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Biological ion pumps with two separate gates can actively transport ions against the concentration gradient. Developing an artificial nanofluidic device with multiple responsive sites is of great importance to improve its controllability over ion transport to further explore its logic function and mimic the biological process. Here, we propose an electrochemical polymerization method to fabricate electrochemically switchable double-gate nanofluidic devices. The ion transport of the double-gate nanofluidic device can be in situ and reversibly switched among four different states. The logic function of this nanofluidic device is systematically investigated by assuming the gate state as the input and the transmembrane ionic conductance as the output. A biomimetic electrochemical ion pump is then established by alternately applying two different specific logic combinations, realizing an active ion transport under a concentration gradient. This work would inspire further studies to construct complex logical networks and explore bioinspired ion pump systems.

A facile electrochemical immunosensor based on graphene-three dimensional nanostructure gold nanocomposites (G-3D Au) using simple and rapid one-step electrochemical co-reduction technique was developed for sensitive detection of topoisomerase. The resultant G-3D Au nanocomposites were characterized by scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy, and then were used as a substrate for construction of the "sandwich-type" immunosensor. Amperometric current-time curve was employed to monitor the immunoreaction on the protein modified electrode. The proposed method could respond to topoisomerase with a linear calibration range from 0.5 ng mL(-1) to 50 ng mL(-1) with a detection limit of 10 pg mL(-1). This new biosensor exhibited a fast amperometric response, high sensitivity and selectivity, and was successfully used in determining the topoisomerase which was added in human serum with a relative standard deviation (n=5)<5%. The immunosensor served as a significant step toward the practical application of the immunosensor in clinical diagnosis and prognosis monitor., (Copyright © 2014 Elsevier B.V. All rights reserved.)

A strategy for label-free oligonucleotide (DNA) analysis has been proposed by measuring the DNA-morpholino hybridization hindered diffusion flux of probe ions Fe(CN)(6)(3-) through nanochannels of a porous anodic alumina (PAA) membrane. The flux of Fe(CN)(6)(3-) passing through the PAA nanochannels is recorded using an Au film electrochemical detector sputtered at the end of the nanochannels. Hybridization of the end-tethered morpholino in the nanochannel with DNA forms a negatively charged DNA-morpholino complex, which hinders the diffusion of Fe(CN)(6)(3-) through the nanochannels and results in a decreased flux. This flux is strongly dependent on ionic strength, nanochannel aperture, and target DNA concentration, which indicates a synergetic effect of steric and electrostatic repulsion effects in the confined nanochannels. Further comparison of the probe flux with different charge passing through the nanochannels confirms that the electrostatic effect between the probe ions and DNA dominates the hindered diffusion process. Under optimal conditions, the present nanochannel array-based DNA biosensor gives a detection limit of 0.1 nM.

The electrochemistry of a macrocyclic metal complex Fe(notpH(3)) [notpH(6)=1,4,7-triazacyclononane-1,4,7-triyl-tris(methylene-phosphonic acid)] reveals that the protonation/deprotonation of the non-coordinated P-OH groups in Fe(notpH(3)) affects its formal potential value (E(0)') considerably. Plotting E(0)' as function of solution pH gives a straight line with a slope of -585 mV pH(-1) in the pH range of 3.4-4.0, which is about ten times larger than the theoretical value of -58 mV pH(-1) for a reversible proton-coupled single-electron transfer at 20 °C. A sensitive pH responsive electrochemical switch sensor is thus developed based on Fe(notpH(3)) which shows an "on/off" switching at pH ∼ 4.0., (Copyright © 2010 Elsevier B.V. All rights reserved.)

In this paper, a micro/nanofluidic preconcentration device integrated with an electrochemical detector has been used to study the enrichment of enzymes and homogeneous enzyme reaction kinetics. The enzymes are first concentrated in front of a nanochannel via an exclusion-enrichment effect (EEE) mechanism of the nanochannel integrated in a microfluidics device. If a substrate is electrokinetically transported to the concentrated enzymes, homogeneous enzymatic reaction occurs. The enzymatic reaction product can penetrate through the nanochannel to be detected electrochemically. In this device, the enriched enzymes can be well retained and repeatedly used, thus, the enzymatic reaction occurs in a continuous-flow mode. For demonstration, Glucose oxidase (GOx) was chosen as the model enzyme to study the influence of enzyme concentration on its reaction kinetics. The different concentration of GOx in front of the nanochannel was simply achieved by using different enrichment time. When substrate glucose was introduced electrokinetically, a rapid electrochemical steady-state response could be obtained. It was found that the electrochemical response to a constant glucose concentration increased with the increase of enzyme enrichment time, which is expected for homogeneous enzymatic reactions. Under proper conditions, the electrochemical responds linearly to the glucose concentration ranging from 0 to 15 mM, and the Michaelis constants (K(m)) are relatively low, which indicates a more efficient complex formation between enzyme and substrate. These results suggest that the present micro/nanofluidics device is promising for the study of enzymatic reaction kinetics and other bioassays such as cell assays, drug discovery, and clinical diagnosis.

A novel experimental methodology based on the unique characteristics of chitosan-branched ferrocene (CS-Fc) and gold nanoparticles (Au NPs) was developed to design a label-free amperometric immunosensor for the sensitive detection of hepatitis B surface antigen (HBsAg) as a model protein. The controllable electrodeposition of CS-Fc solution formed a three-dimensional robust film with good biocompatibility and large surface area for the assembly of Au NPs and further immobilization of hepatitis B surface antibody (HBsAb) on an electrode. The morphologies and electrochemistry of the formed nanocomposite biofilm were investigated by using scanning electron microscopy and electrochemical techniques including cyclic voltammetry and electrochemical impedance spectroscopy, respectively. The HBsAg concentration was measured through the decrease of amperometric responses in the corresponding specific binding of antigen and antibody. The decreased differential pulse voltametric values were proportional to the HBsAg concentration in the range of 0.05-305ngmL(-1) with a detection limit 0.016ng. This would provide an approach for the application of mediator in immunoassays.

Nickel hexacyanoferrate film modified gold electrode was prepared by a simple chemical deposition procedure from a fresh prepared solution containing ferricyanide, Ni(2+), and sodium nitrate. The resultant films have solo composition and are significantly stable as compared to the electrochemically deposited NiHCF films. For different concentrations of Na(+) in the solution, the formal potential values of NiHCF shift according to the Nernstian behavior with a slope of 48 mV in the range of 10(-4) to 1.0M. The NiHCF film was also used for the electrocatalytic oxidation of ascorbic acid. The anodic peak current observed in cyclic voltammetry increased with the ascorbic acid concentration. At a fixed potential under hydrodynamic conditions, the calibration plot was linear over the ascorbic acid concentration range 0.1-12 mM.

The direct electrochemistry of cytochrome c (cyt c) on a gold electrode modified with 3-mercaptopropylphosphonic acid [HS-(CH(2))(3)-PO(3)H(2), MPPA] self-assembled monolayers (SAMs) was for the first time investigated. Electrochemical measurements and surface-enhanced infrared absorption spectroscopic reveal that the adsorption kinetics of cyt c on the MPPA-SAMs is very fast (saturation adsorption is completed within 5s) and the immobilized cyt c molecules retain their native secondary protein structure. The nature of interaction between cyt c and -PO(3)H(2) groups is mainly the electrostatic interaction. The direct electrochemistry of the immobilized cyt c on the -PO(3)H(2) terminated SAMs with short chain is nearly reversible. Its formal potential (E(0)'=18+/-3 mV vs. SCE) is very close to that of cyt c in an aqueous solution (E(0)'=18-22 mV vs. SCE). In addition, the electron transfer rate of cyt c immobilized on -PO(3)H(2) terminated SAMs is relatively slow as compared to -SO(3)H and -COOH terminated SAMs, indicating excess negative charge density on the SAMs surface will decrease the electron transfer rate of cyt c.

A novel polycalconcarboxylic acid (CCA) modified glassy carbon electrode (GCE) was fabricated by electropolymerization and then successfully used to simultaneously determine ascorbic acid (AA), norepinephrine (NE) and uric acid (UA). The characterization of electrochemically synthesized Poly-CCA film was investigated by atomic force microscopy (AFM), electrochemical impedance spectroscopy (EIS) and voltammetric methods. It was found that the electrochemical behavior of the polymer-modified electrode depended on film thickness, i.e., the electropylmyerization time. Based on the electrochemical data, the charge transfer coefficient (alpha) and the surface coverage (Gamma) were calculated. This poly-CCA modified GCE could reduce the overpotential of ascorbic acid (AA), norepinephrine (NE) and uric acid (UA) oxidation in phosphate buffer solution (pH 6.0), while it increases the peak current significantly. The current peak separations of AA/NE, NE/UA and AA/UA on this modified electrode are 91mV, 256mV and 390mV in CV at 100mVs(-1), respectively. Therefore, the voltammetric responses of these three compounds can be well resolved on the polymer-modified electrode, and simultaneously determination of these three compounds can be achieved. In addition, this modified electrode can be successfully applied to determine AA and NE in injection and UA in urine samples without interferences.

We used polyethyleneglycol (PEG) as a modulator to manipulate pore and cell sizes in the porous anodic alumina (PAA) fabrication. It is shown for the first time that continuous manipulation of the pore size of PAA can be realized. Combined with the coexistent cell-size controlling effect, the morphology and properties of this important nanoscale template and separation membrane can be precisely regulated. The pore size modulation mechanism is proposed on the basis of the morphological and electrochemical results. The presence of PEG in the electrolyte results in a more compacted structure of the barrier layer alumina (BLA), although the barrier layer thickness does not change considerably. In addition, the additive can obviously restrain the chemical dissolution of alumina and shape smaller pores. These two effects combined with the increased viscosity of the electrolyte slow down the ion transportation and diminish the anodization current. Thus, the burning-down phenomena of the aluminum substrates can be avoided at relatively high voltage anodization, and an interpore distance up to 610 nm can be achieved.

Although most of enzyme catalytic reactions are specific, the amperometric detection of the enzymatic reaction products is largely nonselective. How to improve the detection selectivity of the enzyme-based electrochemical biosensors has to be considered in the sensor fabrication procedures. Herein, a highly selective amperometric glucose biosensor based on the concept of diffusion layer gap electrode pair which we previously proposed was designed. In this biosensor, a gold tube coated with a conductive layer of glucose oxidase/Nafion/graphite was used to create an interference-free region in its diffusion layer by electrochemically oxidizing the interfering electroactive species at proper potentials. A Pt probe electrode was located in this diffusion layer of the tube electrode to selectively detect hydrogen peroxide generated from the enzyme catalytic oxidation of glucose in the presence of oxygen in the solution. In practical performance of the microdevice, parameters influencing the interference-removing efficiency, including the tip-tube opening distance, the tube electrode potential and the electrolyzing time had been investigated systematically. Results showed that glucose detection free from interferents could be achieved at the electrolyzing time of 30s, the tip-tube opening distance of 3mm and the tube electrode potential of 0.4V. The electrochemical response showed linear dependence on the concentration of glucose in the range of 1 x 10(-5) to 4 x 10(-3) M (the correlation coefficient: 0.9936, without interferents; 0.9995, with interferents). In addition, the effectiveness of this device was confirmed by numerical simulation using a model system of a solution containing interferents. The simulated results showed good agreement with the experimental data.

The end of separation channel in a microchip was electrochemically mapped using the feedback imaging mode of scanning electrochemical microscopy (SECM). This method provides a convenient way for microchannel-electrode alignment in microchip capillary electrophoresis. Influence of electrode-to-channel positions on separation parameters in this capillary electrophoresis-electrochemical detection (CE-ED) was then investigated. For the trapezoid shaped microchannel, detection in the central area resulted in the best apparent separation efficiency and peak shape. In the electrode-to-channel distance ranging from 65 to 15mum, the limiting peak currents of dopamine increased with the decrease of the detection distance due to the limited diffusion and convection of the sample band. Results showed that radial position and axial distance of the detection electrode to microchannel was important for the improvement of separation parameters in CE amperometric detection.

This paper presents an electrochemical detector for poly(dimethylsiloxane) (PDMS) microchip CE with a three-dimensional adjustor which makes it possible to accurately align a separate working electrode that can be easily fabricated in laboratory to the uncertain PDMS microchannel outlet. The substantial influence of the electrode-PDMS microchannel distance was investigated. The optimal electrode-outlet distance was found to be 10 microm for the PDMS microchannel with the width of 50 microm due to its relatively slow electroosmotic flow. Adrenaline and catechol were well separated, with a linear response range from 20 microM to 1 mM, and a detection limit of 2 microM for catechol, using carbon disk electrode (diameter of 300 microm). Furthermore, arginine and histidine can be well separated and detected directly in the PDMS microchannel using a Cu disk electrode (diameter of 150 microm).