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Register a new userPolyelectrolytes in the presence of multivalent ions: gelation versus segregation
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Added by
Aleksander Ermoshkin
Publication date
2002
fields
Physics
and research's language is
English
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We analyze solutions of strongly charged chains bridged by linkers such as multivalent ions. The gelation induced by the strong short range electrostatic attractions is dramatically suppressed by the long range electrostatic correlations due to the charge along the uncrosslinked monomers and ions. A modified Debye-Huckel approach of crosslinked clusters of charged chains is used to determined the mean field gelation transition self-consistently. Highly dilute polyelectrolyte solutions tend to segregate macroscopically. Semidilute solutions can form gels if the Bjerrum length $l_B$ and the distance between neighboring charged monomers along the chain $b$ are both greater than the ion size $a$.
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The collapse of flexible polyelectrolytes in a solution of multivalent counterions is studied by means of a two state model. The states correspond to rod-like and spherically collapsed conformations respectively. We focus on the very dilute monomer concentration regime where the collapse transition is found to occur when the charge of the multivalent salt is comparable (but smaller) to that of the monomers. The main contribution to the free energy of the collapsed conformation is linear in the number of monomers $N$, since the internal state of the collapsed polymer approaches that of an amorphous ionic solid. The free energy of the rod-like state grows as $Nln N$, due to the electrostatic energy associated with that shape. We show that practically all multivalent counterions added to the system are condensed into the polymer chain, even before the collapse.
Polyelectrolytes such as single and double stranded DNA and many synthetic polymers 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. Solis and M. Olvera de la Cruz, {it J. Chem. Phys.} {bf 112} (2000) 2030]. 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 $mu$ and the inverse screening length $kappa$. The transition point also depends on the charge distribution along the chain but is almost independent of the molecular weight and degree of flexibility of the polyelectrolytes. We generate a diagram of $mu$ versus $kappa^2$ where we find two regions of expanded conformations, one with charged chains and 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.
We investigate the properties of rigid polyelectrolyte solutions in presence of monovalent salt. The free energy within the Debye-Huckel-Bjerrum (DHBj) theory [M. E. Fisher and Y. Levin, {it Phys. Rev. Lett.} 71, 3826 (1993)] is constructed. It is found that at thermodynamic equilibrium the polyelectrolyte solution consists of clusters composed of one polyion and various counterions. The distribution of the cluster densities is determined by finding the minimum of the Helmholtz free energy. The osmotic pressure and the average charge of the cluster are found and their dependence on Manning parameter $xi$ is elucidated. A good agreement with the experimental results is obtained.
The effective force between two parallel DNA molecules is calculated as a function of their mutual separation for different valencies of counter- and salt ions and different salt concentrations. Computer simulations of the primitive model are used and the shape of the DNA molecules is accurately modelled using different geometrical shapes. We find that multivalent ions induce a significant attraction between the DNA molecules whose strength can be tuned by the averaged valency of the ions. The physical origin of the attraction is traced back either to electrostatics or to entropic contributions. For multivalent counter- and monovalent salt ions, we find a salt-induced stabilization effect: the force is first attractive but gets repulsive for increasing salt concentration. Furthermore, we show that the multivalent-ion-induced attraction does not necessarily correlate with DNA overcharging.
We discuss the distribution of ions around highly charged PEs when there is competition between monovalent and multivalent ions, pointing out that in this case the number of condensed ions is sensitive to short-range interactions, salt, and model-dependent approximations. This sensitivity is discussed in the context of recent experiments on DNA aggregation, induced by multivalent counterions such as spermine and spermidine.
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