Search

Polyelectrolyte brushes can introduce functionality to surfaces and because of this, these brushes have been studied extensively. In many applications, these brushes are used in solutions that contain a variety of molecules. While the interaction between polyelectrolyte brushes and molecules has been studied via coarse-grained simulations and experiments, such interaction has not been studied in molecular detail. An understanding of interactions in such molecular detail may prove crucial in the design of future brush coatings that can enable desired adsorption of different organic and biological molecules. Therefore, we present a first all-atom molecular dynamics simulations study of poly(sodium acrylate) brushes in contact with a small organic molecule, γ-butyrolactone. Within this molecular framework, we study the interaction of this lactone molecule with the brush layer and study the ensuing absorption and dynamics of the lactone inside the brush layer. The lactone is found to prefer to remain in the bulk solution; however, when absorbed, lactone molecules are found to have significantly reduced mobilities as compared to that in the bulk solution and are able to massively influence the properties of the brush-entrapped water molecules. These findings provide unprecedented details about the absorption-driven changes to molecular structure and dynamics of the lactone molecules and the water molecules inside the brush layer and can only be uncovered by our all-atom MD simulations. Such explicit and atomistically-resolved information, taking into account the specific chemical nature of the interacting systems, is rare in the context of designing polymer and PE brush-based coatings. Thus, we anticipate that our findings will be crucial in the design of future brush coatings aimed at providing adsorption platforms for different organic and biomolecules.

Under the influence of electric fields, the chains in polyelectrolyte brushes can stretch and collapse, which changes the structure of the brush. Copolymer brushes with charged and uncharged monomers display a similar behavior. For pure polyelectrolyte and random copolymer brushes, the field-induced structure changes only the density of the brush and not its local composition, while the latter could be affected if charges are distributed inhomogeneously along the polymer backbone. Therefore, we systematically study the switching behavior of gradient polyelectrolyte brushes in electric fields for different solvent qualities, grafting densities, and charges per chain via coarse-grained molecular dynamics simulations. Similar to random copolymers and pure polyelectrolytes, these brushes show a mixed-phase transition: intermediate states between fully stretched and collapsed are characterized by a bimodal chain-end distribution. Additionally, we find that the total charge of the brush plays a key role in the critical field required for a complete transition. Finally, we find that gradient polyelectrolyte brushes are charge-enriched at the brush-solvent interface under stretched conditions and charge-depleted under collapsed conditions, allowing for control over the local composition and thus the surface charge of the brush due to the inhomogeneous charge along the grafted chains.

Molecules can partition from a solution into a polymer coating, leading to a local enrichment. If one can control this enrichment via external stimuli, one can implement such coatings in novel separation technologies. Unfortunately, these coatings are often resource intensive as they require stimuli in the form changes of bulk solvent conditions such as acidity, temperature, or ionic strength. Electrically driven separation technology may provide an appealing alternative, as this will allow local, surface-bound stimuli instead of system-wide bulk stimuli to induce responsiveness. Therefore, we investigate via coarse grained molecular dynamics simulations the possibility of using coatings with charged moieties, specifically gradient polyelectrolyte brushes, to control the enrichment of the neutral target molecules near the surface with applied electric fields. We find that targets which interact more strongly with the brush show both more absorption and a larger modulation by electric fields. For the strongest interactions evaluated in this work, we obtained absorption changes of over 300 % between the collapsed and extended state of the coating., (© 2023 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

Polymer brushes in gaseous environments absorb and adsorb vapors of favorable solvents, which makes them potentially relevant for sensing applications and separation technologies. Though significant amounts of vapor are sorbed in homopolymer brushes at high vapor pressures, at low vapor pressures sorption remains limited. In this work, we vary the structure of two-component polymer brushes and investigate the enhancement in vapor sorption at different relative vapor pressures compared to homopolymer brushes. We perform molecular dynamics simulations on two-component block and random copolymer brushes and investigate the influence of monomer miscibility and formation of high-energy interfaces between immiscible monomers on vapor sorption. Additionally, we present absorption isotherms of pure homopolymer, mixed binary brush and 2-block, 4-block, and random copolymer brushes. Based on these isotherms, we finally show that random copolymer brushes absorb more vapor than any other architecture investigated thus far. Random brushes display enhanced sorption at both high and low vapor pressures, with the largest enhancement in sorption at low vapor pressures.

Polymer brushes attract vapors that are good solvents for polymers. This is useful in sensing and other technologies that rely on concentrating vapors for optimal performance. It was recently shown that vapor sorption can be enhanced further by incorporating two incompatible types of polymers A and B in the brushes: additional vapor adsorbs at the high-energy polymer-polymer interface in these binary brushes. In this article, we present a model that describes this enhanced sorption in binary brushes of immiscible A-B polymers. To do so, we set up a free-energy model to predict the interfacial area between the different polymer phases in binary brushes. This description is combined with Gibbs adsorption isotherms to determine the adsorption at these interfaces. We validate our model with coarse-grained molecular dynamics simulations. Moreover, based on our results, we propose design parameters (A-B chain fraction, grafting density, vapor, and A-B interaction strength) for optimal vapor absorption in coatings composed of binary brushes.

Vapors in the air around us can provide useful information about our environment, but we need sensitive vapor sensors to access this information, especially because those vapors are often present at very low concentrations. We report molecular dynamics simulations of a concept that can significantly increase the sensitivity of vapor sensors at low concentrations. By coating the sensor surfaces with end-anchored immiscible polymers, surface-bound polymer blends are formed that can concentrate vapors, reaching sorption enhancements of more than one order of magnitude, especially at low vapor concentrations., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Polymer brushes can absorb vapors from the surrounding atmosphere, which is relevant for many applications such as in sensing and separation technologies. In this article, we report on the absorption of binary mixtures of solvent vapors (A and B) with a thermodynamic mean-field model and with grand-canonical molecular dynamics simulations. Both methods show that the vapor with the strongest vapor-polymer interaction is favored and absorbs preferentially. In addition, the absorption of one vapor (A) influences the absorption of another (B). If the A-B interaction is stronger than the interaction between vapor B and the polymers, the presence of vapor A in the brush can aid the absorption of B: the vapors absorb collaboratively as friends. In contrast, if the A-polymer interaction is stronger than the B-polymer interaction and the brush has reached its maximum sorption capacity, the presence of A can reduce the absorption of B: the vapors absorb competitively as foes., Competing Interests: The authors declare no competing financial interest., (© 2020 American Chemical Society.)