A molecular study on the behavior of polyethoxylated alkyl ethers surfactants in a water/n-alkane interface

Luz, Arthur M.; Santos, Thiago José Pinheiro dos; Barbosa, Gabriel D.; Camargo, Carla Luciane Manske; Tavares, Frederico W.

doi:10.1016/j.colsurfa.2022.129627

Cited by 8 publications

(10 citation statements)

References 51 publications

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“…Much progress has been achieved in this field, as for example, summarized by Maestro and Gutfreund for Langmuir monolayers or by the combination of tensiometry with direct interfacial coverage methods, such as X-ray reflectometry. , We should also pay much more attention to the viscoelasticity of adsorbed layers particularly measured in a broader frequency range . The combination of different experimental methods and supporting information from molecular modeling work , appear to be the most efficient approaches for further progress.…”

Section: Discussionmentioning

confidence: 99%

“…70,71 We should also pay much more attention to the viscoelasticity of adsorbed layers particularly measured in a broader frequency range. 72 The combination of different experimental methods and supporting information from molecular modeling work 61,64 appear to be the most efficient approaches for further progress. The Gibbs fundamental equation remains the most important coupling element between the interfacial parameters, such as Π, Γ, and E, and therefore plays a key role.…”

Section: Discussionmentioning

confidence: 99%

“…One of these studies combined the adsorption free energy to the bare air/water interface with the interfacial equation of state, Π(Γ), to predict the adsorption and pressure isotherms, Γ( c ) and Π( c ), respectively . A very recent study reported the surface activity of ethoxylated alkyl ether surfactants for oil/water interfaces as a function of the headgroup length . A challenge that remains is to consider the surfactant’s chemical potentials in all their coexisting states, including isolated surfactants in bulk, surfactants in micelles, and surfactants adsorbed to the surface as a function of the surface coverage.…”

Section: Theoretical Simulations Of Adsorbed Surfactantsmentioning

confidence: 99%

“…63 A very recent study reported the surface activity of ethoxylated alkyl ether surfactants for oil/water interfaces as a function of the headgroup length. 64 A challenge that remains is to consider the surfactant's chemical potentials in all their coexisting states, including isolated surfactants in bulk, surfactants in micelles, and surfactants adsorbed to the surface as a function of the surface coverage. Quantum chemical calculations can be employed to analyze the behavior of adsorbed monolayers, which for example allow one to estimate intermolecular interaction parameters, i.e., the values of the parameters a ij in the eqs 4 and 5.…”

Section: Theoretical Simulations Of Adsorbed Surfactantsmentioning

confidence: 99%

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Surfactant Adsorption Layers: Experiments and Modeling

et al. 2023

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During recent years, great progress has been made in understanding the adsorption of surfactants at liquid interfaces. In addition to tensiometry, new efficient methodologies have been developed, in particular interfacial selective optical methods which allow direct access to the adsorbed amounts and interfacial layer compositions. In addition to these new experimental tools, the thermodynamic description by equations of state now allows one to provide a quantitative picture of surfactant interfacial layers. This is most notable for surfactant layers at water/oil interfaces. Additional knowledge about the structure of interfacial layers was gained through different types of molecular modeling. Improved interrelationships between these three aspects are the challenges for current and future work. Particular attention must be paid to dilational interfacial rheology studies, as these mechanical quantities are much more sensitive to small changes in the interfacial composition and structure.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: Theoretical Simulations Of Adsorbed Surfactantsmentioning

confidence: 99%

Section: Theoretical Simulations Of Adsorbed Surfactantsmentioning

confidence: 99%

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Surfactant Adsorption Layers: Experiments and Modeling

et al. 2023

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“…Finally, we have to point out that there are alternative approaches for calculating transfer free energies, which could also be used for our problem. Arguably the most popular are umbrella-sampling simulations, ,,, which may be more straightforward to implement, but have certain disadvantages. For instance, pulling the test surfactant out of a deformable micelle or interface gives rise to local distortions that can lead to poor convergence.…”

Section: Simulation Methodsmentioning

confidence: 99%

Interface Adsorption versus Bulk Micellization of Surfactants: Insights from Molecular Simulations

Kanduč

Miller

Schneck

2023

J. Chem. Theory Comput.

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Surfactants play essential roles in many commonplace applications and industrial processes. Although significant progress has been made over the past decades with regard to model-based predictions of the behavior of surfactants, important challenges have remained. Notably, the characteristic time scales of surfactant exchange among micelles, interfaces, and the bulk solution typically exceed the time scales currently accessible with atomistic molecular dynamics (MD) simulations. Here, we circumvent this problem by introducing a framework that combines the general thermodynamic principles of self-assembly and interfacial adsorption with atomistic MD simulations. This approach provides a full thermodynamic description based on equal chemical potentials and connects the surfactant bulk concentration, the experimental control parameter, with the surfactant surface density, the suitable control parameter in MD simulations. Self-consistency is demonstrated for the nonionic surfactant C 12 EO 6 (hexaethylene glycol monododecyl ether) at an alkane/water interface, for which the adsorption and pressure isotherms are computed. The agreement between the simulation results and experiments is semiquantitative. A detailed analysis reveals that the used atomistic model captures well the interactions between surfactants at the interface but less so their adsorption affinities to the interface and incorporation into micelles. Based on a comparison with other recent studies that pursued similar modeling challenges, we conclude that the current atomistic models systematically overestimate the surfactant affinities to aggregates, which calls for improved models in the future.

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