Simulations of Polyelectrolyte Adsorption to a Dielectric Like-Charged Surface

Santos, Alexandre Pereira dos; Girotto, Matheus; Levin, Yan

doi:10.1021/acs.jpcb.6b06002

Cited by 38 publications

(44 citation statements)

References 64 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…5, the like charge adsorption at s = 0.3 s * ≈ 3.7 × 10 −3 takes place without the occurrence of the CI. This shows the absence of one-to-one mapping between the membrane CI and the like-charge polyelectrolyte-membrane complexation driven by the "salt-induced" image interaction excess; in agreement with the observation of recent Monte-Carlo (MC) simulations [19], the like-charge polyelectrolyte binding may occur at membrane charge strengths well below the threshold (88) required for the onset of the CI. To summarize, at moderate membrane charges s > s * , the like-charge polyelectrolyte binding can occur exclusively as a result of the salt-induced "image-charge" effect enhanced by the dense cations in the close vicinity of the membrane.…”

Section: Strong Membrane Charges: Like-charge Adsorption By Membrane supporting

confidence: 90%

“…Taking also into account the 1l limit of the self-energy ∆Ω (1) pp that will be obtained below from Eq. (24), the 1l-level polyelectrolyte grand potential (19) becomes…”

Section: One-loop Formalism Of Electrostatic Interactionsmentioning

confidence: 99%

“…In recent adsorption experiments [15][16][17][18] and numerical simulations of DNA molecules at anionic membranes [14,19], the like-charge polyelectrolyte-membrane attraction was found to be strongly enhanced by multivalent counterions. Since the electrostatic coupling strength of the system grows with the ion valency, this observation points out ionic correlations as the driving force of the like-charge polyelectrolyte-membrane complexation, either at intermediate coupling stemming from the fluctuations around the mean-field ground state, or at strong coupling conditions where they are the result of altogether non-mean-field like states [8].…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Orientational transition and complexation of DNA with anionic membranes: Weak and intermediate electrostatic coupling

Buyukdagli

Podgornik

2019

Phys. Rev. E

View full text Add to dashboard Cite

We characterize the role of charge correlations in the adsorption of a short, rod-like anionic polyelectrolyte onto a similarly charged membrane. Our theory reveals two different mechanisms driving the like-charge polyelectrolyte-membrane complexation: in weakly charged membranes, repulsive polyelectrolyte-membrane interactions lead to the interfacial depletion and a parallel orientation of the polyelectrolyte with respect to the membrane; while in the intermediate membrane charge regime, the interfacial counterion excess gives rise to an attractive "salt-induced" image force. This furthermore results in an orientational transition from a parallel to a perpendicular configuration and a subsequent short-ranged like-charge adsorption of the polyelectrolyte to the substrate. A further increase of the membrane charge engenders a charge inversion, originating from surface-induced ionic correlations, that act as a separate mechanism capable of triggering the like-charge polyelectrolyte-membrane complexation over an extended distance interval from the membrane surface. The emerging picture of this complexation phenomenon identifies the interfacial "salt-induced" image forces as a powerful control mechanism in polyelectrolyte-membrane complexation.

show abstract

Section: Strong Membrane Charges: Like-charge Adsorption By Membrane supporting

confidence: 90%

“…Taking also into account the 1l limit of the self-energy ∆Ω (1) pp that will be obtained below from Eq. (24), the 1l-level polyelectrolyte grand potential (19) becomes…”

Section: One-loop Formalism Of Electrostatic Interactionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Orientational transition and complexation of DNA with anionic membranes: Weak and intermediate electrostatic coupling

Buyukdagli

Podgornik

2019

Phys. Rev. E

View full text Add to dashboard Cite

show abstract

“…The biological functions of this anionic molecule are intimately related to its electrostatic coupling with the surrounding macromolecular charges. In this context, the like-charge attraction phenomenon plays a capital role in DNA packing around histones [1], the condensation of polymer solutions [2][3][4][5][6][7][8][9], DNA adsorption on anionic substrates [10][11][12][13], and gene delivery techniques [14]. The characterization of like-charge attraction is thus of paramount importance for understanding and controlling in vivo and in vitro biological processes involving DNA molecules.…”

Section: Introductionmentioning

confidence: 99%

Like-charge attraction and opposite-charge decomplexation between polymers and DNA molecules

Buyukdagli

2017

Phys. Rev. E

View full text Add to dashboard Cite

We scrutinize the effect of polyvalent ions on polymer-DNA interactions. We extend a recently developed test-charge theory [S. Buyukdagli et al., Phys. Rev. E 94, 042502 (2016)] to the case of a stiff polymer interacting with a DNA molecule in an electrolyte mixture. The theory accounts for one-loop level electrostatic correlation effects such as the ionic cloud deformation around the strongly charged DNA molecule as well as image-charge forces induced by the low DNA permittivity. Our model can reproduce and explain various characteristics of the experimental phase diagrams for polymer solutions. First, the addition of polyvalent cations to the electrolyte solution results in the attraction of the negatively charged polymer by the DNA molecule. The glue of the like-charge attraction is the enhanced shielding of the polymer charges by the dense counterion layer at the DNA surface. Second, through the shielding of the DNA-induced electrostatic potential, mono-and polyvalent cations of large concentration both suppress the like-charge attraction. Within the same formalism, we also predict a new opposite-charge repulsion effect between the DNA molecule and a positively charged polymer. In the presence of polyvalent anions such as sulfate or phosphate, their repulsion by the DNA charges leads to the charge screening deficiency of the region around the DNA molecule. This translates into a repulsive force that results in the decomplexation of the polymer from DNA. This opposite-charge repulsion phenomenon can be verified by current experiments and the underlying mechanism can be beneficial to gene therapeutic applications where the control over polymer-DNA interactions is the key factor.

show abstract

“…The nontrivial effects of surface polarization due to dielectric mismatch have also been addressed in numerous studies in the literature. [16][17][18][19][20][21][22][23] It is shown that polarization effects become particularly pronounced at high dielectric contrasts, [16][17][18][19][20] in the presence of multivalent ions, 21,22 and at highly curved interfaces. 22,23 Essentially, the electric field generated by the ions inside the confinement space polarizes the interface between the media, leading to nonzero induced charges that attract or repel the ions approaching the interface.…”

mentioning

confidence: 99%

Manipulation of Confined Polyelectrolyte Conformations through Dielectric Mismatch

Nguyen

Cruz

2019

ACS Nano

View full text Add to dashboard Cite

We demonstrate that a highly charged polyelectrolyte confined in a spherical cavity undergoes reversible transformations between amorphous conformations to a four-fold symmetry morphology as a function of dielectric mismatch between the media inside and outside the cavity. Surface polarization due to dielectric mismatch exhibits an extra "confinement" effect, which are most pronounced within a certain range of the cavity radius and the electrostatic strength between the monomers and counterions and multivalent counterions. For cavities with a charged surface, surface polarization leads to an increased amount of counterions adsorbed in the outer side, further compressing the confined polyelectrolyte into a four-fold symmetry morphology. The equilibrium conformation of the chain is dependent upon several key factors including the relative permittivities of the media inside and outside the cavity, multivalent counterion concentration, cavity radius relative to the chain length, and interface charge density. Our findings offer insights into the effects of dielectric mismatch in packaging and delivery of polyelectrolytes across media with different relative permittivities. Moreover, the reversible transformation of the polyelectrolyte conformations in response to environmental permittivity allows for potential applications in biosensing and medical monitoring.

show abstract

Simulations of Polyelectrolyte Adsorption to a Dielectric Like-Charged Surface

Cited by 38 publications

References 64 publications

Orientational transition and complexation of DNA with anionic membranes: Weak and intermediate electrostatic coupling

Orientational transition and complexation of DNA with anionic membranes: Weak and intermediate electrostatic coupling

Like-charge attraction and opposite-charge decomplexation between polymers and DNA molecules

Manipulation of Confined Polyelectrolyte Conformations through Dielectric Mismatch

Contact Info

Product

Resources

About