Ion peak narrowing by applying additional AC voltage (ripple voltage) to FAIMS extractor electrode

The use of a non-uniform electric field in a high-field asymmetric waveform ion mobility spectrometry (FAIMS) analyzer increases sensitivity but decreases resolution. The application of an additional AC voltage to the extractor electrode (“ripple” voltage, U _ripple ) can overcome this effect, which decreases the FAIMS peak width. In this approach, the diffusion ion loss remains minimal in the non-uniform electric field in the cylindrical part of the device, and all ion losses under U _ripple occur in a short portion of their path. Application of the ripple voltage to the extractor electrode is twice as efficient as the applying of U _ripple along the total length of the device.     

Determination of mercury(II) using a modified electrode with zeolite

Summary Chemically modified carbon paste electrodes are prepared by incorporating appropriate quantities of a zeolite directly into the paste mixture. Trace levels of mercury(II) can be preconcentrated on these electrodes. Cyclic voltammetry is used to quantify the accumulated ions. The response is characterized with respect to preconcentration, pH, and other variables. The procedure exhibits good linearity for 0.11 g/ml–2.2 g/ml mercury(II) ions and the peak current varies linearly with preconcentration time between 1 and 6 min for the conditions used.

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Bestimmung von Quecksilber(II) mit einer Zeolith-modifizierten Elektrode

     

Determination of cadmium(II) using carbon paste electrode modified with a Cd-ion imprinted polymer

We have synthesized cadmium(II) ion-imprinted polymers (IIP) and non-imprinted polymers (NIP) using 1-(2-pyridylazo)-2-naphthol as a ligand. The materials were used to prepare a carbon paste electrode for the determination of Cd(II). Polymerization was performed with (a) methacrylic acid as a functional monomer, (b) ethyleneglycol dimethacrylate as the crosslinking monomer, and (c) 2,2′-azobis(isobutyronitrile) as the initiator. Imprinted cadmium ion was removed from the polymeric matrix using nitric acid. The measurements were carried out in an closed circuit after accumulation at ?1.2?V, this followed by electrolysis of the accumulated Cd(II) by voltammetric scanning from ?1.0 to ?0.6?V. The parameters governing the response of the electrode were studied. Under optimized conditions, the response of the electrode is linear in the range from 2.0 to 200?ng?mL^?1. The detection limit is 0.31?ng?mL^?1. The relative standard deviations are ±3.4 and ±2.1?% for 7 successive determinations of 20.0 and 50.0?ng?mL-1 of Cd(II), respectively. The method was applied to the determination of cadmium (II) in water and food samples.

Voltammetric determination of N-acetylcysteine using a carbon paste electrode modified with copper(II) hexacyanoferrate(III)

The preparation and electrochemical characterization of a carbon paste electrode modified with copper(II) hexacyanoferrate(III) (CuHCF) as well as its behavior as electrocatalyst toward the oxidation of N-acetylcysteine were investigated. The electrochemical behavior of the modified electrode and the electrooxidation of N-acetylcysteine were explored using sweep linear voltammetry. The best voltammetric response was observed for a paste composition of 20% (w/w) copper(II) hexacyanoferrate(III) complex, acetate buffer solution at pH of 6.0 as the electrolyte and scan rate of 10 mV s^− 1. A linear voltammetric response for N-acetylcysteine was obtained in the concentration range from 1.2 × 10^− 4 to 8.3 × 10^− 4 mol L^− 1, with a detection limit of 6.3 × 10^− 5 mol L^− 1. The proposed electrode is useful for the quality control and routine analysis of N-acetylcysteine in pharmaceutical formulations.     

Voltammetric determination of mercury(II) using a modified pencil graphite electrode with 4-(4-methylphenyl aminoisonitrosoacetyl)biphenyl

A sensitive and selective method for determination of mercury(II) with “4-(4-methylphenyl aminoisonitrosoacetyl)biphenyl (TKO)-modified pencil graphite electrode” was developed. All factors affecting determination process were optimized. Differential pulse voltammetry with 4-(4-methylphenyl aminoisonitrosoacetyl)biphenyl-modified electrode showed a linear response between 1.0 × 10^?5 and 1.0 × 10^?3 M (R ² = 0.9994). The detection limit of this electrode was found as 5.85 × 10^?7 M (S/N = 3). The effects of different cations on the determination of mercury(II) were investigated and found that modified electrode is highly selective. The developed method was applied for mercury determination in different water samples.     

Determination of the chemical oxygen demand (COD) using a copper electrode: a clean alternative method

A clean alternative method for the determination of chemical oxygen demand (COD) was developed using a copper electrode as an electrocatalytic sensor. The measuring principle is based on oxidation current of organic compounds in the wastewater. The effects of important experimental conditions, such as electrolytic solution concentration and potential scan rate, on analytical performance have been investigated. Analytical linear range of 53.0–2,801.4 mg l⁻¹ COD with detection limit of 20.3 mg l⁻¹ COD was achieved. The procedure was successfully applied to the COD determination in wastewater from soft industries. The results obtained using the proposed method were in good agreement with those obtained using the conventional (i.e., dichromate) COD method. In this fashion, the COD value of a sample can be determined in a simple, rapid, accurate manner, and the end products do not contain toxic metals.     

Speciation of aluminium(III) in natural waters using differential pulse voltammetry with a pyrocatechol violet-modified electrode

A differential pulse voltammetric (DPV) procedure is proposed for the speciation of aluminium in natural waters using Pyrocatechol Violet chemically modified electrodes (PCV-CMEs). This novel speciation idea is based on the selective determination of different AlIII forms under two pH conditions. The labile monomeric Al fraction (mainly inorganic Al) is analysed at pH 4.8 (0.20 mol dm(-3) NaOAc-HOAc) and the total monomeric Al fraction is analysed at pH 8.5 (0.20 mol dm(-3) NH3.H2O-NH4Cl). The difference is thought to be caused by the weak competition ability of PCV to sequester AlIII from AlIII-natural organic matter complexes. This sensitive and simple speciation method has been applied successfully to aluminium speciation in natural waters sampled from different regions of China. Five fractions are measured directly or indirectly: (i) labile monomeric Al; (ii) total monomeric Al; (iii) acid reactive Al; (iv) non-labile monomeric Al; and (v) acid soluble Al. The results are in satisfactory agreement with those obtained by Driscoll's 8-hydroxyquinoline extraction-ion exchange method.     

Anodic stripping voltammetry of silver(I) using a carbon paste electrode modified with multi-walled carbon nanotubes

We describe a silver(I)-selective carbon paste electrode modified with multi-walled carbon nanotubes and a silver-chelating Schiff base, and its electrochemical response to Ag(I). Effects of reduction potential and time, accumulation time, pH of the solution and the stripping medium were studied by differential pulse anodic stripping voltammetry and optimized. The findings resulted in a method for the determination of silver over a linear response range (from 0.5 to 235 ng?mL^?1) and with a detection limit as low as 0.08 ng?mL^?1. The sensor displays good repeatability (with the RSD of ±?2.75 % for 7 replicates) and was applied to the determination of Ag(I) in water samples and X-ray photographic films.

Determination of selenium(IV) by cathodic stripping voltammetry using a copper-modified mercury-film electrode modified with copper

The behavior of selenium(IV) at a mercury-film electrode previously modified with copper was studied by cathodic stripping voltammetry using an automatic system for replacing solutions without opening the circuit. The effect of chemical (the composition and concentration of the supporting electrolyte, the concentrations of mercury (II) and copper(II)) and electrochemical parameters (the potential and time of electrolysis) on the analytical signal of selenium was studied at each stage of the stripping cycle (the formation of the mercury-film electrode modified with copper, the electrochemical preconcentration of selenium, and the subsequent stripping of the concentrate). The detection limit for selenium(IV) was found to be 40 ng/L (5.0 × 10^?10 M) at an electrolysis time of 10 min.     

Anodic stripping voltammetric determination of titanium(IV) using a carbon paste electrode modified with cetyltrimethylammonium bromide

A method is described for the voltammetric determination of titanium(IV) using a carbon paste electrode modified in situ with cetyltrimethylammonium bromide. The cationic micellar surfactant adsorbs onto the electrode particularly at negative potentials, simultaneously preconcentrating titanium(IV) as the oxalate complex with reduction to titanium(III). Anodic stripping voltammetry exploiting reoxidation can be used for the determination of trace levels of titanium(IV). Linearity between current and concentration exists between 5 and 160 mug l(-1) Ti(IV) (preconcentration time 2 min). The limit of detection (calculated as 3sigma) is 0.1 mug l(-1), with a preconcentration time of 10 min.     

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.     

Simultaneous trace-levels determination of Hg(II) and Pb(II) ions in various samples using a modified carbon paste electrode based on multi-walled carbon nanotubes and a new synthesized Schiff base

A modified carbon paste electrode based on multi-walled carbon nanotubes (MWCNTs) and 3-(4-methoxybenzylideneamino)-2-thioxothiazolodin-4-one as a new synthesized Schiff base was constructed for the simultaneous determination of trace amounts of Hg(II) and Pb(II) by square wave anodic stripping voltammetry. The modified electrode showed an excellent selectivity and stability for Hg(II) and Pb(II) determinations and for accelerated electron transfer between the electrode and the analytes. The electrochemical properties and applications of the modified electrode were studied. Operational parameters such as pH, deposition potential and deposition time were optimized for the purpose of determination of traces of metal ions at pH 3.0. Under optimal conditions the limits of detection, based on three times the background noise, were 9.0 × 10⁻⁴ and 6.0 × 10⁻⁴ μmol L⁻¹ for Hg(II) and Pb(II) with a 90 s preconcentration, respectively. In addition, the modified electrode displayed a good reproducibility and selectivity, making it suitable for the simultaneous determination of Hg(II) and Pb(II) in real samples such as sea water, waste water, tobacco, marine and human teeth samples.     

Anodic stripping voltammetric determination of arsenic(III) using a glassy carbon electrode modified with gold-palladium bimetallic nanoparticles

We have developed a method for the determination of the three catecholamines (CAs) epinephrine (EP), norepinephrine (NE), and dopamine (DA) at sub-nanomolar levels. It is found that the luminescence of the complexes formed between the CAs and Tb³⁺ ion is strongly enhanced in the presence of colloidal silver nanoparticles (Ag-NPs). The Ag-NPs cause a transfer of the resonance energy to the fluorophores through the interaction of the excited-state fluorophores and surface plasmon electrons in the Ag-NPs. Under the optimized condition, the luminescence intensity of the system is linearly related to the concentration of the CAs. Linearity is observed in the concentration ranges of 2.5–110?nM for EP, 2.8–240?nM for NE, and 2.4–140?nM for DA, with limits of detection as low as 0.25?nM, 0.64?nM and 0.42?nM, respectively. Relative standard deviations were determined at 10?nM concentrations (for n?=?10) and gave values of 0.98%, 1.05% and 0.96% for EP, NE and DA, respectively. Catecholamines were successfully determined in pharmaceutical preparations, and successful recovery experiments are demonstrated for urine and serum samples.

Voltammetric determination of levofloxacin using a glassy carbon electrode modified with poly(o-aminophenol) and graphene quantum dots

A strategy was developed for the voltammetric determination of the antibiotic drug levofloxacin (LV) based on a glassy carbon electrode modified with a composite consisting of poly(o-aminophenol) and graphene quantum dots (PoAP/GQD) that was fabricated by electropolymerization. The PoAP/GQD composite provides a large surface area and sensing interface and strongly promotes the oxidation current of LV. Under optimal conditions, the modified GCE displays an oxidation peak current (best measured at a working voltage of 1.05 V vs. SCE) that is linearly related to the levofloxacin concentration in the range from 0.05 to 100 μM, and the detection limit is 10 nM (at an S/N of 3). The method was applied to the determination of levofloxacin in spiked milk samples where is gave recoveries between 96.0 and 101.0 %.

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Graphical Abstract We describe a one-step electrochemical polymerization method to synthesize a layer of conductive film of poly(o-aminophenol) and graphene quantum dots (PoAP/GQD) onto a glassy carbon electrode (GCE) surface. The composite film exhibited high electro catalytic activity for the quantitative determination of levofloxacin by stripping voltammetry.

     

Indirect electrochemical determination of antioxidant capacity with hexacyanoferrate(III) reduction using a gold nanoparticle-coated o-phenylenediamine-aniline copolymer electrode

In spite of the many unstandardized literature methods for the determination of the antioxidant activity/capacity (AOA/AOC) of food extracts, there are a very limited number of documented voltammetric nanosensors, despite the fact that commercial electrochemical devices for rapid AOA estimation are on the rise. The mechanism of the developed sensor is based on the chemical reduction of hexacyanoferrate(III) to hexacyanoferrate(II) by antioxidants, followed by the decrement of the cathodic current intensity of hexacyanoferrate(III) in proportion to antioxidant concentration. During voltammetric measurements, the surface of the glassy carbon electrode was coated with an o-phenylenediamine-aniline copolymer and gold nanoparticles were accumulated on this electrode surface to increase the conductivity. It was shown that the developed electrode gave a reversible voltammogram for the hexacyanoferrate(III)/(II) redox couple, and that the cathodic peaks due to strong antioxidants having a standard redox potential less than that of this couple (E^o < 0.36 V) continuously emerged at very close peak potentials. Single antioxidants as well as binary–ternary mixtures were analyzed with this electrode using square wave voltammetry. The trolox-equivalent antioxidant capacities of selected antioxidants were evaluated with this electrode. The modified voltammetric sensor allowed precise measurement of the total antioxidant capacity of plant tea samples such as green tea, lime, and coral moss, and was not interfered by the food preservative sulfite. The results of the developed voltammetric sensor were statistically compared with those of a reference differential pulse voltammetry-cupric reducing antioxidant capacity electrochemical method established in literature.     

Voltammetric detection of lead(II) and mercury(II) using a carbon paste electrode modified with thiol self-assembled monolayer on mesoporous silica (SAMMS)

The anodic stripping voltammetry at a carbon paste electrode modified with thiol terminated self-assembled monolayer on mesoporous silica (SH-SAMMS) provides a new sensor for simultaneous detection of lead (Pb2+) and mercury (Hg2+) in aqueous solutions. The overall analysis involved a two-step procedure: an accumulation step at open circuit, followed by medium exchange to a pure electrolyte solution for the stripping analysis. Factors affecting the performance of the SH-SAMMS modified electrodes were investigated, including electrode activation and regeneration, electrode composition, preconcentration time, electrolysis time, and composition of electrolysis and stripping media. The most sensitive and reliable electrode contained 20% SH-SAMMS and 80% carbon paste. The optimal operating conditions were a sequence with a 2 min preconcentration period, then a 60 s electrolysis period of the preconcentrated species in 0.2 M nitric acid, followed by square wave anodic stripping voltammetry from -1.0 V to 0.6 V in 0.2 M nitric acid. The areas of the peak responses were linear with respect to metal ion concentrations in the ranges of 10-1500 ppb Pb2+ and 20-1600 ppb Hg2+. The detection limits for Pb2+ and Hg2+ were 0.5 ppb Pb2+ and 3 ppb Hg2+ after a 20 min preconcentration period.     

Amperometric determination of As(III) and Cd(II) using a platinum electrode modified with acetylcholinesterase,ruthenium(II)-tris(bipyridine) and graphene oxide

The authors describe an amperometric biosensor for the determination As(III) and Cd(II) based on the inhibition of the enzyme acetylcholineesterase (AChE). A platinum electrode was modified with ruthenium(II)-tris(bipyridyl), graphene oxide and AChE and then showed redox peaks at 0.06 and 0.2 V vs Ag/AgCl in the presence of acetylthiocholine chloride (ATChCl). Amperometry unveiled a steady-state turnover rate with the release of thiocholine. In the presence of arsenic(III) and cadmium(II), AChE showed an inhibitive response at 0.214 and 0.233 V vs Ag/AgCl, respectively. The electrode exhibits a detection limit and linear range of 0.03 μM and 0.05–0.8 μM for As(III) and 0.07 μM and 0.02–0.7 μM for Cd(II), respectively. Type of inhibition and inhibition constants induced by As(III) and Cd(II) on the catalytic sites of AChE were determined from Dixon and Lineweaver-Burk plots. The modified electrode was applied to the determination of As³⁺ and Cd²⁺ in river, tap and waste water, and the results proved that the method is sensitive and can be an alternative to chromatographic and spectroscopic techniques.

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Graphical abstract Schematic presentation of Pt/Ru(II)-tris(bipy)-GO/AChE electrode in absence and presence of metal ions (As³⁺/Cd²⁺).

     

Voltammetric immunoassay for the carcinoembryonic antigen by using a glassy carbon electrode modified with poly(3,4-ethylenedioxythiophene) doped with tannic acid and grafted with poly(ethylene glycol)

The authors describe a voltammetric immunoassay for the carcinoembryonic antigen (CEA). A GCE was modified by electrodeposition of poly(3,4-ethylenedioxythiophene) (PEDOT) doped with tannic acid (TA). Subsequently, four-armed poly(ethylene glycol) (PEG) was assembled onto the modified surface through hydrogen bonding. The fabrication steps were characterized by scanning electron microscopy, energy dispersive spectroscopy, fourier transform infrared spectroscopy, contact angle measurements, electrochemical impedance spectroscopy and differential pulse voltammetry. The PEG/TA-PEDOT surface is shown be super-hydrophilic and to possess anti-fouling capability. Antibody against CEA was then covalently immobilized on the electrode. By using hexacyanoferrate as an electrochemical probe and at a working potential of 0.18 V vs SCE, the amperometric response is linear in the 10 ag·mL^?1 to 1.0 ng·mL^?1 CEA concentration range, and the detection limit is as low as 4.8 ag·mL^?1 (at an S/N ratio of 3). The assay was applied to the quantification of CEA in 1:10 diluted human serum samples. Recoveries ranged from 103.7 to 108.7%, and relative standard deviations from 2.9 to 4.8%.

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Graphical abstract Schematic of an electrochemical immunosensor for the carcinoembryonic antigen (CEA). It is based on the use of tannic acid (TA) and poly(ethylene glycol) (PEG), both deposited on a glassy carbon electrode (GCE), and using hexacyanoferrate as the electrochemical probe. The sensor has a wide linear range and a 4.8 ag·mL^?1 detection limit.

     

Determination of the stability constant of Np(V) fluoride complex using a fluoride ion selective electrode

Fluoride complexing of Np(V) has been studied using fluoride ion selective electrode (F-ISE). Free fluoride ion concentrations in the presence of Np(V) were measured at 0.1 and 1.0M ionic strength. The data were used to calculate the stability constant of the fluoride complex of Np(V) and the values obtained are reported here.