Multivalent ions induce lateral structural inhomogeneities in polyelectrolyte brushes

Yu, Jing; Jackson, Nicholas E.; Xu, Xin; Brettmann, Blair; Ruths, Marina; Pablo, Juan J. de; Tirrell, Matthew

doi:10.1126/sciadv.aao1497

Cited by 94 publications

(119 citation statements)

References 49 publications

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“…Depending on the chain stiffness, brush condensates adopt diverse morphological patterns that vary from semi-spherical octopus-like micelle domains to cylindrical bundles of rigid chains which protrude from the grafting surface. It was shown that when the grafting density is in a proper range, multivalent counterions can collapse flexible PE brush even in good solvent into octopus-like surface micelles displaying substantial lateral heterogeneity [42][43][44] , which has recently been confirmed experimentally for polystyrene sulfonate brush condensates in Y(NO 3 ) 3 solution 45 .…”

Section: Introductionmentioning

confidence: 81%

From octopus to dendrite—Semiflexible polyelectrolyte brush condensates in trivalent counterion solution

Liu

Hyeon

2018

The Journal of Chemical Physics

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Interplay between counterion-mediated interaction and stiffness inherent to polymer chain can bring substantial complexity to the morphology and dynamics of polyelectrolyte brush condensates. Trivalent counterions induce collapse of flexible polyelectrolyte brushes, over a certain range of grafting density, into octopus-like surface micelles; however, if individual chains are rigid enough, the ion-mediated local nematic ordering assembles the brush chains into fractal-like dendritic condensates whose relaxation dynamics is significantly slower than that in the surface micelles. Notably, the trivalent ions condensed in the dendritic condensates are highly mobile displaying quasi-one-dimensional diffusion in parallel along the dendritic branches. Our findings in this study are potentially of great significance to understanding the response of cellular organization such as chromosomes and charged polysaccharides on membranes to the change in ionic environment. arXiv:1803.00167v1 [cond-mat.soft]

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Section: Introductionmentioning

confidence: 81%

From octopus to dendrite—Semiflexible polyelectrolyte brush condensates in trivalent counterion solution

Liu

Hyeon

2018

The Journal of Chemical Physics

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“…The collapse of polyelectrolyte brushes is largely caused by multivalent‐ion‐mediated interchain crosslinks . Both divalent and trivalent counterions can cause the collapse of polyelectrolyte brushes, but divalent ions show high ion specificity .…”

Section: Sfa Measurements On Polyelectrolyte Brushesmentioning

confidence: 99%

“…In contrast, a low concentration of Y 3+ ions (cf. Figure ) causes the collapse of the brush into a heterogeneous film, with apparent aggregation ascribed to the bridging of different chains by the multivalent ions …”

Section: Afm Measurements On Polyelectrolyte Brushesmentioning

confidence: 99%

“…[33d] The collapse of polyelectrolyteb rushes is largely caused by multivalent-ion-mediated interchainc rosslinks. [37] Both divalent and trivalent counterions can cause the collapse of polyelectrolyte brushes, but divalent ions show high ion specificity. [33d] The collapse of PSS brushes follows the trend Ba 2+ + > Ca 2+ + > Mg 2+ + ,w hich follows the order of their ionic radii.…”

Section: Normal and Friction Force Measurements By Sfamentioning

confidence: 99%

“…b) MD simulations haveshown that multivalent-ion-induced effects driveastrong phase separation of polyelectrolyte brushes. Adapted with permission from Ref [37]…”

mentioning

confidence: 99%

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Structure and Functionality of Polyelectrolyte Brushes: A Surface Force Perspective

Billing

Ruths

et al. 2018

Chemistry An Asian Journal

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The unique functionality of polyelectrolyte brushes depends on several types of specific interactions, including solvent structure effects, hydrophobic forces, electrostatic interactions, and specific ion interactions. Subtle variations in the solution environment can lead to conformational and surface structural changes of the polyelectrolyte brushes, which are mainly discussed from a surface-interaction perspective in this Focus Review. A brief overview is given of recent theoretical and experimental progress in the structure of polyelectrolyte brushes in various environments. Two important techniques for surface-force measurements are described, the surface forces apparatus (SFA) and atomic force microscopy (AFM), and some recent results on polyelectrolyte brushes are shown. Lastly, this Focus Review highlights the use of these surface-grafted polyelectrolyte brushes in the creation of functional surfaces for various applications, including nonfouling surfaces, boundary lubricants, and stimuli-responsive surfaces.

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Simulation Study of the Conformational Properties of Diblock Polyelectrolytes in Salt Solutions

Dabhade

Chaudhury

2021

Chemistry An Asian Journal

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Coarse‐grained molecular dynamics simulations are performed to understand the behavior of diblock polyelectrolytes in solutions of divalent salt by studying the conformations of chains over a wide range of salt concentrations. The polymer molecules are modeled as bead spring chains with different charged fractions and the counterions and salt ions are incorporated explicitly. Upon addition of a divalent salt, the salt cations replace the monovalent counterions, and the condensation of divalent salt cations onto the polyelectrolyte increases, and the chains favor to collapse. The condensation of ions changes with the salt concentration and depends on the charged fraction. Also, the degree of collapse at a given salt concentration changes with the increasing valency of the counterion due to the bridging effect. As a quantitative measure of the distribution of counterions around the polyelectrolyte chain, we study the radial distribution function between monomers on different polyelectrolytes and the counterions inside the counterion worm surrounding a polymer chain at different concentrations of the divalent salt. Our simulation results show a strong dependence of salt concentration on the conformational properties of diblock copolymers and indicate that it can tune the self‐assembly behaviors of such charged polyelectrolyte block copolymers.

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Multivalent ions induce lateral structural inhomogeneities in polyelectrolyte brushes

Abstract: Polymer chain bridging by multivalent ions and solvophobic attractions drives structure formation in charged polymer brushes.

Cited by 94 publications

References 49 publications

From octopus to dendrite—Semiflexible polyelectrolyte brush condensates in trivalent counterion solution

From octopus to dendrite—Semiflexible polyelectrolyte brush condensates in trivalent counterion solution

Structure and Functionality of Polyelectrolyte Brushes: A Surface Force Perspective

Simulation Study of the Conformational Properties of Diblock Polyelectrolytes in Salt Solutions

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