Lab‐on‐a‐Chip Sensor with Evaporated Bismuth Film Electrode for Anodic Stripping Voltammetry of Zinc

In this work, we report on the development of a lab‐on‐a‐chip electrochemical sensor that uses an evaporated bismuth electrode to detect zinc using square wave anodic stripping voltammetry. The microscale electrochemical cell consists of a bismuth working electrode, an integrated silver/silver chloride reference electrode, and a gold auxiliary electrode. The sensor exhibits a linear response in 0.1 M acetate buffer at pH 6 with zinc concentrations in the 1–30 μM range and a calculated detection limit of 60 nM. The sensor successfully detected zinc in a bovine serum extract and the results were corfirmed by independent AAS measurements. Our results demonstrate the advantageous qualities of this lab‐on‐a‐chip electrochemical sensor for clinical applications, which include small sample volume (µL scale), reduced cost, short response time and high accuracy at low concentrations of analyte.     

Electrochemical Determination of Phenolic Acids at a Zn/Al Layered Double Hydroxide Film Modified Glassy Carbon Electrode

A stable sensor for the determination of gallic acid (GA) and caffeic acid (CA) was fabricated by electrodeposition of Zn‐Al‐NO₃ layered double hydroxide film on a glassy carbon electrode (LDHf/GCE). A sensitive electrochemical method was achieved for the determination of GA and CA in a phosphate buffer solution (pH 3). The differential pulse voltammetry response of the LDHf/GCE to GA has a linear concentration range from 4 µM to 600 µM with a correlation coefficient of 0.9985 and the calculated detection limit of 1.6 µM at a signal‐to‐noise ratio of 3. The differential pulse voltammetry response of the LDHf/GCE to CA has a linear concentration range from 7 µM to 180 µM with a correlation coefficient of 0.9969 and the calculated detection limit of 2.6 µM at a signal‐to‐noise ratio of 3. The constructed sensor was applied to the determination of GA in commercial green tea samples.     

Selective Simultaneous Determination of Paracetamol and Uric Acid Using a Glassy Carbon Electrode Modified with Multiwalled Carbon Nanotube/Chitosan Composite

A multiwalled carbon nanotube/chitosan modified glassy carbon electrode (MWCNTs‐CHT/GCE) has been used for simultaneous determination of paracetamol (PAR) and uric acid (UA). The measurements were carried out using differential pulse voltammetry (DPV), cyclic voltammetry (CV) and chronoamperometry (CA). DPV measurements showed a linear relationship between oxidation peak current and concentration of PAR and UA in phosphate buffer (pH 7) over the concentration range 2 µM to 250 µM, and 10 µM to 400 µM, respectively. The analytical performance of this sensor has been evaluated for detection of PAR and UA in human serum and human urine with satisfactory results.     

Bismuth Film Voltammetric Sensor on Pyrolyzed Photoresist/Alumina Support for Determination of Heavy Metals

Voltammetric sensors based on bismuth film electrodes are an attractive alternative to other sensors for application in electroanalysis of heavy metals. Bismuth film electrodes can be formed by a similar method on the same substrates as mercury. These systems were used most frequently for simultaneous determination of heavy metals such as Pb, Cd and Zn by anodic stripping voltammetry. Our voltammetric sensor was fabricated on an alumina substrate. A photoresist film prepared by pyrolysis of positive photoresist S‐1813 SP15 on the alumina substrate was used as an electrode support for bismuth film deposition. The influence of the Nafion membrane on the measurement sensitivity of the sensor and mechanical stability of the bismuth film were investigated. The sensor was successfully applied for determination of Pb, Cd and Zn in an aqueous solution in the concentration range of 0.2 to 10 µg L^?1 by square wave anodic stripping voltammetry on an in‐situ formed bismuth film electrode with Nafion‐coating. Parameters of the sensor such as sensitivity, linearity, detection limit, repeatability and life‐time were evaluated. In the best case, the detection limits were estimated as 0.07, 0.11 and 0.63 µg L^?1 for Pb, Cd and Zn, respectively. Finally, the applicability of the sensor was tested in analysis of Pb, Cd and Zn in real samples of tap and river water using the method of standard additions.     

Determination of trace metals by anodic stripping voltammetry using a bismuth-modified carbon nanotube electrode

A bismuth-modified carbon nanotube electrode (Bi-CNT electrode) was employed for the determination of trace lead, cadmium and zinc. Bismuth film was prepared by in situ plating of bismuth onto the screen-printed CNT electrode. Operational parameters such as preconcentration potential, bismuth concentration, preconcentration time and rotation speed during preconcentration were optimized for the purpose of determining trace metals in 0.1M acetate buffer solution (pH 4.5). The simultaneous determination of lead, cadmium and zinc was performed by square wave anodic stripping voltammetry. The Bi-CNT electrode presented well-defined, reproducible and sharp stripping signals. The peak current response increased linearly with the metal concentration in a range of 2-100 microg/L. The limit of detection was 1.3 microg/L for lead, 0.7 microg/L for cadmium and 12 microg/L for zinc (S/N=3). The Bi-CNT electrode was successfully applicable to analysis of trace metals in real environments.     

Determination of Trace Tl(I) by Anodic Stripping Voltammetry on Novel Disposable Microfabricated Bismuth‐Film Sensors

This work reports the trace determination of Tl(I) by square‐wave anodic stripping voltammetry (SWASV) on novel microsensors equipped with a bismuth‐film electrode (BiFE). The sensors were fabricated by a multistep microfabrication approach combining sputtering (to deposit the electrode materialm, bismuth‐ and the insulator SiO₂, on the surface of a silicon wafer) and photolithography (to define the geometry of the sensor). The effect of the preconcentration time, the preconcentration potential and the SW stripping parameters were investigated. Using the selected conditions, the 3σ limit of detection was 0.6 µg L^?1 of Tl(I) at a preconcentration time of 240 s and the percent relative standard deviation was 4.3 % at the 10 µg L^?1 level (n=8). In order to eliminate the interference caused by Pb(II) and Cd(II), EDTA was added in the sample solution The method was successfully applied to the determination of Tl(I) in a certified lake water sample. These new sensors exhibit excellent mechanical stability and offer wide scope as mercury‐free disposable sensors for trace metal analysis.     

Bismuth‐Coated Iridium Microwire Electrode for the Determination of Trace Metals by Anodic Stripping Voltammetry

This work reports the utility of an iridium microwire plated in situ with a bismuth film for the simultaneous determination of Pb(II) and Cd(II) by square‐wave anodic stripping voltammetry (SWASV). The experimental variables (concentration of the bismuth plating solution, preconcentration potential, accumulation time) were investigated. The limit of detection was 1 µg L^?1 for Pb(II) and 1.5 µg L^?1 for Cd(II) (at 300 s of preconcentration) and the % relative standard deviations were lower than 4.9 % and 5.5 %, respectively, at the 20 µg L^?1 level (n=8). In addition, a study was made of coating the iridium‐based bismuth‐film microsensor with a film of Nafion for operation in the presence of surfactants. Finally, the electrode was applied to the determination of Pb(II) and Cd(II) in wastewater and tapwater samples.     

Electrocatalytic Nitrite Determination Using Iron Phthalocyanine Modified Gold Nanoparticles

Electrochemical detection of nitrite was achieved via electrodeposition of gold nanoparticles (AuNPs) onto glassy carbon electrodes, followed by 3‐mercaptopropionic acid (MPA) self‐assembly, enabling attachment of an iron(III) monoamino‐phthalocyanine (FeMAPc) catalyst via amide bond formation. The use of scanning electron microscopy, energy dispersive X‐ray spectroscopy and ultraviolet‐visible spectroscopy realised surface characterisation while cyclic voltammetry and electrochemical impedance spectroscopy techniques were applied for electrochemical interrogation. The electrochemical behaviour of nitrite at the bare (GCE), AuNPs/GCE, FeMAPc/GCE and FeMAPc‐MPA/AuNPs/GCE was further scrutinised using differential pulse voltammetry in phosphate buffer solution (0.1 M PBS, pH 5.8). Overall the FeMAPc‐MPA/AuNPs/GCE resulted in sensitivity 14.5 nA/µM, which was double that of AuNPs/GCE, 2.4 times FeMAPc/GCE and 3.5 times the response at a bare GCE, with linear range 1.9 µM–2.04 mM (PBS, pH 5.8) and LOD 0.21 µM. An interference study revealed that the proposed sensor (FeMAPc‐MPA/AuNPs/GCE) exhibited a selective response in the presence of interfering anions and the analytical capability of the sensor was demonstrated via nitrite ion determination in real water samples.     

Voltammetric determination of methidathion insecticide

An electroanalytical method has been developed for the determination of methidathion by squarewave voltammetry on a Nafion®-coated glassy carbon electrode in aqueous solutions with 0.05 M acetate buffer as a supporting electrolyte. The best voltammetric conditions were found to be pH 4.0, a preconcentration potential of 0.45 V, and a preconcentration time of 60 s. The experimental parameters, such as pH, film thickness, preconcentration potential, preconcentration time, and square-wave voltammetric parameters, were optimized. Using this method, the calibration curve is linear in the range 5 × 10^?8?7 × 10^?7 M with a detection limit (S/N = 3) of 30 nM.     

Voltammetric Quantification of Zn and Cu,Together with Hg and Pb,Based on a Gold Microwire Electrode,in a Wider Spectrum of Surface Waters

The simultaneous determination of Zn and Cu by anodic stripping voltammetry (ASV) is prone to errors due to the formation of Cu‐Zn intermetallic compounds. The main aim of this work was to study the possibility of simultaneous determination of Zn and Cu, together with Hg and Pb, using a mercury‐free solid gold microwire electrode. The multi‐element detection was carried out by differential pulse anodic stripping voltammetry (DPASV), in a chloride medium (0.5 M NaCl) under moderate acid conditions (HCl 1.0 mM) in the presence of oxygen, where the gold microwire electrode was used as stationary or vibrating working electrode during the deposition step. Under these conditions, no formation of Cu‐Zn intermetallic compounds were found for concentrations usually determined in surface waters. In addition, quantification of Zn and Cu, together with Hg and Pb, can be performed in a wide range of concentrations (about two orders of magnitude) using the same sample, in a very short period of time. The detection limits for Cu, Hg, Pb and Zn, using a vibrating electrode and 30 s of deposition time, were 0.2 µg L^?1 for Hg, 0.3 µg L^?1 for Pb and 0.4 µg L^?1 for Zn and Cu, respectively. The proposed DPASV methods were successfully applied to the determination of Cu, Hg, Pb, and Zn in a certified reference fresh water, river, tap and coastal sea waters. These results proved the applicability and versatility of the proposed methods for the analysis of different water matrices and showed that a gold microwire electrode is a suitable choice to determine simultaneously Zn and Cu.     

Bismuth Nanoparticles in Stripping Voltammetry of Sulfide Ions

For the first time, carbon screen‐printed electrodes (CSPE) modified with bismuth nanoparticles have been used to determine sulfide ions with stripping voltammetry (SV) by formation of sparingly soluble compounds with the electrode material. The impact of weight, degree of bismuth dispersion on CSPE surface, and Bi₂S₃ accumulation parameters on the sensitivity of the sensor have been studied. It has been established that bismuth nanoparticles (Bi_nano) as agglomerates of about 180 nm exhibit the optimum sensory properties. The linear concentration range has been observed over the interval of 0.93–5 µM sulfide ions during the accumulation time of 75 s. A detection limit of 0.15 µM sulfide ions was achieved.     

Electrochemical Behavior and Electroanalytical Determination of Indole‐3‐Acetic Acid Phytohormone on a Boron‐Doped Diamond Electrode

In this work, a boron‐doped diamond (BDD) electrode was used for the electroanalytical determination of indole‐3‐acetic acid (IAA) phytohormone by square‐wave voltammetry. IAA yielded a well‐defined voltammetric response at +0.93 V (vs. Ag/AgCl) in Britton–Robinson buffer, pH 2.0. The process could be used to determine IAA in the concentration range of 5.0 to 50.0 µM (n=8, r=0.997), with a detection limit of 1.22 µM. The relative standard deviation of ten measurements was 2.09 % for 20.0 µM IAA. As an example, the practical applicability of BDD electrode was tested with the measurement of IAA in some plant seeds.     

Voltammetric Detection of the Herbicide Metamitron at a Bismuth Film Electrode in Nondeaerated Solution

In this work, we present a novel application of bismuth film electrodes (BiFE) for the direct analysis of the herbicide metamitron (4‐amino‐3‐methyl‐6‐phenyl‐1,2,4‐triazin‐5one) in nondeaerated solutions by square‐wave voltammetry (SWV) and differential pulse amperometry. Bismuth films were plated ex‐situ onto carbon paste electrodes (CPE) by 240 s deposition at ?0.600 V from a 0.10 M acetate buffer (pH 4.5) containing 0.50 mM bismuth nitrate. Metamitron SWV analytical signals were registered in 0.10 M acetate buffer (pH 4.5) solutions, where the herbicide reduction takes place at ?0.675 V. The metamitron signals obtained with BiFE have the double sensitivity and a 50 mV positive potential shift when compared to those obtained with plain CPE. Under these conditions, the dynamic linear range of concentrations is comprised between 10 and 200 μM and the detection limit is 2 μM.     

A Highly Sensitive Sensor Based on Reduced Graphene Oxide,Carbon Nanotube and a Co(II) Complex Modified Carbon Paste Electrode: Simultaneous Determination of Isoprenaline,Captopril and Tryptophan

This paper describes the development of a reduced graphene oxide (RGO), carbon nanotube (CNT) and Co(II) complex (cobalt(II) bis (benzoylacetone) ethylenediimino) (CBE) modified carbon paste electrode (CPE) for simultaneous determination of isoprenaline (IP), captopril (CAP) and tryptophan (Try). A pair of well‐defined redox peaks of Co(II) complex were obtained through a direct electron transfer between the Co(II) complex and the CPE. The proposed sensor showed very efficient electrocatalytic activity for anodic oxidation of IP in a 0.1 M phosphate buffer solution (pH 7.0). Square wave voltammetry (SWV) exhibited two linear dynamic ranges of 0.125–30.0 µM and 30.0–300.0 µM for IP. The detection limit for IP was found to be 50 nM. The proposed sensor was successfully applied for the determination of IP in real samples such as human blood serum, urine and IP ampoule.     

Anodic Stripping Voltammetry Combined with Sequential Injection Analysis for Measurements of Trace Metal Ions with Bismuth‐ and Antimony Film Electrodes under Comparable Conditions

Anodic stripping voltammetry combined with sequential injection analysis (ASV‐SIA) was selected to examine the use of bismuth‐ and antimony‐film plated glassy carbon electrodes under comparable conditions for the determination of Pb(II) and Cd(II) ions. Of interest were the conditions for film deposition, as well as the composition of sample/carrier solutions, including concentrations of Sb(III) or Bi(III) and HCl. Then, by the optimized procedure, one could determine Pb(II), Cd(II), and Zn(II) ions at the low µg L^?1 level and ASV‐SIA configuration with both electrodes tested on analysis of a water sample.     

Electrochemical Evaluation of Nucleoside Analogue Lamivudine in Pharmaceutical Dosage Forms and Human Serum

Lamivudine (LAM) is a synthetic nucleoside analogue with activity against human immunodeficiency virus‐type 1 (HIV‐1) and Hepatitis B virus (HBV). The aim of this study was to determine LAM levels in serum and pharmaceutical formulations, by means of electrochemical methods using hanging mercury drop electrode (HMDE). On this electrode, LAM undergoes irreversible reduction at the peak potential near E_p?1.26 V (vs. Ag/AgCl/3 M KCl). Reduction LAM signals were measured by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and square‐wave voltammetry (OSW). DPV and OSW techniques for the determination of LAM in acetate buffer at pH 4.5, which allows quantitation over the 4×10^?6 to 1×10^?4 M range in supporting electrolyte for both methods, were proposed. The linear response was obtained in acetate buffer in the ranges of 2×10^?6 to 2×10^?4 M for spiked serum samples at pH 4.5 for both techniques. The repeatability and reproducibility of the methods for all media were determined. The standard addition method was used in serum. Precision and accuracy were also checked in all media. No electroactive interferences from the endogenous substances were found in serum. With respect to side effects of high doses and short half‐life of LAM, a fast and simple detection method is described in this study.     

Ultrasensitive and selective measurements of tin by adsorptive stripping voltammetry of the tin-tropolone complex

Trace levels of tin can be determined by voltammetry after controlled adsorptive preconcentration of the tin-tropolone complex on a hanging mercury drop electrode. The resulting adsorptive stripping procedure offers better sensitivity and selectivity than conventional stripping methods for tin. Optimal conditions include 4 x 10(-6)M tropolone in a stirred acetate buffer (pH 4.0), a preconcentration potential of -0.40 V, and differential-pulse stripping. For an 8-min preconcentration period, the detection limit is 2.3 x 10(-10)M (28 ng/l.). Linear calibration plots of i(p)vs. C are obtained at low concentrations, with linear plots of 1/i(p)vs. 1/C at high concentrations. The relative standard deviation (at the 6-mug/1. level) is 2.6%. The response is not affected by the presence of lead, cadmium, indium and thallium, which commonly interfere severely in analogous anodic stripping measurements. Results are reported for river and orange-juice samples.     

Detection of Thiols by o‐Quinone Nanocomposite Modified Electrodes

A chemically modified glassy carbon (GC) electrode was developed as an amperometric sensor for detection of biological thiols. The electrode was modified by inclusion of co‐enzyme pyrroloquinoline quinone (PQQ) and a co‐catalyst of oxidized single wall carbon nanotubes (Ox‐SWNT) into a gold polypyrrole (Au‐PPy) nanocomposite matrix. The electrode (PQQ/Ox‐SWNT/Au‐PPy/GC) was characterized using scanning electron microscopy and cyclic voltammetry. Optimal conditions for the PQQ/Ox‐SWNT/Au‐PPy/GC electrode were determined and then utilized for the amperometric detection of L‐cysteine, N‐acetyl‐L‐cysteine, L‐penicillamine and D, L‐glutathione. The electrochemical response for each thiol in pH 3.2 citrate phosphate buffer at +450 mV (vs. Ag/AgCl) was found to be linear with limit of detections (LOD, S/N=3) ranging from 0.50 µM for L‐penicillamine to 1.55 µM for D, L‐glutathione with sensitivities of 30.2 nA/µM and 3.6 nA/µM respectively. The electrode design is simple and easy to construct using a minimum amount of co‐enzyme and co‐catalyst, resulting in detection methods with very good stability and improved sensitivity for thiol detection.     

A Role of the Plating Regime in the Deposition of Bismuth Films onto a Carbon Paste Electrode. Microscopic Study

A microscopic study is presented based on observations of bismuth films deposited from various plating solutions and under different experimental conditions onto the carbon paste surface. Electrolytic plating of bismuth films was performed either as simulation of preconcentration in‐situ from a 0.2 M acetate buffer containing 5×10^?5 M Bi³⁺ (pH 4.25), or as external deposition from various plating solutions: 0.1 M acetate buffer with 5×10^?4 M Bi³⁺ (pH 4.50), 0.5 M HCl with either 0.001 M BiCl₃ or 0.005 M BiCl₃ , 0.5 M HCl+0.5 M KBr+0.005 M BiCl₃ , and 0.5 M HCl+0.5 M KI+0.005 M BiCl₃ (all pH≈0.5). Scanning electron microscopic images of the bismuth films showed a considerable variability in structure and compactness of the deposited layer in dependence on experimental conditions chosen such as the concentration of Bi(III) species, the total acidity of plating media, the stability of complexes of Bi(III) with halogenide anions or the deposition potential applied.     

Simple,Rapid and Sensitive Electrochemical Method for the Determination of the Triketone Herbicide Sulcotrione in River Water Using a Glassy Carbon Electrode

We report a novel, simple, rapid and sensitive electrochemical method for the determination of sulcotrione, a member of the relatively new class of triketone herbicides, using differential pulse voltammetry on a glassy carbon electrode. Its electrochemical behavior including influences of electrolyte composition, pH and scan rate was studied to select optimal experimental parameters for its determination. In Britton? Robinson buffer at pH 3 sulcotrione provided a well‐defined reduction peak at ?0.84 V (vs. Ag/AgCl electrode), with good repeatability (relative standard deviation of 2.3 % for 8 measurements at 10 µM concentration level). With optimized parameters differential pulse voltammetry rendered two linear concentration ranges from 0.2 to 2 µM and from 2 to 50 µM with a detection limit of 0.05 µM. The proposed procedure was successfully applied to the determination of sulcotrione in spiked river water samples with satisfactory recoveries (93–109 %). The developed method may represent a simple, rapid and sensitive alternative to highly toxic mercury electrodes and chromatographic methods.