Precipitation of highly charged polyelectrolyte solutions in the presence of multivalent salts

Cruz, Mónica Olvera de la; Belloni, Luc; Delsanti, M.; Dalbiez, Jean‐Pierre; Spalla, Olivier; Drifford, M.

doi:10.1063/1.470459

Cited by 337 publications

(419 citation statements)

References 25 publications

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“…26. The data show that the effective charge amount was reduced upon an increase in the Ca 2+ concentration.͒ "Ion-bridging effect" may be another reason, 9,33,34 i.e., each multivalent cation replaces the monovalent counterion formerly condensed on the PSS − chain and binds more than one charged monomers so that two chain segments come together. When this bridging effect occurs within the chain, it makes the chain fold into a more compact structure, much smaller than the mere electric screening effect with monovalent salt.…”

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confidence: 85%

“…The phenomenon is observed as the precipitation of the solute in aqueous solution upon the addition of multivalent salts up to a critical amount, and the precipitation redissolves into the solution when the salt concentration is further elevated beyond another value. Such a phenomenon involves almost every kind of soft matter systems carrying charges, including biomacromolecules such as DNA 1-5 and protein, [6][7][8] charged polymers such as polyelectrolytes, [9][10][11][12][13][14] as well as colloidal particles. 15 The mystery of re-entrant condensation has been attracting intensive research interests for decades.…”

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confidence: 99%

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Single chain contraction and re-expansion of polystyrene sulfonate: A study on its re-entrant condensation at single molecular level

Jia

Zhao

2009

The Journal of Chemical Physics

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Single chain conformation of a polyelectrolyte (polystyrene sulfonate, PSS−Na+) during its re-entrant condensation was studied by fluorescence correlation spectroscopy (FCS) with single molecule sensitivity. The contraction and re-expansion of PSS−Na+ chain were observed with the addition of counterions of different valencies. The formation of aggregation and precipitation of PSS−Na+ and its redissolution were observed in accordance with the chain contraction and re-expansion process for the PSS−Na+ chain upon the addition of trivalent La3+ ion. Chain contraction and re-expansion of the PSS−Na+ chain were also observed with the addition of monovalent Cs+ and divalent Ca2+ ions, under which condition, the re-entrant condensation was not observed. The results demonstrate that the high sensitivity of FCS can really study single PSS−Na+ chain under extremely dilute situation.

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confidence: 85%

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confidence: 99%

Single chain contraction and re-expansion of polystyrene sulfonate: A study on its re-entrant condensation at single molecular level

Jia

Zhao

2009

The Journal of Chemical Physics

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“…DNA with short polyamines is a good example of such systems [10,11,12]. In this case, the phase diagram gets another dimension, say, the concentration of PC, p. The effect of PC entropy was discussed in detail in Ref.…”

Section: The Role Of the Translational Entropy Of Polycationsmentioning

confidence: 99%

“…On the other hand, the phase diagram of a solution of DNA and short polyamines was studied in Refs. [10,11,12] in which translational entropy of polyamines plays a very important role. We postpone discussion of the role of translational entropy till the end of this paper (Sec.…”

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Phase diagram of solution of oppositely charged polyelectrolytes

Zhang

Shklovskiǐ

2005

Physica A: Statistical Mechanics and its Applications

144

166

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We study a solution of long polyanions (PA) with shorter polycations (PC) and focus on the role of Coulomb interaction. A good example is solutions of DNA and PC which are widely studied for gene therapy. In the solution, each PA attracts many PCs to form a complex. When the ratio of total charges of PA and PC in the solution, x, equals to 1, complexes are neutral and they condense in a macroscopic drop. When x is far away from 1, complexes are strongly charged. The Coulomb repulsion is large and free complexes are stable. As x approaches to 1, PCs attached to PA disproportionate themselves in two competing ways. One way is inter-complex disproportionation, in which PCs make some complexes neutral and therefore condensed in a macroscopic drop while other complexes become even stronger charged and stay free. The other way is intra-complex disproportionation, in which PCs make one end of a complex neutral and condensed in a small droplet while the rest of the complex forms a strongly charged tail. Thus each complex becomes a "tadpole". These two ways can also combine together to give even lower free energy. We get a phase diagram of PA-PC solution in a plane of x and inverse screening radius of the monovalent salt, which includes phases or phase coexistence with both kinds of disproportionation.

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“…Qg, 61.25.Hq, 87.15.Aa Strongly charged polymers precipitate from a dilute solution into compact structures when high-valence counterions (oppositely charged particles) are added to the solution [1][2][3][4][5][6]. The counterions experience strong electrostatic attractions to the backbone of the chains, and a finite fraction of them "condense", i.e., are found within short distance from the chains [7].…”

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Attractive interactions between rodlike polyelectrolytes: Polarization, crystallization, and packing

1999

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We study the attractive interactions between rod-like charged polymers in solution that appear in the presence of multi-valence counterions. The counterions condensed to the rods exhibit both a strong transversal polarization and a longitudinal crystalline arrangement. At short distances between the rods, the fraction of condensed counterions increases, and the majority of these occupy the region between the rods, where they minimize their repulsive interactions by arranging themselves into packing structures. The attractive interaction is strongest for multivalent counterions. Our model takes into account the hard-core volume of the condensed counterions and their angular distribution around the rods. The hard core constraint strongly suppresses longitudinal charge fluctuations.PACS numbers: 61.20. Qg, 61.25.Hq, 87.15.Aa Strongly charged polymers precipitate from a dilute solution into compact structures when high-valence counterions (oppositely charged particles) are added to the solution [1][2][3][4][5][6]. The counterions experience strong electrostatic attractions to the backbone of the chains, and a finite fraction of them "condense", i.e., are found within short distance from the chains [7]. Counterions are more attracted to compact chains or aggregates of rod-like chains. This creates the possibility of a transition from single chains with a small number of condensed counterions to almost neutral aggregates of chains, or even mono-molecular collapse in the case of flexible polymers. These aggregates are stable only when the internal arrangement of the counterions within them, provides a strong enough cohesive energy.In this letter we study the attraction between two rodlike polyelectrolytes. We show that it is essential to include the size and angular degrees of freedom (around the rods) of the counterions as well as the discrete nature of the charge along the polyelectrolytes to find the origin and strength of the counterion mediated attraction. Our work suggests that these factors are also crucial in determining the collapse of flexible and semi-flexible polyelectrolytes recently studied in Refs. [8][9][10][11][12]. Experimental observations show that the size of the precipitating particles is indeed a relevant parameter in the problem [1,6].It has been argued that longitudinal charge fluctuations resulting from the thermal motion of point counterions induce attractions between rod-like polyelelctrolytes [13,14] and induces "buckling" of semiflexible polyelelctrolytes [11,12]. Here, we show that such charge fluctuation are suppressed when the hard core volume of monomers and counterions are taken into account. Instead, we find that the counterions arrangement around the rods create a non-zero transversal polarization as the distance between the chains decreases. At very short distances between the rods we find strong longitudinal correlations but only at very short wavelengths, implying a crystalline state along the rod, reinforcing, for the case of multivalent counterions, the attractive interactio...

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Precipitation of highly charged polyelectrolyte solutions in the presence of multivalent salts

Cited by 337 publications

References 25 publications

Single chain contraction and re-expansion of polystyrene sulfonate: A study on its re-entrant condensation at single molecular level

Single chain contraction and re-expansion of polystyrene sulfonate: A study on its re-entrant condensation at single molecular level

Phase diagram of solution of oppositely charged polyelectrolytes

Attractive interactions between rodlike polyelectrolytes: Polarization, crystallization, and packing

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