Polyelectrolyte Brushes: Twenty Years After

Guénoun, P.

doi:10.1002/9783527638482.ch6

Cited by 5 publications

(5 citation statements)

References 106 publications

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“…Today, and increasingly so, scientists and engineers are able to prepare polymer coatings on surfaces in a range of architectures and with in-built designer functionalities and responsive properties. , Polymer brushesdense assemblies of polymer chains end-grafted to a substrateare a type of architecture that continues to receive attention . Brushes of weak (ionizable) polyelectrolytes are perhaps the most motivating case as they are both water-soluble and their extension and charge state can be manipulated by changes in environmental conditions like pH, ionic strength, and temperature. , To take one example, this tunable behavior becomes particularly interesting for many aqueous complex fluid applications. Indeed, nanoparticles modified with polyelectrolyte brushes have been shown to act as stimuli-responsive emulsifiers at remarkably low concentrations, perform as steric stabilizing layers in the challenging conditions of high temperature brines, work as oil recovery agents, and found to be highly effective at reducing the boundary lubrication between surfaces. − …”

Section: Introductionmentioning

confidence: 99%

Combined Experimental and Theoretical Study of Weak Polyelectrolyte Brushes in Salt Mixtures

et al. 2019

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The swelling behavior of a hydrophobic poly(2diisopropylamino)ethyl methacrylate (PDPA) brush immersed in aqueous solutions of single and mixed salts has been investigated using ellipsometry and numerical self-consistent field (nSCF) theory. As a function of solution ionic strength, the osmotic and salted brush regimes of weak polyelectrolyte brushes as well as substantial specific anion effects in the presence of K + salts of Cl – , NO 3 – , and SCN – are found. For solutions containing mixtures of NO 3 – and Cl – , the brush swelling is the same as one would expect on the basis of the concentration-weighted average of the brush behavior in the single salt solutions. However, in mixtures of SCN – and Cl – , the swelling response is more complicated and substantial divergence from ideal behavior is observed. Mean-field theory shows excellent qualitative agreement with the ellipsometry findings. nSCF reveals that for the SCN – /Cl – cases the swelling behavior of the PDPA brush most likely arises from the predominant localization of the weakly hydrated SCN – within the brush compared to the more strongly hydrated Cl – .

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Section: Introductionmentioning

confidence: 99%

Combined Experimental and Theoretical Study of Weak Polyelectrolyte Brushes in Salt Mixtures

et al. 2019

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“…Brushes formed from weak polyelectrolytes (composed of ionizable monomers) show particularly rich behavior with the solvent quality affected by both pH and ionic strength . The swelling behavior of hydrophilic polyelectrolyte brushes in simple 1:1 electrolytes has been well characterized, and close agreement between experiment and theory is possible . However, recent experiments show that these theories are incomplete, with brush behavior found to be strongly dependent on the hydrophobicity of the polymer and the identity of the anion used. , …”

Section: Introductionmentioning

confidence: 99%

Influence of Anion Hydrophilicity on the Conformation of a Hydrophobic Weak Polyelectrolyte Brush

et al. 2016

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The conformation of a hydrophobic, weak cationic poly(2-diisopropylamino)ethyl methacrylate (PDPA) brush was studied using neutron reflectometry as a function of aqueous solution pH, ionic strength, and anion identity. In pH 4, 10 mM potassium nitrate the brush is highly charged, resulting in an extended, dilute conformation; at pH 9 the uncharged brush collapses to a single, dense layer. The brush response to added salt at constant pH (4.5) for varying concentrations of the potassium salts of acetate, nitrate, and thiocyanate revealed ion-specific conformations of the brush. At low ionic strength (0.1 mM) the brush was collapsed, independent of salt identity, while at higher ionic strengths (up to 500 mM) the conformation was dependent on counterion identity. The brush exhibited extended conformations in the presence of kosmotropic acetate counterions, while collapsed conformations were retained in the presence of strongly chaotropic thiocyanate counterions. The brush showed a richer set of behaviors in the solutions containing the weakly chaotropic nitrate anion, being similar to acetate (swollen) at intermediate concentrations but similar to thiocyanate (collapsed) at high salt concentrations. Numerical self-consistent field (nSCF) simulations indicate that the response of the brush to pH changes is dominated by the hydrophobicity of the polymer at pH values near the pK a. Furthermore, the simulations reveal that the addition of a single Flory–Huggins interaction parameter analogous to the hydrophilicity of the counterion is sufficient to replicate the observed specific anion response of a hydrophobic weak polyelectrolyte brush.

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“…Leaving an enormous number of PE brush studies to reviews (see, e.g., refs. [ 42 , 43 ]), we mention here only few publications on scaling models [ 44 , 45 , 46 , 47 ], analytical [ 48 , 49 , 50 ] and numerical [ 51 , 52 ] Poisson–Boltzmann frameworks, and computer simulations [ 20 , 53 , 54 , 55 , 56 , 57 ] that have illuminated important aspects of the PE brush behavior.…”

Section: Introductionmentioning

confidence: 99%

Polyelectrolyte Cylindrical Brushes in Hairy Gels

Zhulina,

Borisov

2023

Polymers

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We considered dispersions of cylindrical polyelectrolyte (PE) brushes with stiff backbones, and polymer-decorated nanorods with tunable solubility of the brush-forming PE chains that affected thermodynamic stability of the dispersions. We focused on thermo-induced and deionization-induced conformational transition that provokes loss of aggregative dispersion stability of nanorods decorated with weakly ionized polyions. A comparison between theoretical predictions and experiments enabled rationalization and semi-quantitative interpretation of the experimental results.

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Polyelectrolyte Brushes: Twenty Years After

Cited by 5 publications

References 106 publications

Combined Experimental and Theoretical Study of Weak Polyelectrolyte Brushes in Salt Mixtures

Combined Experimental and Theoretical Study of Weak Polyelectrolyte Brushes in Salt Mixtures

Influence of Anion Hydrophilicity on the Conformation of a Hydrophobic Weak Polyelectrolyte Brush

Polyelectrolyte Cylindrical Brushes in Hairy Gels

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