Enhancing Sustainable Energy Conversion Efficiency by Incorporating Photoelectric Responsiveness into Multiporous Ionic Membrane.

The evolution of porous membranes has revitalized their potential application in sustainable osmotic-energy conversion. However, the performance of multiporous membranes deviates significantly from the linear extrapolation of single-pore membranes, primarily due to the occurrence of ion-concentration polarization (ICP). This study proposes a robust strategy to overcome this challenge by incorporating photoelectric responsiveness into permselective membranes. By introducing light-induced electric fields within the membrane, the transport of ions is accelerated, leading to a reduction in the diffusion boundary layer and effectively mitigating the detrimental effects of ICP. The developed photoelectric-responsive covalent-organic-framework membranes exhibit an impressive output power density of 69.6 W m-2 under illumination, surpassing the commercial viability threshold by ≈14-fold. This research uncovers a previously unexplored benefit of integrating optical electric conversion with reverse electrodialysis, thereby enhancing energy conversion efficiency.

Hierarchical Capillarity-Assisted Liquid Invasion in Multilayered Paper Channels for Nanoelectrokinetic Preconcentration.

A nanoelectrokinetic phenomenon called ion concentration polarization (ICP) has been recently applied to microfluidic paper-based devices for the high fold preconcentration of low-abundant analytes. The inherent microstructural characteristics of cellulose papers can sufficiently stabilize the chaotic electroconvection of ICP, which is a significant annoyance for typical engineered microfluidic channels. However, a high electrical voltage to induce ICP in a paper-fluidic channel can increase unavoidable electrophoretic forces over drag forces so that the preconcentrated plug is rapidly receded with severe dispersion. In order to enhance the hydraulic drag force that helps the preconcentration of analytes, here we introduce a multilayered paper structure into paper-fluidic channel. We theoretically and experimentally demonstrate that a hierarchical capillary structure in a multilayered paper-fluidic channel can effectively increase the hydraulic drag force. For the practical utility in the field of diagnostics, the mechanism is verified by a simple example of the immunoassay using biotin-streptavidin complexation.

Laser-Assisted Scalable Pore Fabrication in Graphene Membranes for Blue-Energy Generation.

The osmotic energy from a salinity gradient (i. e. blue energy) is identified as a promising non-intermittent renewable energy source for a sustainable technology. However, this membrane-based technology is facing major limitations for large-scale viability, primarily due to the poor membrane performance. An atomically thin 2D nanoporous material with high surface charge density resolves the bottleneck and leads to a new class of membrane material the salinity gradient energy. Although 2D nanoporous membranes show extremely high performance in terms of energy generation through the single pore, the fabrication and technical challenges such as ion concentration polarization make the nanoporous membrane a non-viable solution. On the other hand, the mesoporous and micro porous structures in the 2D membrane result in improved energy generation with very low fabrication complexity. In the present work, we report femtosecond (fs) laser-assisted scalable fabrication of µm to mm size pores on Graphene membrane for blue energy generation for the first time. A remarkable osmotic power in the order of µW has been achieved using mm size pores, which is about six orders of magnitudes higher compared to nanoporous membranes, which is mainly due to the diffusion-osmosis driven large ionic flux. Our work paves the way towards fs laser-assisted scalable pore creation in the 2D membrane for large-scale osmotic power generation.

Predicting ion concentration polarization and analyte stacking/focusing at nanofluidic interfaces.

We report on the investigation of electropreconcentration phenomena in micro-/nanofluidic devices integrating 100 µm long nanochannels using 2D COMSOL simulations based on the coupled Poisson-Nernst-Planck and Navier-Stokes system of equations. Our numerical model is used to demonstrate the influence of key governing parameters such as electrolyte concentration, surface charge density, and applied axial electric field on ion concentration polarization (ICP) dynamics in our system. Under sufficiently extreme surface-charge-governed transport conditions, ICP propagation is shown to enable various transient and stationary stacking and counter-flow gradient focusing mechanisms of anionic analytes. We resolve these spatiotemporal dynamics of analytes and electrolyte ICP over disparate time and length scales, and confirm previous findings that the greatest enhancement is observed when a system is tuned for analyte focusing at the charge, excluding microchannel, nanochannel electrical double layer (EDL) interface. Moreover, we demonstrate that such tuning can readily be achieved by including additional nanochannels oriented parallel to the electric field between two microchannels, effectively increasing the overall perm-selectivity and leading to enhanced focusing at the EDL interfaces. This approach shows promise in providing added control over the extent of ICP in electrokinetic systems, particularly under circumstances in which relatively weak ICP effects are observed using only a single channel.

Enhanced immunoassay in a nanofluidic preconcentrator utilizing nano-interstices among self-assembled gold nanoparticles.

In this study, we developed a microfluidic device for a dual work of protein preconcentration and subsequent capture by an immunoassay system. The fabrication of nano-interstices (nanochannels) to generate ion concentration polarization effect (ICP) for the preconcentration was simply performed by exploiting the loose association of glass-on-modified AuNPs to the polydimethylsiloxane (PDMS) channel pads as well as spaces between the substrate and the PDMS pad caused by these AuNPs. As a result, 65-fold concentration enhancement was achieved when performed on a sample of fluorescein isothiocyanate-labeled bovine serum albumin (FITC-BSA). Furthermore, a modification procedure of antibodies responsible for capturing target proteins was performed on gold electrodes integrated into the proposed chip. After preconcentration, the immunoassay system was worked, and showed a good performance in capturing targets. Through this study, we demonstrated that the device can work efficiently for the dual purpose, has the potential to apply widely for the analysis and capture of various targets.

Portable Seawater Desalination System for Generating Drinkable Water in Remote Locations.

A portable seawater desalination system would be highly desirable to solve water challenges in rural areas and disaster situations. While many reverse osmosis-based portable desalination systems are already available commercially, they are not adequate for providing reliable drinking water in remote locations due to the requirement of high-pressure pumping and repeated maintenance. We demonstrate a field-deployable desalination system with multistage electromembrane processes, composed of two-stage ion concentration polarization and one-stage electrodialysis, to convert brackish water and seawater to drinkable water. A data-driven predictive model is used to optimize the multistage configuration, and the model predictions show good agreement with the experimental results. The portable system desalinates brackish water and seawater (2.5-45 g/L) into drinkable water (defined by WHO guideline), with the energy consumptions of 0.4-4 (brackish water) and 15.6-26.6 W h/L (seawater), respectively. In addition, the process can also reduce suspended solids by at least a factor of 10 from the source water, resulting in crystal clear water (<1 NTU) even from the source water with turbidity higher than 30 NTU (i.e., cloudy seawater by the tide). We built a fully integrated prototype (controller, pumps, and battery) packaged into a portable unit (42 × 33.5 × 19 cm3, 9.25 kg, and 0.33 L/h production rate) controlled by a smartphone, tested for battery-powered field operation. The demonstrated portable desalination system is unprecedented in size, efficiency, and operational flexibility. Therefore, it could address unique water challenges in remote, resource-limited regions of the world.

Recent advances in paper-based preconcentrators by utilizing ion concentration polarization.

One of the most cited limitations of biochemical detection is its poor sensitivity, owing to the relatively high complexity of micro-samples. Moreover, some samples cannot be easily self-replicated and their abundance cannot be increased through traditional technologies. Therefore, the preconcentration of low-abundance samples is a key requirement for microfluidic biological analysis. In recent years, the ion-concentration polarization phenomenon has aroused widespread interest in the application of microfluidic technology. In addition, paper-based materials are readily available, easy to modify, and exhibit good hydrophilicity. The study of the ion-concentration polarization preconcentration of micro-samples in paper-based microfluidic chips is of considerable significance. In this review, we discuss the development and applications of ion-concentration polarization paper-based preconcentrator in the past 5 years, with emphasis on key progresses in chip fabrication and performance optimization under different conditions. The current needs and development prospects in this field have also been discussed.

Semi-Continuous Desalination and Concentration of Small-Volume Samples.

Electrodialysis is an electric-field-mediated process separating ions exploiting selective properties of ion-exchange membranes. The ion-exchange membranes create an ion-depleted zone in an electrolyte solution adjacent to the membrane under DC polarization. We constructed a microfluidic system that uses the ion-depleted zone to separate ions from the processed water solution. We tested the separation performance by desalting a model KCl solution spiked with fluorescein for direct observation. We showed both visually and by measuring the conductivity of the output solutions that the system can work in three modes of operation referred to as continuous desalination, desalination by accumulation, and unsuccessful desalination. The mode of operation can easily be set by changing the control parameters. The desalination factors for the model KCl solution reached values from 80 to 100%, depending on the mode of operation. The concentration factor, given as a ratio of concentrate-to-feed concentrations, reached zero for desalination by accumulation when only diluate was produced. The water recovery, therefore, was infinite at these conditions. Independent control of the diluate and concentrate flow rates and the DC voltage turned our system into a versatile platform, enabling us to set proper conditions to process various samples.

Rapid pre-concentration of Escherichia coli in a microfluidic paper-based device using ion concentration polarization.

We report a microfluidic paper based analytical device implementing ion concentration polarization (ICP) for rapid pre-concentration of Escherichia coli in water. The fabricated device consists of a paper channel with a Nafion® membrane and in-built micro wire electrodes to supply electric voltage to induce the ICP effect. E. coli cells were stained with SYTO 9 and fluorescence was used as a sensing method. The device achieved high concentration factor up to 2 × 105 within minutes. The effect of total ion concentration, on ICP and fluorescence intensity was studied. The reported device and method are suitable and effective for detection of E. coli during ballast water quality monitoring, coastal water quality monitoring where high salinity water is present.

A numerical study on ion concentration polarization and electric circuit performance of an electrokinetic battery.

Ion concentration polarization (ICP) imposes remarkable adverse effects on the energy conversion performance of the pressure-driven electrokinetic (EK) flows through a capillary system that can be equivalently treated as a battery. An optimized dimensionless numerical method is proposed in this study to investigate the causes and the effects of the ICP. Results show that remarkable ICP phenomena are induced under certain conditions such as high applied pressure, high surface charge density, and small inversed Debye length at dimensionless values of 6000, -10, and 0.5. Meanwhile, different factors influence the ICP and the corresponding electric properties in different ways. Particularly for the overall electric resistance, the applied pressure and the surface charge density mainly affect the variation amplitude and the level of the overall electric resistance when varying the output electric potential, respectively. Differently, the Debye length affects the overall electric resistance in both aspects. Ultimately, the induced ICP leads to significant nonlinear current-potential curves.

Techno-economic analysis of multi-stage ion concentration polarization with recirculation for treatment of oil produced water.

The concept of recirculation of diluate/concentrate stream is implemented in multi-stage ion concentration polarization (ICP) desalination to deal with the issue of uncontrolled concentrate streams and deteriorated overall recovery rate to treat highly concentrated oil produce water from refineries. An improved empirical optimization model was established to calculate total energy consumption for operating cost and required membrane area for capital cost for a given set of operating parameters, feed salinity, salt removal ratio, and flow velocity. Using the empirical optimization model, a techno-economic analysis is performed to evaluate the feasibility of two-stage ICP system with recirculation loops. Brine of 160 g/kg is set as the system feed stream, whereas other operating conditions such as dilaute and concentrate streams are being controlled/fixed with 20 g/kg and ~250 g/kg respectively. Also, the system can be flexibly controlled to produce a specific concentration of product water and a recovery ratio with a corresponding water cost. With careful choices of recirculation rates, one can significantly increase the recovery ratio of two-stage ICP brine treatment process (from 25% to 39%) with only minor increase in overall cost (from $16.4-25.9/m3 to $20.6-22.54/m3), which is favourable for brine waste treatment application.

dCas9-mediated Nanoelectrokinetic Direct Detection of Target Gene for Liquid Biopsy.

The-state-of-the-art bio- and nanotechnology have opened up an avenue to noninvasive liquid biopsy for identifying diseases from biomolecules in bloodstream, especially DNA. In this work, we combined sequence-specific-labeling scheme using mutated clustered regularly interspaced short palindromic repeats associated protein 9 without endonuclease activity (CRISPR/dCas9) and ion concentration polarization (ICP) phenomenon as a mechanism to selectively preconcentrate targeted DNA molecules for rapid and direct detection. Theoretical analysis on ICP phenomenon figured out a critical mobility, elucidating two distinguishable concentrating behaviors near a nanojunction, a stacking and a propagating behavior. Through the modulation of the critical mobility to shift those behaviors, the C-C chemokine receptor type 5 ( CCR5) sequences were optically detected without PCR amplification. Conclusively, the proposed dCas9-mediated genetic detection methodology based on ICP would provide rapid and accurate micro/nanofluidic platform of liquid biopsies for disease diagnostics.

Simultaneous isolation and preconcentration of exosomes by ion concentration polarization.

Exosomes carry microRNA biomarkers, occur in higher abundance in cancerous patients than in healthy ones, and because they are present in most biofluids, including blood and urine, these can be obtained noninvasively. Standard laboratory techniques to isolate exosomes are expensive, time consuming, provide poor purity, and recover on the order of 25% of the available exosomes. We present a new microfluidic technique to simultaneously isolate exosomes and preconcentrate them by electrophoresis using a high transverse local electric field generated by ion-depleting ion-selective membrane. We use pressure-driven flow to deliver an exosome sample to a microfluidic chip such that the transverse electric field forces them out of the cross flow and into an agarose gel which filters out unwanted cellular debris while the ion-selective membrane concentrates the exosomes through an enrichment effect. We efficiently isolated exosomes from 1× PBS buffer, cell culture media, and blood serum. Using flow rates from 150 to 200 µL/h and field strengths of 100 V/cm, we consistently captured between 60 and 80% of exosomes from buffer, cell culture media, and blood serum as confirmed by both fluorescence spectroscopy and nanoparticle tracking analysis. Our microfluidic chip maintained this recovery rate for more than 20 min with a concentration factor of 15 for 10 min of isolation.

Development of a low flow-resistive charged nanoporous membrane in a microchip for fast electropreconcentration.

A nanoporous poly-(styrene sulfonate) (poly-SS) membrane was developed for fast and selective ion transport in a microfluidic chip. The poly-SS membrane can be photopolymerized in-situ at arbitrary location of a microchannel, enabling integrated fluidics design in the microfluidic chip. The membrane is characterized by a low hydraulic resistance and a high surface charge to maximize the electroosmotic flow and charge selectivity. The membrane characteristics were investigated by charge-selective electropreconcentration method. Experimental results show membranes with various percentages of poly-SS are able to concentrate anions (fluorescein and TRITC-labeled BSA). The anion-selective electropreconcentration process is stable and 26-times faster than previously reported poly-AMPS (2-acrylamido-2-methyl-1-propanesulfonic acid) based system. The electropreconcentration was also demonstrated to depend on the sample valency and buffer concentration.

Pressure-driven spontaneous ion concentration polarization using an ion-selective membrane.

In this study, the spontaneous ion concentration polarization phenomenon induced by pressure via a cation-selective membrane was theoretically and experimentally investigated. Unlike conventional electrokinetic ion concentration polarization, which uses electric current as a driving flux of cations through the membrane, advection caused by pressure is used as a transmembrane driving flux of cations to spontaneously and stably form an ion depletion zone in the present ion concentration polarization technique. The ion depletion zone produced in a simple experimental setup was used to filter electrolyte and preconcentrate ions and microparticles. Different from the general assumption of the negligible thickness of the electric double layer in microchannels, the low concentration in the ion depletion zone considerably increased the length of the electric double layer. This enhanced the formation of the ion depletion zone. The present results can improve the understanding on ion transport in the ion concentration polarization system and can be utilized to develop a portable water desalination device for rural/remote areas and for preconcentrating biomolecules.

Direct numerical simulation of continuous lithium extraction from high Mg2+/Li+ ratio brines using microfluidic channels with ion concentration polarization.

A novel ion concentration polarization-based microfluidic device is proposed for continuous extraction of Li+ from high Mg2+/Li+ ratio brines. With simultaneous application of the cross-channel voltage that drives electroosmotic flow and the cross-membrane voltage that induces ion depletion, Li+ is concentrated much more than other cations in front of the membrane in the microchannel. The application of external pressure produces a fluid flow that drags a portion of Li+ (and Na+) to flow through the microchannel, while keeping most of Mg2+ (and K+) blocked, thus implementing continuous Li+ extraction. Two-dimensional numerical simulation using a microchannel of 120 µm length and 4 µm height and a model, highly concentrated brine, shows that the system may produce a continuous flow rate of 1.72 mm/s, extracting 25.6% of Li+, with a Li+/Mg2+ flux ratio of 2.81×103, at a pressure of 100 Pa and cross-membrane voltage of 100 times of thermal voltages (25.8 mV). Fundamental mechanisms of the system are elaborated and effects of the cross-membrane voltage and the external pressure are analyzed. These results and findings provide clear guidance for the understanding and designing of microfluidic devices not only for Li+ extraction, but also for other ionic or molecular separations.

A multi-module microfluidic platform for continuous pre-concentration of water-soluble ions and separation of oil droplets from oil-in-water (O/W) emulsions using a DC-biased AC electrokinetic technique.

A novel continuous flow microfluidic platform specifically designed for environmental monitoring of O/W emulsions during an aftermath of oil spills is reported herein. Ionized polycyclic aromatic hydrocarbons which are toxic are readily released from crude oil to the surrounding water phase through the smaller oil droplets with enhanced surface area. Hence, a multi-module microfluidic device is fabricated to form ion enrichment zones in the water phase of O/W emulsions for the ease of detection and to separate micron-sized oil droplets from the O/W emulsions. Fluorescein ions in the water phase are used to simulate the presence of these toxic ions in the O/W emulsion. A DC-biased AC electric field is employed in both modules. In the first module, a nanoporous Nafion membrane is used for activating the concentration polarization effect on the fluorescein ions, resulting in the formation of stable ion enrichment zones in the water phase of the emulsion. A 35.6% amplification of the fluorescent signal is achieved in the ion enrichment zone; corresponding to 100% enrichment of the fluorescent dye concentration. In this module, the main inlet is split into two channels by using a Y-junction so that there are two outlets for the oil droplets. The second module located downstream of the first module consists of two oil droplet entrapment zones at two outlets. By switching on the appropriate electrodes, either one of the two oil droplet entrapment zones can be activated and the droplets can be blocked in the corresponding outlet.

Regulating Current Rectification and Nanoparticle Transport Through a Salt Gradient in Bipolar Nanopores.

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.

Preconcentration and Separation of Mixed-Species Samples Near a Nano-Junction in a Convergent Microchannel.

A fluidic microchip incorporating a convergent microchannel and a Nafion-nanoporous membrane is proposed for the preconcentration and separation of multi-species samples on a single platform. In the device, sample preconcentration is achieved by means of the ion concentration polarization effect induced at the micro/nano interface under the application of an external electric field, while species separation is achieved by exploiting the different electrophoretic mobilities of the sample components. The experimental results show that the device is capable of detecting C-reactive protein (CRP) with an initial concentration as low as 9.50 × 10(-6) mg/L given a sufficient preconcentration time and driving voltage. In addition, it is shown that a mixed-species sample consisting of three negatively-charged components (bovine serum albumin (BSA), tetramethylrhodamine(TAMRA) isothiocyanate-Dextran and fluorescent polymer beads) can be separated and preconcentrated within 20 min given a driving voltage of 100 V across 1 cm microchannel in length. In general, the present results confirm the feasibility of the device for the immunoassay or detection of various multi-species samples under low concentration in the biochemical and biomedical fields. The novel device can therefore improve the detection limit of traditional medical facilities.

Enhanced Salt Removal of Fresh Water by Recovery-Reduced Ion Concentration Polarization Desalination.

Here, we examine electromembrane systems for low-concentration desalination applicable to ultrapure water production. In addition to electrodialysis and ion concentration polarization (ICP) desalination, we propose a recovery-reduced ICP strategy for reducing the width of the desalted outlet for a higher salt removal ratio (SRR). The correlation between conductivity changes and thickness of the ion depletion zone is identified for electrodialysis, ICPH (1:1), and ICPQ (3:1) with a low-concentration feed solution (10 mM, 1 mM, 0.1 mM NaCl). Based on the experimental results, the scaling law and SRR for the electroconvection zone are summarized, and current efficiency (CE) and energy per ion removal (EPIR) depending on SRR are also discussed. As a result, the SRR of electrodialysis is mostly around 50%, but that of recovery-reduced ICP desalination is observed up to 99% under similar operating conditions. Moreover, at the same SRR, the CE of recovery-reduced ICP is similar to that of electrodialysis, but the EPIR is calculated to be lower than that of electrodialysis. Considering that forming an ion depletion zone up to half the channel width in the electromembrane system typically requires much power consumption, an ICP strategy that can adjust the width of the desalted outlet for high SRR can be preferable.