Simultaneous determination of flavonoids and anthraquinones in chrysanthemum by capillary electrophoresis with amperometry detection

A high-performance capillary electrophoresis with amperometry detection method （CE-AD） has been developed for the analysis of flavonoids and anthraquinones （emodin, kaempferol, apigenin, luteolin and rhein） in chrysanthemum. Under optimum conditions, these five analytes were base-line separated within 17 min using a borate-phosphate running buffer （1.5 ×10^-2 mol/L borate-3× 10^-2 mol/L phosphate running buffer, pH 9.0） at a working potential of ＋0.90 V （vs. SCE） and a separation voltage of 19 kV. The linear relationship between concentration and current response was obtained with detection limits （S/N = 3） ranging from 1.0 × 10^-7 to 2.1 × 10^-7 g/mL for all analytes. This proposed method was successfully used in the analysis of four kinds of chrysanthemum with relatively simple extraction procedures, the assay results were satisfactory.

Examining the Effects of Common Laboratory Methods on the Sensitivity of Carbon Fiber Electrodes in Amperometric Recordings of Dopamine

Carbon fiber microelectrodes (CFEs) are useful when combined with electrochemical techniques for measuring changes in neurotransmitter concentrations. We addressed conflicting details regarding the use of CFEs. Experimental groups consisted of CFEs at different ages (1 week, 1 month, or 2 months), cleaned in solvents (isopropanol or xylene), and exposed to in vitro use (flow cell calibrations) or in vivo use (in brain tissue). In order to determine if any of these factors affect CFE sensitivity, the present study utilized fixed potential amperometry and a flow injection system to calibrate CFEs for the measurement of dopamine. The sensitivity index (nA/μM per 100 μm of exposed carbon fiber) was not affected by the age of CFEs or pre-cleaning with xylene or isopropanol. CFE sensitivity of the in vitro exposure group also did not differ from untreated CFEs, indicating the calibration process did not alter sensitivity. However, in vivo use in brain tissue did reduce sensitivity. This effect was negated and sensitivity restored by cleaning CFEs in isopropanol or xylene following in vivo brain recordings. Given that variations in CFE sensitivity can skew results, our findings can help standardize CFE use and explain discrepancies between researchers.

Amperometric Sensors for Determination of Hydrogen Peroxide Based on Electron Transfer Between Horseradish Peroxidase and 1，1＇－Dimethylferrocene

hydrogen peroxide electrode with 1,1'-dimethylferrocene(DMFc)used as an electron transfer mediator has been described.Using Nafion, DMFc was modified on a glassy carbon electrode(GCE)surface,and horseradish peroxidase(HRP)was then immobiliged on the DMFc-Nafion film,forming a HRp-DMFc-Nafion modi- fied electrode. The chracteristics of the sensor has been shown by cyclic voltam- metry and constant potential measurements,The sensor responds fastly to hydro- gen peroxide,the time required to reach 95%of the steady-state current is less than 50s. The sensor displays a sensitive catalytic current response to hydrogen peroxide and can be operated at a potential range in which the oxidation of common interfering species,such as ascorbic acid and uric acid,does not occur. The sensor is stable for 20 days and its detection limit is 1 μmol/L.

Flow Injection Amperometric Determination of Phenol and Chlorophenols at Single Wall Carbon Nanotube Modified Glassy Carbon Electrode

Single wall carbon nanotube modified glassy carbon electrode (SWCNT/GCE) was used for flow-injection analysis (FIA) for phenolic compounds (phenol (P), 4-chlorophenol (CP), 2,4-dichlorophenol (DCP), 2,4,6-trichlorphenol (TCP) and pentachlorophenol (PCP)). Experimental variables such as the detection potential, flow rate and pH of the carrier solution, 0.1 M sodium acetate, were optimized. Under these conditions, the designed electrode showed a very good performance for the amperometric measurements, with no need to apply a cleaning or pre-treatment procedure. The operational stability was tested with 20 repetitive injections of each analyte and was found to be good. The analytical performance of the SWCNT/GCE electrode under flow through conditions was tested and was found to be impressive. When it is compared with other enzymatic and non-enzymatic sensors, it shows wider dynamic range for the detection of phenolic compounds with low limits of detection. These results suggest that the method is quite useful for monitoring and analyzing phenols and chlorophenols.

N-methyl-D-aspartate (NMDA) mediates vascular relaxation via nitric oxide (NO) in rats but not in mice

Amperometric studies have indicated that substance P as well as NMDA stimulates release of NO in rat aortic rings. These data have been confirmed by functional observations of vaso-relaxant action of NMDA within noradrenaline pre-contracted aortic rings, supporting the presence of NMDA receptor in rat aortic rings. It is known that the enzyme endothelial NO synthase (eNOS) mediates vasodilatation not only in rats, but also in C57BL6 mice aortic ring, indicating that in this blood vessel NO is the endogenous endothelium-derived vasodilator. In this work, amperometry together with specifically nitrites insensitive micro-biosensors have been applied to examine the effect of NMDA and substance P upon NO release in rat and in two strains of mice aortic rings. The electrochemical data monitored demonstrate that NMDA mediates vascular relaxation via NO in rats but not in mice. These results are supported by functional data, therefore they suggest that NMDA receptors are “not responding” within these experimental conditions in mice aortic rings.

Transparent Electrode Materials for Simultaneous Amperometric Detection of Exocytosis and Fluorescence Microscopy

We have developed and tested transparent microelectrode arrays capable of simultaneous amperometric measurement of oxidizable molecules and fluorescence imaging through the electrodes. Surface patterned microelectrodes were fabricated from three different conducting materials: Indium-tin-oxide (ITO), nitrogen-doped diamond-like carbon (DLC) deposited on top of ITO, or very thin (12 - 17 nm) gold films on glass substrates. Chromaffin cells loaded with lysotracker green or acridine orange dye were placed atop the electrodes and vesicle fluorescence imaged with total internal reflection fluorescence (TIRF) microscopy while catecholamine release from single vesicles was measured as amperometric spikes with the surface patterned electrodes. Electrodes fabricated from all three materials were capable of detecting amperometric signals with high resolution. Unexpectedly, amperometric spikes recorded with ITO electrodes had only about half the amplitude and about half as much charge as those detected with DLC or gold electrodes, indicating that the ITO electrodes are not as sensitive as gold or DLC electrodes for measurement of quantal catecholamine release. The lower sensitivity of ITO electrodes was confirmed by chronoamperometry measurements comparing the currents in the presence of different analytes with the different electrode materials.

Analytical expressions of steady-state concentrations of species in potentiometric and amperometric biosensor

A mathematical model of potentiometric and amperometric enzyme electrodes is discussed. The model is based on the system of non-linear steady-state coupled reaction diffusion equations for Michaelis-Menten formalism that describe the concentrations of substrate and product within the enzymatic layer. Analytical expressions for the concentration of substrate, product and corresponding flux response have been derived for all values of parameters using Homotopy analysis method. The obtained solution allow a full characterization of the response curves for only two kinetic parameters (The Michaelis constant and the ratio of overall reaction and the diffusion rates). A simple relation between the concentration of substrate and products for all values of parameter is also reported. All the analytical results are compared with simulation results (Scilab/Matlab program). The simulated results are agreed with the appropriate theories. The obtained theoretical results are valid for the whole solution domain.

Integrated Carbon Nanotubes Electrodes in Microfluidic Chip via MWPCVD

An on-chip electrochemical detector for microfluidic chips was described, based on integrated carbon nanotube （CNT） electrodes directly onto the chip substrate through microwave plasma chemical vapor deposition （MWPCVD）. The attractive performance of the integrated CNT electrodes was demonstrated for the amperometric detection of sucrose, glucose and D-fructose. The integrated CNT electrodes showed stronger electrocatalytic activity than gold electrodes.

Review of Electrochemical Sensors and Biosensors Based on First-Row Transition Metals,Their Oxides,and Noble Metals Nanoparticles

The use of electrochemical sensors for sensitive disease diagnosis and detecting various species with pharmacological,therapeutic,industrial,food-related,and environmental origins is now widely accepted.A catalytic or binding event resulting from the sensor’s electroactive component recognizing its analyte creates an electrical signal proportionate to the analyte concentration,which is then monitored by a transducer.The development of morphologically distinct metal and metal oxide nanoparticles formed from first-row transition elements(Mn,Cr,Fe,Co,Ti,Ni,Cu,Zn)and noble metals(Pt,Au,Ag,Pd)is described in this review.The effect of these metal nanoparticles has been studied using Tetracyanoquinodimethane(TCNQ),Ferrocene,and other organic compounds as electroactive species using carbon paste-modified electrodes.Electroanalytical sensors,mostly based on ferrocene,are exceedingly sensitive,selective,affordable,and for detecting numerous biomolecules like glucose,dopamine,NADH,ascorbic acid,and a few dyes and are simple to build.In recent decades,charge transfer organic species-based chemosensors have become a prominent study area.This paper outlines current developments in electrochemical biosensors based on transition metal nanoparticles,covering glucose,ascorbic acid,uric acid,and other inorganic and organic analytes.The importance of transition metal and transition metal oxide nanoparticles as potential electrode modifiers for developing sensors is highlighted.A discussion of the present problem and possible solutions,and plausible future directions marks the review’s conclusion.

Preparation, Electrochemical Behavior and Electrocatalytic Activity of a Copper Hexacyanoferrate Modified Ceramic Carbon Electrode

A copper hexacyanoferrate modified ceramic carbon electrode （CuHCF/CCE） had been prepared by two-step sol-gel technique and characterized using electrochemical methods. The resulting modified electrode showed a pair of well-defined surface waves in the potential range of 0.40 to 1.0 V with the formal potential of 0.682 V （vs. SCE） in 0.050 mol·dm^-3 HOAc-NaOAc buffer containing 0.30 mol·dm^-3 KCl. The charge transfer coefficient （a） and charge transfer rate constant （ks） for the modified electrode were calculated. The electrocatalytic activity of this modified electrode to hydrazine was also investigated, and chronoamperometry was exploited to conveniently determine the diffusion coefficient （D） of hydrazine in solution and the catalytic rate constant （kcat）. Finally, hydrazine was determined with amperometry using the resulting modified electrode. The calibration plot for hydrazine determination was linear in 3.0 × 10^-6--7.5 × 10^-4 mol·dm^-3 with the detection limit of 8.0 × 10^-7 molodm^-3. This modified electrode had some advantages over the modified film electrodes constructed by the conventional methods, such as renewable surface, good long-term stability, excellent catalytic activity and short response time to hydrazine.

Electrochemical synthesis of silver nanoparticles-coated gold nanoporous film electrode and its application to amperometric detection for trace Cr(VI)

A simple and rapid approach for the electrochemical synthesis of Ag nanoparticles-coated gold nanoporous film (AgGNF) on a gold substrate was reported. The solid gold electrode (SGE) was directly anodized under a high potential of 5 V, and then reduced to obtain gold nanoporous film (AuNF) by freshly prepared ascorbic acid. The Ag nanoparticles (AgNPs) were grown on the AuNF electrode by potential-step electrodeposition. The resulting AgGNF composites electrodes were characterized by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy and cyclic voltammetry (CV). As-prepared AgGNF electrode was used as a kind of superior sensor for Cr(VI) detection, which exhibited better electrocatalytic behavior than those of AuNF and SGE under identical conditions. Such a designed AgGNF nanocomposites electrode showed outstanding sensitivity (about 0.15 nA/ppb) and favorable reproducibility for Cr(VI) detection. The dependence of reduction current on Cr(VI) concentration is linear from 2 to 370 ppb with a low detection limit of 0.65 ppb. Interferences from other heavy metals ions (Cr3+, Cu2+, Pb2+, As3+ and Hg2+) associated with Cr(VI) analysis could be effectively diminished. The present method proves to be rapid, reliable, sensitive and low-cost.

Trends in Gunshot Residue Detection by Electrochemical Methods for Forensic Purpose

Gunshot Residue(GSR)has been a subject of interest for the forensic fraternity.Numerous analytical contributions towards the GSR analysis have been reported.Sensitivity,portability,cost-effectiveness,speed,etc.are such factors of electrochemical methods that have attracted the researchers across the globe to test the applicability of these as a potential analytical tool for forensic evaluation of GSR.With the development of scientific technology,efforts have been made towards the handheld device for the on-field analysis of GSR.Recently,chemometric treatment of data generated from the electrochemical analysis of GSR has offered more effective approach.It makes the analysis more conclusive and minimizes the chances of false-positive detection.It will be very fruitful to anticipate the analytical potential of electrochemical tools for GSR analysis.This article reviews the research progress towards the development of electrochemical sensor for GSR detection reported during 2013-2020 along with challenges and future perspectives.

Sensitive voltammetric and amperometric responses of respiratory toxins at hemin-adsorbed carbon-felt

A hemin [iron-Fe（III） protoporphyrin IX chloride] was adsorbed onto a carbon-felt （CF）, which is a microelectrode ensemble of micro carbon fiber （ca. 7 ~tm diameter）. The resulting hemin-adsorbed-CF （hemin-CF） showed a well-defined redox wave based on the hemin- Fe（III）/Fe（II） redox process with the formal potential of -0.225 V vs. Ag/AgC1 in deoxygenated phosphate]citrate buffer solution （0.1 mol/L, pH 5.0）. The apparent heterogenous electron transfer rate constant was estimated to be 8.6 sec-1. In air-saturated electrolyte solution, the hemin-CF exhibited an excellent electrocatalytic activity for the reduction of dioxygen （O2）. This activity was reversibly inhibited by respiratory toxins such as cyanide and azide, which bind sixth coordination position of iron active center of hemin. The electrocatalytic Oz reduction current at the hemin-CF was modulated by the toxins in a concentration-depending manner. Based on the relationship between the %inhibition and the toxin concentration, apparent inhibition constants of cyanide and azide were evaluated to be 4.52 and 1.98 Ixmol/L, respectively. When the hemin-CF was used as a working electrode unit of the CF-based electrochemical flow-through detector with air-saturated carrier, the injection of the azide induced peak-shape current responses, which allowed rapid and continuous flow-amperometric determination of azide with high sensitivity.

Real-time and dynamic transduction technique for simultaneous detection of O_2 and CO_2

OXYGEN and carbon dioxide are the coexistent gases closely related to life processes. In our pre-

PC12 cell integrated biosensing neuron devices for evaluating neuronal exocytosis function upon silver nanoparticles exposure

In this research, we explored a rapid assessment of silver nanoparticles(Ag-NPs) neurotoxicity at a single-cell level. Traditional nanotoxicity assays on large cell-populations may hide the important heterogeneity of individual cells often found in neuronal cells. The development in the area of new nanomaterial discoveries is far ahead of the development of advanced tools to measure these materials' toxicity. Development of alternative approaches to assess nanomaterials toxicity rapidly, reliably, and accurately is desirable. Here, we present a chip-based, cell-integrated microwell-array device for rapid assessment of neurotoxicity of Ag-NPs by monitoring the exocytosis function of a PC12 cell. Results presented here confirm the dose-dependent toxicity of Ag-NPs and the immediate alteration of their exocytosis function when exposed to NPs.

Determination of zidovudine using anion exchange chromatography with integrated pulsed amperometric detection

A rapid and practical method for direct detection of zidovudine in high performance anion exchange chromatography （HPAEC） has been developed with integrated pulsed amperometric detection （IPAD）. Dionex AS18 （250mm × 2mm） and AG18 （50 mm× 2 mm） columns and 11 mmol/L NaOH solution were used for separation. Multi-step potential waveform parameters were optimized to maximize the signal-to-noise ratio （S/N）. Utilizing an optimized waveform, the repeatability （intra-day） precision and intermediate （inter-day） precision are obtained with relative standard deviation （RSD） of 1.88, 2.27, respectively. The limit of quantification （LOQ） and limit of detection （LOD） were found to be 9.70, 3.0 ng/mL, respectively, with correlation coefficients of 0.9992 over concentration range 0.01-10 μg/mL. The present method was successfully applied to the determination of zidovudine in human plasma. The recoveries of plasma sample spiked by 0.7 μg/mL, 2.7 μg/mL obtained were 95.3-101.5%, with relative standard deviation （RSD） of 2.54%, 2.21%, respectively.

A sensitive xanthine oxidase electrode with silk net for estimating fish freshness

An enzyme biosensor was constructed using a plate platinum electrode and immobilized xanthine oxidase (XOD). Only a very small quantity of enzyme was chemically immobilized on a special silk net. Hydrogen peroxide released during the enzymatic reaction was detected by the electrode at +0.65 V (vs. Ag/AgCl). The electrode was very sensitive to hypoxanthine and its detection limit was 1X10(-7) mol/L. When it was applied to the determination of fish freshness, the results agreed well with those obtained by traditional methods-determination of total volatile basic nitrogen (TVB-N) and microbial count. A range for estimating the freshness of river fish was suggested.

Determination of lisinopril using anion exchange chromatography with integrated pulsed amperometric detection

A rapid and practical method for direct detection of lisinopril in anion exchange chromatography（AEC） has been developed with integrated pulsed amperometric detection（IPAD）.Dionex AS 18（250 mm×2 mm） and AG 18（50 mm×2 mm） columns and 40 mmol/L NaOH solution were used for separation.Multi-step potential waveform parameters were optimized to maximize the signal-to-noise ratio（S/N）.Utilizing the optimized waveform,the repeatability（intra-day） precision and intermediate（inter-day） precision were obtained with relative standard deviation（RSD） of 0.74,0.93,respectively.The limit of quantification（LOQ） and limit of detection（LOD） were found to be 0.37,0.12ng/mL,respectively,with the correlation coefficient of 0.9998 over concentration range 0.01-1μg/mL.The present method was successfully applied to the determination of lisinopril in human plasma.The recoveries of plasma sample spiked by 0.2μg/mL,0.8μg/mL lisinopril were 98.31-103.23%with RSD of 1.41%, 0.61%,respectively.