Stopped-flow sensor for dissolved oxygen

Stopped-flow hydrodynamic modulation voltammetry is applied to membrane electrodes to minimize some of the problems that characterize steady-state dissolved oxygen probes. Mass-transport properties, sensitivity, precision, and linearity of response are reported. The low stopped-flow background current allows a limit of detection for dissolved oxygen near 36 μg l^-1. The relative standard deviation at the mg l^-1 level is 3% Glassy carbon electrodes are used, replacing the commonly used metal cathodes, to minimize passivation effects. The method is sensitive, reproducible, and simple.     

A simple approach for fabrication of dual-disk electrodes with a nanometer-radius electrode and a micrometer-radius electrode

We developed a new simple approach to fabricate dual-disk electrodes with a nanometer-radius electrode and a micrometer-radius electrode. First, nanometer-sized electrodes and micrometer-sized electrodes were constructed using 10-μm-radius metal wires, respectively. To fabricate the nanometer-sized electrode, after the apex of the 10-μm-radius metal wire was electrochemically etched to an ultrafine point with a nanometer-radius, the metal wire was electrochemically coated with a phenol-allyphenol copolymer film. The micrometer-sized electrode was fabricated by directly electrochemical coating the metal wire with an extremely thin phenol-allyphenol copolymer film. Then, the nanometer-radius electrode (the first electrode) and the 10-μm-radius electrode (the second electrode) were inserted into two sides of a thick-septum borosilicate theta (θ) tubing, respectively. The second electrode protruded from the top of the θ tubing. The top of the θ tubing was sealed with insulating ethyl α-cyanoacrylate. The top of the θ tubing with both electrodes was ground flat and polished successively with fine sandpaper and aluminum oxide powder until the tip of the first electrode was exposed. Since the second electrode protruded from the top of the θ tubing, its 10-μm-radius tip was naturally formed during polishing. The dual-disk electrodes were characterized by scanning electron microscopy and cyclic voltammetry. The success rate for fabrication of the dual-disk electrodes is ∼80% due to double insurance from two coating layers of different polymers.     

Electroanalysis at modified carbon-paste electrodes containing natural ionic polysaccharides

The strong affinity of natural ionic polysaccharides for certain metal ions is exploited in the design of a new class of voltammetric sensing devices. In particular, carbon-paste electrodes containing pectic and alginic acids are used for the nonelectrolytic collection and subsequent voltammetric determination of copper and lead, respectively. Cyclic and differential pulse voltammetry are used to quantify the accumulated ions. The response is characterized with respect to modifier loading, preconcentration period, metal concentration, reproducibility, possible interferences and other variables. Titrimetric experiments illustrate the potential of polysaccharide electrodes for speciation work. Preliminary data are also given for analogous measurements of copper at heparin-modified electrodes. Detection limits are 1 mug/ml and the relative standard deviation is 4.8%.     

Electrochemical behavior of methyl viologen at graphite electrodes modified with Nafion sol–gel composite

Electrodes were prepared by spin-coating spectroscopic graphite rods with a Nafion doped sol. Coating solutions consisting of Nafion:TEOS (tetraethoxysilane) ratios of 3:1 and 4:1 gave smooth films on the electrode surface. These modified electrodes were evaluated and compared with Nafion modified and bare spectroscopic graphite electrodes using methyl viologen (MV²⁺) as a representative cationic electroactive probe. Substantial partitioning of MV²⁺ into the Nafion:sol–gel matrix to the electrode surface was observed by cyclic voltammetry and square wave voltammetry. Cyclic voltammograms of MV²⁺ in 0.1 M NaCl at Nafion:sol–gel 4:1 modified electrodes showed a reversible reduction to MV⁺ with E^0′=−0.695 V vs. Ag/AgCl. Results of scan rate variation showed the wave to be characterized by semi-infinite diffusion for scan rates in the range 50–500 mV/s. Slowing the scan rate below 50 mV/s resulted in a transition to thin-layer behavior. MV²⁺ partitioned much more quickly into the sol–gel-Nafion modified electrodes compared to pure Nafion modified electrodes. Reversibility of the MV²⁺-loaded modified Nafion-doped sol–gel coatings on electrodes was obtained by soaking in 1 M NaCl solution. Concentration calibration plots for MV²⁺ at the sol–gel-Nafion modified electrodes were nonlinear. Substantial enhancement of current signal at low concentrations was observed by square wave voltammetry.     

Simultaneous determination of cadmium(II), lead(II) and copper(II) by using a screen-printed electrode modified with mercury nano-droplets

We are presenting a strategy for the fabrication of disposable screen-printed electrodes modified with mercury nano-droplets and capable of sensing heavy metal ions. They were prepared by coating electrodes with a mixture of multi-walled carbon nanotubes and chitosan, this followed by adsorption of mercury. The resulting sensor was characterized by cyclic voltammetry and impedance spectroscopy. Also the effects caused by adsorption of mercury were investigated. It is shown that square wave anodic stripping voltammetry enables simultaneous determination of cadmium(II), lead(II) and copper(II), for which detection limits of 12, 23 and 20 nM, respectively, are found. Relative standard deviations for ten determinations at 0.6 µM concentrations of these ions are in the range of 3.0 to 5.7%. The applicability was tested by analyzing river water and showed recoveries between 94.1 and 104.6%, thus demonstrating its utility for in-field monitoring of these heavy metal ions.     

Analytical possibilities of microelectrode use for stripping voltammetry

The analytical utility of microelectrodes for stripping voltammetry is discussed from several points of view. The application of microelectrodes for microanalysis is demonstrated using a novel capillary flow injection system. Heavy metals at g l^–1 concentrations have been determined in l-samples. The influence of electrode size and convection during the deposition period of anodic stripping voltammetry on the reproducibility of trace metal determination was studied for various types of electrodes. In the case of mercury film microelectrodes, the precision can be improved if the accumulation of the analyte is performed under quiescent conditions. Practical examples of stripping voltammetry with microelectrodes such as copper determination in whisky and trace metal measurements in drinking water are given.     

Application of an autoranging amplifier in the simultaneous determination of trace heavy metals by anodic stripping voltammetry

An autoranging amplifier with a gain of 1–1000 is described, together with its possible application in anodic stripping voltammetry. The performance of the amplifier is demonstrated by differential-pulse anodic stripping voltammetric analysis of stored sea-water, in the subtractive mode with two working electrodes. It is suggested that the autoranging amplifier could save considerable analysis time by eliminating the need for trial runs for gain adjustments and by relieving the operator from the need to change the recorder scale during the analysis.     

Mercury Films on Commercial Carbon Screen‐Printed Devices for the Analysis of Heavy Metal Ions: a Critical Evaluation

The suitability of mercury films on commercial screen‐printed electrodes for the analysis of heavy metal ions is critically tested for the particular case of Pb(II)‐ions. Although determination is possible by anodic stripping voltammetry with a reasonable detection limit (8.9 µg L^?1), important drawbacks are noticed as a consequence of the heterogeneous deposition of mercury on the rough surface of screen‐printed devices.     

Development and characterization of a new conducting carbon composite electrode

A new conducting composite flexible material prepared from cellulose acetate (CA) polymer and graphite has been developed and used for the fabrication of electrodes, which were then characterized by cyclic voltammetry and electrochemical impedance spectroscopy. Scanning electron microscopy (SEM) was used to provide information concerning the morphology of the composite electrode surface. The potential window, background currents and capacitance were evaluated by cyclic voltammetry in the pH range from 4.6 to 8.2. The voltammetry of model electroactive species demonstrates a close to reversible electrochemical behaviour, under linear diffusion control. The electroactive area of the composite electrodes increases after appropriate electrode polishing and electrochemical pre-treatment. The electrodes were used as substrate for the electropolymerisation of the phenazine dye neutral red, for future use as redox mediator in electrochemical biosensors. The composite electrodes were also successfully used for the amperometric detection of ascorbate at 0.0 V vs. SCE, and applied to the measurement of ascorbate in Vitamin C tablets; the sensor exhibits high sensitivity and a low detection limit of 7.7 μM. Perspectives for use as a versatile, mechanically flexible and robust composite electrode of easily adaptable dimensions are indicated.     

Voltammetric oxidation of pharmaceutical organic compounds at a new modified electrode: The aluminum graphite spray-covered electrode

A new graphite spray-modified aluminum electrode has been used to determine clozapine, clothiapine, and loxapine in acetate buffer at pH 4.7 and 20% methanol, down to 5 × 10⁻⁶ M concentrations using differential pulse voltammetry. Reproducibility exceeds that of other solid electrodes, being in the range of 1 to 2%. The electrochemical oxidation products of the latter two compounds are strongly adsorbed, causing diminished electrode response, but response is readily restored by polishing of the sprayed electrode.     

Disposable Gold Electrode Array for Simultaneous Electrochemical Studies

An efficient and inexpensive eight gold electrode array has been manufactured by a combination of screen printing and gold electrodeposition techniques. Gold electrodeposition was performed in potentiostatic and galvanostatic conditions. Different treatments, involving temperature and polishing control, led to electrodes with different roughness. The electrochemical behavior of the generated gold surface was studied by cyclic voltammetry showing the characteristic response of polycrystalline gold, in contrast with disposable gold electrodes fabricated by screen printing from gold inks. The electrodes were chemically modified through the adsorption of alkanethiols self‐assembled monolayers and the coupling of a model protein. Both reactions were followed by cyclic voltammetry and Electrochemical Impedance Spectroscopy (EIS). The electrodes have shown high reproducibility in their electrochemical behavior as well as in their modifications.     

First-Row Transition-Metal Cations (Co2+, Ni2+, Mn2+, Fe2+) and Graphene (Oxide) Composites: From Structural Properties to Electrochemical Applications

Composites of graphene (oxide) (GO) and first-row transition-metal cations (Co²⁺, Ni²⁺, Mn²⁺, Fe²⁺) are prepared by mixing GO and aqueous metal salt solutions. The amount of metal cation bound to GO nanosheets is calculated by using inductively coupled plasma mass spectrometry (ICP-MS) and the possible binding sites of the metals are investigated by means of attenuated total reflectance infrared (ATR-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) measurements. Electrodes loaded with the metal/GO composites are prepared by a simple drop-casting technique without any binders or conductive additives. The effect of electrochemical reduction on the structure of the composite electrodes is investigated by Raman spectroscopy, XPS, X-ray diffraction (XRD) analysis, and field emission scanning electron microscopy (FESEM). A detailed electrochemical characterization is performed for the utilization of the composite electrodes for electrochemical capacitors and possible oxygen reduction reaction electrocatalysts by cyclic voltammetry (CV) and rotating disk electrode measurements. The highest areal capacitance is achieved with the as-deposited Fe/GO composite (38.7 mF cm⁻² at 20 mV s⁻¹). In the cyclic stability measurements, rCo/GO, rNi/GO, rMn/GO, and rFe/GO exhibit a capacitance retention of 44, 1.1, 73, and 87 % after 3000 cycles of CV at 100 mV s⁻¹, respectively.     

Determination of copper, lead and cadmium in whole blood by stripping voltammetry with the use of graphite electrodes

The problem with toxic metal ion determination in blood is the adsorption of organic compounds on the electrode surface and the formation of complexes between metal ions and organic constituents of blood. This is the reason why usually preliminary acid digestion or other sample pretreatment is used. Two kinds of electrodes have been used: “Ultra-Trace Electrode”, made from impregnated graphite (I), and thick film graphite disposable electrodes (II). The analysis of whole blood with different sample preparation methods shows, that chemical digestion is not necessary for the analysis. Electrochemical two-stage sample preparation provides the possibility for analysing whole blood with the mentioned electrodes. Thick film disposable electrodes are less sensitive to the interference of organic constituents of blood. These electrodes give the possibility to determine total cadmium, lead and copper concentration in whole blood without special sample pretreatment. The application of “Ultra-Trace Electrode” for blood analysis is possible only after preliminary pretreatment of blood by chemical digestion or electrochemical sample preparation.     

All‐Polystyrene 3D‐Printed Electrochemical Device with Embedded Carbon Nanofiber‐Graphite‐Polystyrene Composite Conductor

Carbon nanofibres (CNFs) and graphite flake microparticles were added to thermoplastic polystyrene polymer with the aim of making new conductive blends suitable for 3D‐printing. Various polymer/carbon blends were evaluated for suitability as printable, electroactive material. An electrically conducting polystyrene composite was developed and used with commercially available polystyrene (HIPS) to manufacture electrodes suitable for electrochemical experiments. Electrodes were produced and evaluated for cyclic voltammetry of aqueous 1,1’‐ferrocenedimethanol and differential pulse voltammetry detection of aqueous Pb²⁺ via anodic stripping. A polystyrene/CNF/graphite (80/10/10 wt%) composite provides good conductivity and a stable electrochemical interface with well‐defined active geometric surface area. The printed electrodes form a stable interface to the polystyrene shell, give good signal to background voltammetric responses, and are reusable after polishing.     

Determination of trace cobalt(II) by adsorptive stripping voltammetry on disposable microfabricated electrochemical cells with integrated planar metal-film electrodes

This work reports the determination of trace Co(II) by adsorptive stripping voltammetry on disposable three-electrode cells with on-chip metal-film electrodes. The heart of the sensors was a bismuth-film electrode (BiFE) with Ag and Pt planar strips serving as the reference and counter electrodes, respectively. Metals were deposited on a silicon chip by sputtering while the areas of the electrodes were patterned via a metal mask. Co(II) was determined by square wave adsorptive stripping voltammetry (SWAdSV) after complexation with dimethylglyoxime (DMG). The experimental variables (the DMG concentration, the preconcentration potential, the accumulation time and the SW parameters), as well as potential interferences, were investigated. Using the selected conditions, the 3σ limit of detection was 0.09 μg l⁻¹ of Co(II) (for 90 s of preconcentration) and the relative standard deviation for Co(II) was 3.8% at the 2 μg l⁻¹ level (n = 8). The method was applied to the determination of Co(II) in a certified river water sample. These mercury-free electrochemical devices present increased scope for field analysis and μ-TAS applications.     

Electrochemical Impedance Characterization of Nafion‐Coated Carbon Film Resistor Electrodes for Electroanalysis

Carbon film disk electrodes with Nafion coatings have been characterized by electrochemical impedance spectroscopy (EIS) with a view to a better understanding of their advantages and limitations in electroanalysis, particularly in anodic stripping voltammetry of metal ions. After initial examination by cyclic voltammetry, spectra were recorded over the full potential range in acetate buffer solution at the bare electrodes, electrodes electrochemically pretreated in acid solution, and Nafion‐coated pretreated electrodes in the presence and absence of dissolved oxygen. EIS equivalent circuit analysis clearly demonstrated the changes between these electrode assemblies. In order to simulate anodic stripping voltammetry conditions, spectra were also obtained in the presence of cadmium and lead ions in solution at Nafion‐coated electrodes, both after metal ion deposition and following re‐oxidation. Permanent changes to the structure of the Nafion film occurred, which has implications for use of these electrode assemblies in anodic stripping voltammetry at relatively high trace metal ion concentrations.     

Electrochemistry at carbon fibers : Part 1. Characteristics of the Mercury Film Carbon Fiber Electrode in Differential Pulse Anodic Stripping Voltammetry

Carbon fibers are proposed as a support electrode for a mercury film electrode. The response of these electrodes is evaluated for use in differential pulse anodic stripping voltammetry. The mercury film is deposited in situ in aqueous solution and used to quantify cadmium in solutions of cadmium salts and organo cadmium compounds in the 1–10 μg l^-1 (ppb) concentration range. The good resolution and extremely low background current obtained allow a limit of detection at 0.04 μg Cd l^-1.     

Development of an anodic stripping voltammetric assay, using a disposable mercury-free screen-printed carbon electrode, for the determination of zinc in human sweat

This paper reports on the development of a novel electrochemical assay for Zn²⁺ in human sweat, which involves the use of disposable screen-printed carbon electrodes (SPCEs). Initially, SPCEs were used in conjunction with cyclic voltammetry to study the redox characteristics of Zn²⁺ in a selection of supporting electrolytes. The best defined cathodic and anodic peaks were obtained with 0.1 M NaCl/0.1 M acetate buffer pH 6.0. The anodic peak was sharp and symmetrical which is typical for the oxidation of a thin metal film on the electrode surface. This behaviour was exploited in the development of a differential pulse anodic stripping voltammetric (DPASV) assay for zinc. It was shown that a deposition potential of −1.6 V versus Ag/AgCl and deposition time of 60 s with stirring (10 s equilibration) produced a well-defined stripping peak with E_pa = −1.2 V versus Ag/AgCl. Using these conditions, the calibration plot was linear over the range 1 × 10⁻⁸ to 5 × 10⁻⁶ M Zn²⁺. The precision was examined by carrying out six replicate measurements at a concentration of 2 × 10⁻⁶ M; the coefficient of variation was calculated to be 5.6%. The method was applied to the determination of the analyte in sweat from 10 human volunteers. The concentrations were between 0.39 and 1.56 μg/mL, which agrees well with previously reported values. This simple, low-cost sensitive assay should have application in biomedical studies and for stress and fatigue in sports studies.     

Modification of carbon screen-printed electrodes by adsorption of chemically synthesized Bi nanoparticles for the voltammetric stripping detection of Zn(II), Cd(II) and Pb(II)

A simple procedure for the chemical synthesis of bismuth nanoparticles and subsequent adsorption on commercial screen-printed carbon electrodes offer reliable quantitation of trace zinc, cadmium and lead by anodic stripping square-wave voltammetry in nondeareated water samples. The influence of two hydrodynamic configurations (convective cell and flow cell) and the effect of various experimental variables upon the stripping signals at the bismuth-coated sensor are explored. The square-wave peak current signal is linear over the low ng mL⁻¹ range (120 s deposition), with detections limits ranging from 0.9 to 4.9 ng mL⁻¹ and good precision. Applicability to waste water certified reference material and drinking water samples is demonstrated. The attractive behaviour of the new disposable Bi nanoparticles modified carbon strip electrodes, coupled with the negligible toxicity of bismuth, hold great promise for decentralized heavy metal testing in environmental and industrial effluents waters.     

Disposable Gold Electrodes with Reproducible Area Using Recordable CDs and Toner Masks

The fabrication and characterization of very cheap disposable gold disk electrodes with reproducible area is reported. The innovation of the proposed procedure is the use of toner masks to define reproducible areas on uniform gold surfaces obtained from recordable compact disks (CD‐R). Toner masks are drawn in a laser printer and heat transferred to gold surfaces, defining exactly the electrodes area. The electrochemical behavior of these disposable electrodes was investigated by cyclic voltammetry in Fe(CN)₆^4? solutions. The relative standard deviation for signals obtained from 10 different gold electrodes was below 1 %. The size of the disk electrodes can be easily controlled, as attested by voltammetric responses recorded by using electrodes with radii varying from 0.5 to 3.0 mm. The advantages of using this kind of electrode for analytical measurements of substances that strongly adsorb on the electrode surface such as cysteine are also addressed.