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Exploring the Free Energy Landscape To Predict the Surfactant Adsorption Isotherm at the Nanoparticle-Water Interface.

ABSTRACT: The long-lasting stability of nanoparticle (NP) suspensions in aqueous solution is one of the main challenges in colloidal science. The addition of surfactants is generally adopted to increase the free energy barrier between NPs and hence to ensure a more stable condition avoiding the NP sedimentation. However, a tailored prediction of surfactant concentration enabling a good dispersion of NPs is still an ambitious objective. Here, we demonstrate the efficiency of coupling steered molecular dynamics (SMD) with the Langmuir theory of adsorption in the low surfactant concentration regime, to predict the adsorption isotherm of sodium-dodecyl-sulfate (SDS) on bare ?-alumina NPs suspended in aqueous solution. The resulting adsorption free energy landscapes (FELs) are also investigated by tuning the percentage of SDS molecules coating the target bare NP. Our findings shed light on the competing role of enthalpic and entropic interaction contributions. On one hand, the adsorption is highly promoted by the tail-NP and tail-tail nonbonded interaction adhesion; on the other hand, our results unveil the entropic nature of water and surfactant steric effects occurring at the NP surface and preventing the adsorption. Finally, a thorough analysis on the steering works emphasizes the role of the NP curvature in the FEL of adsorption. In particular, we show that, moving from a solid infinite flat surface to a nanoscale particle, a deviation from a Markovian dynamics of adsorption occurs in close proximity to a curved solid-liquid interface. Here, both the NP curvature effect and nanoscale morphology promote a modification of the thermodynamics state of adsorption with a consequent splitting of the free energy profiles and the identification of specific sites of adsorption. The modeling framework suggested in this Article provides physical insights in the surfactant adsorption onto spherical NPs and suggests some guidelines to rationally design stable NP suspensions in aqueous solutions.

SUBMITTER: De Angelis P

PROVIDER: S-EPMC6891862 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

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Exploring the Free Energy Landscape To Predict the Surfactant Adsorption Isotherm at the Nanoparticle-Water Interface.

De Angelis Paolo P Cardellini Annalisa A Asinari Pietro P

ACS central science 20191105 11

The long-lasting stability of nanoparticle (NP) suspensions in aqueous solution is one of the main challenges in colloidal science. The addition of surfactants is generally adopted to increase the free energy barrier between NPs and hence to ensure a more stable condition avoiding the NP sedimentation. However, a tailored prediction of surfactant concentration enabling a good dispersion of NPs is still an ambitious objective. Here, we demonstrate the efficiency of coupling steered molecular dyna ...[more]

PMID: 31807682

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Project description:Graphene oxide (GO) has proved itself as a nanomaterial capable of acting as a surfactant by lowering the interfacial tension of the oil-water interface due to its polar oxygen groups. However, the surfactant behavior of the pure graphene sheet─since prevention of edge oxidation in experimental setups is nontrivial─is still an unresolved issue in graphene research despite significant progress in the field in recent years. Here, we conduct both atomistic and coarse-grained simulations to demonstrate that─surprisingly─even pristine graphene, which only consists of hydrophobic carbon atoms, is attracted to the octanol-water interface and consequently reduces its surface tension by 2.3 kBT/nm2 or about 10 mN/m. Interestingly, the location of the free energy minimum is not precisely at the oil-water interface itself but is rather buried about two octanol layers into the octanol phase, being about 0.9 nm from the water phase. We demonstrate that the observed surfactant behavior is purely entropically driven and can be attributed to the unfavorable lipid-like structuring of octanol molecules at the free octanol-water interface. In essence, graphene enhances the inherent lipid-like behavior of octanol at the water interface rather than directly acting as a surfactant. Importantly, graphene does not display surfactant-like behavior in corresponding Martini coarse-grained simulations of the octanol-water system since the free liquid-liquid interface loses essential structure at the lower coarse-grained resolution. However, a similar surfactant behavior is recovered in coarse-grained simulations of longer alcohols such as dodecan-1-ol and hexadecan-1-ol. The observed discrepancies at different model resolutions enable us to construct a comprehensive model of the surfactant behavior of graphene at the octanol-water interface. The here-gained insights may facilitate the broader utilization of graphene in numerous domains of nanotechnology. Furthermore, since a drug's octanol-water partition coefficient is a crucial physicochemical parameter in rational drug discovery, we also believe that the universality of the here-illustrated entropic surfactant behavior of planar molecules deserves special attention in the drug design and development field.

Project description:For more than a century, monolayer adsorptions in which adsorbate molecules and adsorbing sites behave ideally have been successfully described by Langmuir's adsorption isotherm. For example, the amount of adsorbed material, as a function of concentration of the material which is not adsorbed, obeys Langmuir's equation. In this paper, we argue that this relation is valid only for macroscopic systems. However, when particle numbers of adsorbate molecules and/or adsorbing sites are small, Langmuir's model fails to describe the chemical equilibrium of the system. This is because the kinetics of forming, or the probability of observing, occupied sites arises from two-body interactions, and as such, ought to include cross-correlations between particle numbers of the adsorbate and adsorbing sites. The effect of these correlations, as reflected by deviations in predicting composition when correlations are ignored, increases with decreasing particle numbers and becomes substantial when only few adsorbate molecules, or adsorbing sites, are present in the system. In addition, any change that augments the fraction of occupied sites at equilibrium (e.g., smaller volume, lower temperature, or stronger adsorption energy) further increases the discrepancy between observed properties of small systems and those predicted by Langmuir's theory. In contrast, for large systems, these cross-correlations become negligible, and therefore when expressing properties involving two-body processes, it is possible to consider independently the concentration of each component. By applying statistical mechanics concepts, we derive a general expression of the equilibrium constant for adsorption. It is also demonstrated that in ensembles in which total numbers of particles are fixed, the magnitudes of fluctuations in particle numbers alone can predict the average chemical composition of the system. Moreover, an alternative adsorption equation, predicting the average fraction of occupied sites from the value of the equilibrium constant, is proposed. All derived relations were tested against results obtained by Monte Carlo simulations.

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Exploring the Free Energy Landscape To Predict the Surfactant Adsorption Isotherm at the Nanoparticle-Water Interface.

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Exploring the Free Energy Landscape To Predict the Surfactant Adsorption Isotherm at the Nanoparticle-Water Interface.

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