Electrode Calibration Research Articles

Temporal and Spatial Variability of Surface Motor Activation Zones in Hemiplegic Patients During Functional Electrical Stimulation Therapy Sessions.

The goal of this study was to investigate surface motor activation zones and their temporal variability using an advanced multi-pad functional electrical stimulation system. With this system motor responses are elicited through concurrent activation of electrode matrix pads collectively termed "virtual electrodes" (VEs) with appropriate stimulation parameters. We observed VEs used to produce selective wrist, finger, and thumb extension movements in 20 therapy sessions of 12 hemiplegic stroke patients. The VEs which produce these three selective movements were created manually on the ergonomic multi-pad electrode by experienced clinicians based on visual inspection of the muscle responses. Individual results indicated that changes in VE configuration were required each session for all patients and that overlap in joint movements was evident between some VEs. However, by analyzing group data, we defined the probability distribution over the electrode surface for the three VEs of interest. Furthermore, through Bayesian logic we obtained preferred stimulation zones that are in accordance with our previously reported heuristically obtained results. We have also analyzed the number of active pads and stimulation amplitudes for these three VEs. Presented results provide a basis for an automated electrode calibration algorithm built on a priori knowledge or the starting point for manual selection of stimulation points.

Remote controlled water craft for water measurement

This paper presents a remote controlled water craft and automatic calibrator for water quality parameter measurement. To determine the water condition as temperature, conductance, pH, O2,NO3- and NH4+ ion concentration were used. All apparatus was placed on our own-design catamaran. The measurements are taken automatically on the craft, transmitted wirelessly to a PC-based control station and saved there in a dedicated database. The drone was built in such a way that it can be easily expanded using new measurement equipment and analysis software. Hence, the modularity and extensibility are important advantages of the catamaran. Using the Modbus based communication protocol enables easy measurement equipment expansion for the end-user. An important aspect in taking the measurements is the calibration of the multiple electrodes. To provide good accuracy, calibration has to be undertaken before each use. Calibration undertaken manually is very time-consuming and inconvenient; that is why the automatic calibration station was built. The proposed hardware and software were created within Project-Based Learning classes.

Towards a minimally invasive device for beta-lactam monitoring in humans

Antimicrobial resistance is a leading patient safety issue. There is a need to develop novel mechanisms for monitoring and subsequently improving the precision of how we use antibiotics. A surface modified microneedle array was developed for monitoring beta-lactam antibiotic levels in human interstitial fluid. The sensor was fabricated by anodically electrodepositing iridium oxide (AEIROF) onto a platinum surface on the microneedle followed by fixation of beta-lactamase enzyme within a hydrogel. Calibration of the sensor was performed to penicillin-G in buffer solution (PBS) and artificial interstitial fluid (ISF). Further calibration of a platinum disc electrode was undertaken using amoxicillin and ceftriaxone. Open-circuit potentials were performed and data analysed using the Hill equation and log(concentration [M]) plots. The microneedle sensor demonstrated high reproducibility between penicillin-G runs in PBS with mean Km (±1SD)=0.0044±0.0013M and mean slope function of log(concentration plots) 29±1.80mV/decade (r2=0.933). Response was reproducible after 28days storage at 4°C. In artificial ISF, the sensors response was Km (±1SD)=0.0077±0.0187M and a slope function of 34±1.85 mv/decade (r2=0.995). Our results suggest that microneedle array based beta-lactam sensing may be a future application of this AEIROF based enzymatic sensor.

Background Signal as an in Situ Predictor of Dopamine Oxidation Potential: Improving Interpretation of Fast-Scan Cyclic Voltammetry Data.

Background-subtracted fast-scan cyclic voltammetry (FSCV) has emerged as a powerful analytical technique for monitoring subsecond molecular fluctuations in live brain tissue. Despite increasing utilization of FSCV, efforts to improve the accuracy of quantification have been limited due to the complexity of the technique and the dynamic recording environment. It is clear that variable electrode performance renders calibration necessary for accurate quantification; however, the nature of in vivo measurements can make conventional postcalibration difficult, or even impossible. Analyte-specific voltammograms and scaling factors that are critical for quantification can shift or fluctuate in vivo. This is largely due to impedance changes, and the effects of impedance on these measurements have not been characterized. We have previously reported that the background current can be used to predict electrode-specific scaling factors in situ. In this work, we employ model circuits to investigate the impact of impedance on FSCV measurements. Additionally, we take another step toward in situ electrode calibration by using the oxidation potential of quinones on the electrode surface to accurately predict the oxidation potential for dopamine at any point in an electrochemical experiment, as both are dependent on impedance. The model, validated both in adrenal slice and live brain tissue, enables information encoded in the shape of the background voltammogram to determine electrochemical parameters that are critical for accurate quantification. This improves data interpretation and provides a significant next step toward more automated methods for in vivo data analysis.

Protein Pretreatment of Microelectrodes Enables in Vivo Electrochemical Measurements with Easy Precalibration and Interference-Free from Proteins.

In vivo electrochemistry is one powerful strategy for probing brain chemistry. However, the decreases in sensitivity mainly caused by the adsorption of proteins onto electrode surface in short-term in vivo measurements unfortunately render great challenges in both electrode calibration and selectivity against the alternation of proteins. In this study, we observe that the pretreatment of carbon fiber microelectrodes (CFEs) with bovine serum albumin (BSA) would offer a simple but effective strategy to the challenges mentioned above. We verify our strategy for dopamine (DA) with conventionally used CFEs and for ascorbate with our previously developed carbon nanotube-modified CFEs. We find that, in artificial cerebral spinal fluid (aCSF) solution containing BSA, the current responses of the microelectrodes equilibrate shortly and the results for precalibration carried out in this solution are found to be almost the same as those for the postcalibration in pure aCSF. This observation offers a new solution to electrode calibration for in vivo measurements with a technical simplicity. Furthermore, we find that the use of BSA pretreated CFEs to replace bare CFEs would minimize the interference from the alternation of proteins in the brain. This study offers a new general and effective approach to in vivo electrochemistry with a high reliability and a simplified procedure.

Evolution of Surface Motor Activation Zones in Hemiplegic Patients During 20 Sessions of FES Therapy with Multi-pad Electrodes.

The purpose of this study was to examine surface motor activation zones for wrist, fingers and thumb extension movements and their temporal change during 20 therapy sessions using advanced multi-pad functional electrical stimulation system. Results from four hemiplegic patients indicate that certain zones have higher probability of eliciting each of the target movements. However, mutual overlap and variations of the zones are present not just between the subjects, but also on the intrasubject level, reflected through these session to session transformations of the selected virtual electrodes. The obtained results could be used as a priori knowledge for semi-automated optimization algorithm and could shorten the time required for calibration of the multi-pad electrode.

Electrochemical oxidation of phenanthrenequinone dioxime and its quantification using sensing at boron doped diamond electrode

Nowadays, there is small number of analytical procedures for the quantification of the phenanthrene and its derivatives, quinones and quinonedioximes. In recent years, different studies shows that potential application of these compounds and their complexes possess important role in many search areas, medicine, catalysis, sensors and bioorganic systems. In this paper, for the first time, we offer fast, sensitive, selective and reliable electroanalytical procedure for quantification of phenanthrenequinone dioxime (PQD) based on its oxidation. Also, its electrochemical behavior in water acidic media is given. Possible electrode mechanism based on these measurements was proposed. It was found that by employing differential pulse voltammetry (DPV) in Britton–Robinson buffer solution (BRBS) at pH3.0 using boron-doped diamond (BDD) electrode calibration curve for PQD quantification was linear in the range of 0.3 to 7.0μM with detection limit of 0.22μM. Proposed method was successfully applied for the determination of PQD in blood samples with satisfactory recovery (96–102%). Proposed method can be beneficial in the chemistry of dioximes due to advantages of BDD electrode and sensitivity and selectivity of the electroanalytical procedures.

The dependence on ionic strength of the protonation of water-insoluble flavonoids chrysin and daidzein in NaClO4 non-aqueous solutions

The acid–base equilibria of two water-insoluble flavonoids, chrysin and daidzein, were studied using combined spectrophtometric/potentiometric measurements at constant temperature (25.0±0.1) °C. The investigation was performed over a wide range of ionic strengths of 0.101–3.503molkg−1 NaClO4 medium in ethanol-water mixture (1:1 v/v). The Gran's method was used for glass electrode calibration to obtain pH readings based on the concentration scale (pcH). Data process for calculation of the protonation constants was done using the STAR computer program. The dependence on ionic strength of the constants was successfully modeled by means of the Brönsted–Guggenheim–Scatchard Specific Ion Interaction Theory (SIT). Other than the specific interaction parameters of the ionic species, the protonation constants at infinite dilution (zero ionic strength) were obtained. The thermodynamic functions ΔG0 (standard Gibbs free energy change) for the protonation processes were also calculated at different ionic strengths.

Thermodynamic Study on the Acid-Base Properties of Antioxidant Compound Ascorbic Acid in Different NaClO4Aqueous Ethanol Solutions

The proton dissociation equilibria of ascorbic acid were investigated using a combination of spectrophotometric/potentiometric techniques at constant temperature 25.0 ± 0.1 °C. The study was carried out over a wide range of ionic strengths of 0.1-3.0 mol dm-3 NaClO4 in ethanol-water mixture (1:1). The Gran's method was used for glass electrode calibration to obtain pH readings based on the concentration scale (pcH). Data process for calculation of the protonation constants was done using the STAR (stability constants by absorbance reading) computer program. The dependence on ionic strength of the constants was analyzed by means of the SIT approach (specific ion interaction theory). In addition to the specific interaction parameters of the ionic species, the protonation constants at infinite dilution (zero ionic strength) were obtained. Finally, the thermodynamic functions ΔG0 (standard Gibbs free energy change) for the protonation processes were also calculated at different ionic strengths.

A non-linearity criterion applied to the calibration curve method involved with ion-selective electrodes.

Some rational functions of the Padé type, y=y(x; n,m), were applied to the calibration curve method (CCM), and compared with a parabolic function. The functions were tested on the results obtained from calibration of ion-selective electrodes: NH4-ISE, Ca-ISE, and F-ISE. A validity of the functions y=y(x; 2,1), y=y(x; 1,1), and y=y(x; 2,0) (parabolic) was compared. A uniform, integral criterion of nonlinearity of calibration curves is suggested. This uniformity is based on normalization of the approximating functions within the frames of a unit area.

Pitzer ion activities in mixed electrolytes for calibration of ion-selective electrodes used in clinical chemistry

Metrological comparability as well as reliability of ion activity results measured with ion-selective electrodes (ISE) was investigated within the framework of an interlaboratory comparison between eight partners from national metrology institutes and expert laboratories. Two electrolyte solutions containing the clinically most relevant ions sodium, potassium, magnesium, calcium and chloride having ion activities near the physiological range served as samples. The calibration of the measurement set-ups of the participants was carried out using gravimetrically prepared aqueous electrolyte solutions. The ion activities of these calibration standards were calculated by means of the semi-empirical Pitzer model. The measurement uncertainty of the measurement results was calculated according to the guide to the expression of uncertainty in measurement, GUM. Based on a new scale for ion activities traceable to the SI system of units, comparability and reliability of ISE measurement results of clinically relevant ions is realised.

In Situ Electrode Calibration Strategy for Voltammetric Measurements In Vivo

Technological advances have allowed background-subtracted fast-scan cyclic voltammetry to emerge as a powerful tool for monitoring molecular fluctuations in living brain tissue; however, there has been little progress to date in advancing electrode calibration procedures. Variability in the performance of these handmade electrodes renders calibration necessary for accurate quantification; however, experimental protocol makes standard postcalibration difficult or in some cases impossible. We have developed a model that utilizes information contained in the background charging current to predict electrode sensitivity to dopamine, ascorbic acid, hydrogen peroxide, and pH shifts at any point in an electrochemical experiment. Analysis determined a high correlation between predicted sensitivity and values obtained using the traditional postcalibration method, across all analytes. To validate this approach in vivo, calibration factors obtained with this model at electrodes in brain tissue were compared to values obtained at these electrodes using a traditional ex vivo calibration. Both demonstrated equal power of predictability for dopamine concentrations. This advance enables in situ electrode calibration, allowing researchers to track changes in electrode sensitivity over time and eliminating the need to generalize calibration factors between electrodes or across multiple days in an experiment.

Spectrophotometric Calibration of pH Electrodes in Seawater Using Purified m-Cresol Purple

This work examines the use of purified meta-cresol purple (mCP) for direct spectrophotometric calibration of glass pH electrodes in seawater. The procedures used in this investigation allow for simple, inexpensive electrode calibrations over salinities of 20–40 and temperatures of 278.15–308.15 K without preparation of synthetic Tris seawater buffers. The optimal pH range is ∼7.0–8.1. Spectrophotometric calibrations enable straightforward, quantitative distinctions between Nernstian and non-Nernstian electrode behavior. For the electrodes examined in this study, both types of behavior were observed. Furthermore, calibrations performed in natural seawater allow direct determination of the influence of salinity on electrode performance. The procedures developed in this study account for salinity-induced variations in liquid junction potentials that, if not taken into account, would create pH inconsistencies of 0.028 over a 10-unit change in salinity. Spectrophotometric calibration can also be used to expeditiously determine the intercept potential (i.e., the potential corresponding to pH 0) of an electrode that has reliably demonstrated Nernstian behavior. Titrations to ascertain Nernstian behavior and salinity effects can be undertaken relatively infrequently (∼weekly to monthly). One-point determinations of intercept potential should be undertaken frequently (∼daily) to monitor for stable electrode behavior and ensure accurate potentiometric pH determinations.

Electrode calibration with a microfluidic flow cell for fast-scan cyclic voltammetry

Fast-scan cyclic voltammetry (FSCV) is a common analytical electrochemistry tool used to measure chemical species. It has recently been adapted for measurement of neurotransmitters such as dopamine in awake and behaving animals (in vivo). Electrode calibration is an essential step in FSCV to relate observed current to concentration of a chemical species. However, existing methods require multiple components, which reduce the ease of calibrations. To this end, a microfluidic flow cell (μFC) was developed as a simple device to switch between buffer and buffer with a known concentration of the analyte of interest--in this case dopamine--in a microfluidic Y-channel. The ability to quickly switch solutions yielded electrode calibrations with faster rise times and that were more stable at peak current values. The μFC reduced the number of external electrical components and produced linear calibrations over a range of concentrations. To demonstrate this, an electrode calibrated with the μFC was used in FSCV recordings from a rat during the delivery of food reward--a stimulus that reliably evokes a brief increase in current due to the oxidation of dopamine. Using the linear calibration, dopamine concentrations were determined from the current responses evoked during the behavioral task. The μFC is able to easily and quickly calibrate FSCV electrode responses to chemical species for both in vitro and in vivo experiments.

Novel CeO2-based screen-printed potentiometric electrodes for pH monitoring

Nuclear waste repositories are being installed in deep excavated rock formations in some places in Europe to isolate and store radioactive waste. In France, the Callovo-Oxfordian formation (COx) is a possible candidate for nuclear waste storage. This work investigates the applicability of CeO2-based oxides (CeO2, Ce0.8Sm0.2O2 and Ce0.8Zr0.2O2) for monitoring the pH of the COx pore water (T=25°C). The study is limited to the pH range between 5.5 and 13.2, which includes the pH values that have been encountered or are anticipated in the COx formation during its evolution as radioactive waste repository due mainly to alkalinisation, an increase in salinity, and a decrease in redox potential. Screen-printing was done to assemble electrodes and rapidly generate data sets. The electrochemical behavior of CeO2-based screen-printed electrodes (CeO2-based SPEs) was determined by cyclic voltammetry and electrochemical impedance spectroscopy. The use of the electrodes for pH sensing was then evaluated by potentiometric measurements. The feasibility of measuring pH with CeO2-based SPEs was first tested in NH4Cl/NH3 buffer solutions, leading to electrode calibration over the widest range of pH, from around neutral to basic pH. Experiments were then conducted in NaHCO3/Na2CO3 buffer samples similar to conditions prevailing in the COx formation. Ce0.8Zr0.2O2 SPEs exhibit a near-Nernstian behavior (sensitivity −(51±2)mV/pH) in the pH range of 5.5–13.2 at 25°C. Electrode response was slightly affected by the direction of the pH change. Electrode reliability was clearly demonstrated for pH monitoring. Probes based on the same components, but more durably designed, could be considered for pH measurements in radioactive waste repositories.

Nonenzymatic glucose sensing based on deposited palladium nanoparticles on epoxy-silver electrodes

A new approach for nonenzymatic glucose sensing, based on a simple modification of epoxy-silver surfaces deposited on the tip of commercial copper electric wires, is presented. Palladium was galvanically displaced on the surface of the epoxy-silver surface in order to obtain metal nanoparticles that act as catalyst for the direct oxidation of glucose. Scanning electron microscopy revealed the formation of the metal nanoparticles. X-ray photoelectron spectroscopy confirmed the metallic nature of the formed nanostructures on the surface. Electrochemical characterization and calibration of the palladium-modified epoxy-silver electrode is reported, obtaining a linear range of 1–20 mM for the detection of glucose with low interference of ascorbic acid and uric acid. A simple 3-step coulometry was used as the detection technique. The developed sensing material is believed to be a great candidate for integration in small devices for clinical essays, due to the simplicity and cost effectiveness of the presented approach, compared to the state-of-the-art devices reported recently in the literature. Simplicity in the coulometry determinations makes these Pd-modified epoxy-silver sensors a good candidate for easy glucose determinations.

Mitochondrial Isolation from Skeletal Muscle

Mitochondria are organelles controlling the life and death of the cell. They participate in key metabolic reactions, synthesize most of the ATP, and regulate a number of signaling cascades2,3. Past and current researchers have isolated mitochondria from rat and mice tissues such as liver, brain and heart4,5. In recent years, many researchers have focused on studying mitochondrial function from skeletal muscles. Here, we describe a method that we have used successfully for the isolation of mitochondria from skeletal muscles 6. Our procedure requires that all buffers and reagents are made fresh and need about 250-500 mg of skeletal muscle. We studied mitochondria isolated from rat and mouse gastrocnemius and diaphragm, and rat extraocular muscles. Mitochondrial protein concentration is measured with the Bradford assay. It is important that mitochondrial samples be kept ice-cold during preparation and that functional studies be performed within a relatively short time (~1 hr). Mitochondrial respiration is measured using polarography with a Clark-type electrode (Oxygraph system) at 37°C7. Calibration of the oxygen electrode is a key step in this protocol and it must be performed daily. Isolated mitochondria (150 μg) are added to 0.5 ml of experimental buffer (EB). State 2 respiration starts with addition of glutamate (5mM) and malate (2.5 mM). Then, adenosine diphosphate (ADP) (150 μM) is added to start state 3. Oligomycin (1 μM), an ATPase synthase blocker, is used to estimate state 4. Lastly, carbonyl cyanide p-[trifluoromethoxy]-phenyl-hydrazone (FCCP, 0.2 μM) is added to measurestate 5, or uncoupled respiration 6. The respiratory control ratio (RCR), the ratio of state 3 to state 4, is calculated after each experiment. An RCR ≥4 is considered as evidence of a viable mitochondria preparation. In summary, we present a method for the isolation of viable mitochondria from skeletal muscles that can be used in biochemical (e.g., enzyme activity, immunodetection, proteomics) and functional studies (mitochondrial respiration).

Mitochondrial Isolation from Skeletal Muscle

Mitochondria are organelles controlling the life and death of the cell. They participate in key metabolic reactions, synthesize most of the ATP, and regulate a number of signaling cascades. Past and current researchers have isolated mitochondria from rat and mice tissues such as liver, brain and heart. In recent years, many researchers have focused on studying mitochondrial function from skeletal muscles. Here, we describe a method that we have used successfully for the isolation of mitochondria from skeletal muscles. Our procedure requires that all buffers and reagents are made fresh and need about 250-500 mg of skeletal muscle. We studied mitochondria isolated from rat and mouse gastrocnemius and diaphragm, and rat extraocular muscles. Mitochondrial protein concentration is measured with the Bradford assay. It is important that mitochondrial samples be kept ice-cold during preparation and that functional studies be performed within a relatively short time (~1 hr). Mitochondrial respiration is measured using polarography with a Clark-type electrode (Oxygraph system) at 37°C⁷. Calibration of the oxygen electrode is a key step in this protocol and it must be performed daily. Isolated mitochondria (150 μg) are added to 0.5 ml of experimental buffer (EB). State 2 respiration starts with addition of glutamate (5 mM) and malate (2.5 mM). Then, adenosine diphosphate (ADP) (150 μM) is added to start state 3. Oligomycin (1 μM), an ATPase synthase blocker, is used to estimate state. Lastly, carbonyl cyanide p-[trifluoromethoxy]-phenyl-hydrazone (FCCP, 0.2 μM) is added to measurestate, or uncoupled respiration. The respiratory control ratio (RCR), the ratio of state 3 to state 4, is calculated after each experiment. An RCR ≥ 4 is considered as evidence of a viable mitochondria preparation. In summary, we present a method for the isolation of viable mitochondria from skeletal muscles that can be used in biochemical (e.g., enzyme activity, immunodetection, proteomics) and functional studies (mitochondrial respiration).

Design optimization and standardization of an environmental availability test under both acidic and alkaline conditions

The objective of this study was to design a procedure for an environmental availability test under both acidic and alkaline conditions for solid wastes and recycled materials and products. The procedure was designed on the basis of the Dutch availability test NEN 7371. Bottom ash from a municipal solid waste incinerator and copper slag were used as test materials. The influences of the type and intensity of liquid stirring apparatus and the open area ratio of the top of the leaching vessel were investigated experimentally, and partial least-squares modeling was applied as multivariate data analysis for the simultaneous evaluation of the three leaching conditions. Interlaboratory validation was then carried out with the participation of seven laboratories in accordance with JIS Z 8402-2/ISO 5725-2. Both repeatability and reproducibility were found to be acceptable, but precise calibration of the pH electrode is required. The proposed procedure will provide sufficient accuracy as a standard test method.

New methods applicable for calibration of indicator electrodes

The new methods applicable for calibration of indicator electrodes, based on standard addition and standard subtraction methods, are suggested. Some of the methods enable the slope of an indicator electrode and equivalence volume Veq to be determined simultaneously from a single set of potentiometric titration data. Some other methods known hitherto were also taken into account. A new model, based on a standard addition method, applicable also in nonlinear range for the ISE slope (S) is suggested, and its applicability was confirmed experimentally in calibration of calcium ISE.