to screening of the electrostatic repulsion between the polymer backbone charges; [22][23][24][25] therefore changing ionic strength is a convenient way to alter the configuration of the polymer molecule systematically.…”

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Persistence Length Control of the Polyelectrolyte Layer-by-Layer Self-Assembly on Carbon Nanotubes

et al. 2005

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We have studied layer-by-layer polyelectrolyte self-assembly on pristine individual single-wall carbon nanotubes as a function of solution ionic strength. We report the existence of an ionic strength threshold for the deposition, below which the majority of nanotubes remain uncoated. Once the ionic strength reaches the threshold value, the majority of the individual nanotubes become coated with polyelectrolytes. Our results indicate that the self-assembly process likely involves wrapping of polymer chains around nanotubes and that the polymer chain's ability to bend in order to accommodate the nanotube curvature is one of the critical parameters controlling layer-by-layer electrostatic self-assembly on these one-dimensional templates.

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“…It should be noted that, though slopes of about -0.5 were reported for several intrinsically flexible or weakly stiff polyelectrolytes, 23 • 24 they were derived from q data estimated without consideration of excluded-volume effects.…”

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confidence: 99%

Electrostatic Contributions to Chain Stiffness and Excluded-Volume Effects in Sodium Poly(styrenesulfonate) Solutions

Iwamoto

Hirose

Norisuye

2000

Polym J

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ABSTRACT:Intrinsic viscosities for sodium poly(styrenesulfonate) in aqueous sodium chloride at 25°C have been determined for 15 samples ranging in weight-average molecular weight from 3.8 X 10 3 to 6.5 X 10 5 at five salt concentrations C, between 0.05 and 2 M. Their molecular weight dependence at each C, is fairly satisfactorily explained by the theory ofYoshizaki et al. for unperturbed wormlike chains combined with the quasi-two-parameter theory for excludedvolume effects. The estimated persistence length q and excluded-volume strength B both increase with decreasing C,. This increase in q is not quantitatively described by the known theories for the electrostatic persistence length when the previously determined q of 0.69 nm in 4.17 M aqueous NaCl at the theta point is used for the intrinsic persistence length. It is also shown that the values of B computed on the conventional bead model and the rodlike segment model in the Debye-Htickel approximation with the ion condensation hypothesis are too large compared to the experimental estimates at lower C, of0.05 and 0.1 M though the latter model gives considerably smaller B than does the former one.KEY WORDS Polyelectrolyte I Poly(styrenesulfonate) / Wormlike Chain/ Chain Stiffness/ Electrostatic Persistence Length/ Excluded-Volume Effect/ According to the current polyelectrolyte theory, 1 -4 the persistence length q of a charged linear polymer, modeled by the Kratky-Porod wormlike chain,5 in aqueous salt increases with lowering salt concentration Cs. Although much experimental work on this electrostatic stiffening effect has been reported in the past two decades, our understanding of it still leaves much to be desired, at least, for intrinsically flexible or weakly stiff polyelectrolytes. 6 The problem 7 • 8 is that the effects of chain stiffness and volume exclusion in those polymers can hardly be separated without resort to a relevant excluded-volume theory, but no such theory is, of course, as yet known. In this situation, it is intriguing and probably significant to estimate q and the excluded-volume strength B (or the binary cluster integral) from data for the intrinsic viscosity [1]] or the radius of gyration with the aid of the quasi-two-parameter (QTP) theory 9 -11 for uncharged wormlike or helical wormlike chains,9 since the theory is capable of almost quantitatively explaining the radius and viscosity expansion factors for nonionic polymers, both flexible 9 and stiff. 12In a series of previous studies, 7 • 13 -15 we made such attempts for aqueous NaCl solutions of sodium hyaluronate, a charged polysaccharide with a q of about 4 nm at high ionic strength and a linear charge density of 1 nm-1 , and drew the following conclusions. 1. The QTP scheme is applicable to this polysaccharide down to Cs = 0.01 M. 2. The electrostatic contribution to q obtained as a function of Cs is considerably larger than predicted by the known theories.1 -4 3. The dependence of estimated B on Cs is in moderate agreement with the FixmanSkolnick theory 16 for the excluded volum...

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Comparison of experimental and theoretical persistence length of some polyelectrolytes at various ionic strengths

Cited by 178 publications

References 12 publications

The electrostatic persistence length of polymers beyond the OSF limit

The electrostatic persistence length of polymers beyond the OSF limit

Persistence Length Control of the Polyelectrolyte Layer-by-Layer Self-Assembly on Carbon Nanotubes

Electrostatic Contributions to Chain Stiffness and Excluded-Volume Effects in Sodium Poly(styrenesulfonate) Solutions

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