Square-wave cathodic adsorptive stripping voltammetric determination of trace amounts of 2-mercaptobenzimidazole in water samples

A sensitive, simple and reproducible square-wave cathodic adsorptive stripping voltammetric method is developed for the determination of 2-mercaptobenzimidazole (MBIM) in different water samples using a static mercury drop electrode (SMDE) as a working electrode. The solution conditions and instrumental parameters were optimized for the determination of MBIM by square-wave cathodic adsorptive stripping voltammetry. This method is based on a sensitive adsorptive reduction peak of the MBIM at ?0.532 V vs. Ag/AgCl reference electrode in a Britton-Robinson buffer at pH 10.0. The linear concentration range was 20–600 ng ml^?1 when using 0.0 V as the accumulation potential. The detection limit of the method was calculated to be 8.41 ng ml^?1. The precision was excellent with relative standard deviations (n = 20) of 2.30%, 1.71%, 2.25% and 1.33% at MBIM concentrations of 40, 90, 200 and 500 ng ml^?1, respectively. The proposed voltammetric method is used for the determination of MBIM in different spiked water samples.     

Hg(II) immobilized MWCNT graphite electrode for the anodic stripping voltammetric determination of lead and cadmium

The preparation of Hg(II)-modified multi walled carbon nanotube (MWCNT) by reaction of oxidized MWCNT with aqueous HgCl₂ was carried out. The Hg(II)-modified multi walled carbon nanotube (Hg(II)/MWCNT) dispersed in Nafion solution was used to coat the polished graphite electrode surface. The Hg(II)/MWCNT modified graphite electrode was held at a cathodic potential (−1.0 V) to reduce the coordinated Hg(II) to Hg forming nanodroplets of Hg. The modified electrode was characterized by FESEM/EDAX which provided useful insights on the morphology of the electrode. The SEM images showed droplets of Hg in the size of around 260 nm uniformly distributed on the MWCNT. Differential pulse anodic stripping voltammetry (DPASV) and electrochemical impedance spectroscopy were used to study the Hg(II) binding with MWCNT. Differential pulse anodic stripping voltammetry of ppb levels of cadmium and lead using the modified electrode yielded well-defined peaks with low background current under a short deposition time. Detection limit of 0.94 and 1.8 ng L⁻¹ were obtained following a 3 min deposition for Pb(II) and Cd(II), respectively. Various experimental parameters were characterized and optimized. High reproducibility was observed from the RSD values for 20 repetitive measurements of Pb(II) and Cd(II) (1.7 and 1.9%, respectively). The determination of Pb(II) and Cd(II) in tap water and Pb(II) in human hair samples was carried out. The above method of fabrication of Hg(II)/MWCNT modified graphite electrode clearly suggests a safe route for preparing Hg immobilized electrode for stripping analysis.     

Self-assembled monolayers of alkaneselenolates on (111) gold and silver

Self-assembled monolayers (SAMs) formed from didodecyl diselenide (C12SeSeC12) and didodecyl selenide (C12SeC12) on (111) Au and Ag substrates were extensively characterized by several complementary techniques. C12SeSeC12 was found to form contamination-free, densely packed, and well-ordered C12Se SAMs on both substrates, whereas the adsorption of C12SeC12 occurred only on Au and resulted in the formation of a SAM-like C12SeC12 film with a low packing density and a conformational disorder. The properties of the C12Se SAMs were compared with those of dodecanethiolate (C12S) SAMs. The packing density, orientational order, and molecular inclination in C12Se/Au and C12S/Au were found to be very similar. In contrast, C12Se/Ag exhibited significantly lower packing density, a lower degree of the conformational and orientational order, and a larger molecular inclination than C12S/Ag. The results suggest a sp3 bonding configuration for the selenium atom on Au and Ag and indicate a larger corrugation of the headgroup-substrate binding energy surface in C12Se/Ag than in C12S/Ag.     

Selenium-coated carbon electrode for anodic stripping voltammetric determination of copper(II)

We describe a new and promising type of selenium film electrode for anodic stripping voltammetry. This method is based on formation of copper selenide onto an in-situ formed selenium-film carbon electrode, this followed by Osteryoung square-wave anodic stripping voltammetry. Copper(II) is also in-situ electroplated in a test solution containing 0.01 mol L^-1 hydrochloric acid, 0.05 mol L^?1 potassium chloride and 500 µg L^?1 Se(IV) at a deposition potential of ?300 mV. The well-defined anodic peak current observed at about 200 mV is directly proportional to the Cu(II) concentration over the range from 1.0 to 100 µg L^?1 under the optimized conditions. The detection limit (three sigma level) is 0.2 µg L^?1 Cu(II) at 180 s deposition time. Relatively less interferences are shown from most of metal ions except for antimony(III). The method can be applied to analyses of river water and oyster tissue with good accuracy.     

Catalytic adsorptive stripping voltammetric determination of copper(II) on a carbon paste electrode

A catalytic adsorptive stripping voltammetric method for the determination of copper(II) on a carbon paste electrode (PCE) in an alizarin red S (ARS)-K₂S₂O₈ system is proposed. In this method, copper(II) is effectively enriched by both the formation and adsorption of a copper(II)-ARS complex on the PCE, and is determined by catalytic stripping voltammetry. The catalytic enhancement of the cathodic stripping current of the Cu(II) in the complex results from a redox cycle consisting of electrochemical reduction of Cu(II) ion in the complex and subsequent chemical oxidation of the Cu(II) reduction product by persulfate, which reduces the contamination of the working electrode from Cu deposition and also improves analytical sensitivity. In Britton-Robinson buffer (pH 4.56±0.1) containing 3.6×10⁻⁵ mol L⁻¹ ARS and 1.6×10⁻³ mol L⁻¹ K₂S₂O₈, with 180 s of accumulation at −0.2 V, the second-order derivative peak current of the catalytic stripping wave was proportional to the copper(II) concentration in the range of 8.0×10⁻¹⁰ to ∼3.0×10⁻⁸ mol L⁻¹. The detection limit was 1.6×10⁻¹⁰ mol L⁻¹. The proposed method was evaluated by analyzing copper in water and soil.     

Adsorptive stripping voltammetric determination of copper(II) ion using phenyl pyridyl ketoneoxime (PPKO)

A sensitive and selective procedure is presented for the voltammetric determination of copper(II) ion. The procedure involves an adsorptive accumulation of Cu2+-PPKO on a hanging mercury drop electrode, followed by a stripping voltammetric measurement of reduction current of adsorbed complex at about -0.30 V (vs. SCE). The optimum conditions for the analysis of copper(II) ion include pH (5.8-7.0), 60 microgM PPKO and an accumulation potential of -0.5 V (vs. SCE). The peak current is proportional to the concentration of copper over the range 0.3-76 ng mL(-1) with a detection limit of 0.01ng mL(-1) with an accumulation time of 60 s. The speciation of different forms of complex between copper(II) ion and PPKO, using the Best (Martell program), followed pH measurement were examined. The method was applied to the determination of copper(II) ion content in real samples successfully.     

Electromembrane extraction and anodic stripping voltammetric determination of mercury(II) using a glassy carbon electrode modified with gold nanoparticles

This study presents a method for the selective determination of Hg(II) using electromembrane extraction (EME), followed by square wave anodic stripping voltammetry (SWASV), using a gold nanoparticle-modified glassy carbon electrode, (AuNP/GCE). By applying an electrical potential of typically 60 V for 12 min through a thin supported liquid membrane (1-octanol), Hg(II) ions are extracted from a donor phase (i.e., the sample solution) to an acidic acceptor solution (15 μL) placed in the lumen of a hollow fiber. The influences of experimental parameters during EME were optimized using face-centered central composite design. The calibration plot, established at a working voltage of 0.55 V (vs. Ag/AgCl), extends from 0.2 to 10 μg^.L^?1 of Hg(II). The limit of detection, at a signal to noise ratio of 3, is 0.01 μg^.L^?1 and the relative standard deviations (for 5 replicate determinations at 3 concentration levels) are between 7.5 and 8.7 %. The method was successfully applied to the determination of Hg(II) in spiked real water samples to give recoveries ranging from 89 to 97 %. The results were validated by cold vapor atomic absorption spectroscopy.

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Graphical abstract Hg(II) ions were extracted from a donor phase into an acidic acceptor phase (15 μL) placed in the lumen of a hollow fiber using electromembrane extraction. The acceptor phase was then analyzed using anodic stripping voltammetry.

     

A screen-printed carbon electrode modified with a bismuth film and gold nanoparticles for simultaneous stripping voltammetric determination of Zn(II), Pb(II) and Cu(II)

The authors report on a disposable sensor for the differential pulse anodic stripping voltammetric (DPASV) determination of the ions Zn(II), Pb(II) and Cu(II). Simultaneous detection is accomplished by using a screen-printed carbon electrode (SPCE) co-modified with an in-situ plated bismuth (Bi)) film and gold nanoparticles (AuNPs). The synergistic effect of the Bi film, and the large surface and good electrical conductivity of the AuNPs strongly assist in the co-deposition of the three ions. Four well-defined and fully separated anodic stripping peaks, at 540 mV for Zn(II), 50 mV for Pb(II), 140 mV for Bi(III) and 295 mV for Cu(II), all vs. Ag/AgCl, can be seen. The modified SPCE was characterized by scanning electron microscopy, X-ray diffraction, cyclic voltammetry and electrochemical impedance spectroscopy. Under the optimized conditions, the sensor has a good response to these ions. The detection limits (at an S/N ratio of 3) are 50 ng·L^?1 for Zn(II), 20 ng·L^?1 for Pb(II), and 30 ng·L^?1 for Cu(II). The method was applied to the determination of the 3 ions in spiked lake water samples.

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Graphical abstract Schematic of screen-printed carbon electrode (SPCE) co-modified with a bismuth film and gold nanoparticles for electrochemical simultaneous determination of Zn(II), Pb(II) and Cu(II) by differential pulse anodic stripping voltammetric (DPASV).

     

Colorimetric determination of Hg(II) via the gold amalgam induced deaggregation of gold nanoparticles

A method is described for the colorimetric determination of mercury(II). In the absence of Hg(II), aminopropyltriethoxysilane (APTES) which is positively charged at pH 7 is electrostatically absorbed on the surface of gold nanoparticles (AuNPs). This neutralizes the negative charges of the AuNPs and leads to NP aggregation and a color change from red to blue-purple. However, in the presence of Hg(II), reduced Hg (formed through the reaction between Hg(II) and citrate on the AuNP surface) will replace the APTES on the AuNPs. Hence, the formation of aggregates is suppressed and the color of the solution does not change. The assay is performed by measuring the ratio of absorbances at 650 and 520 nm and can detect Hg(II) at nanomolar levels with a 10 nM limit of detection. The specific affinity between mercury and gold warrants the excellent selectivity for Hg(II) over other environmentally relevant metal ions.

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Graphical Abstract Schematic of the method for determination of Hg²⁺ based on the gold amalgam-induced deaggregation of gold nanoparticles in the presence of APTES with the LOD of 10.1 nM.

     

Adsorptive stripping voltammetric determination of antimony

A new method is described for the determination of antimony based on the cathodic adsorptive stripping of Sb(III) complexed with 2′,3,4′,5,7-pentahydroxyflavone(morin) at a static mercury drop electrode (SMDE). The reduction current of the adsorbed antimony complex was measured by 1.5th-order derivative linear-sweep adsorption voltammetry. The peak potential is at −0.51 V (vs. SCE). The effects of various parameters on the response are discussed. The optimized analytical conditions were found to be: supporting electrolyte, chloroacetic acid (0.04 mol/l, pH 2.3); concentration of morin, 5×10⁻⁶ mol/l; accumulation potential, −0.25 V (vs. SCE); scan rate, 100 mV/s. The limit of detection and the linear range were 7×10⁻¹⁰ mol/l and 1.0×10⁻⁹3.0×10⁻⁷ mol/l Sb(III) for a 2-min accumulation time, respectively. This method has been applied to the determination of Sb(III) in steel and brass samples and satisfactory results were obtained. The adsorptive voltammetric characteristics and composition of the Sb(III)–morin complex were studied.     

Adsorptive stripping voltammetric determination of ofloxacin

The fluoroquinolone antibacterial agent ofloxacin was studied by adsorptive stripping voltammetry. Controlled interfecial accumulation of ofloxacin on a static mercury drop electrode in the hanging mercury drop mode provides high sensitivity. The linear concentration range was 0.079–197.5 μg ml^?1 when using a 60-s preconcentration at ?1 V vs. Ag/AgCl in Britton-Robinson buffer of pH 6.00. The detection limit of ofloxacin was 1 ng ml^?1. The precision is excellent with a relative standard deviation of ca. 0.75% at a concentration of 0.848 μg ml^?1.     

Adsorptive stripping voltammetric properties of fentanyl at Hg electrode

Cyclic voltammetry shows that in a supporting electrolyte of NaOH, fentanyl (FENT) has a pair of cathodic and anodic peaks at Hg electrode. The peak potentials, E(pc) and E(pa), are -1.47 and -1.44 V (vs. Ag/AgCl), respectively. Fentanyl can be adsorbed on Hg surface, so the cathodic peak shows adsorptive properties. The adsorptive characteristics of fentanyl are explored in detail with various methods. The adsorbed species is considered to be fentanyl neutral molecule. The method for measuring trace amount of fentanyl by adsorptive stripping voltammetry is established. Under the optimised condition, the detection limit may reach 5 x 10(-8)M with a 10-min preconcentration.     

Self-assembled monolayers of ferrocene-substituted biphenyl ethynyl thiols on gold

Homogeneous and mixed [with biphenylthiol (BPT)] self-assembled monolayers (SAMs) of ferrocene-substituted biphenyl ethynyl thiols (Fc) were prepared on Au(111) substrates and characterized by several complementary spectroscopic techniques. The mixed films were fabricated either by subsequent immersion of the substrates into the BPT and Fc solutions or by immersion of the substrate into a mixed solution of BPT and Fc. The first procedure resulted in the preparation of high-quality mixed SAMs, in which the Fc molecules were stochastically distributed in the BPT matrix and well-separated from each other. The portion of these molecules in such films could be precisely varied from ca. 7 to 42% by selection of the immersion time in the BPT solution. The films prepared from the mixed solution exhibited a phase separation between the Fc and BPT constituents. These films contained mostly the Fc molecules ( approximately 80-90%), showing, thus, a significant deviation from the relative content of the target molecules in the primary solution (a 1:1 ratio). This finding shows that the Fc molecules, when competing with BPT, preferably adsorb onto Au(111) substrate, suggesting a significant impact of the ferrocene groups onto the structure-building interactions responsible for molecular self-assembly.     

Differential pulse adsorption stripping voltammetric determination of copper(II) with 2-mercaptobenzimidazol at a hanging mercury-drop electrode.

Copper(II) was selectively accumulated on a hanging mercury-drop electrode by using 2-mercaptobenzimidazole. Ensuing measurements were carried out by differential pulse adsorption stripping voltammetry. Factors affecting the accumulation, reduction, and stripping steps were investigated and a procedure was developed. The optimum conditions for the analysis of copper were pH 5.0, 5.33 x 10(-5) M 2-mercaptobenzimidazole and an accumulation potential of -0.10 V (vs. Av/AgCl). A linear range was obtained in the concentration range 0.2-100 ng/ml with a 90 s accumulation time and a scan rate of 16 mV/s. For ten successive determinations of 1.0, 20.0 and 70.0 ng/ml copper(II), relative standard deviations of 4.2, 3.5 and 2.8%, respectively, were obtained. The developed method was applied to the determination of copper in commercial salts and aluminium alloys.     

Lead(II) Transport processes in anodic stripping voltammetric analysis

The principal lead(II) transport processes occurring in anodic stripping voltammetric analysis of sea water have been studied by liquid scintillation spectrometry of ²¹⁰Pb. From an initial lead(II) concentration of 6.3 · 10^?9 M (ca. 1.3 p.p.b.), the concentration after 95 min is reduced by: (1) 84 % at pH 8.2, (2) 78 % at pH 4.6, and (3) 39 % at pH 3.0. Primary losses are due to adsorption onto cell and electrode materials. Significant chemisorption of lead(II) associated with chloride occurs at the platinum wire counter electrode. The data support a diffusion-limited adsorption mechanism as the primary transport for lead(II) from solution.     

Automatic kinetic determination of Hg(II) by anodic stripping potentiometry with constant current oxidation

A new kinetic method for the determination of Hg(II) is proposed. It is based on the kinetic evolution of the anodic stripping potentiometric curves yielded by a gold electrode previously coated with mercury upon passage of constant electrical currents. The method features a linear determination range between 40 and 800 ppb of Hg(II) and a relative standard deviation of 5% (n = 9) for a mercury concentration of 200 ppb. The experiments were conducted on a customized automatic set-up, and instrumentation, data acquisition and processing were all governed by means of a QBASIC program (PSAKINEL) written by the authors.     

Self-assembled monolayers of organosulfur derivative on gold nanoparticles as electrochemical sensor for determination of isoprenaline

In this paper, the use of molecular self-assembled monolayers of 5-(1,3-dithiolan-2-eyl)-3-methyl banzen-1,2-diol (DMD) on gold nanoparticles was described (DMD-AuNPs). The redox properties of modified electrode at various scan rates were investigated by cyclic voltammetry. A pair of well-defined quasi-reversible redox peaks of DMD were obtained at the modified electrode. Dramatically enhanced electrocatalytic activity was exemplified at the DMD-AuNPs, as an electrochemical sensor to investigate the electro-oxidation of isoprenaline (IP). With this modified electrode, the oxidation potential of the IP was shifted about 235 mV toward a less positive potential value than that of an unmodified electrode. The values of electron transfer coefficients (α = 0.5), catalytic rate constant (ks = 9.2 s^?1) and diffusion coefficient (D = 8.9 × 10^?5 cm² s^?1) were calculated for IP. The response of catalytic current with IP concentration showed a linear relation in the range from 0.5 to 800 µM with a detection limit of 0.21 µM. Finally, this modified electrode was used for the determination of IP in IP injections.     

Fullerene-based anodic stripping voltammetry for simultaneous determination of Hg(II), Cu(II), Pb(II) and Cd(II) in foodstuff

Various carbon nanomaterials for use in anodic stripping voltammetric analysis of Hg(II), Cu(II), Pb(II) and Cd(II) are screened. Graphene, carbon nanotubes, carbon nanofibers and fullerene (C₆₀), dispersed in chitosan (Chit) aqueous solution, are used to modify a glassy carbon electrode (GCE). The fullerene-chitosan modified GCE (C₆₀-Chit/GCE) displays superior performance in terms of simultaneous determination of the above ions. The electrodes and materials are characterized by electrochemical impedance spectroscopy, cyclic voltammetry, scanning electron microscopy, Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The excellent performance of C₆₀-Chit/GCE is attributed to the good electrical conductivity, large surface area, strong adsorption affinity and unique crystalline structure of C₆₀. Using differential pulse anodic stripping voltammetry, the assay has the following features for Hg(II), Cu(II), Pb(II) and Cd(II), respectively: (a) Peak voltages of +0.14, ?0.11, ?0.58 and???0.82 V (vs SCE); (b) linear ranges extending from 0.01–6.0 μM, 0.05–6.0 μM, 0.005–6.0 μM and 0.5–9.0 μM; and (c), detection limits (3σ method) of 3 nM (0.6 ppb), 14 nM (0.9 ppb), 1 nM (0.2 ppb) and 21 nM (2.4 ppb). Moreover, the modified GCE is well reproducible and suitable for long-term usage. The method was successfully applied to the simultaneous determination of these ions in spiked foodstuff.

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Graphical abstract Compared with graphene, carbon nanotubes and carbon nanofibers, an electrode modified with fullerene in chitosan electrode displays superior performance for the simultaneous anodic stripping voltammetric detection of Hg(II), Cu(II), Pb(II) and Cd(II).

     

Cathodic voltammetric determination of gold

Cathodic voltammetry at a carbon paste electrode has been evaluated as a technique for the analysis of gold. In the absence of interfering elements the technique is suitable for determinations at concentrations down to 10^?6M. Differentiation of the reduction peak current increases the sensitivity, permitting the determination of gold at concentrations of 10^?7M.