Inherently aligned microfluidic electrodes composed of liquid metal

This paper describes the fabrication and characterization of microelectrodes that are inherently aligned with microfluidic channels and in direct contact with the fluid in the channels. Injecting low melting point alloys, such as eutectic gallium indium (EGaIn), into microchannels at room temperature (or just above room temperature) offers a simple way to fabricate microelectrodes. The channels that define the shape and position of the microelectrodes are fabricated simultaneously with other microfluidic channels (i.e., those used to manipulate fluids) in a single step; consequently, all of the components are inherently aligned. In contrast, conventional techniques require multiple fabrication steps and registration (i.e., alignment of the electrodes with the microfluidic channels), which are technically challenging. The distinguishing characteristic of this work is that the electrodes are in direct contact with the fluid in the microfluidic channel, which is useful for a number of applications such as electrophoresis. Periodic posts between the microelectrodes and the microfluidic channel prevent the liquid metal from entering the microfluidic channel during injection. A thin oxide skin that forms rapidly and spontaneously on the surface of the metal stabilizes mechanically the otherwise low viscosity, high surface tension fluid within the channel. Moreover, the injected electrodes vertically span the sidewalls of the channel, which allows for the application of uniform electric field lines throughout the height of the channel and perpendicular to the direction of flow. The electrodes are mechanically stable over operating conditions commonly used in microfluidic applications; the mechanical stability depends on the magnitude of the applied bias, the nature of the bias (DC vs. AC), and the conductivity of the solutions in the microfluidic channel. Electrodes formed using alloys with melting points above room temperature ensure mechanical stability over all of the conditions explored. As a demonstration of their utility, the fluidic electrodes are used for electrohydrodynamic mixing, which requires extremely high electric fields (~10(5) V m(-1)).     

Interdigitated array microelectrode based impedance immunosensor for detection of avian influenza virus H5N1

Continuous outbreaks of avian influenza (AI) in recent years with increasing threat to animals and human health have warranted the urgent need for rapid detection of pathogenic AI viruses. In this study, an impedance immunosensor based on an interdigitated array (IDA) microelectrode was developed as a new application for sensitive, specific and rapid detection of avian influenza virus H5N1. Polyclonal antibodies against AI virus H5N1 surface antigen HA (Hemagglutinin) were oriented on the gold microelectrode surface through protein A. Target H5N1 viruses were then captured by the immobilized antibody, resulting in a change in the impedance of the IDA microelectrode surface. Red blood cells (RBCs) were used as biolabels for further amplification of the binding reaction of the antibody-antigen (virus). The binding of target AI H5N1 onto the antibody-modified IDA microelectrode surface was further confirmed by atomic force microscopy. The impedance immunosensor could detect the target AI H5N1 virus at a titer higher than 10³ EID₅₀/ml (EID₅₀: 50% Egg Infective Dose) within 2 h. The response of the antibody-antigen (virus) interaction was shown to be virus titer-dependent, and a linear range for the titer of H5N1 virus was found between 10³ and 10⁷ EID₅₀/ml. Equivalent circuit analysis indicated that the electron transfer resistance of the redox probe [Fe(CN)₆]^3−/4− and the double layer capacitance were responsible for the impedance change due to the protein A modification, antibody immobilization, BSA (bovine serum albumin) blocking, H5N1 viruses binding and RBCs amplification. No significant interference was observed from non-target RNA viruses such as Newcastle disease virus and Infectious Bronchitis disease virus. (The H5N1 used in the study was inactivated virus.)     

Prussian Blue-coated interdigitated array electrodes for possible analytical application

Thin films of iron(III) hexacyanoferrate(II) (Prussian Blue) were electrochemically deposited on interdigitated array (IDA) electrodes, yielding systems which can be considered as chemiresistors in sensing alkali metal ion concentrations in an adjacent electrolyte. This is due to the fact that the conductivity of the film being measured by a steady-state current on application of a voltage to the two-fingered electrodes of the IDA depends on both the redox stare of the film and the cation concentration in the electrolyte. From the dependence of the steady-state current on the electrode (bias) potential at variable cation concentrations for different alkali metal ions and for mixtures of alkali metal ions, the possibilities of analytical application were elucidated. In addition, by using the methods of staircase coulometry and scanning conductivity, the electron diffusion coefficient D_e was determined as a function of the redox state of Prussian Blue. It is concluded that Prussian Blue-coated IDA electrodes are, in principle, suitable as chemiresistors for the determination of alkali metal ion concentrations with increasing selectivity in the series Li < Na < K < Rb < Cs.     

Coaxial Cu-Si@C array electrodes for high-performance lithium ion batteries

A new concept for fabricating novel triple-layered nanorod array electrodes made of coaxial Cu-Si@C arrays has been developed. They exhibit excellent electrochemical performance resulting from peculiar new sandwiched architectures: robust Cu nanopillar cores/amorphous Si layers/elastic carbon shells.     

1,4-丁二醇在Pt及其修饰电极上吸附氧化过程研究

运用电化学循环伏安和石英晶体微天平研究了1，4-丁二醇(1，4-BDL)在Pt电极及以Sb和S吸附原子修饰的Pt(Pt／Sbad和Pt／Sad)电极上的吸附和氧化过程．结果表明，1，4-丁二醇的氧化与电极表面氧物种有着极其密切的关系，表面质量变化提供了吸附原子电催化作用的新数据．Pt电极表面Sb吸附原子能在较低的电位下吸附氧，可显提高1，4-丁二醇电催化氧化活性．与Pt电极相比，1，4-丁二醇在饱和吸附Sb原子的Pt电极上氧化的峰电位负移了0．20V，峰电流增加了1．5倍．相反，Pt电极表面S吸附原子的氧化会消耗表面氧物种，饱和吸附的S原子抑制了1，4-丁二醇的氧化．     

Sputtering deposition of Pt nanoparticles on vertically aligned multiwalled carbon nanotubes for sensing L-cysteine

A highly sensitive electrochemical sensor for determination of L-cysteine (CySH) is presented. It is based on vertically aligned multiwalled carbon nanotubes modified with Pt nanoparticles by magnetron sputtering deposition. The morphology of the nanocomposite was characterized by scanning electron microscopy, transmission electron microscopy and energy-dispersive. The electrochemistry of CySH was investigated by cyclic voltammetry, differential pulse voltammetry and chronoamperometry. The mechanism for the electrochemical reaction of CySH at the modified electrode at different pH values is discussed. The electrode exhibits a higher electrocatalytic activity towards the oxidation of CySH than comparable other electrodes. It displays a linear dependence (R ²?=?0.9980) on the concentration of CySH in the range between 1 and 500 μM and at an applied potential of +0.45 V, a remarkably low detection limit of 0.5 μM (S/N?=?3), and an outstandingly high sensitivity of 1.42?×?10³ μA?mM^?1?cm^?2, which is the highest value ever reported. The electrode also is highly inert towards other amino acids, creatinine and urea. The sensor was applied to the determination of CySH in urine with satisfactory recovery, thus demonstrating its potential for practical applications.

Fabrication and electrochemical behaviour of vertically aligned boron-doped diamond nanorod forest electrodes

Vertically aligned boron-doped diamond nanorod forests (BDDNF) were successfully fabricated by depositing a diamond film onto silicon nanowires (SiNWs) using hot filament chemical vapor deposition (HFCVD). The boron-doped diamond nanorods were characterized by Raman spectroscopy and scanning electron microscopy (SEM). The BDDNF obtained from the SiNWs on the silicon wafer could be directly used as an electrode and its electrochemical behaviour is discussed here. Compared to a flat boron-doped diamond (BDD) electrode, the BDDNF electrode showed high sensitivity in the amperometric detection of adenine.     

Seed layer-free electrodeposition and characterization of vertically aligned ZnO nanorod array film

Vertically aligned arrays of ZnO nanorod (ZNR) were rapidly synthesized on ITO glass without needing a pre-prepared seed layer of ZnO via a hexamethylenetetramine (HMT)-assisted electrodeposition route. The effect of HMT on the ZNR electrodeposition process was investigated by the cyclic voltammetric curve and the current–time curve. An electrodeposition growth model based on the capping effect of HMT–4H was proposed. The as-synthesized ZNRs possess single crystalline, a wurtzite crystal structure with markedly preferential growth orientation along [0001] direction determined by transmission electron microscopy and powder X-ray diffraction. As compared with the electrodeposited ZnO film without HMT assistance, the ZNR arrays showed the high transmittance (90%) in the visible wavelength range and the blue-shift of the band gap energy. Moreover, the presence of an optical-phonon E₂ (high) at 437.3 cm^?1 in Raman spectrum and strong ultraviolet emission at 376 nm but weak defect-related deep level emission in the room temperature photoluminescence spectrum also indicated that such ZNR arrays are of good crystal quality. More importantly, the rapid synthesis of ZNRs could provide the feasibility for preparation of ZnO nanotubes within a shorter time by a subsequent electrochemical dissolution process.     

Addressable electrode array device with IDA electrodes for high-throughput detection

An electrochemical device is proposed for high-throughput electrochemical detection that consists of 32 row and 32 column electrodes on a single glass substrate. The row and column electrodes are connected to interdigitated array (IDA) electrodes to form 1024 (32 × 32) addressable sensor points in the device. Electrochemical responses from each of the 1024 sensors were successfully acquired on the device within 1 min using redox cycling at individual IDA electrodes, which ensures application of the device to comprehensive, high-throughput electrochemical detection for enzyme-linked immunosorbent assay (ELISA), reporter gene assay for monitoring gene expressions, and DNA analysis.     

Electrooxidation of methanol on upd-Ru and upd-Sn modified Pt electrodes

The electrochemical oxidation of methanol has been investigated on underpotentially deposited-ruthenium-modified platinum electrode (upd-Ru/Pt) and on underpotentially deposited-tin-modified platinum electrode (upd-Sn/Pt). The submonolayers of upd-Ru and upd-Sn on a Pt electrode increased the rate of methanol electrooxidation several times as large as that on a pure Pt electrode. The best performance for methanol electrooxidation was obtained on a ternary platinum based catalyst modified by upd-Ru and upd-Sn simultaneously. The influence of the submonolayers of upd-Ru adatoms and upd-Sn adatoms on the oxidation of methanol in acid has been investigated. The effect of Ru on methanol electrooxidation lies on the distribution of Ru adatoms on a Pt surface. It has been shown that as long as the amount of upd-Ru deposits were controlled in a proper range, upd-Ru deposits would enhance the methanol oxidation obtained on a Pt electrode at whichever deposition potential the upd-Ru deposits were obtained. The effects of tin are sensible to the potential range. The enhancement effect of upd-Sn adatoms for the oxidation of methanol will disappear as the electrode potential is beyond a certain value. It is speculated that there exists a synergetic effect on the Pt electrode as adatoms Ru and Sn participate simultaneously in the methanol oxidation.     

Electroreduction activity of hydrogen peroxide on Pt and Au electrodes

Hydrogen peroxide electroreduction on both catalytically active Pt and inactive Au surfaces are studied by using both surface-enhanced Raman spectroscopy (SERS) and density functional theory (DFT) calculations. SERS measurements on Pt show the presence of Pt-OH at negative potentials, which suggests that hydroxide is formed as an intermediate during the electroreduction process. Additionally, the O-O stretch mode of H(2)O(2) is observed on Pt, which shifts to lower energy as potential is swept negatively, indicating that the O-O bond is elongated. For comparison, there is no variation in the energy of the same O-O mode on Au surfaces, and there is no observation of Au-OH. DFT calculations show that H(2)O(2) adsorption on Pt(110) results in the dissociation of O-O bond and the formation of Pt-OH bond. On Au, O-O bond elongation is calculated to occur only on the (110) face. However, the magnitude of the elongation is much smaller than that found on Pt(110).     

Pt nanoparticles modified Au nanowire array for amperometric and potentiometric detection of glucose

A new glucose biosensor, based on the modification of highly ordered Au nanowire arrays (ANs) with Pt nanoparticles (PtNPs) and subsequent surface adsorption of glucose oxidase (GOx), is described. Morphologies of ANs and ANs/PtNPs were observed by scanning electron microscope. The electrochemical properties of ANs, ANs/GOx, ANs/PtNPs, and ANs/PtNPs/GOx electrodes were compared by cyclic voltammetry. Results obtained from comparison of the cyclic voltammograms show that PtNPs modification enhances electrochemical catalytic activity of ANs to H₂O₂. Hence, ANs/PtNPs/GOx biosensor exhibits much better sensing to glucose than ANs/GOx. Optimum deposition time of ANs/PtNPs/GOx biosensor for both amperometric and potentiometric detection of glucose was achieved to be 150 s at deposition current of 1?×?10^?6 A. A sensitivity of 0.365 μA/mM with a linear range from 0.1 to 7 mM was achieved for amperometric detection; while for potentiometric detection the sensitivity is 33.4 mV/decade with a linear range from 0.1 to 7 mM.     

Nano-fibrous scaffolds for tissue engineering

With the ability to form nano-fibrous structures, a drive to mimic the extracellular matrix (ECM) and form scaffolds that are an artificial extracellular matrix suitable for tissue formation has begun. These nano-fibrous scaffolds attempt to mimic collagen, a natural extracellular matrix component, and could potentially provide a better environment for tissue formation in tissue engineering systems. Three different approaches toward the formation of nano-fibrous materials have emerged: self-assembly, electrospinning and phase separation. Each of these approaches is very different and has a unique set of characteristics, which lends to its development as a scaffolding system. For instance, self-assembly can generate small diameter nano-fibers in the lowest end of the range of natural extracellular matrix collagen, while electrospinning has only generated large diameter nano-fibers on the upper end of the range of natural extracellular matrix collagen. Phase separation, on the other hand, has generated nano-fibers in the same range as natural extracellular matrix collagen and allows for the design of macropore structures. These attempts at an artificial extracellular matrix have the potential to accommodate cells and guide their growth and subsequent tissue regeneration.     

Vertically aligned carbon nanotube based electrodes: Fabrication, characterisation and prospects

We present a methodology to fabricate carbon nanotube based electrodes using plasma enhanced chemical vapour deposition. The metal catalyst nanoparticles used to promote nanotube growth are removed using a water plasma treatment in combination with an acid attack. The final integrated microelectrode-based devices present excellent electrocatalytic properties that make them suitable for electrochemical applications. The presented methodology enables the construction of highly regular and dense vertically aligned carbon nanotube (VACNT) forests that can be confined within the patterned bounds of a desired surface. These VACNT electrodes display very low capacitive currents and are amenable to further chemical modifications.     

Nanowire-based nanogap electrodes by annealing of multisegmented Pt/Au/Pt nanowires in air

A simple thermally lithographic method for fabricating nanowire-based metallic nanogap electrodes is presented, in which the multisegmented Pt/Au/Pt nanowires were electrodeposited in the pores of porous anodic aluminum oxide (AAO) templates first and then thermally annealed to form a nanoscale gap at the interface of Au/Pt. We proposed that the breaking of the multisegmented Pt/Au/Pt nanowires is due to the chemical and physical transformations of the Au segment with O₂. These electrodes are ideally suited for electron-transport studies of chemically synthesized nanostructures, and their utility is demonstrated here by measuring the electronic conduction of short (54-base-pairs) double-stranded (ds) DNA molecules in a dry state.     

Electrochemistry of polystyrene intercalated vertically aligned single- and double-walled carbon nanotubes on gold electrodes

Electrochemical electrodes incorporating double- and single-walled carbon nanotubes (CNTs) were fabricated on cysteamine modified flat gold substrates. Through covalent coupling of the amine end groups with carboxyl functionalized CNTs, a dense forest of vertically aligned CNTs was produced. To these a 30 nm thick insulating polystyrene layer was spin coated, resulting in exposure of the uppermost carbon nanotube ends. The electrochemical performance of each electrode was then determined using the redox probe ruthenium hexaamine. Once surrounded by polymer, the double-walled CNTs (DWCNTs) showed an improved electron transfer rate, compared to the single-walled electrode. This improvement was attributed to the protection of the electronic properties of the inner wall of the DWCNT during the chemical modification and suggests that DWCNTs may offer a useful alternative to SWCNTs in future electrochemical sensors and biosensors.     

Biodegradable elastomer for soft tissue engineering

In this work we present the synthesis of a biodegradable, elastomeric material with a wide range of mechanical properties. The synthesis of the material was done by condensation polymerization of malic acid and 1,12–dodecandiol. The synthesized materials have low Young’s modulus ranging from about 1 to 4 MPa and a high elongation at break of 25–737% depending on the crosslinking density of the system. The cell growth observed under microscope showed good proliferation at 3 days of culture indicating good biocompatibility and support of L929 cells growth. The fabrication of 3D scaffold from these materials using the super critical CO₂ foaming method was also attempted. This method of scaffold fabrication is appropriate for materials that are easily hydrolysable and it also has the advantage of being a solvent free process. These materials are generally soft, biocompatible and biodegradable making them suitable for tissue engineering of soft tissues that are elastic in nature like muscles and blood vessels.     

Surface characterization of Pt electrodes using underpotential deposition of H and Cu: Part III. Surface improvement of the flame-annealed Pt(100) and Pt(111) electrodes via potential cycling

In Parts I and II of this series it was shown that the Pt(100) and Pt(111) surfaces pretreated by flame-annealing and quenching in aqueous electrolyte contain a high density of defects such as vacancies, Pt adatoms and clusters of Pt adatoms. In this paper we show that potential cycling including scans into the oxygen region in sulfuric or perchloric acid removes most of these sites and that a limited number of cycles yield hydrogen adsorption-desorption profiles (cyclic voltammograms) that compare favorably with those published by authors who established the structure using electron diffraction techniques. Some loss of longer-range surface order as a result of the potential cycling is indicated by an increase in the width at half-height of the monolayer copper stripping peaks. The possibility of surface improvement in the absence of surface oxidation and reduction is explored by potential cycling in hydrochloric acid.     

Large-scale fabrication of aligned single-walled carbon nanotube array and hierarchical single-walled carbon nanotube assembly

Aligned single-walled carbon nanotubes (SWNTs) and hierarchical SWNT assembly were fabricated by electrospinning. The high fiber elongation and high DC electric field applied during the electrospinning process result in the orientation of the SWNTs along the axial direction of the fiber. The alignment of the electropsun composite fiber transfers this local SWNT orientation to macroscopically aligned SWNTs. After removing the polymer component from the aligned composite fiber, we produced large area aligned SWNTs. The results show that the directional control of SWNT alignment and debundling of SWNTs into individual tubes can be simultaneously realized.     

Validation of doubling exponent models for the impedance of well-aligned MWCNT array electrodes

The capacitive and faradaic responses of well-aligned MWCNT array electrodes were determined by cyclic voltammetry and impedance spectroscopy. The impedance responses of the array electrodes were modeled by transition line models.