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Affinity of small-molecule solutes to hydrophobic, hydrophilic, and chemically patterned interfaces in aqueous solution.

ABSTRACT: Performance of membranes for water purification is highly influenced by the interactions of solvated species with membrane surfaces, including surface adsorption of solutes upon fouling. Current efforts toward fouling-resistant membranes often pursue surface hydrophilization, frequently motivated by macroscopic measures of hydrophilicity, because hydrophobicity is thought to increase solute-surface affinity. While this heuristic has driven diverse membrane functionalization strategies, here we build on advances in the theory of hydrophobicity to critically examine the relevance of macroscopic characterizations of solute-surface affinity. Specifically, we use molecular simulations to quantify the affinities to model hydroxyl- and methyl-functionalized surfaces of small, chemically diverse, charge-neutral solutes represented in produced water. We show that surface affinities correlate poorly with two conventional measures of solute hydrophobicity, gas-phase water solubility and oil-water partitioning. Moreover, we find that all solutes show attraction to the hydrophobic surface and most to the hydrophilic one, in contrast to macroscopically based hydrophobicity heuristics. We explain these results by decomposing affinities into direct solute interaction energies (which dominate on hydroxyl surfaces) and water restructuring penalties (which dominate on methyl surfaces). Finally, we use an inverse design algorithm to show how heterogeneous surfaces, with multiple functional groups, can be patterned to manipulate solute affinity and selectivity. These findings, importantly based on a range of solute and surface chemistries, illustrate that conventional macroscopic hydrophobicity metrics can fail to predict solute-surface affinity, and that molecular-scale surface chemical patterning significantly influences affinity-suggesting design opportunities for water purification membranes and other engineered interfaces involving aqueous solute-surface interactions.

SUBMITTER: Monroe JI

PROVIDER: S-EPMC7821046 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:In this work the electrostatic complexation of two strong polyelectrolytes (PEs) was studied, the hydrophilic and positively charged poly (diallyldimethylammonium chloride) (PDADMAC) and the hydrophobic and negatively charged poly (styrene-co-sodium styrene sulfonate) (P(St-co-SSNa)), which was prepared at different sulfonation rates. The latter is known to adopt a pearl necklace conformation in solution for intermediate sulfonation rates, suggesting that a fraction of the P(St-co-SSNa) charges might be trapped in these hydrophobic domains; thus making them unavailable for complexation. The set of complementary techniques (DLS, zetametry, ITC, binding experiment with a cationic and metachromatic dye) used in this work highlighted that this was not the case and that all anionic charges of P(St-co-SSNa) were in fact available for complexation either with the polycationic PDADMAC or the monocationic o-toluidine blue dye. Only minor differences were observed between these techniques, consistently showing a complexation stoichiometry close to 1:1 at the charge equivalence for the different P(St-co-SSNa) compositions. A key result emphasizing that (i) the strength of the electrostatic interaction overcomes the hydrophobic effect responsible for pearl formation, and (ii) the efficiency of complexation does not depend significantly on differences in charge density between PDADMAC and P(St-co-SSNa), highlighting that PE chains can undergo conformational rearrangements favoring the juxtaposition of segments of opposite charge. Finally, these data have shown that the formation of colloidal PECs, such as PDADMAC and P(St-co-SSNa), occurs in two distinct steps with the formation of small primary complex particles (<50 nm) by pairing of opposite charges (exothermic step) followed by their aggregation within finite-size clusters (endothermic step). This observation is in agreement with the previously described mechanism of PEC particle formation from strongly interacting systems containing a hydrophobic PE.

Project description:Endpoints density functional theory (DFT) provides a framework for calculating the excess chemical potential of a solute in solution using solvent distribution functions obtained from both physical endpoints of a hypothetical charging process which transforms the solvent density from that of the pure liquid to the solution state. In this work, the endpoints DFT equations are formulated in terms of the indirect (solvent-mediated) contribution ω(x) to the solute-solvent potential of mean force, and their connections are established with the conventional DFT expressions which are based on the use of direct correlation functions. ω actually corresponds to the free-energy cost to move a cavity particle (a tagged solvent molecule which interacts with the other solvent molecules but not the solute) from the bulk to the configuration x of a solvent molecule relative to the solute and is a suitable variable to describe the solvent effects on the solute-solvent interactions. HNC and PY type approximations are then used to integrate the DFT charging integral involved in the exact expression for the excess chemical potential. With these approximations, molecular simulations are to be performed at the two endpoints of solute insertion: pure solvent without the solute and the solution system with the fully coupled solute-solvent interaction. An endpoints method thus utilizes the ensembles of intermolecular configurations of physical interest, which are often readily accessible with MD simulations given the present computational power. To illustrate properties of the formulation, we perform simulations of model systems consisting of a cavity particle in an aqueous solution containing a spherical hydrophobic solute of three different sizes from which ω(x) and the solute chemical potential can be calculated using endpoints DFT expressions. These are compared with corresponding results obtained using the approximations needed in order to evaluate the endpoints DFT charging integral when cavity particle simulation data is not available. We analyze a new approximation (two-points quadratic HNC) to the DFT charging integral which captures the correct behavior of the cavity distributions at both endpoints of the solute insertion. The behavior of the cavity particle in simple and complex liquids plays an important role in various theoretical treatments of the solute chemical potential. For pure Lennard-Jones fluids, the free energy to bring a cavity particle from the bulk to the center of a fluid particle is negative. However, for solutes of varying size, this is not generally true for Lennard-Jones fluids or the systems studied in this work. We carry out energetic and structural analyses of the cavity particle in aqueous solution with hydrophobic solutes of varying size and discuss the results in the context of the hydrophobic effect.

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Affinity of small-molecule solutes to hydrophobic, hydrophilic, and chemically patterned interfaces in aqueous solution.

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