Biporous silica nanostructure-induced nanovortex in microfluidics for nucleic acid enrichment, isolation, and PCR-free detection.

Efficient pathogen enrichment and nucleic acid isolation are critical for accurate and sensitive diagnosis of infectious diseases, especially those with low pathogen levels. Our study introduces a biporous silica nanofilms-embedded sample preparation chip for pathogen and nucleic acid enrichment/isolation. This chip features unique biporous nanostructures comprising large and small pore layers. Computational simulations confirm that these nanostructures enhance the surface area and promote the formation of nanovortex, resulting in improved capture efficiency. Notably, the chip demonstrates a 100-fold lower limit of detection compared to conventional methods used for nucleic acid detection. Clinical validations using patient samples corroborate the superior sensitivity of the chip when combined with the luminescence resonance energy transfer assay. The enhanced sample preparation efficiency of the chip, along with the facile and straightforward synthesis of the biporous nanostructures, offers a promising solution for polymer chain reaction-free detection of nucleic acids.

Programming Anisotropic Functionality of 3D Microdenticles by Staggered-Overlapped and Multilayered Microarchitectures.

Natural sharkskin features staggered-overlapped and multilayered architectures of riblet-textured anisotropic microdenticles, exhibiting drag reduction and providing a flexible yet strong armor. However, the artificial fabrication of three-dimensional (3D) sharkskin with these unique functionalities and mechanical integrity is a challenge using conventional techniques. In this study, it is reported on the facile microfabrication of multilayered 3D sharkskin through the magnetic actuation of polymeric composites and subsequent chemical shape fixation by casting thin polymeric films. The fabricated hydrophobic sharkskin, with geometric symmetry breaking, achieves anisotropic drag reduction in frontal and backward flow directions against the riblet-textured microdenticles. For mechanical integrity, hard-on-soft multilayered mechanical properties are realized by coating the polymeric sharkskin with thin layers of zinc oxide and platinum, which have higher hardness and recovery behaviors than the polymer. This multilayered hard-on-soft sharkskin exhibits friction anisotropy, mechanical robustness, and structural recovery. Furthermore, coating the MXene nanosheets provides the fabricated sharkskin with a low electrical resistance of ≈5.3 Ω, which leads to high Joule heating (≈229.9 °C at 2.75 V). The proposed magnetomechanical actuation-assisted microfabrication strategy is expected to facilitate the development of devices requiring multifunctional microtextures.

Electroconvective viscous fingering in a single polyelectrolyte fluid on a charge selective surface.

When a low-viscosity fluid displaces into a higher-viscosity fluid, the liquid-liquid interface becomes unstable causing finger-like patterns. This viscous fingering instability has been widely observed in nature and engineering systems with two adjoined fluids. Here, we demonstrate a hitherto-unrealizable viscous fingering in a single fluid-solid interface. In a single polyelectrolyte fluid on a charge selective surface, selective ion rejection through the surface initiates i) stepwise ion concentration and viscosity gradient boundaries in the fluid and ii) electroconvective vortices on the surface. As the vortices grow, the viscosity gradient boundary pushes away from the surface, resulting viscous fingering. Comparable to conventional one with two fluids, i) a viscosity ratio ([Formula: see text]) governs the onset of this electroconvective viscous fingering, and ii) the boundary properties (finger velocity and rheological effects) - represented by [Formula: see text], electric Rayleigh ([Formula: see text]), Schmidt ([Formula: see text]), and Deborah ([Formula: see text]) numbers - determine finger shapes (straight v.s. ramified, the onset length of fingering, and relative finger width). With controllable onset and shape, the mechanism of electroconvective viscous fingering offers new possibilities for manipulating ion transport and dendritic instability in electrochemical systems.

Induced-charge membrane capacitive deionization enables high-efficient desalination with polarized porous electrodes.

Exposure of a conducting porous material to an electric field in electrolytes induces an electric dipole, which results in capacitive charging of cations and anions at opposite poles. In this letter, we investigate a novel desalination method using this induced-charge capacitive deionization (ICCDI). To do this, we devise a microscale ICCDI platform that can visualize in situ ion concentrations, pH shifts, and fluid flows, and study ion transport dynamics and desalination performances compared to conventional CDI with unipolar / bipolar connections. Similar ion concentration and fluid flow characteristics were observed in Ohmic, limiting, and over-limiting regimes, but variations in desalination performance trends were noted based on the number of stacks. In a single cell, ICCDI generates a higher electric field at the opposite poles of porous electrodes than simple conducted electrodes in CDIs with unipolar/bipolar connections, leading to superior salt removal and/or lower ionic current at a given applied voltage. This marks a clear contrast from CDI with bipolar connection, which lacks any advantage over CDI with unipolar connection in a single cell. These metrics of ICCDI however deteriorated as the stack number increased, likely due to short-circuiting between the dipoles. As a result, ICCDI in current form shows higher desalination efficient than conventional CDIs with low stack numbers (< 6), so we offer the scale-up module by repeating 4-stack ICCDI units. Our study enhances comprehension of ion transport dynamics and desalination performance in ICCDI, and the results could aid in the development of ICCDI for energy/cost-efficient desalination.

An epifluidic electronic patch with spiking sweat clearance for event-driven perspiration monitoring.

Sensory neurons generate spike patterns upon receiving external stimuli and encode key information to the spike patterns, enabling energy-efficient external information processing. Herein, we report an epifluidic electronic patch with spiking sweat clearance using a sensor containing a vertical sweat-collecting channel for event-driven, energy-efficient, long-term wireless monitoring of epidermal perspiration dynamics. Our sweat sensor contains nanomesh electrodes on its inner wall of the channel and unique sweat-clearing structures. During perspiration, repeated filling and abrupt emptying of the vertical sweat-collecting channel generate electrical spike patterns with the sweat rate and ionic conductivity proportional to the spike frequency and amplitude over a wide dynamic range and long time (> 8 h). With such 'spiking' sweat clearance and corresponding electronic spike patterns, the epifluidic wireless patch successfully decodes epidermal perspiration dynamics in an event-driven manner at different skin locations during exercise, consuming less than 0.6% of the energy required for continuous data transmission. Our patch could integrate various on-skin sensors and emerging edge computing technologies for energy-efficient, intelligent digital healthcare.

Pattern Formation of Three-Dimensional Electroconvection on a Charge Selective Surface.

When a charge selective surface consumes or transports only cations or anions in the electrolyte, biased ion rejection initiates hydrodynamic instability, resulting in vortical fluid motions called electroconvection. In this Letter, we describe the first laboratory observation of three-dimensional electroconvection on a charge selective surface. Combining experiment and scaling analysis, we successfully categorized three distinct patterns of 3D electroconvection according to [(Ra_{E})/(Re^{2}Sc)] [electric Rayleigh number (Ra_{E}), Reynolds number (Re), Schmidt number (Sc)] as (i) polygonal, (ii) transverse, or (iii) longitudinal rolls. If Re increases or Ra_{E} decreases, pure longitudinal rolls are presented. On the other hand, transverse rolls are formed between longitudinal rolls, and two rolls are transformed as polygonal one at higher Ra_{E} or lower Re. In this pattern selection scenario, Sc determines the critical electric Rayleigh number (Ra_{E}^{*}) for the onset of each roll, resulting in Ra_{E}^{*}∼Re^{2}Sc. We also verify that convective ion flux by electroconvection (represented by an electric Nusselt number Nu_{E}) is fitted to a power law, Nu_{E}∼[(Ra_{E}-Ra_{E}^{*})/(Re^{2}Sc)]^{α_{1}}Re^{α_{2}}Pe^{α_{3}} [Péclet number (Pe)], where each term represents the characteristics of electroconvection, shear flow, and ion transport.

Simultaneous electric production and sizing of emulsion droplets in microfluidics.

Microscale emulsions are widely used in fundamental and applied sciences. To expand their utilization, various methods have been developed for manipulating and measuring the physical properties of fabricated emulsions inside microchannels. Herein, we present an electric emulsification platform that can produce emulsions and simultaneously detect their physical properties (size and production speed). The characterization of the emulsion properties during the fabrication process will broaden the application fields for microscale emulsions because it can avoid time-consuming post image processing and simplify the emulsification platform. To accomplish this, a "bottleneck" channel is implanted between two reservoirs of immiscible fluids (continuous and dispersion phases). This channel can not only confine one fluid within the other when the electric field is on, resulting in emulsification via electrohydrodynamically induced Rayleigh instability, but also act as a resistive pulse sensor (RPS). The fluctuation of the liquid/liquid interface during emulsification induces the fluctuation of the electric resistance in the bottleneck channel, as the two fluid phases have different electrical conductivities. With this simple but dual-functional channel, the emulsion size (radius of 5-10 µm) and production speed (7-12 Hz) can be controlled by adjusting the electric field and the channel-neck geometry. Additionally, the properties can be measured using the RPS; the data obtained through the RPS exhibit high correlations with the validated data obtained using a high-speed camera and microscopy (>95%). The proposed buffer-less electric emulsification with the embedded RPS is a simple and cost-effective emulsion production method that allows real-time emulsion characterization with a limited sample volume.

Microscale electrodeionization: In situ concentration profiling and flow visualization.

Electrodeionization (EDI) is membrane-based desalination utilizing ion exchange membranes and ion exchange resins. By combining Electrodialysis and Ion exchanger, EDI can produce ultrapure water in a continuous-flow manner. Although its theoretical mechanisms are well documented, there is no experimental platform that can provide microscopic details inside of the system. In this paper, we present microscale EDI that can visualize in situ ion concentration, pH, and fluid flows. The platform was fabricated by filling ion exchange resins as a monolayer in a transparent polydimethylsiloxane channel between cation and anion exchange membranes. According to operating voltages (0-15V), distinct behaviors of ion concentration profile, pH shift, and fluid flows were observed in Ohmic, limiting, and overlimiting regimes. It is noteworthy that overlimiting regimes can be sub-categorized as water-splitting and electroconvection regimes. In the early stage (4-8V), water-splitting is dominant with pH change near the membranes and resins; under a higher voltage (8-15V), electroconvection starts to occur even water-splitting tries to suppress the development of the extended space charge layer and corresponding electroconvective instability. Accelerated ionic migration by electroconvection can improve current efficiency up to 80%. This is a clear departure from overlimiting dynamics in electrodialysis (with electroconvection only), ion exchanger (with no distinct regime), and even from that in previous EDI experiments (with water splitting only).

Corrigendum: Purification of High Salinity Brine by Multi-Stage Ion Concentration Polarization Desalination.

This corrects the article DOI: 10.1038/srep31850.

Half-Cell Ion Concentration Polarization on Nafion-Coated Electrode.

On ion-selective membranes, cation/anion-selective transport under electric field initiates ion concentration polarization (ICP); ion concentration increases at one side of the membrane (ion enrichment), whereas it decreases at the other side (ion depletion). This polarization always occurs as the pair of ion enrichment and ion depletion. Departing from such pair generation, we demonstrate that only half of ICP (either ion enrichment or ion depletion) can be solitary on a Nafion-coated electrode. Current-voltage-time responses and conductance measurement capture this half-cell ICP with qualitative in situ pH/ion concentration visualization. In this half-cell, ion depletion hinders an ion flux, whereas ion enrichment facilitates the flux, so a diode-like current rectification is observed even in high-voltage regime (<±200 V) with a rectification factor up to 500. The results in this work give us deeper understanding about ICP on the electrodes and also open the possibility to use half-cell ICP as a high-voltage ionic diode and related sensing/energy applications.

Merging Ion Concentration Polarization between Juxtaposed Ion Exchange Membranes to Block the Propagation of the Polarization Zone.

The ion concentration polarization (ICP) phenomenon is one of the most prevailing methods to preconcentrate low-abundance biological samples. The ICP induces a noninvasive region for charged biomolecules (i.e., the ion depletion zone), and targets can be preconcentrated on this region boundary. Despite the high preconcentration performances with ICP, it is difficult to find the operating conditions of non-propagating ion depletion zones. To overcome this narrow operating window, we recently developed a new platform for spatiotemporally fixed preconcentration. Unlike preceding methods that only use ion depletion, this platform also uses the opposite polarity of the ICP (i.e., ion enrichment) to stop the propagation of the ion depletion zone. By confronting the enrichment zone with the depletion zone, the two zones merge together and stop. In this paper, we describe a detailed experimental protocol to build this spatiotemporally defined ICP platform and characterize the preconcentration dynamics of the new platform by comparing them with those of the conventional device. Qualitative ion concentration profiles and current-time responses successfully capture the different dynamics between the merged ICP and the stand-alone ICP. In contrast to the conventional one that can fix the preconcentration location at only ~5 V, the new platform can produce a target-condensed plug at a specific location in the broad ranges of operating conditions: voltage (0.5-100 V), ionic strength (1-100 mM), and pH (3.7-10.3).

Partially Cured Photopolymer with Gradient Bingham Plastic Behaviors as a Versatile Deformable Material.

We present rheological and mechanical behaviors of a partially cured photopolymer. When an ultraviolet (UV)-curable resin is exposed to UV light in atmospheric conditions, a partially cured layer is formed on the top of the resin owing to inhibitory effects of oxygen. Interestingly, such a partially cured resin behaves like a Bingham plastic with a yield stress, being a rigid solid at low shear stress and a viscous liquid at high stress. Unlike typical Bingham plastic materials, however, deformation rate saturation is observed with an increase in applied stress, which is attributed to the gradient in the degree of photopolymerization of the resin (termed "gradient Bingham plastic"). This gradient Bingham plastic can be utilized for the robust fabrication of diverse 3D, multiscale structures.

Nanopore Sensing in Aqueous Two-Phase System: Simultaneous Enhancement of Signal and Translocation Time via Conformal Coating.

Nanofluidic resistive pulse sensing (RPS) has been extensively used to measure the size, concentration, and surface charge of nanoparticles in electrically conducting solutions. Although various methods have been explored for improving detection performances, intrinsic problems including the extremely low particle-to-pore volume ratio (<0.01%) and fast nanoparticle translocation (10-1000 µs) still induce difficulties in detection, such as low signal magnitudes and short translocation times. Herein, we present an aqueous two-phase system (ATPS) in a nanofluidic RPS for amplifying translocation signals and decreasing translocation speeds simultaneously. Two immiscible aqueous liquids build a liquid-liquid interface inside nanopores. As particles translocate from a high-affinity liquid phase into a lower-affinity one, the high-affinity liquid forms a conformal coating on the particles, which increases the effective particle size and amplifies the current-blockage signal. The translocation time is also increased, as the ATPS interface impedes the particle translocation. For 20 nm particles, 7.92-fold and 5.82-fold enhancements of signal magnitude and translocation time can be achieved. To our knowledge, this is the first attempt to improve nanofluidic RPS by treating an interface of solution reservoirs for manipulating target particles rather than nanopores. This direct particle manipulation allows us to solve the two intrinsic problems all at once.

Purification of High Salinity Brine by Multi-Stage Ion Concentration Polarization Desalination.

There is an increasing need for the desalination of high concentration brine (>TDS 35,000 ppm) efficiently and economically, either for the treatment of produced water from shale gas/oil development, or minimizing the environmental impact of brine from existing desalination plants. Yet, reverse osmosis (RO), which is the most widely used for desalination currently, is not practical for brine desalination. This paper demonstrates technical and economic feasibility of ICP (Ion Concentration Polarization) electrical desalination for the high saline water treatment, by adopting multi-stage operation with better energy efficiency. Optimized multi-staging configurations, dependent on the brine salinity values, can be designed based on experimental and numerical analysis. Such an optimization aims at achieving not just the energy efficiency but also (membrane) area efficiency, lowering the true cost of brine treatment. ICP electrical desalination is shown here to treat brine salinity up to 100,000 ppm of Total Dissolved Solids (TDS) with flexible salt rejection rate up to 70% which is promising in a various application treating brine waste. We also demonstrate that ICP desalination has advantage of removing both salts and diverse suspended solids simultaneously, and less susceptibility to membrane fouling/scaling, which is a significant challenge in the membrane processes.

Microfluidic paper-based biomolecule preconcentrator based on ion concentration polarization.

Microfluidic paper-based analytical devices (µPADs) for molecular detection have great potential in the field of point-of-care diagnostics. Currently, a critical problem being faced by µPADs is improving their detection sensitivity. Various preconcentration processes have been developed, but they still have complicated structures and fabrication processes to integrate into µPADs. To address this issue, we have developed a novel paper-based preconcentrator utilizing ion concentration polarization (ICP) with minimal addition on lateral-flow paper. The cation selective membrane (i.e., Nafion) is patterned on adhesive tape, and this tape is then attached to paper-based channels. When an electric field is applied across the Nafion, ICP is initiated to preconcentrate the biomolecules in the paper channel. Departing from previous paper-based preconcentrators, we maintain steady lateral fluid flow with the separated Nafion layer; as a result, fluorescent dyes and proteins (FITC-albumin and bovine serum albumin) are continuously delivered to the preconcentration zone, achieving high preconcentration performance up to 1000-fold. In addition, we demonstrate that the Nafion-patterned tape can be integrated with various geometries (multiplexed preconcentrator) and platforms (string and polymer microfluidic channel). This work would facilitate integration of various ICP devices, including preconcentrators, pH/concentration modulators, and micro mixers, with steady lateral flows in paper-based platforms.

Enhanced Salt Removal by Unipolar Ion Conduction in Ion Concentration Polarization Desalination.

Chloride ion, the majority salt in nature, is ∼52% faster than sodium ion (DNa+ = 1.33, DCl- = 2.03[10(-9)m(2)s(-1)]). Yet, current electrochemical desalination technologies (e.g. electrodialysis) rely on bipolar ion conduction, removing one pair of the cation and the anion simultaneously. Here, we demonstrate that novel ion concentration polarization desalination can enhance salt removal under a given current by implementing unipolar ion conduction: conducting only cations (or anions) with the unipolar ion exchange membrane stack. Combining theoretical analysis, experiment, and numerical modeling, we elucidate that this enhanced salt removal can shift current utilization (ratio between desalted ions and ions conducted through electrodes) and corresponding energy efficiency by the factor ∼(D- - D+)/(D- + D+). Specifically for desalting NaCl, this enhancement of unipolar cation conduction saves power consumption by ∼50% in overlimiting regime, compared with conventional electrodialysis. Recognizing and utilizing differences between unipolar and bipolar ion conductions have significant implications not only on electromembrane desalination, but also energy harvesting applications (e.g. reverse electrodialysis).

Spatiotemporally Defining Biomolecule Preconcentration by Merging Ion Concentration Polarization.

The ion concentration polarization (ICP) phenomenon at micronanofluidic interfaces has been extensively utilized to preconcentrate low-abundance biological samples. Although preconcentration by ICP is robust, its multiphysics phenomenon does not permit a clear prediction of the preconcentration conditions and sites. Here, we present a new method for spatiotemporally defining preconcentration, which can generate target-condensed plugs in a very specific region (<100 µm) regardless of the operating conditions (time, applied voltage, ionic strength, and pH). In contrast to previous devices that use only ion depletion, this device uses merged ICP zones with opposite polarity, i.e., ion depletion and ion enrichment. In this regard, ICP is initiated between two line-patterned cation exchange membranes. When voltage is applied across two membranes, an ion depletion (enrichment) zone occurs on the anodic (cathodic) side of the membranes. Two ICP zones are then merged and confined between the membranes. Consequently, the preconcentration action is also confined between the membranes. We demonstrate that fluorescent dyes are always preconcentrated at the designated location at all lengths of operating time and at broad voltage (0.5-100 V), ionic strength (1-100 mM KCl), and pH (3.7-10.3) ranges. This device successfully condenses proteins up to 10000-fold in a specific region of the channel (100 × 50 × 10 µm(3)) in 10 min. This work not only characterizes the unique scientific phenomenon of ICP overlapping but also opens the possibility of integrating ICP preconcentrators into commercial analysis equipment, which requires a known, stationary preconcentration site.

Paper-Based Flow Fractionation System Applicable to Preconcentration and Field-Flow Separation.

We present a novel paper-based flow fractionation system for preconcentration and field-flow separation. In this passive fluidic device, a straight channel is divided into multiple daughter channels, each of which is connected with an expanded region. The hydrodynamic resistance of the straight channel is predominant compared with those of expanded regions, so we can create steady flows through the straight and daughter channels. While the expanded regions absorb a great amount of water via capillarity, the steady flow continues for 10 min without external pumping devices. By controlling the relative hydrodynamic resistances of the daughter channels, we successfully divide the flow with flow rate ratios of up to 30. Combining this bifurcation system with ion concentration polarization (ICP), we develop a continuous-flow preconcentrator on a paper platform, which can preconcentrate a fluorescent dye up to 33-fold. In addition, we construct a field-flow separation system to divide two different dyes depending on their electric polarities. Our flow fractionation systems on a paper-based platform would make a breakthrough for point-of-care diagnostics with specific functions including preconcentration and separation.