Complexation of semiflexible chains with oppositely charged cylinder

Cherstvy, Andrey G.; Winkler, Roland G.

doi:10.1063/1.1707015

Cited by 53 publications

(43 citation statements)

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“…The thermodynamic ensemble considered in Ref. [208] is different since the cylinder self-energy was not subtracted; it consequently gives results very different from our scheme. We compare two morphologies, namely a helical arrangement of the PE, where a single helix, characterized by the length ratio of the wrapped polymer section and the cylinder length, wraps around the cylinder (see Fig.21b), and the straight morphology, where n parallel strands of PE adsorb on the cylinder.…”

Section: Polyelectrolytes At Charged Cylindersmentioning

confidence: 98%

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Statics and dynamics of strongly charged soft matter

Boroudjerdi¹,

Kim²,

Naji³

et al. 2005

Physics Reports

347

523

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Soft matter materials, such as polymers, membranes, proteins, are often electrically charged. This makes them water soluble, which is of great importance in technological application and a prerequisite for biological function. We discuss a few static and dynamic systems that are dominated by charge effects. One class comprises complexation between oppositely charged objects, for example the adsorption of charged ions or charged polymers on oppositely charged substrates of different geometry. Here the main questions are whether adsorption occurs and what the effective charge of the resulting complex is. We explicitly discuss the adsorption behavior of polyelectrolytes on substrates of planar, cylindrical and spherical geometry with specific reference to DNA adsorption on supported charged lipid layers, DNA adsorption on oppositely charged cylindrical dendro-polymers, and DNA binding on globular histone proteins, respectively. In all these systems salt plays an important role, and some of the important features can already be obtained on the linear Debye-Hückel level. The second class comprises effective interactions between similarly charged objects. Here the main theme is to understand the experimental finding that similarly and highly charged bodies attract each other in the presence of multi-valent counterions. This is demonstrated using field-theoretic arguments as well as Monte-Carlo simulations for the case of two homogeneously charged bodies. Realistic surfaces, on the other hand, are corrugated and also exhibit modulated charge distributions, which is important for static properties such as the counterion-density distribution, but has even more pronounced consequences for dynamic properties such as the counterion mobility. More pronounced dynamic effects are obtained with highly condensed charged systems in strong electric fields. Likewise, an electrostatically collapsed highly charged polymer is unfolded and oriented in strong electric fields. All charged systems occur in water, and water by itself is not a very well understood material. At the end of this review, we give a very brief and incomplete account of the behavior of water at planar surfaces. The coupling between water structure and charge effects is largely unexplored, and a few directions for future research are sketched. On an even more nanoscopic level, we demonstrate using ab-initio methods that specific interactions between oppositely charged groups (which occur when their electron orbitals start to overlap) are important and cause ion-specific effects that have recently moved into the focus of interest.

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Section: Polyelectrolytes At Charged Cylindersmentioning

confidence: 98%

“…b) The two posibble wrapping morphologies that are theoretically studied and compared. 208,209]. Experimentally, such complexes itself fold up into toroidal or stem-like structures under dilute conditions [210,211]; in more concentrated solutions, bundles and networks are observed [212].…”

Section: Polyelectrolytes At Charged Cylindersmentioning

confidence: 99%

Statics and dynamics of strongly charged soft matter

Boroudjerdi¹,

Kim²,

Naji³

et al. 2005

Physics Reports

347

523

View full text Add to dashboard Cite

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“…For strong PE-rod adsorption, a polymer ordering and helical-like wrapping have been quantified in a number of theoretical studies. [50][51][52] These results might find their applications in the cutting edge area of DNA interactions with carbon nanotubes. For the latter, a helical wrapping of flexible singlestranded DNA chains around single-wall carbon nano-tubes with a well-defined helical pitch has recently been systematically examined in experiments, [53][54][55] quantified by theoretical modeling, [56][57][58] and mimicked by computer simulations.…”

Section: Possible Extensions and Perspectivesmentioning

confidence: 99%

Polyelectrolyte adsorption onto oppositely charged interfaces: unified approach for plane, cylinder, and sphere

Cherstvy

Winkler

2011

Phys. Chem. Chem. Phys.

113

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A universal description is presented for weak adsorption of flexible polyelectrolyte chains onto oppositely charged planar and curved surfaces. It is based on the WKB (Wentzel-Kramers-Brillouin) quantum mechanical method for the Green function equation in the ground state dominance limit. The approach provides a unified picture for the scaling behavior of the critical characteristics of polyelectrolyte adsorption and the thickness of the adsorbed polymer layer formed adjacent to the interface. We find, particularly at low-salt conditions, that curved convex surfaces necessitate much larger surface charge densities to trigger polyelectrolyte adsorption, as compared to a planar interface in the same solution. In addition, we demonstrate that the different surface geometries yield very distinct scaling laws for the critical surface charge density required to initiate chain adsorption. Namely, in the low-salt limit, the surface charge density scales cubical with the inverse Debye screening length for a plane, quadratic for an adsorbing cylinder, and linear for a sphere. As the radius of surface curvature grows, the parameter of critical chain adsorption onto a rod and a sphere turns asymptotically into that of a planar interface. The transition occurs when the radius of surface curvature becomes comparable to the Debye screening length. The general scaling trends derived appear to be consistent with the complex-formation experiments of polyelectrolyte chains with oppositely charged spherical and cylindrical micelles. Finally, the WKB results are compared with the existing theories of polyelectrolyte adsorption and future perspectives are outlined.

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“…Here, the chain entropy becomes less important; the pattern is rather governed by maximization of polyelectrolyte-sphere attraction and minimization of polyelectrolyte-polyelectrolyte repulsion. Within a simple model, the solution of the linear Poisson-Boltzmann equation for such charge patterns predicts that neutral and undercharged complexes are favored [30,31].…”

Section: -2mentioning

confidence: 99%

Critical Adsorption of Polyelectrolytes onto Charged Spherical Colloids

Winkler

Cherstvy

2006

Phys. Rev. Lett.

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The adsorption of a flexible polyelectrolyte in a salt solution onto an oppositely charged spherical surface is investigated. An analytical solution is derived, which is valid for any sphere radius and consistently recovers the result of a planar surface in the limit of large sphere radii, by substituting the Debye-Hückel potential via the Hulthén potential. Expressions for critical quantities such as the critical radius and the critical surface charge density are provide. A comparison of our theoretical results with experiments and computer simulations yields remarkable good agreement. DOI: 10.1103/PhysRevLett.96.066103 PACS numbers: 68.43.De, 82.35.Rs The complexation of charged macroions by oppositely charged polyelectrolytes is a fundamental process in biological systems and many technical applications. Particular examples are the complexation of histone proteins by DNA in nucleosomal core particles [1,2] as well as complexes of polyelectrolytes with charged colloids and micelles [3]. Industrial applications are as diverse as stabilization of colloidal suspensions, water treatment, and paper making [4].The understanding of the complexation between a polyion and a macroion surface accompanied by screening effects due to counterions and salt posses a major theoretical challenge [5]. Despite significant efforts and progresses [5][6][7][8][9][10][11], the understanding of charged complexes is still unsatisfactory and lacks behind that of neutral complexes. Certain insight into the complexation process is typically obtained by approximation schemes, e.g., variational calculations [6 -9], which, however, may lead to controversial results [12] and often apply only in limiting situations such as pointlike particles [9] or large colloidal radii [6].The theoretical studies of the adsorption behavior of polyelectrolytes onto spherical surfaces [7,10,11,13,14] lead to the observation of a phase-transition-like behavior; i.e., a bound polymer state appears at certain critical conditions which depend on, e.g., the sphere radius and screening of the Coulomb interaction. The variational calculations of Muthukumar and his co-workers [6,8] have provided useful insight into this transition in the limit of large sphere radii. Experiments on polyelectrolyte-protein and -micelle complexes [15] and computer simulations [14], however, typically yield dependencies of the critical quantities on the Debye screening length which deviate from the theoretical predictions. To understand and interpret the experimental results correctly, an analytical solution of the adsorption problem valid for any sphere radius is mandatory.In this Letter, we will present an exact solution for the critical adsorption of a flexible polyelectrolyte onto an oppositely charged spherical macroion. Expressions for critical quantities are provided, which are valid for any sphere radius. In particular, in the limit of zero macroion curvature, the results for a planar surface are obtained. In general, we find a significantly different dependence of the critica...

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Complexation of semiflexible chains with oppositely charged cylinder

Cited by 53 publications

References 54 publications

Statics and dynamics of strongly charged soft matter

Statics and dynamics of strongly charged soft matter

Polyelectrolyte adsorption onto oppositely charged interfaces: unified approach for plane, cylinder, and sphere

Critical Adsorption of Polyelectrolytes onto Charged Spherical Colloids

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