Lipid-Carbon Nanotube Self-Assembly in Aqueous Solution

One major drawback associated with single-walled carbon nanotubes (SWNTs) in the liquid phase is their hydrophobicity-induced aggregation, which prevents utilization of the unique physical and chemical properties of single SWNTs. Recently it has been found that lysophospholipids, or single-tailed phospholipids, can readily form supramolecular complexes with SWNTs and the resultant SWNT solubility is superior to that provided by nucleic acids, proteins, and surfactants such as sodium dodecyl sulfate. Using transmission electron microscopy, lysophospholipids were observed forming striations on SWNTs in a vacuum. Although the morphology of the striations seemingly favors the hemimicellular model, serious doubts remain about the arrangement of individual lipids within the striations. Here we present an in silico study of the binding of zwitterionic lysophosphatidylcholine to an SWNT. We present compelling evidence that the binding of lipid surfactants to cylindrical nanostructures in the liquid phase does not obey any of the three popular models in the literature. Understanding the binding of lipid amphiphiles to SWNTs facilitates the bottom-up design of novel nanostructures for supramolecular chemistry and nanotechnology and fuels new field studies of nanotoxicity and nanomedicine

Lipid-Carbon Nanotube Self-Assembly in Aqueous Solution

One major drawback associated with single-walled carbon nanotubes (SWNTs) in the liquid phase is their hydrophobicity-induced aggregation, which prevents utilization of the unique physical and chemical properties of single SWNTs. Recently it has been found that lysophospholipids, or single-tailed phospholipids, can readily form supramolecular complexes with SWNTs and the resultant SWNT solubility is superior to that provided by nucleic acids, proteins, and surfactants such as sodium dodecyl sulfate. Using transmission electron microscopy, lysophospholipids were observed forming striations on SWNTs in a vacuum. Although the morphology of the striations seemingly favors the hemimicellular model, serious doubts remain about the arrangement of individual lipids within the striations. Here we present an in silico study of the binding of zwitterionic lysophosphatidylcholine to an SWNT. We present compelling evidence that the binding of lipid surfactants to cylindrical nanostructures in the liquid phase does not obey any of the three popular models in the literature. Understanding the binding of lipid amphiphiles to SWNTs facilitates the bottom-up design of novel nanostructures for supramolecular chemistry and nanotechnology and fuels new field studies of nanotoxicity and nanomedicine

Structure, Thermodynamics, and Dynamics of Thin Brine Films in Oil–Brine–Rock Systems

Thin brine films are ubiquitous in oil–brine–rock systems such as oil reservoirs and play a crucial role in applications such as enhanced oil recovery. We report the results of molecular simulations of brine films that are confined between model oil (n-decane) and rock (neutral or negatively charged quartz slabs), with a focus on their structure, electrical double layers (EDLs), disjoining pressure, and dynamics. As brine films are squeezed to ∼0.7 nm (∼3 water molecule layers), the structures of the water–rock and water–oil interfaces change only marginally, except that the oil surface above the brine film becomes less diffuse. As the film is thinned from ∼1.0 to ∼0.7 nm, ions are enriched (depleted) near the rock (oil) surface, especially at a bath ion concentration of 0.1 M. These changes are caused primarily by the reduced dielectric screening of water and the weakened ion hydration near water–oil interfaces and, to a smaller extent, by the increased confinement. When the brine film is ∼1.0 nm thick, hydration and EDL forces contribute to the disjoining pressure between the charged rock and the oil. The EDL forces are reduced substantially as the ion concentration increases from 0.1 to 1.0 M, and the magnitude of the reduction is close to that predicted by the Poisson–Boltzmann equation. When the brine film is thinned from ∼1.0 to ∼0.7 nm, the disjoining pressure increases by ∼10 MPa, which is mostly due to an increase in the hydration forces. The first layer of water on the rock surface is nearly stagnant, even in 0.74 nm-thick brine films, whereas the viscosity of water beyond the first layer is bulk-like, and the slip coefficient of oil–water interfaces is close to that under unconfined conditions. The insights that are obtained here help lay a foundation for the rational application of technologies such as low-salinity waterflooding

Effects of Water on Mica–Ionic Liquid Interfaces

A growing body of work shows that water can affect the structure and properties of the ionic liquids near solid surfaces, which has rich ramifications in applications of ionic liquids such as lubrication and energy storage. Using molecular dynamics simulations, we investigate how water affects the three-dimensional structure of ionic liquids [BMIM]­[Tf₂N] near mica surfaces with two different charge densities. We show that water can alter not only the layering of ions near the mica surface but also their lateral and orientation ordering and the aggregation of cations’ hydrophobic tails. Water often, but not always, weakens the structuring of interfacial ionic liquids. The multifaceted impact of water on the interfacial structure of ionic liquids can be traced back to the fact that water is both a dielectric solvent and a molecular liquid. Based on the additional observations that the adsorption of water at mica–ionic liquid interfaces is enhanced by ionic liquids and surface charge, we suggest that the structure of ionic liquids near solid surfaces is governed by the three-way coupling between the self-organization of ions, the adsorption of interfacial water, and the electrification of the solid surfaces

The Role of Disjoining Pressure and Thermal Activation in the Invasion of Droplets into Nanopores

Multiphase transport at a nanoscale level plays a key role in applications including drying of nanoporous materials and gas/oil recovery from low permeability rocks. A frequently encountered scenario in multiphase transport is the presence of droplets near nanopores. Whether droplets invade the nanopores or become trapped at their entrance greatly affects the operation of engineered systems. Here we analyze the free energy profile of nanometer-sized droplets entering the nanopore and how the profile is affected by the pressure difference and the size of the droplet and the nanopore. We show that, for nanopores whose surface is fully wetted by water but not the droplet, a droplet larger than the pore diameter must overcome a higher free energy barrier than that predicted by classical theories due to the large disjoining pressure. For smaller nanodroplets, the threshold pressure for their invasion into a given nanopore can be lowered by thermal activation. When a droplet is slightly narrower than a pore, and thus is often assumed to enter the pore freely, a large energy barrier for droplet entry can actually exist. The droplet cannot easily enter the pore even with hydrodynamic drag by moving fluids. Entering the pore through Brownian motion is possible, and the mean entry time depends sensitively on the pore size and can reach seconds or even longer. These findings provide molecular insights on the invasion of droplets into nanopores and lay foundations for large-scale modeling of multiphase nanofluidic transport

Self-Diffusiophoresis of Janus Catalytic Micromotors in Confined Geometries

The self-diffusiophoresis of Janus catalytic micromotors (JCMs) in confined environment is studied using direct numerical simulations. The simulations revealed that, on average, the translocation of a JCM through a short pore is moderately slowed down by the confinement. This slowdown is far weaker compared to the transport of particles through similar pores driven by forces induced by external means or passive diffusiophoresis. Pairing of two JCMs facilitates the translocation of the one JCM entering the pore first but slows down the second JCM. Depending on its initial orientation, a JCM near the entrance of a pore can exhibit different rotational motion, which determines whether it can enter the pore. Once a JCM enters a narrow pore, it can execute a self-alignment process after which it becomes fully aligned with the pore axis and moves to the center line of the pore. Analysis of these results showed that, in addition to hydrodynamic effect, the translation and rotation of JCM is also affected by the “chemical effects”, i.e., the modification of the chemical species concentration around a JCM by confining walls and neighboring JCMs. These chemical effects are unique to the self-diffusiophoresis of JCMs and should be considered in design and operations of JCMs in confined environment

Enhanced Recovery of Oil Mixtures from Calcite Nanopores Facilitated by CO₂ Injection

Slow production, preferential recovery of light hydrocarbons, and low recovery factors are common challenges in oil production from unconventional reservoirs dominated by nanopores. Gas injection-based techniques such as CO2 Huff-n-Puff have shown promise in addressing these challenges. However, a limited understanding of the recovery of oil mixtures on the nanopore scale hinders their effective optimization. Here, we use molecular dynamics simulations to study the recovery of an oil mixture (C10 + C19) from a single 4 nm-wide calcite dead-end pore, both with and without CO2 injection. Without CO2 injection, oil recovery is much faster than expected from oil vaporization and features an undesired selectivity, i.e., the preferential recovery of lighter C10. With CO2 injection, oil recovery is accelerated and its selectivity toward C10 is greatly mitigated. These recovery behaviors are understood by analyzing the spatiotemporal evolution of C10, C19, and CO2 distributions in the calcite pore. In particular, we show that interfacial phenomena (e.g., the strong adsorption of oil and CO2 on pore walls, their competition, and their modulation of transport behavior) and bulk phenomena (e.g., solubilization of oil by CO2 in the middle portion of the pore) play crucial roles in determining the oil recovery rate and selectivity

Self-Diffusiophoresis of Janus Catalytic Micromotors in Confined Geometries

The self-diffusiophoresis of Janus catalytic micromotors (JCMs) in confined environment is studied using direct numerical simulations. The simulations revealed that, on average, the translocation of a JCM through a short pore is moderately slowed down by the confinement. This slowdown is far weaker compared to the transport of particles through similar pores driven by forces induced by external means or passive diffusiophoresis. Pairing of two JCMs facilitates the translocation of the one JCM entering the pore first but slows down the second JCM. Depending on its initial orientation, a JCM near the entrance of a pore can exhibit different rotational motion, which determines whether it can enter the pore. Once a JCM enters a narrow pore, it can execute a self-alignment process after which it becomes fully aligned with the pore axis and moves to the center line of the pore. Analysis of these results showed that, in addition to hydrodynamic effect, the translation and rotation of JCM is also affected by the “chemical effects”, i.e., the modification of the chemical species concentration around a JCM by confining walls and neighboring JCMs. These chemical effects are unique to the self-diffusiophoresis of JCMs and should be considered in design and operations of JCMs in confined environment

Graphene Oxide and Its Derivatives as Adsorbents for PFOA Molecules

Effective, low-cost adsorbents are needed to remove perfluoroalkyl and polyfluoroalkyl substances (PFAS) from water sources. Carbon-based materials are promising PFAS adsorbents. Here, we explore the potential of graphite oxide (GO) and its derivatives as PFAS adsorbents by studying the adsorption of perfluorooctanoic acid (PFOA), a model PFAS molecule, on GO surfaces with O/C ratios up to 16.7% using molecular dynamics simulations. An adsorption free energy of approximately −30 kJ/mol (or −310 meV) is obtained for pristine graphene in pure water, and adsorbed PFOA molecules diffuse rapidly. As the O/C ratio increases, hydrophobic interactions’ contribution to PFOA adsorption diminishes, but that by electrostatic interactions becomes important. Overall, adsorption is weakened, but favorable adsorption still occurs at an O/C ratio of 16.7%. The in-plane diffusion coefficient of adsorbed PFOA molecules decreases by more than 45 times as the O/C ratio increases to 8.3% but increases significantly when the O/C ratio increases further to 16.7%. Adding salt improves the adsorption owing to the salting-out and screening effects but slows the diffusion of adsorbed PFOA molecules, and these effects are more pronounced at low O/C ratios. These results show that GOs are effective PFOA adsorbents. Such effectiveness, along with GO’s potentially low cost and the possibility of regenerating spent GO by removing adsorbed PFOA molecules through a mild electrical potential, makes GO a promising adsorbent for PFOA and similar molecules. The insights from the present study can help the rational design of GOs to realize their full potential

Marangoni Flow Induced Collective Motion of Catalytic Micromotors

A new collective motion of non-bubble-propelled spherical Janus catalytic micromotors has been observed. When the local concentration of micromotors is high, bubbles start to form between the motors. As the bubble grows, micromotors move collectively toward the center of the bubble regardless of the orientations of their catalyst surface, eventually become aggregated, and captured around the perimeter of the bubble. It is suggested that this collective motion of the micromotors, too fast for the diffusiophoresis, can be caused by the entrainment of micromotors by the evaporation-induced Marangoni flow near the bubble. Numerical simulations confirmed that the direction and strength of such Marangoni flow are consistent with the fast, collective motion of micromotors observed experimentally