Electrokinetic transport of CTAB induces multiphasic behavior during capillary adsorption and desorption.

Cationic surfactant coatings (e.g., CTAB) are commonly used in CE to control EOF and thereby improve separation efficiencies.

Nanofluidic diodes based on asymmetric bio-inspired surface coatings in straight glass nanochannels.

In this study, we present nanofluidic diodes fabricated from straight glass nanochannels and functionalized using bio-inspired polydopamine (PDA) and poly-L-lysine (PLL) coatings. The resulting PDA coatings are shown to be asymmetric due to a combination of transport considerations which can be leveraged to provide a measure of control over the effective channel geometry. By subsequently introducing a layer of amine-bearing PLL chains covalently bound to the PDA, we enhance heterogeneities in the charge and ion distributions within the channel and enable significant current rectification between forward-bias and reverse-bias modes; our PDA-PLL-coated channels yielded a rectification ratio greater than 1000 in a 100 nm channel filled with 0.

Electrooxidation of Phenol on Polyelectrolyte Modified Carbon Electrodes for Use in Insulin Pump Infusion Sets.

Background: Many type 1 diabetes patients using continuous subcutaneous insulin infusion (CSII) suffer from the phenomenon of unexplained hypoglycemia or "site loss." Site loss is hypothesized to be caused by toxic excipients, for example, phenolic compounds within insulin formulations that are used as preservatives and stabilizers. Here, we develop a bioinspired polyelectrolyte-modified carbon electrode for effective electrooxidative removal of phenol from insulin and eventual incorporations into an infusion set of a CSII device.

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.

Real-Time Zeta Potential Analysis of Microchannel Surfaces during Aminosilane Deposition and Exposure Using Current Monitoring.

Surface coatings are extensively used in capillary electrophoresis to increase separation efficiency and resolution. The stability of these coatings across a wide pH range is desirable to achieve repeatable migration times; therefore, a comprehensive understanding of coating degradation timescales is needed. We present a novel platform for automated zeta potential analysis based upon current monitoring that delivers improved time resolution over the existing methods.

Molecular Design of a New Diboronic Acid for the Electrohydrodynamic Monitoring of Glucose.

A new dicationic diboronic acid structure, DBA2+, was designed to exhibit good affinity (K ≈1 mm) and selectivity toward glucose. Binding of DBA2+ to glucose changes the pK of DBA2+ from 9.4 to 6.

Fluorescence-Based Observation of Transient Electrochemical and Electrokinetic Effects at Nanoconfined Bipolar Electrodes.

Bipolar electrodes (BPEs) are conductors that, when exposed to an electric field, polarize and promote the accumulation of counterionic charge near their poles. The rich physics of electrokinetic behavior near BPEs has not yet been rigorously studied, with our current understanding of such bipolar effects being restricted to steady-state conditions (under constant applied fields). Here, we reveal the dynamic electrokinetic and electrochemical phenomena that occur near nanoconfined BPEs throughout all stages of a reaction.

Confinement effects on DNA hybridization in electrokinetic micro- and nanofluidic systems.

Spatial confinement, within cells or micro- and nanofabricated devices, impacts the conformation and binding kinetics of biomolecules. Understanding the role of spatial confinement on molecular behavior is important for comprehending diverse biological phenomena, as well as for designing biosensors. Specifically, the behavior of molecular binding under an applied electric field is of importance in the development of electrokinetic biosensors.

DNA-Stabilized Silver Nanoclusters as Specific, Ratiometric Fluorescent Dopamine Sensors.

Neurotransmitters are small molecules that orchestrate complex patterns of brain activity. Unfortunately, there exist few sensors capable of directly detecting individual neurotransmitters. Those sensors that do exist are either unspecific or fail to capture the temporal or spatial dynamics of neurotransmitter release.

Two-Dimensional Electric Double Layer Structure with Heterogeneous Surface Charge.

In this work we present a systematic study of the lateral (parallel to the wall) and normal (perpendicular to the wall) nanostructure of the electric double layer at a heterogeneous interface between two regions of different surface charges, often found in nanoscale electrochemical devices. Specifically, classical density functional theory (DFT) is used to probe a cation concentration range of 10 mM to 1 M, for valences of +1, + 2, and +3, and a diameter range of 0.15-0.

Optimal MEMS device for mobility and zeta potential measurements using DC electrophoresis.

We have developed a novel microchannel geometry that allows us to perform simple DC electrophoresis to measure the electrophoretic mobility and zeta potential of analytes and particles. In standard capillary geometries, mobility measurements using DC fields are difficult to perform. Specifically, measurements in open capillaries require knowledge of the hard to measure and often dynamic wall surface potential.

A universal design for a DNA probe providing ratiometric fluorescence detection by generation of silver nanoclusters.

DNA-stabilized silver nanoclusters (AgNCs), the fluorescence emission of which can rival that of typical organic fluorophores, have made possible a new class of label-free molecular beacons for the detection of single-stranded DNA. Like fluorophore-quencher molecular beacons (FQ-MBs) AgNC-based molecular beacons (AgNC-MBs) are based on a single-stranded DNA that undergoes a conformational change upon binding a target sequence. The new conformation exposes a stretch of single-stranded DNA capable of hosting a fluorescent AgNC upon reduction in the presence of Ag(+) ions.

(Almost) Stationary Isotachophoretic Concentration Boundary in a Nanofluidic Channel Using Charge Inversion.

The present work is an experimental study of a new means to induce a quasi-stationary boundary for concentration or separation in a nanochannel induced by charge inversion. Instead of using pressure-driven counter-flow to keep the front stationary, we exploit charge inversion by a highly charged electrolyte, Ru(bpy)3Cl2, that changes the sign of the zeta potential in part of the channel from negative to positive. Having a non-charge inverting electrolyte (MgCl2) in the other part of the channel and applying an electric field can create a standing front at the interface between them without added dispersion due to an externally applied pressure-driven counterflow.

Changes in Spectra and Conformation of Hairpin DNA-Stabilized Silver Nanoclusters Induced by Stem Sequence Perturbations.

It is well-known that even small perturbations of the DNA sequence can drastically and unpredictably disrupt or alter the fluorescence of DNA-stabilized silver nanoclusters (DNA-AgNCs). Understanding how the structure of DNA affects the nanocluster that it stabilizes is the key to rationalizing such effects. We approach this challenge by strategically modifying the stem sequence of a hairpin DNA that hosts a spectrally pure, red-emitting nanocluster.

A simple microfluidic aggregation analyzer for the specific, sensitive and multiplexed quantification of proteins in a serum environment.

Portable and low-cost platforms for protein biomarker detection are highly sought after for point of care applications. We demonstrate a simple microfluidic device for the rapid, electrically-based detection of proteins in serum. Our aggregation analyzer relies on detecting the protein-induced aggregation of sub-micron particles, using a one-step procedure followed by a fast, particle-by-particle measurement with a very high count rate.

Electrophoretic mobility of spherical particles in bounded domain.

In this study, we improve on our 3D steady-state model of electrophoretic motion of spherical particles in bounded fluidic channels (Liu et al., 2014) to include the effect of nonsymmetric electrolytes, and further validate this improved model with detailed comparisons to experimental data. Specifically, we use the experimentally-measured particle mobilities from the work of Semenov et al.

Electrocavitation in nanofluidics: unique phenomenon and fundamental platform.

In this paper, we will highlight one phenomenon unique to nanofluidics: electrocavitation. Electrocavitation is defined as cavitation induced by electric fields. Cavitation in general occurs in a liquid when it is subjected to a pressure below its vapor pressure, where the liquid can break apart and form a cavity (bubble).

Quantitative characterization of the colloidal stability of metallic nanoparticles using UV-vis absorbance spectroscopy.

Plasmonic nanoparticles are used in a wide variety of applications over a broad array of fields including medicine, energy, and environmental chemistry. The continued successful development of this material class requires the accurate characterization of nanoparticle stability for a variety of solution-based conditions. Although many characterization methods exists, there is an absence of a unified, quantitative means for assessing the colloidal stability of plasmonic nanoparticles.

Hybridization thermodynamics of DNA oligonucleotides during microchip capillary electrophoresis.

Capillary electrophoresis (CE) is a powerful analytical tool for performing separations and characterizing properties of charged species. For reacting species during a CE separation, local concentrations change leading to nonequilibrium conditions. Interpreting experimental data with such nonequilibrium reactive species is nontrivial due to the large number of variables involved in the system.

Fluorescent silver nanocluster DNA probes for multiplexed detection using microfluidic capillary electrophoresis.

DNA-stabilized fluorescent silver nanoclusters (AgNC DNA) are a new class of fluorophore that are formed by sequence specific interactions between silver and single-stranded DNA. By incorporating both target-binding and fluorescent-reporting sequences into a single synthetic DNA oligomer, AgNC DNA probes eliminate the need to conjugate dye or quencher molecules. In this study, we modify a AgNC DNA probe to demonstrate single-color multiplexed detection of DNA targets.

Label free detection of nucleic acids by modulating nanochannel surfaces.

We develop surface-modified 100 nm silica nanofluidic channels that change in measured conductivity upon exposure to single- or double-stranded DNA. Through careful monitoring of both electromigrative and advective current in the channel, we can detect nanomolar concentrations of DNA. These results can be exploited for inexpensive, all-electronic DNA sensors.

Separation behavior of short single- and double-stranded DNA in 1 micron and 100 nm glass channels.

Micro- and nanofluidic lab-on-chip technology offers the unique capability of high-resolution separation, identification, and manipulation of biomolecules with broad applications in chemistry, biology, and medicine. In this work, we probe the effects of ionic strength on separation of ss- and dsDNA within 1 micron and 100 nm-deep glass channels. Separation behavior of DNA is influenced by a number of parameters, including ionic strength, melting temperature, strand length, strand conformation, and channel size.

Separation of ions in nanofluidic channels with combined pressure-driven and electro-osmotic flow.

Separation of ionic species with the same electrophoretic mobility but different valence in electrolyte systems can occur within nanometer-scale channels with finite electrical double layers (EDLs). This is because EDL thicknesses are a significant fraction of slit height in such channels and can create transverse analyte concentration profiles that allow for unique separation modalities when combined with axial fluid flow. Previous work has shown such separation to occur using either pressure-driven flow or electro-osmotic flow separately.