Impact of Confinement and Zwitterionic Ligand Chemistry on Ion-Ion Selectivity of Functionalized Nanopores.

Membranes incorporating zwitterionic chemistries have recently emerged as promising candidates for facilitating challenging ion-ion separations. Transport of ions in such membranes predominantly occurs in hydrated nanopores lined with zwitterionic monomers. To shed light on the physics of ion-ion selectivity underlying such materials, we conducted molecular dynamics simulations of sodium halide transport in model nanopores grafted with sulfobetaine methacrylate molecules.

Polymer Architecture-Induced Trade-off between Conductivities and Transference Numbers in Salt-Doped Polymeric Ionic Liquids.

Recent experiments have demonstrated that polymeric ionic liquids that share the same cation and anion but possess different architectures can exhibit markedly different conductivity and transference number characteristics when doped with lithium salt. In this study, we used atomistic molecular simulations on polymer chemistries inspired by the experiments to probe the mechanistic origins underlying the competition between conductivity and transference numbers. Our results indicate that the architecture of the polycationic ionic liquid plays a subtle but crucial role in modulating the anion-cation interactions, especially their dynamical coordination characteristics.

Role of Dielectric Drag in Circumventing the Solubility-Diffusivity Trade-off in Zwitterionic Copolymer Membranes.

Recent experiments have revealed that random zwitterionic amphiphilic copolymer (r-ZAC) membranes exhibit excellent Cl/F permselectivity circumventing the solubility-diffusivity trade-off. We conducted molecular dynamics simulations to investigate the origin of the experimental results on the transport of sodium halides in r-ZAC membranes. Our results indicate that the enhancement of Cl/F diffusivity selectivity in r-ZAC membranes (relative to that in bulk water) stems from the increase in dielectric drag dominating over the increase in Stokes drag, zwitterionic group-induced steric hindrance, and ion-polymer interactions.

The influence of counterion structure identity on conductivity, dynamical correlations, and ion transport mechanisms in polymerized ionic liquids.

We used equilibrium and non-equilibrium atomistic simulations to probe the influence of anion chemistry on the true conductivity, dynamical correlations, and ion transport mechanisms in polymeric ionic liquids. An inverse correlation was found between anion self-diffusivities, ionic mobilities, and the anion size for spherical anions. While some larger asymmetric anions had higher diffusivities than smaller spherical anions, their diffusivities and mobilities did not exhibit a direct correlation to the anion volumes.

Impact of Ion-Ion Correlated Motion on Salt Transport in Solvated Ion Exchange Membranes.

The influence of dynamical ion-ion correlations and ion pairing on salt transport in ion exchange membranes remain poorly understood. In this study, we use the framework of Onsager transport coefficients within atomistic molecular dynamics simulations to study the impact of ion-ion correlated motion on salt transport in hydrated polystyrene sulfonate membranes and compare with the results from aqueous salt solutions. At sufficiently high salt concentrations, cation-anion dynamical correlations exert a significant influence on both salt diffusivities and conductivities.

Simultaneous Energy Generation and Flow Enhancement () in Polyelectrolyte Brush Functionalized Nanochannels.

Energy generation through nanofluidics is a topic of great nanotechnological relevance. Here, we conduct all-atom molecular dynamics (MD) simulations of the transport of water and ions in a pressure-driven flow in nanochannels grafted with charged polyelectrolyte (PE) brushes and discover the possibility of simultaneous electrokinetic energy generation and flow enhancement (henceforth denoted as the ). Such PE-brush-functionalized nanochannels have been recently shown to demonstrate an overscreening (OS) effect (characterized by the presence of a greater number of screening counterions within the PE brush layer than needed to screen the PE brush charges), a consequent presence of excess co-ions within the PE brush-free bulk, and a co-ion-driven electroosmotic (EOS) transport in the presence of small to moderate applied axial electric fields.

Overscreening, Co-Ion-Dominated Electroosmosis, and Electric Field Strength Mediated Flow Reversal in Polyelectrolyte Brush Functionalized Nanochannels.

Controlling the direction and strength of nanofluidic electrohydrodyanmic transport in the presence of an externally applied electric field is extremely important in a number of nanotechnological applications. Here, we employ all-atom molecular dynamics simulations to discover the possibility of changing the direction of electroosmotic (EOS) liquid flows by merely changing the electric field strength in a nanochannel functionalized with polyelectrolyte (PE) brushes. In exploring this, we have uncovered three facets of nanoconfined PE brush behavior and resulting EOS transport.

Theoretical study on the massively augmented electro-osmotic water transport in polyelectrolyte brush functionalized nanoslits.

We demonstrate that functionalizing nanoslits with pH-responsive polyelectrolyte brushes can lead to extremely fast electro-osmotic (EOS) water transport, where the maximum centreline velocity and the volume flow rate can be an order of magnitude larger than these quantities in identically charged brush-free nanochannels for a wide range of system parameters. Such an enhancement is most remarkable given that the brushes have been known to retard the transport by imparting additional drag on the fluid flow. We argue that this enhancement stems from the localization of the charge density of the brush-induced electric double layer (and, hence, the EOS body force) away from the nanochannel wall (or the location of the wall-induced drag force).

All-atom molecular dynamics simulations of weak polyionic brushes: influence of charge density on the properties of polyelectrolyte chains, brush-supported counterions, and water molecules.

All atom molecular dynamics (MD) simulations of planar Na+-counterion-neutralized polyacrylic acid (PAA) brushes are performed for varying degrees of ionization (and thereby varying charge density) and varying grafting density. Variation in the PE charge density (or degree of ionization) and grafting density leads to massive changes of the properties of the PE molecules (quantified by the changes in the height and the mobility of the PE brushes) as well as the local arrangement and distribution of the brush-supported counterions and water molecules within the brushes. The effect on the counterions is manifested by the corresponding variation of the counterion mobility, counterion concentration, extent of counterion binding to the charged site of the PE brushes, water-in-salt-like structure formation, and counterion-water-oxygen radial distribution function within the PE brushes.

Strong stretching theory for pH-responsive polyelectrolyte brushes in large salt concentrations.

In this paper, we develop a theory for describing the thermodynamics, configuration, and electrostatics of strongly-stretched, pH-responsive polyelectrolyte (PE) brushes in the presence of large salt concentrations. The aim of the paper, therefore, is to study the properties of a PE brush in a salt concentration regime (namely, large concentrations of several molars) that has been hitherto unexplored theoretically in the context of PE brushes but can be routinely encountered in molecular scale simulations of the problem. The brushes are modelled using our recently developed augmented Strong Stretching Theory (SST), while the effect of the presence of the large salt concentration is accounted for by including the contributions of three different types of non-Poisson-Boltzmann (non-PB) effects to the free energy description of the PE brush induced electric double layer (EDL).

Coating for preventing nonspecific adhesion mediated biofouling in salty systems: Effect of the electrostatic and van der waals interactions.

Development of anti-biofouling coating has attracted immense attention for reducing the massively detrimental effects of biofouling in systems ranging from ship hulls and surgical instruments to catheters, implants, and stents. In this paper, we propose a model to quantify the role of electrostatic and van der Waals (vdW) forces in dictating the efficacy of dielectric coating for preventing the nonspecific adhesion mediated biofouling in salty systems. The model considers a generic charged lipid-bilayer encapsulated vesicle-like structure representing the bio-organism.

Ionic current in nanochannels grafted with pH-responsive polyelectrolyte brushes modeled using augmented strong stretching theory.

In this paper, we provide a theory to quantify the ionic current ( ) in nanochannels grafted with pH-responsive polyelectrolyte (PE) brushes. We consider the PE brushes to be modeled by our recently proposed augmented strong stretching theory (SST) model that improves the existing SST models by incorporating the effects of excluded volume interactions and an extended mass action law. Use of such augmented SST for this problem implies that this is the first study on computing in PE brush-grafted nanochannels accounting for the appropriate coupled configuration-electrostatic description of the PE brushes.

Electrokinetic energy conversion in nanochannels grafted with pH-responsive polyelectrolyte brushes modelled using augmented strong stretching theory.

In this paper, we develop a theory to quantify the electrokinetic energy conversion in electrolyte-filled nanochannels grafted with pH-responsive polyelectrolyte (PE) brushes. A pressure-driven flow drives the mobile electrolyte ions of the electric double layer (EDL) supported by the charged PE brushes leading to the generation of a streaming current, a streaming electric field and eventually an electrical energy. The salient feature of this study is that the brushes are described using our recently developed augmented Strong Stretching Theory (SST) model.

Electrostatics and Interactions of an Ionizable Silica Nanoparticle Approaching a Plasma Membrane.

The surface charge of the plasma membrane (PM) and the large salt content of the extracellular space ensure a significant role of the electrostatic effect dictating the interaction between the PM and an approaching nanoparticle (NP). In this article, we theoretically study the case of an ionizable silica NP approaching the PM. We witness that the surface charge of the silica NP, dictated by the surface ionization of the silica in the electrostatic environment created by the PM surface charge and the extracellular ion concentration, decreases as it approaches the PM.

Interactions of gold and silica nanoparticles with plasma membranes get distinguished by the van der Waals forces: Implications for drug delivery, imaging, and theranostics.

Making a nanoparticle (NP) approach and interact with a plasma membrane (PM) through the receptor-ligand interaction is key for applications like targeted drug delivery, cellular imaging, and theranostics. In this paper, we show that the van der Waals (vdW) interactions dominate the electrostatics ensuring that a gold NP approached the PM more spontaneously as compared to a silica NP. The negative σ (charge density) of a PM induces a negative electrostatic potential at the surface of the approaching gold NP and the silica NP; however, there is very little difference between these induced values due to a small electric double layer at the physiological salt concentration (c).

Revisiting the strong stretching theory for pH-responsive polyelectrolyte brushes: effects of consideration of excluded volume interactions and an expanded form of the mass action law.

In this paper, we develop a theory to account for the effect of excluded volume (EV) interactions in the strong stretching theory (SST) based description of pH-responsive polyelectrolyte (PE) brushes. The existing studies have considered the PE brushes to be present in a θ-solvent and hence have neglected the EV interactions; however, such a consideration cannot describe the situations where the pH-responsive brushes are in a "good" solvent. Secondly, we consider a more expanded form of the mass action law, governing the pH-dependent ionization of the PE molecules, in the SST description of the PE brushes.

Highly enhanced liquid flows via thermoosmotic effects in soft and charged nanochannels.

Enhancing nanoscale liquid flows remains an existing challenge in nanofluidics. Here we propose the generation of highly augmented thermoosmotic (TOS) liquid flows in soft nanochannels (or nanochannels functionalized by grafting with end-charged polyelectrolyte or PE brushes) by employing an axial temperature gradient. The TOS transport is a combination of the induced-electric-field electroosmotic (EOS) transport and a thermo-chemioosmotic (TCOS) transport with the latter resulting from an induced pressure gradient on account of the changes associated with the imposition of the axial temperature gradient.

Ionic Diffusoosmosis in Nanochannels Grafted with End-Charged Polyelectrolyte Brushes.

In this paper, we develop a theory to study the imposed axial salt-concentration-gradient-driven ionic diffusioosmosis (IDO) in soft nanochannels or nanochannels grafted with end-charged polyelectrolyte (PE) brushes. Our analysis first quantifies the diffusioosmotically induced electric field, which is primarily dictated by the imposed concentration gradient (CG) with little contribution of the induced osmosis. This induced electric field triggers an electroosmotic (EOS) transport, while the net diffusioosmotic (DOS) transport results from a combination of this EOS transport and a chemiosmotic (COS) transport arising from the pressure gradient induced by the applied CG.

Efficient electrochemomechanical energy conversion in nanochannels grafted with end-charged polyelectrolyte brushes at medium and high salt concentration.

We develop a theory to study the generation of the streaming potential and the resulting electrochemomechanical energy conversion (ECMEC) in the presence of pressure-driven transport in nanochannels grafted with end-charged polyelectrolyte (PE) brushes. Our theory gives a thermodynamically self-consistent coupled description of the PE-brush and the electrostatics of the electric double layer (EDL) induced by the PE charges. The end-charged brushes localize the maximum EDL charge density away from the wall, thereby enabling a larger magnitude of pressure-driven transport to stream the ions downstream.

Effect of Plasma Membrane Semipermeability in Making the Membrane Electric Double Layer Capacitances Significant.

Electric double layers (or EDLs) formed at the membrane-electrolyte interface (MEI) and membrane-cytosol interface (MCI) of a charged lipid bilayer plasma membrane develop finitely large capacitances. However, these EDL capacitances are often much larger than the intrinsic capacitance of the membrane, and all of these capacitances are in series. Consequently, the effect of these EDL capacitances in dictating the overall membrane-EDL effective capacitance C becomes negligible.