Characterization of poly(3,4-ethylenedioxythiophene):tosylate conductive polymer microelectrodes for transmitter detection

In this paper we investigate the physical and electrochemical properties of micropatterned poly(3,4-ethylenedioxythiophene):tosylate (PEDOT:tosylate) microelectrodes for neurochemical detection. PEDOT:tosylate is a promising conductive polymer electrode material for chip-based bioanalytical applications such as capillary electrophoresis, high-performance liquid chromatography, and constant potential amperometry at living cells. Band electrodes with widths down to 3 μm were fabricated on polymer substrates using UV lithographic methods. The electrodes are electrochemically stable in a range between -200 mV and 700 mV vs. Ag/AgCl and show a relatively low resistance. A wide range of transmitters is shown to oxidize readily on the electrodes. Kinetic rate constants and half wave potentials are reported. The capacitance per area was found to be high (1670 ± 130 μF cm(-2)) compared to other thin film microelectrode materials. Finally, we use constant potential amperometry to measure the release of transmitters from a group of PC 12 cells. The results show how the current response decreases for a series of stimulations with high K(+) buffer.     

Electrochemical Study of Gold Microelectrodes Modified with PEDOT to Quantify Uric Acid in Milk Samples

A gold microelectrode (10 μm diameter) with an electropolymerized layer of poly(3,4‐ethylenedioxythiophene) (PEDOT) was used to quantify uric acid and investigate the antioxidant profile of milk and flavored milks. Comparisons were made with a bare gold microelectrode and a PEDOT‐glassy carbon macroelectrode (3 mm diameter). Two different electropolymerization processes were undertaken in an aqueous and an organic solution, and superior polymer growth was observed for PEDOT polymerized in lithium perchlorate/propylene carbonate. In the presence of a ferri/ferrocyanide redox couple, diffusion‐controlled redox peaks were observed with the PEDOT‐gold microelectrode rather than the plateau current typical of a bare microelectrode. Likewise, an anodic peak for uric acid was observed at the high surface‐area PEDOT‐gold microelectrode, with evidence for pre‐adsorption of uric acid at the electrode. The linear concentration range for uric acid standards was from 6 to 200 μM, and the limit of detection, limit of quantification, and sensitivity were determined to be 7 μM, 24 μM, and 397 μAμM^?1cm², respectively. Cyclic voltammograms of chocolate and espresso flavored milks exhibited significant contributions from the phenolic compounds present. Peak separation was more clearly defined using the PEDOT‐microelectrode compared to a PEDOT‐glassy carbon macroelectrode.     

Bacteria capture, concentration and detection by alternating current dielectrophoresis and self-assembly of dispersed single-wall carbon nanotubes

The high polarizability and dielectrophoretic mobility of single-walled carbon nanotubes (SWNT) are utilized to capture and detect low numbers of bacteria and submicron particles in milliliter-sized samples. Concentrated SWNT solutions are mixed with the sample and a high-frequency (>100 kHz) alternating current (AC) field is applied by a microelectrode array to enhance bulk absorption of the particles (bacteria and nanoparticle substitutes) by the SWNTs via dipole-dipole interaction. The same AC field then drives the SWNT-bacteria aggregates to the microelectrode array by positive-AC dielectrophoresis (DEP), with enhanced and reversed bacteria DEP mobility due to the attached SWNTs. Since the field frequency exceeds the inverse RC time of the electrode double layer, the AC field penetrates deeply into the bulk and across the electrode gap. Consequently, the SWNTs and absorbed bacteria assemble rapidly (<5 min) into conducting linear aggregates between the electrodes. Measured AC impedance spectra by the same trapping electrodes and fields show a detection threshold of 10(4) bacteria/mL with this pathogen trapping and concentration technique.     

Single-cell recording and stimulation with a 16k micro-nail electrode array integrated on a 0.18 μm CMOS chip

To cope with the growing needs in research towards the understanding of cellular function and network dynamics, advanced micro-electrode arrays (MEAs) based on integrated complementary metal oxide semiconductor (CMOS) circuits have been increasingly reported. Although such arrays contain a large number of sensors for recording and/or stimulation, the size of the electrodes on these chips are often larger than a typical mammalian cell. Therefore, true single-cell recording and stimulation remains challenging. Single-cell resolution can be obtained by decreasing the size of the electrodes, which inherently increases the characteristic impedance and noise. Here, we present an array of 16,384 active sensors monolithically integrated on chip, realized in 0.18 μm CMOS technology for recording and stimulation of individual cells. Successful recording of electrical activity of cardiac cells with the chip, validated with intracellular whole-cell patch clamp recordings are presented, illustrating single-cell readout capability. Further, by applying a single-electrode stimulation protocol, we could pace individual cardiac cells, demonstrating single-cell addressability. This novel electrode array could help pave the way towards solving complex interactions of mammalian cellular networks.     

Resident neuroelectrochemical interfacing using carbon nanofiber arrays

Carbon nanofiber electrode architectures are used to provide for long-term, neuroelectroanalytical measurements of the dynamic processes of intercellular communication between excitable cells. Individually addressed, vertically aligned carbon nanofibers are incorporated into multielement electrode arrays upon which excitable cell matrixes of both neuronal-like derived cell lines (rat pheochromocytoma, PC-12) and primary cells (dissociated cells from embryonic rat hippocampus) are cultured over extended periods (days to weeks). Electrode arrays are characterized with respect to their response to easily oxidized neurotransmitters, including dopamine, norepinephrine, and 5-hydroxytyramide. Electroanalysis at discrete electrodes following long-term cell culture demonstrates that this platform remains responsive for the detection of easily oxidized species generated by the cultured cells. Preliminary data also suggests that quantal release of easily oxidized transmitters can be observed at nanofiber electrodes following direct culture and differentiation on the arrays for periods of at least 16 days.     

The effect of surface wettability on induction and growth of neurites from the PC-12 cell on a polymer surface

Surface properties of polymeric devices that are used to regenerate nervous damage are a point to be considered for axon regeneration in nerve system. In our previous studies, we prepared a wettability gradient on polyethylene (PE) surfaces using a corona discharge treatment from a knife-type electrode whose power increases gradually along the sample length. The PE surfaces were oxidized gradually with increasing power. The effect of surface wettability on the different types of cells has an important role for cell adhesion and proliferation. The purpose of this study is to investigate neurite formation on polymer surfaces with different wettability. Induction and growth of neurites from the rat pheochromocytoma (PC-12) cells attached on the polymer surfaces with different hydrophilicity were investigated using the wettability gradient PE surfaces prepared by a corona discharge treatment. Neurites were investigated for number and length of neurites in terms of surface wettability. It was observed that neurite formation of PC-12 cells was increased more onto the positions with moderate hydrophilicity of the wettability gradient surface than onto the more hydrophobic or hydrophilic positions. From those results, it could be assumed that initial adhesion of PC-12 cells was caused by more calf serum (CS) protein than nerve growth factor (NGF), whereas the neurite formation of PC-12 cells was caused by more NGF than CS protein. It follows from what has been said thus far that PC-12 cells are a differentiated neuronal phenotype with a long neurite at around the position 2.5 cm (water contact angle of about 55 deg). In conclusion, surface wettability plays an important role for neurite formation on the polymer surfaces for axon regeneration.     

Recessed microelectrode array for a micro flow-through system allowing on-line multianalyte determination in vivo

Using CMOS-compatible processes, a microelectrode system for use in a micro flow-through cell was manufactured. The electrode was specially designed to enable multianalyte determination with immobilized oxidase enzymes and combines minimal flow dependency with a very small dead volume (< 1 μL) of the cell. This allows biomedical applications like measurements of glucose and lactate in interstitial fluid, which can be collected by ultrafiltration. Besides a 3-electrode system with 4 individually addressable platinum working electrodes, the sensor contains 2 electrodes that measure the conductivity of the sample as well as a Pt thermoresistor to measure the temperature. The temperature dependence in enzyme reactions can thus be controlled during on-line measurements. The 4 working electrodes comprise multielectrode arrays, each comprising 192 micro-holes with a diameter of 3.6 μm. They are arranged symmetrically around the central counter electrode, which is surrounded by a circular Ag/AgCl reference electrode. Between the array and the reference electrode are the loops of the Pt thermoresistor. The thermoresistor is electrically insulated from the measurement solution by a Si₃N₄ layer. A method for the pretreatment of platinum thin-film electrodes that increases the reversibility of the electrode process is described. The chemical modification of the working electrodes by electropolymerization of a resorcinol/1,3-diaminobenzene mixture enables interference-free measurement in blood and plasma as well as protection against electrode fouling.     

Functionalised electrode array for the detection of nitric oxide released by endothelial cells using different NO-sensing chemistries

In a preliminary study aimed at developing strategies for the simultaneous detection of various biologically important molecules, a procedure is described that allows the electrochemical detection of nitric oxide (NO) released by a population of human umbilical vein endothelial cells (HUVEC) by using an array of electrodes comprising three individually addressable electrodes. Each electrode in the array was modified with a different NO-sensitive electrocatalyst, thereby demonstrating the possibility of modifying the individual electrodes in an array with different sensing chemistries. This study opens a doorway to the development of arrays of electrodes for the simultaneous detection of multiple analytes in a complex environment by suitably tailoring the sensitivity and selectivity of each electrode in the array to a specific analyte in the test medium.     

Site-selectively functionalizing microelectrode arrays: the use of Cu(I)-catalysts

Site-selective Cu(I)-catalyzed reactions have been developed on microelectrode arrays. The reactions are confined to preselected electrodes on the arrays using oxygen as the confining agent. Conditions initially developed for the Cu(I)-catalyzed click reaction have proven general for the coupling of amine, alcohol, and sulfur nucleophiles to both vinyl and aryl iodides. Differences between reactions run on 1-K arrays and reactions run on 12-K arrays can be attributed to the 1-K array reactions being divided cell electrolyses and the 12-K array reactions being undivided cell electrolyses. Reactions on the 12-K arrays benefit from the use of a non-sugar-derived porous reaction layer for the attachment of substrates to the surface of the electrodes. The reactions are sensitive to the nature of the ligand used for the Cu catalyst.     

Voltammetric Characterization of Micro‐ and Submicrometer‐Electrode Arrays of Conical Shape for Electroanalytical Use

Densely packed micro‐ and submicrometer electrode arrays of platinum and gold (the nominal number, N, of electrodes in each array varies between 225 and 3600) are fabricated by photolithographic technique and vapor deposition processes of metal films. The electrodes are conical‐shaped and only their apexes are exposed to the electrolytic solution. The electrode arrays are characterized electrochemically in Ru(NH₃)₆Cl₃ aqueous solutions by using cyclic voltammetry at low scan rates, to establish the number of electrochemically active electrodes (N_ac) in each array; the geometric characterization is performed by scanning electron microscopy. All the investigated arrays provide steady‐state voltammograms, indicating diffusionally independent behavior of each microelectrode. The number of microelectrodes that are active in the fabricated arrays depends on microelectrode density. In particular, for the arrays with N=3600 and N=225, the fraction of active sites is about 45% and 90%, respectively. The analytical performance of some of the Pt version of the arrays is tested in hydrogen peroxide solutions, allowing verifying that linear calibration plots over the concentration range (0.1–20 mM) are obtained. This dynamic range is larger than that typically recorded at smooth polycrystalline platinum electrodes (0.5–5 mM), and the better performance is attributed to both the higher aspect ratio of the cone geometry and the higher mass transport associated to each microelectrode of the array. Reproducibility (within 3.5%, r.s.d.) and long‐term stability (within 5%, r.s.d., after 8 h continuous use) of the electrode systems are satisfactory. A low detection limit, based on the signal to noise ratio equal to 3, of 0.05 mM is found, which is adequate for a rapid monitoring of H₂O₂ in real samples and industrial processes.     

Electroanalysis of Bromate,Iodate and Chlorate at Tungsten Oxide Modified Platinum Microelectrode Arrays

This article describes the direct detection of Bromate, but also of chlorate and iodate, using modified arrays of platinum ultramicroelectrodes. The detection limits for these ions are IO =0.76 μM; BrO =2.34 μM and ClO =133.2 μM. The formation of a suitable tungsten oxide layer and the optimum analytical conditions are described. These oxide layers are formed electrochemically from hydrogen peroxide‐tungstanate solutions in acid conditions. Although film stability may be an issue, particularly at pH>3, these modified arrays of microelectrodes can be used for analytical purposes. After the analysis, the modifying oxide is easily removed and the Pt microelectrode array recovers its original properties.     

Analytical performance characteristics of thin and thick film amperometric microcells

The analytical performance of amperometric microcells with different electrode geometries is compared for enzyme activity measurements. The microcells were fabricated with thin film photolithography or thick film screen-printing in four different designs. The cells made with the thin film process used flexible substrate with microelectrode array or a circular, disk-shaped working electrode. The screen-printed working electrodes had semicircle or disk shape on ceramic chips. Putrescine oxidase (PUO) activity measurement was used as a model. The determination of PUO activity is important in the clinical diagnosis of premature rupture of the amniotic membrane. An electropolymerized m-phenylenediamine size-exclusion layer was used to eliminate common interferences. The size exclusion layer revealed also to be advantageous in protecting the electrodes from fouling by putrescine (enzyme substrate). The electrode fouling of bare electrodes was insignificant for screen-printed electrodes, but very severe for electroplated platinum working electrodes. The microelectrode array electrodes demonstrated smaller RSD and higher normalized sensitivities for hydrogen peroxide and PUO activity. All the other electrodes were demonstrating comparable analytical performances.     

Analytical performance characteristics of thin and thick film amperometric microcells

The analytical performance of amperometric microcells with different electrode geometries is compared for enzyme activity measurements. The microcells were fabricated with thin film photolithography or thick film screen-printing in four different designs. The cells made with the thin film process used flexible substrate with microelectrode array or a circular, disk-shaped working electrode. The screen-printed working electrodes had semicircle or disk shape on ceramic chips. Putrescine oxidase (PUO) activity measurement was used as a model. The determination of PUO activity is important in the clinical diagnosis of premature rupture of the amniotic membrane. An electropolymerized m-phenylenediamine size-exclusion layer was used to eliminate common interferences. The size exclusion layer revealed also to be advantageous in protecting the electrodes from fouling by putrescine (enzyme substrate). The electrode fouling of bare electrodes was insignificant for screen-printed electrodes, but very severe for electroplated platinum working electrodes. The microelectrode array electrodes demonstrated smaller RSD and higher normalized sensitivities for hydrogen peroxide and PUO activity. All the other electrodes were demonstrating comparable analytical performances.     

Effects of solid polymer electrolyte coating on the composition and morphology of the solid electrolyte interphase on Sn anodes

In order to discuss the effect of polymer coating layer on the Sn anode, the composition and morphology of the solid electrolyte interphase (SEI) film on the surface of Sn and Sn@PEO anode materials have been investigated. Compared with the bare cycled Sn electrode, the SEI on the surface of cycled Sn@PEO electrode is thinner, smoother, and more stable. Therefore, the Sn@PEO nanoparticles can basically keep the original appearance during cycling. Based on the results obtained from X-ray photoelectron spectroscopy (XPS), the SEI formed on the Sn@PEO electrode is characterized by inorganic components (Li₂CO₃)-rich outer layer and organic components-rich inner which could make the SEI more stable and inhibit the electrolyte immerging into the active materials. In particular, the elastic ion-conductive polyethylene oxide (PEO) coating could increase the toughness of SEI and allow the SEI to endure the stress variation in repetitive lithium insertion and extraction process. As a result, the Sn@PEO electrodes show significantly better capacity retention than bare Sn electrodes. The findings can serve as the theoretical foundation for the design of lithium-ion battery electrode with high energy density and long cycle life.     

COLLOID CHEMICAL APPROACH TO THE CONSTRUCTION OF HIGH ENERGY DENSITY RECHARGEABLE LITHIUM - ION BATTERIES

Abstract

The layer-by-layer self-assembly of poly(diallyldimethyl-ammonium) chloride, PDDA; graphite oxide, G, nanoplatelets; and polyethylene oxide, PEO, onto transparent indium tin oxide substrates, S, have provided cationic working electrodes which, with lithium wires as reference and counter electrodes, functioned as high energy density rechargeable lithium-ion batteries. Specifically, very high specific capacities (1232 and 1134 mAh.g^?1) have been determined for batteries which had positive electrodes of ten sandwich layers of self-assembled films: S-(PDDA/GO/PEO)₁₀ and S-(PDDA/PEO)₁₀. The importance of the exfoliating GO into nanoplatelets and the colloid chemistry of self-assembly are discussed.     

Spatiotemporally controlled contraction of micropatterned skeletal muscle cells on a hydrogel sheet

We have developed gel sheet-supported C(2)C(12) myotube micropatterns and combined them with a microelectrode array chip to afford a skeletal muscle cell-based bioassay system. Myotube line patterns cultured on a glass substrate were transferred with 100% efficiency to the surface of fibrin gel sheets. The contractile behavior of each myotube line pattern on the gel was individually controlled by localized electrical stimulation using microelectrode arrays that had been previously modified with electropolymerized poly(3,4-ethylenedioxythiophene) (PEDOT). We successfully demonstrated fluorescent imaging of the contraction-induced translocation of the glucose transporter, GLUT4, from intracellular vesicles to the plasma membrane of the myotubes. This device is applicable for the bioassay of contraction-induced metabolic alterations in a skeletal muscle cell.     

Site-selective, cleavable linkers: quality control and the characterization of small molecules on microelectrode arrays

A "safety-catch" linker strategy has been used to release a portion of the products of a Diels-Alder reaction conducted on a microelectrode array for characterization of stereochemistry. The attachment and cleavage of organic compounds from the surface of selected electrodes in the array can be accomplished by site-selective generation of base or acid at the electrode. It was found that the surface of the array had a minor influence on the stereochemistry of the Diels-Alder reaction, leading to slightly more of the exo-product relative to a similar solution-phase reaction.     

基于WOx/PEDOT:PSS复合空穴传输层的高效稳定平面异质结钙钛矿太阳电池

在基于钙钛矿/富勒烯平面异质结的钙钛矿太阳电池中,PEDOT:PSS是最常使用的空穴传输材料. 但PEDOT:PSS呈酸性,会腐蚀金属氧化物透明电极,使器件的电极界面稳定性欠佳. 本文将高功函的氧化钨（WO_x）插入到PEDOT:PSS和FTO之间,形成WO_x/PEDOT:PSS复合空穴传输层,这样既可以避免PEDOT:PSS与FTO直接接触,提高器件的稳定性,又可以进一步降低电极界面的接触势垒,从而提升器件的性能. 作者研究了复合传输层对透光率、钙钛矿形貌、钙钛矿结晶、光伏性能及器件稳定性的影响. 基于WO_x/PEDOT:PSS复合空穴传输层的电池效率可以达到12.96%,比单纯的PEDOT:PSS的电池效率(10.56%)提升了22.7%,同时器件的稳定性也得到大幅改善.     

辣根过氧化酶在纳米金／氧化锌球腔微电极阵列上的直接电化学研究

利用Langmuir - Blodgett技术和溶胶-凝胶(sol -gel)法在氧化铟锡(ITO)电极表面制备了有序的纳米金／氧化锌(nano-Au/ZnO)球腔阵列,并采用扫描电镜表征了nano-Au/ZnO球腔阵列的形貌.该阵列的循环伏安曲线具有微电极特性.将辣根过氧化酶(HRP)直接固定于nano-Au/ZnO...