Synergistic Effect of Salt and Anionic Surfactants on Interfacial Tension Reduction: Insights from Molecular Dynamics Simulations.

Surfactants are commonly utilized in chemical flooding processes alongside salt to effectively decrease interfacial tension (IFT). However, the underlying microscopic mechanism for the synergistic effect of salt and surfactants on oil displacement remains ambiguous. Herein, the structure and properties of the interface between water and n-dodecane are studied by means of molecular dynamics simulations, considering three types of anionic surfactants and two types of salts. As the salt concentration (ρsalt) increases, the IFT first decreases to a minimum value, followed by a subsequent increase to higher values. The salt ions reduce the IFT only at low ρsalt due to the salt screening effect and ion bridging effect, both of which contribute to a decrease in the nearest head-to-head distance of surfactants. By incorporating salt doping, the IFTs can be reduced by at most 5%. Notably, the IFTs of different surfactants are mainly determined by the hydrogen bond interactions between oxygen atoms in the headgroup and water molecules. The presence of a greater number of oxygen atoms corresponds to lower IFT values. Specifically, for alkyl ethoxylate sulfate, the ethoxy groups play a crucial role in reducing the IFTs. This study provides valuable insights into formulating anionic surfactants that are applicable to oil recovery processes in petroleum reservoirs using saline water.

Mechanochemical Cellular Membrane Internalization of Nanohydrogels: A Large-Scale Mesoscopic Simulation.

By combining large-scale dissipative particle dynamics and steered molecular dynamics simulations, we investigate the mechanochemical cellular internalization pathways of homogeneous and heterogeneous nanohydrogels and demonstrate that membrane internalization is determined by the crosslink density and encapsulation ability of nanohydrogels. The homogeneous nanohydrogels with a high crosslink density and low encapsulation ability behave as soft nanoparticles partially wrapped by the membrane, while those with a low crosslink density and high encapsulation ability permeate into the membrane. Regardless of the crosslink density, the homogeneous nanohydrogels undergo typical dual morphological deformations. The local lipid nanodomains are identified at the contacting region between the membrane and nanohydrogels because of different diffusion behaviors between lipid and receptor molecules during the internalization process. The yolk@shell heterogeneous nanohydrogels present a different mechanochemical cellular internalization pathway. The yolk with strong affinity is directly in contact with the membrane, resulting in partial membrane wrapping, and the contacting area is much reduced when compared to homogenous nanohydrogels, leading to a smaller lipid nanodomain and thus avoiding related cellular toxicity. Our findings provide a critical mechanism understanding of the biological pathways of nanohydrogels and may guide the molecular design of the hydrogel-based materials for controlled release drug delivery, tissue engineering, and cell culture.

Molecular Dynamics Simulation Insight into Interfacial Stability and Fluidity Properties of Microemulsions.

Although the interfacial properties of microemulsions have been extensively studied in both experimental and simulation research studies, the molecular mechanisms of stability and fluidity about microemulsion are still poorly understood. Herein, we report a molecular dynamics simulation study to elaborate the motion of an emulsion droplet involving dichain surfactant Aerosol OT (AOT) and its dynamics evolution at the oil-water interface. By varying the concentrations of AOT, we show that the interfacial thickness and emulsification rate display a piecewise change as the interfacial coverage increases and the W/O emulsion is more stable than the O/W one while O/W emulsion presents better fluidity. In addition, the dispersed system combined with water/AOT/n-heptane tends to form a W/O microemulsion instead of an O/W microemulsion due to the structural collapse of the latter. This work provides a molecular understanding of microemulsion interfacial stability and fluidity.