A method for simultaneously concentrating and separating analytes in a buffer-filled microfluidic channel is reported. The approach is based on modulation of the local electric field within the channel and the corresponding opposition of electrophoretic and electroosmotic flow (EOF) velocities. Dye molecules having different electrophoretic mobilities are focused at different locations within the channel where concentration takes place. At least three species, all small dye molecules, can be simultaneously concentrated and separated, with localized enrichment factors up to approximately 600 achieved within 400 s. The enrichment zones affect the electric field profile, as evidenced by significant differences in focusing of single versus multiple analytes. The EOF could be modulated by modifying the channel walls with an appropriate polymer, and this had the effect of increasing both the enrichment factors and resolution of the separation. Numerical simulations provide insights into the underlying fundamental principles for the experimental findings.

The complex interplay of electrophoretic, electroosmotic, bulk convective, and diffusive mass/charge transport in a hybrid poly(dimethylsiloxane) (PDMS)/glass microchannel with embedded floating electrode is analyzed. The thin floating electrode attached locally to the wall of the straight microchannel results in a redistribution of local field strength after the application of an external electric field. Together with bulk convection based on cathodic electroosmotic flow, an extended field gradient is formed in the anodic microchannel segment. It imparts a spatially dependent electrophoretic force on charged analytes and, in combination with the bulk convection, results in an electric field gradient focusing at analyte-specific positions. Analyte concentration in the enriched zone approaches a maximum value which is independent of its concentration in the supplying reservoirs. A simple approach is shown to unify the temporal behavior of the concentration factors under general conditions.

Electrokinetic transport within a buffer-filled microchannel incorporating a flat bipolar electrode is investigated. The key finding is that the presence of the electrode disrupts the passage of electrical current through the microchannel and thereby alters the uniformity of the local electric field. Electroosmotic flow further modulates the local field gradient. These dynamics are demonstrated experimentally by utilizing the field gradient for concentration enrichment of negatively charged tracer molecules, and a set of computer simulations is presented to interpret the underlying electrokinetics.

Bipolar electrode focusing at discontinuous bipolar electrodes (BPEs) provides new insight into the faradaic current and electric field characteristics associated with the technique and allows for the controlled transport of a focused anionic tracer in a microfluidic channel. The findings corroborate our previously reported simulation results, which describe the formation of an extended electric field gradient leading to concentration enrichment. This gradient has been attributed to the passage of faradaic current through a BPE affixed to the floor of the microchannel. Our results demonstrate that the onset of faradaic current is coincident with the onset of concentration enrichment. Utilizing an array of microband electrodes, the tracer may be passed from one stationary position to another by rapidly relocating the BPE. However, the tracer movement is limited to one direction, confirming that the electrophoretic velocity of the analyte exceeds the electroosmosis-driven bulk fluid flow velocity at only the cathodic edge of the BPE.

The electrokinetics and hydrodynamics in a hybrid microfluidic/nanofluidic pore network configuration and its effect on the concentration enrichment of charged analytes are described. A hydrogel microplug, photopolymerized in a microfluidic channel, with negative surface charge serves as a nanoporous membrane and dictates the electrokinetic behavior within the adjoining microchannel compartments. The nanoporous hydrogel with a mean pore size on the order of the electrical double layer thickness imparts ion-permselectivity (cation-selectivity) to the migration of ionic species which, under the influence of an applied electrical field, drives concentration polarization in bulk solution near the interfaces between the two microchannel compartments and the hydrogel-based nanopores. The concentration enrichment efficiency for charged analytes depends on this concentration polarization, which strongly affects the distribution of local electrical field strength. In addition, electroosmotic flow in the device plays a critical role in determining the location of the analyte enrichment zone. A theoretical model and simulations are presented to explain the interplay of concentration polarization and electroosmotic flow with respect to the observed concentration enrichment of negatively charged analytes at the cathodic hydrogel plug-microchannel solution interface.

Bipolar electrode (BPE) focusing is a developing technique for enrichment and separation of charged analytes in a microfluidic channel. The technique employs a bipolar electrode that initiates faradaic processes that subsequently lead to formation of an ion depletion zone. The electric field gradient resulting from this depletion zone focuses ions on the basis of their individual electrophoretic mobilities. The nature of the gradient is of primary importance to the performance of the technique. Here, we report dynamic measurements of the electric field gradient showing that it is stable over time and that its axial position in the microchannel is directly correlated to the location of an enriched tracer band. The position of the gradient can be tuned with pressure-driven flow. We also show that a steeper electric field gradient decreases the breadth of the enriched tracer band and therefore enhances the enrichment process. The slope of the gradient can be tuned by altering the buffer concentration: higher concentrations result in a steeper gradient. Coating the channel with the neutral block co-polymer Pluronic also results in enhanced enrichment.

The role of stagnant zones in hydrodynamic dispersion is studied for creeping flow through a fixed bed of spherical permeable particles, covering several orders of characteristic time and length scales associated with fluid transport. Numerical simulations employ a hierarchical model to cope with the different temporal and spatial scales, showing good agreement with our experimental results on diffusionlimited mass transfer, transient, and asymptotic longitudinal dispersion. These data demonstrate that intraparticle liquid holdup in macroscopically homogeneous porous media clearly dominates over contributions caused by the intrinsic flow field heterogeneity and boundary-layer mass transfer. DOI: 10.1103/PhysRevLett.88.234501 PACS numbers: 47.15.Gf, 05.60. -k, 47.55.Mh A detailed understanding of transport in porous media over the intrinsic temporal and spatial scales is important in many technological and environmental processes [1]. For example, natural and industrial materials such as soil, rock, filter cakes, or catalyst pellets often contain lowpermeability zones with respect to hydraulic flow of liquid through the medium or even stagnant regions which then remain purely diffusive. The relevance of stagnant zones stems from their influence on dispersion: Fluid molecules entrained in the deep diffusive pools cause a substantial holdup contribution and thereby affect the time scale of transient dispersion, as well as the value of the asymptotic dispersion coefficient (if the asymptotic long-time limit can be reached at all) [2][3][4]. Consequently, the associated kinetics of mass transfer between fluid percolating through the medium and stagnant fluid becomes rate limiting in a number of dynamic processes, including the separation and reaction efficiency of chromatographic columns and reactors, or economic oil recovery from a reservoir.In this respect, transport phenomena observed in model systems such as random packings of spheres may help to characterize materials with a higher disorder [5][6][7]. For random packings of nonporous (impermeable) particles, for example, the long-time longitudinal dispersion coefficient is dominated by the boundary-layer contribution (due to the no-slip condition at the solid-liquid interface) or by medium and large-scale velocity fluctuations in the flow field depending on the actual disorder of the medium and the Peclet number, Pe u ay d p D m (with u ay , the average velocity; d p , particle diameter; and D m , the molecular diffusivity) [6,8]. This behavior contrasts with random packings of porous (permeable) particles. In that case, liquid holdup associated with stagnant zones inside the particles may dominate dispersion when convective times t c uayt dp significantly exceed the dimensionless time for diffusion, t d. In many situations, however, both a macroscopic flow heterogeneity and solute trapping in stagnant zones contribute to transient and asymptotic dispersion [3,7,9].Despite numerous theoretical, experimental, and numerical studies (e.g., [1,7,8,[10][11][12]),...

The performance of nanoporous hydrogel microplugs with varying surface charge density is described in concentrating charged analytes electrokinetically in a microfluidic device. A neutral hydrogel plug with a mean pore size smaller than the size of charged analytes acts as a simple size-exclusion membrane. The presence of fixed charges on the backbone of a nanoporous hydrogel creates ion-permselectivity which results in charge-selective transport through the hydrogel. This leads to the development of concentration polarization (CP) in the adjoining bulk electrolyte solutions under the influence of an applied electrical field. CP strongly affects the distribution of the local electrical field strength, in particular, in the vicinity of the hydrogel plug which can significantly reduce the concentration enrichment factors compared to the neutral hydrogel. A theoretical model and simulations are presented, together with experimental data, to explain the interplay of hydrogel or membrane cation-selectivity, electrical field-induced CP, and the distribution of the local electrical field strength with respect to concentration enrichment of negatively charged analytes at the cathodic membrane-solution interface.