RESUMEN

Bioinspired, artificial functional nanochannels for intelligent molecular and ionic transport control have versatile potential applications in nanofluidics, energy conversion, and controlled drug release. To simulate the gating and rectification functions of biological ion channels, we model the electrokinetic ion transport phenomenon in an asymmetric double-gated nanochannel having a pH-regulated, zwitterionic surface. Taking account of the effect of electroosmotic flow (EOF), the conductance of the nanochannel and its ion current rectification (ICR) behavior are investigated and the associated mechanisms interpreted. In particular, the influences of the solution pH, the bulk salt concentration, and the base opening radius and the surface curvature of the nanochannel on these behaviors are examined. We show that through adjusting the base opening radius and the surface curvature of a nanochannel, its ICR behavior can be tuned effectively. In addition to proposing underlying mechanisms for the phenomena observed, the results gathered in this study also provide necessary information for designing relevant devices.

RESUMEN

Chemically functionalized bioinspired nanopores are widely adopted to control the ionic transport for various purposes. A detailed understanding of the underlying mechanisms is not only desirable but also necessary for device design and experimental data interpretation. Here, the conductance and the ion selectivity of a conical nanopore surface modified by a polyelectrolyte (PE) layer are studied through adjusting the pH, the bulk salt concentration, and the level of the applied potential bias. Possible mechanisms are proposed and discussed in detail. We show that the conductance is sensitive to the variation in the solution pH. The ion selectivity of the nanopore is influenced significantly by both the solution pH and the level of the applied potential bias. In particular, a cation-selective nanopore might become anion-selective through raising the applied potential bias. The ion transport behavior can be tuned easily by adjusting the level of pH, salt concentration, and applied potential bias, thereby providing useful information for the design of nanopore-based sensing devices.

RESUMEN

Extending previous electrokinetic analyses based on a Newtonian fluid to power-law fluids, we investigate the behaviors of the ion current rectification (ICR) and the ion selectivity S of a conical nanopore having a pH-regulated surface. The bulk salt concentration Cbulk, the solution pH, and the power-law index n are examined in detail for their influences on these behaviors. We show that the ICR ratio for the case where pH is lower than the isoelectric point (IEP) of the nanopore surface is different both quantitatively and qualitatively from that for the case where pH > IEP. The relative magnitude of the ICR ratio as n varies depends largely on the level of Cbulk. In contrast, S (pH < IEP) is qualitatively similar to that for S(pH > IEP), where |S| decreases with increasing Cbulk and/or decreasing n. In addition, S is very sensitive to n, for example, a decrease of n from 1.0 (Newtonian fluid) to 0.9 (pseudoplastic fluid) can yield a 245% increase in S at Cbulk = 100 mM. Implying that the performance of ion separation can be improved by tuning the fluid viscosity. Mechanisms are proposed for explaining the observed behaviors in the ICR ratio.

RESUMEN

Taking account of the influence of electroosmotic flow, the behavior of the ion current rectification of a charged conical nanochannel is studied theoretically focusing on the effect of ionic valence. A continuum-based model comprising coupled Poisson-Nernst-Planck (PNP) equations for the ionic mass transport and Navier-Stokes equations for the hydrodynamic field is adopted. We show that if the bulk salt concentration is fixed, the behavior of the current-voltage curve depends highly on the ionic valence, which arises from the difference in ionic strength and ion diffusivity. As the bulk salt concentration varies, the rectification factor shows a local maximum, and the bulk salt concentration at which it occurs depends upon the salt valence: the higher the valence the lower that concentration. However, regardless of the salt valence, the ionic strength at which that local maximum occurs is essentially the same, implying that the thickness of electric double layer is the key factor. Due to the difference in ionic diffusivity, the magnitude of the rectification factor depends upon the type of salt. For example, the rectification factor of KCl is larger than that of KNO3. The qualitative behavior of the ion current rectification of a positively charged conical nanochannel is similar to that of a negatively charged nanochannel.

RESUMEN

The ion current rectification behavior of bioinspired nanopores is modeled by adopting a bullet-shaped nanopore having a pH-tunable zwitterionic surface, focusing on discussing the underlying mechanisms. We show that with its specific geometry, such nanopore is capable of exhibiting several interesting behaviors, including ion concentration polarization and ion current rectification. The influences of the nanopore shape, solution pH, and bulk salt concentration on the associated ion current rectification behavior are examined. We found that if pH exceeds the isoelectric point, the rectification factor has a local maximum as the curvature of the nanopore surface varies, and if it is lower than the isoelectric point, that factor increases (rectification effect decreases) monotonically with increasing surface curvature. In addition to capable of interpreting relevant electrokinetic phenomena, the results gathered also provide necessary information for a sophisticated design of relevant devices.

RESUMEN

The potential of separating colloidal particles through simultaneous application of a salt gradient and a pH gradient, or pH-assisted diffusiophoresis, is evaluated by considering the case of spherical polyelectrolytes (PEs) having different equilibrium dissociation constants in an aqueous solution with KCl as the background salt. The simulation results gathered reveal that the dependence of the particle velocity on pH is more sensitive than that in pH-assisted electrophoresis, where an electric field and a pH gradient are applied simultaneously. This implies that the separation efficiency of pH-assisted diffusiophoresis can be better than that of pH-assisted electrophoresis. In particular, two types of PE having different equilibrium dissociation constants can be separated effectively by applying the former by enhancing/reducing their diffusiophoretic velocities.

RESUMEN

Due to their specific geometry, conical nanochannels/nanopores are capable of exhibiting several interesting electrokinetic phenomena including, for example, ion concentration polarization (ICP) and ion current rectification (ICR). Extending previous analyses, we consider two types of nanochannels: only the inner surface of a nanochannel is functionalized by a polyelectrolyte (PE) layer in a type I nanochannel, and both its outer and inner surfaces are functionalized in a type II nanochannel. The influences of the thickness of a double layer and that of the PE layer on ICR are examined through numerical simulation. We show that the ICP of a type I nanochannel is more significant than that of the corresponding type II nanochannel. The behavior of the rectification factor of the former as the bulk salt concentration varies also differs significantly from that of the latter. In particular, the rectification factor of a type I nanochannel at a low bulk salt concentration shows an inversion.

RESUMEN

Extending previous analysis for the diffusiophoresis of a toroidal PE having a fixed charge density, we consider the case where it is pH-regulated and the liquid phase contains multiple ionic species so that the underlying assumptions are more realistic. The diffusiophoretic behaviors of the toroidal PE considered under various conditions are examined by varying its functional group density, size, and softness, and the solution pH and bulk salt concentration. We show that the behavior of a toroidal PE can be different both quantitatively and qualitatively from the corresponding spherical PE. The effective charge of the present PE is also different both quantitatively and qualitatively from the corresponding PE having fixed charge density. In particular, both the magnitude and the direction of diffusiophoretic velocity depend highly on the conditions assumed, implying that an efficient separation process can be designed. A three-dimensional velocity-pH-Debye length plot is constructed for that purpose.

RESUMEN

Considering recent application of concentration driven motion of charged nanoparticles in sensing technology, we model the diffusiophoresis of an isolated toroidal polyelectrolyte (PE) for the first time. Choosing an aqueous KCl solution for illustration, its behavior under various conditions is simulated by varying the double layer thickness, the size of toroid, and its softness and fixed charge density. We show that the behavior of the present PE can be different both quantitatively and qualitatively from that of the corresponding spherical PE. This arises from the competition of the hydrodynamic force and the electric force acting on a PE. The geometry and the nature of a PE can also influence appreciably its behavior, yielding complicated and interesting results.

RESUMEN

Salinity gradient power is a promising, challenging, and readily available renewable energy. Among various methods for harvesting this clean energy, nanofluidic reverse electrodialysis (NRED) is of great potential. Since ionic transport depends highly on the temperature, so is the efficiency of the associated power generated. Here, we conduct a theoretical analysis on the influences of temperature and nanopore size on NRED, focusing on the temperature and nanopore size. The results gathered reveal that the maximum power increases with increasing temperature, but the conversion efficiency depends weakly on temperature. In general, the smaller the nanopore radius or the longer the nanopore, the better the ion selectivity. These results provide desirable and necessary information for improving the performance of NRED as well as designing relevant units in renewable energy plants.

RESUMEN

Since non-Newtonian fluid behavior are not uncommon in practice, especially in modern applications of colloid and interface science, assessment of how serious is the deviation of the existing results for Newtonian fluids due to fluid nature is highly desirable and necessary. Here, we extend previous analyses for the diffusiophoresis of a particle in a Newtonian fluid to that in a non-Newtonian fluid choosing Carreau fluids as an example. Results gathered reveal that due to the shear-thinning property of the fluid considered, the difference between the particle mobility in a Carreau fluid and that in the corresponding Newtonian fluid can be on the order of 100%. In addition, this difference has a local minimum as the thickness of double layer varies.

RESUMEN

The behavior of ionic current rectification (ICR) in a conical nanopore with its surface modified by pH-tunable polyelectrolyte (PE) brushes connecting two large reservoirs subject to an applied electric field and a salt gradient is investigated. Parameters including the solution pH, types of ionic species, strength of applied salt gradient, and applied potential bias are examined for their influences on the ionic current and rectification factor, and the mechanisms involved are investigated comprehensively. The ICR behavior depends highly on the charged conditions of the PE layer, the level of pH, the geometry of nanopore, and the thickness of the double layer. In particular, the distribution of ionic species and the local electric field near the nanopore openings play a key role, yielding profound and interesting results that are informative to device design as well as experimental data interpretation.

RESUMEN

Extending previous analyses on rigid particles to non-rigid ones, we model the diffusiophoresis of a pH-regulated polyelectrolyte (PE) in a solution containing multiple ionic species. For the first time, the effects of temperature, pH, type of ionic species and bulk concentration are taken into account, and therefore, the conditions considered are more comprehensive and closer to reality than those of the available results in the literature. Numerical simulation is conducted to examine the diffusiophoretic behaviors of a PE under various conditions, and empirical relationships are developed for the dependence of its mobility on the factors mentioned above. We show that temperature and pH influence appreciably the charged conditions of a PE, the ionic diffusivities, and the fluid viscosity, yielding complicated and interesting behaviors that are informative to device design.

RESUMEN

The electroosmotic flow in an elliptic channel having constant surface potential (CSP) or charge density (CSCD) is considered at low potential and arbitrary double layer thickness. Analytical expressions for the flow velocity and the corresponding asymptotic results for thick double layers that are readily applicable to experimentalists are recovered. For the range of salt concentration usually encountered in practice, the mean flow velocity for the case of CSP differs both quantitatively and qualitatively from that for the case of CSCD. Using an equivalent circular channel to simulate an elliptic one is inappropriate, in general, neither is assuming electroneutrality on the channel axis even when double layer is ca. 1/3 of the equivalent channel radius.

RESUMEN

The ionic current rectification (ICR) is studied theoretically by considering a pH-regulated, conical nanopore. In particular, the effect of electroosmotic flow (EOF), which was often neglected in previous studies, is investigated by solving a set of coupled Poisson, Nernst-Planck, and Navier-Stokes equations. The behaviors of ICR under various conditions are examined by varying solution pH, bulk ionic concentration, and applied electric potential bias. We show that the EOF effect is significant when the bulk ionic concentration is medium high, the pH is far away from the iso-electric point, and the electric potential bias is high. The percentage deviation in the current rectification ratio arising from neglecting the EOF effect can be on the order of 100%. In addition, the behavior of the current rectification ratio at a high pH taking account of EOF is different both qualitatively and quantitatively from that without taking account of EOF.

RESUMEN

Tuning of ion and nanoparticle transport is validated through applying a salt gradient in two types of nanopores: the inner wall of a nanopore has bipolar charges and its outer wall neutral (type I), and both the inner and outer walls of a nanopore have bipolar charges (type II). The ion current rectification (ICR) behavior of these nanopores can be regulated by an applied salt gradient: if it is small, the degree of ICR in type II nanopore is more significant than that in type I nanopore; a reversed trend is observed at a sufficiently large salt gradient. If the applied salt gradient and electric field have the same direction, type I nanopore exhibits two significant features that are not observed in type II nanopore: (i) a cation-rich concentration polarization field and an enhanced funneling electric field are present near the cathode side of the nanopore, and (ii) the magnitude of the axial electric field inside the nanopore is reduced. These features imply that applying a salt gradient to type I nanopore is capable of simultaneously enhancing the nanoparticle capture into the nanopore and reducing its translocation velocity inside, so that high sensing performance and resolution can be achieved.

RESUMEN

Considering recent applications of electrophoresis conduced in nanoscaled devices, where particle-particle interaction can play a role, we studied for the first time the electrophoresis of two rigid spheres along their center line, taking account of the hydrodynamic, electric, and van der Waals interactions between them. Under the conditions of constant surface potential and surface charge density, the influences of the level of surface potential/charge density, the bulk salt concentration, and the particle-particle distance on their electrokinetic behaviors are examined. Numerical simulation reveals that these behaviors are much more complicated and interesting than those of isolated particles. In particular, we show that care must be taken in choosing an appropriate particle concentration in relevant experiment to avoid obtaining unreliable mobility data.

Asunto(s)

RESUMEN

The diffusiophoresis of a non-spherical polyelectrolyte (PE) is modeled theoretically by considering an ellipsoidal PE of fixed volume and varying aspect ratio, capable of simulating porous entities such as DNAs, proteins, and synthetic polymeric particles. A continuum model comprising coupled Poisson-Nernst-Planck equations and Stokes equations is adopted. Parameters including the physicochemical properties of a PE, the degree of deformation, and the bulk ionic concentration are examined in detail for their influence on the diffusiophoretic behavior of the PE. We show that the effects of double-layer polarization, polarization of the condensed counterions inside a PE, and the chemiosmotic retardation flow inside it yield complicated diffusiophoretic behavior. In particular, the mobility of an elliptic PE can differ both quantitatively and qualitatively from that of a spherical PE. This phenomenon, which has not been reported previously, provides valuable information for both experimental data interpretation and device design.

RESUMEN

The diffusiophoresis of a soft, pH-regulated particle comprising a rigid core and a polyelectrolyte (PE) layer in an aqueous salt solution containing multiple ionic species is modeled theoretically. We show that the diffusiophoretic behavior of a soft particle can be different appreciably from that of a rigid one. In particular, both the sign and the magnitude of the mobility of a soft particle can vary with the friction coefficient of its PE layer. In an aqueous KCl solution, if that coefficient is sufficiently large, the particle always moves towards the opposite direction as that of the applied concentration gradient, regardless of the pH level, an interesting observation which has not been reported previously. In an aqueous NaCl solution, if pH is sufficiently low, the particle mobility increases with increasing friction coefficient, an interesting and unexpected finding. The results obtained provide valuable and necessary information for both interpreting experimental data and design diffusiophoresis devices.

RESUMEN

The sedimentation of an isolated, charged polyelectrolyte (PE) subjected to an applied field is modeled theoretically, taking into account the variation of its shape. In particular, the effects of double-layer relaxation, effective charge density, and strength of the induced relaxation electric field are examined. We show that the interaction of these effects yields complex and interesting sedimentation behaviors. For example, the behavior of the electric force acting on a loosely structured PE can be different from that on a compactly structured one; the former is dominated mainly by the convective fluid flow. For thick double layers, electric force has a local maximum as the Reynolds number varies, but tends to increase monotonically with increasing Reynolds number if the layer is thin. The drag factor is found to behave differently from literature results. The shape of a PE significantly influences its sedimentation behavior by affecting the amount of counterions attracted to its interior and the associated local electric field. Interestingly, a more stretched PE has a higher effective charge density but experiences a weaker electric force.