Linear Stripping Research Articles

Electrochemical redox of arsenic (III) and Cu (II) mixtures with ultraflat Au(111) thin films in water

The ability to detect trace concentrations of arsenite, As (III), in real water solutions is impacted by co-contamination of other metals and co-occurring ions. The presence of copper (II) ions are the most likely co-contaminant in natural waters to interfere with electrochemical As (III) detection, due to the close oxidation potentials of Cu (II) and As (III). The use of well-oriented ultraflat Au(111) thin film electrodes provided increased peak separation and sensitivity for electrochemical deposition and oxidation of Cu (II) and As (III) in 0.5 M sulfuric acid compared to an Au wire electrode. However, mixtures of Cu (II) and As (III) altered the oxidation peak positions during both cyclic voltammetry (CV) and linear stripping voltammetry (LSV) analysis. Calibration curves using the standard additions method in trace concentrations were conducted for Cu, As, and Cu & As solutions. Sweeping the potential at 10 mV s−1 during CV in Cu & As mixtures resulted in a sequential deposition condition where a layer of Cu inhibited co-deposition of As to the electrode. In contrast, the rapid potential stepping of LSV to a potential where Cu and As reduction simultaneously occurs produced a peak profile different from Cu or As alone. A larger oxidation peak during LSV was also observed when both Cu and As were present. X-ray photoelectron spectroscopy indicates a Cu-As alloy is formed on the surface after LSV deposition.SYNOPSIS: Analysis of Cu (II), As (III) and Cu (II) & As (III) mixtures suggests that a Cu3As intermetallic phase is formed during LSV which impacts trace As detection even in trace Cu conditions. This has important implications for the ability to determine As concentrations near the MCL of 10 µg L−1 in natural water systems which may contain Cu (II) and other co-contaminants.

Oxidative Stripping of Starch-AgNPs for Nanomolar Indirect Electrochemical Sensing of BSA Using an L-Cysteine Modified Glassy Carbon Electrode

In this study, an L-cystine-modified glassy carbon electrode (GCE) was developed as an electrochemical platform based on AgNP oxidative stripping for nanomolar indirect detection of bovine serum albumin (BSA) biomacromolecules. The Poly-L-Cys was formed by L-cysteine (L-Cys) monomers electro-polymerization on the GCE surface. L-Cys pending groups interacted with AgNPs through Ag-S chemical bonds while it interacted with BSA through van der Waals forces and hydrogen bonding. To characterize the bare GCE and GCE/L-Cys, cyclic voltammetry and electrochemical impedance spectroscopy were used. The oxidative stripping of AgNPs by the addition of BSA was monitored using linear sweep stripping analysis.

Effect of red clover (Trifolium pratense L.) aqueous extract as an additive on nickel electrodeposition: Experimental and theoretical study

Enhancements in nickel electrodeposition have been achieved using organic additives, some of which are not environmentally friendly and may produce undesirable deposits. Red clover leaf extract (RCLE) containing isoflavones was extracted aqueously from the Trifolium pratense L. plant. It was used as a green additive for nickel electrodeposition on a copper substrate in an acid-sulfate bath. The mechanism of Ni2+ electrodeposition was examined by anodic linear stripping voltammetry, cyclic voltammetry, and cathodic polarization. The surface morphology of the Ni2+ coatings were examined using SEM, EDX, XRD, and AFM. The adsorption of RCLE on the Cu substrate inhibited Ni2+ deposition and resulted in finer-grained, smoother, more uniform, and stronger hardness deposits. The corrosion protection of nickel coatings in a marine environment containing a 3.5 % NaCl solution was also investigated. The findings demonstrated that the addition of RCLE enhanced the corrosion resistance of Ni2+ deposition. The optimal structures of RCLE molecules and their active sites were examined using DFT computations. The results provide concise explanations of the precise atoms and functional groups responsible for the donation and acceptance of electrons. Thus, RCLE showed significant improvements in the process of nickel electrodeposition on a copper substrate in an acid sulfate solution.

Highly sensitive voltammetric determination of hydrochlorothiazide using a glassy carbon electrode modified with Super P carbon black nanoparticles.

Hydrochlorothiazide is an extremely important diuretic that regulates body functions, which can prevent several diseases. However, the abuse of this diuretic is concerning since it does not require a medical prescription, particularly for aesthetic purposes such as weight loss, which can lead to various health problems, including ventricular arrhythmia. The present work aims to use a glassy carbon electrode modified with Super P carbon black (SPCB/GCE) to quantify hydrochlorothiazide through Linear Sweep Adsorptive Stripping Voltammetry (LSAdSV). The modification of the GCE with SPCB significantly improved the response of hydrochlorothiazide. Furthermore, due to the adsorptive nature of charge transport, applying preconcentration time enhanced sensitivity. The optimized system provided a linear range of 0.5 to 30.0 μmol L-1 with a detection limit of 0.083 μmol L-1. Pharmaceutical tablet analyses indicated approximately 25 mg per tablet, which was confirmed by the UV-vis and in agreement with that indicated by the manufacturer. Furthermore, analyses of the tea, synthetic urine, tap water and lake water samples indicated recovery values close to 100%, demonstrating that there was no matrix effect. Therefore, it is possible to infer that the proposed method together with the sensor modified with carbon black nanoparticles presented excellent results, demonstrating that it can be an alternative method of monitoring this drug in different samples.

Redox Behavior of Arsenic (III) and Copper (II) Mixtures on Ultraflat Au (111) Thin Film Electrodes

The electrochemical behavior of arsenic on gold (Au) electrodes surfaces is of great interest as As is well-recognized as a highly toxic and relatively ubiquitous ground water species. The United States Environmental Protection Agency (USEPA) and World Health Organization (WHO) drinking water standards for arsenic are 10 PPB, or 𝜇g L-1 [1]. These minute ion concentrations necessitate the use of analytical methods with high sensitivity and a low susceptibility to cross interferences. Electrochemical stripping voltammetry is a well-established electroanalytical method for arsenic ions [2]. Polycrystalline gold electrodes are often used due to their high redox stability and relatively low overpotential for hydrogen evolution. We recently explored the use of ultra-flat, thin film, Au(111) electrodes to replace polycrystalline Au for As stripping voltammetry. Previous studies on oriented single crystals showed relatively narrow stripping peaks with greatly improved peak to background ratios on the (111) surfaces [3]. We observed comparatively similar or better stripping behavior on the Au(111) thin film electrodes with correspondingly far less gold usage per electrode. Unfortunately, copper is a known interference for arsenic stripping electroanalysis, with a strong affinity for UPD deposition on gold. We therefore studied the deposition behavior of Cu on Au(111) thin film electrodes and the co- deposition of Cu and As on the Au(111) thin film electrodes to evaluate cross interference effects. Copper redox behavior in 0.5M H2SO4 was characterized by cyclic voltammetry, electro- deposition and linear stripping voltammetry (LSV) measurements. Strong Cu UPD behavior was observed on Au(111) thin films with sharper, better defined redox peaks than polycrystalline electrodes. Arsenic and Cu ions were also co-deposited over a wide range of Cu (II) and As (III) concentrations. Complex redox behavior was observed with strong indications of Cu-As alloy formation. This was confirmed via angle resolved, X-ray Photoemission Spectroscopy (XPS) measurements. Our results also indicate that the electrodeposition efficiency during LSV of As is increased by the co-deposition of Cu. The results of this study have important implications for understanding the nature of Cu (II) interference with electrochemical detection of trace As (III) in water.[1] USEPA. National Secondary Drinking Water Regulations. 2009. https://www.epa.gov/sdwa/drinking-water- regulations-and-contaminants (accessed.[2] USEPA. METHOD 7063: ARSENIC IN AQUEOUS SAMPLES AND EXTRACTSBY ANODIC STRIPPING VOLTAMMETRY (ASV). 1996.[3] Casuse-Driovínto, T. Q.; Rizo, R.; Benavidez, A.; Brearley, A. J.; Cerrato, J. M.; Garzon, F. H.; Herrero, E.; Feliu, J. M. Increased Sensitivity and Selectivity for As(III) Detection at the Au(111) Surface: Single Crystals and Ultraflat Thin Films Comparison. The Journal of Physical Chemistry C 2022, 126 (48), 20343-20353. DOI: 10.1021/acs.jpcc.2c05541.

Ionic liquid-modified multi-walled carbon nanotube paste electrode for cadmium and lead ion determinations

The detection of trace heavy metal ions is important in monitoring water quality, a vital freshwater source. This study presents the preparation of a multi-walled carbon nanotube (MWCNTs) paste electrode using a pasting mixture of 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid ([Bmim][PF6] IL) and paraffin oil for the determination of Cd2+ and Pb2+. Scanning electron microscopy, Fourier-transform infrared spectroscopy, and Raman spectroscopy were applied to characterize the paste composites. The electrochemical behavior of the fabricated electrodes was analyzed by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) techniques. The [Bmim][PF6]-MWCNTs electrode showed enhanced sensitivity for Cd2+ and Pb2+ detections over linear sweep anodic stripping voltammetry (LSASV) performances. Experimental results showed that the MWCNTs-IL-1 electrode using a pasting mixture of 10 μL of [Bmim][PF6] and 190 μL of paraffin oil was the most suitable for Cd2+ and Pb2+ determinations. The LSASV conditions for Cd2+ and Pb2+ analysis at the MWCNTs-IL-1 electrode were optimized, including the deposition potential, deposition time, and pH of the working solution. The stripping peak currents were linearly correlated with the concentration ranges of Cd2+ (1–35 μg/L) and Pb2+ (1–90 μg/L) for both individual and simultaneous determinations. The MWCNTs-IL-1 electrode exhibited high repeatability, reproducibility, and stability over a 30-day storage period. The real applicability of the MWCNTs-IL-1 electrode was demonstrated by successful determinations of Cd2+ and Pb2+ concentrations in tap water and surface water samples, which agreed with the results obtained by inductively coupled plasma mass spectrometry.

Adsorptive stripping voltammetric determination of carbofuran in food using novel type of modified carbon-based electrode with grafted layers of nickel

A voltammetric determination of carbofuran (CBF) was developed using a novel type of carbon-containing electrode (CCE) modified with carbon ink (CI) and a chromatographic sorbent (CS) based of chromaton (Ch), polyethylene glycol and nickel acetylacetonate with grafted layers of nickel (NiCS, stands for Ni modified CS) further denoted as CI/NiCS/CCE. The surface morphology of this modified electrode was investigated by scanning electron microscopy (SEM) and by electrochemical impedance spectroscopy (EIS). CBF which is not electrochemically oxidizable was first hydrolyzed in alkaline medium to give anodically active phenolic analogue CBFP. The electrochemical reactions of CBFP at CI/NiCS/CCE were studied in phosphate buffer (PB) by cyclic voltammetry (CV) and linear sweep adsorptive stripping voltammetry (LSAdSV) using linear scan voltammetry in the first derivative mode (LSVFD). Linear concentration dependences in the concentration ranges from 0.1 to 10 μM and from 10 to 100 μM were obtained by the LSAdSV with limit of detection (LOD) and limit of quantification (LOQ) 0.06 and 0.19 μM, respectively. The novel modified CI/NiCS/CCE showed good stability and selectivity and was successfully used to determine CBF in real samples of vegetables and fruits with LOD 0.01 mg kg−1.

Immunoassay based on peroxidase silver conjugate for the determination of human immunoglobulins against tick‐borne borreliosis (lyme disease) by voltammetry and spectrophotometry

AbstractIn this work two strategies for the synthesis of peroxidase silver conjugates for the qualitative and quantitative determination of immunoglobulins (IgG) to ixodid tick‐borne borreliosis (ITBB) (Lyme disease) in human serum were proposed. The first approach for Ab‐HRP@AgNP conjugate synthesis involved silver nanoparticles (Ag NPs) capped with a commercial peroxidase conjugate (Ab‐HRP) by passive adsorption. The second strategy was based on the initial coupling of Ag NPs with human anti‐species antibodies (Ab) by passive adsorption followed by the introduction of horseradish peroxidase (HRP) enzyme into the reaction mixture as a blocking reagent for Ab@AgNP@HRP conjugate synthesis. The formation of peroxidase silver conjugates was proved by UV/Vis spectroscopy and Transmission Electron Microscopy (TEM). The catalytic activity of Ab‐HRP@AgNP and Ab@AgNP@HRP conjugates was evaluated by Michaelis‐Menten kinetics. A commercially available 96‐well microtiter plate with recombinant antigens to ITBB was used as a platform for immobilization of analyzed IgG. The HRP in Ab‐HRP@AgNP conjugate was found to retain a sufficient level of activity for interaction with the H2O2 substrate to form an intensely colored reaction product. Therefore Ab‐HRP@AgNP conjugate can be used in enzyme‐linked immunosorbent assay (ELISA) with spectrophotometric detection of 3,3’,5,5’‐Tetramethylbenzidine (TMB Ox) for quantitative determination of IgG to ITBB in human serum in the concentration range 12.5–800 ng ml−1 with LOD 2 ng ml−1. Ab@AgNP@HRP conjugate is recommended for the electrochemical determination of IgG to ITBB in human serum at LOD 3 ng ml−1 with registration of silver oxidation by linear sweep anodic stripping voltammetry (LSASV). Ag NPs in Ab‐HRP@AgNP and Ab@AgNP@HRP conjugates do not change electrochemical activity during storage and can be used as an electrochemical label in LSASV method in case of HRP inactivation. The immunoassay based on peroxidase silver conjugates expands the analytical potential for the determination of IgG to ITBB especially during the period of increasing incidence.

Development and characterization of a clay-HDTMABr composite for the removal of Cr(VI) from aqueous solutions with special emphasis on the electrochemical interface

This research aims to study the removal of chromium in its toxic form, Cr (VI), from wastewater, using clay and modified clay with Hexadecyltrimethyl ammonium bromide (HDTMABr)as adsorbents. The modified clay is obtained by impregnating a known quantity of HDTMABr into the clay. The two materials were characterized by different techniques, such as X-ray diffraction, which is used to determine the inorganic composition and the phyllite structures it contains. Thermal analysis TGA isused to understand the thermal behavior as function of the sintering temperature. Nitrogen adsorption/desorption is used to get the pores' size and surface area, using the Brunauer-Emmett-Teller (BET) theory. Scanning electron microscopy (SEM) coupled with Energy Dispersive X-ray Spectroscopy (SEM/EDAX) is used to study the surface morphology of the bare clay and the HDTMABr/clay. The operating conditions, such as contact times, pH, and adsorption temperatures, were studied, and optimized to improve the efficiency of the adsorption process. The adsorption is favored in acidic medium and room temperature, giving adsorption capacities for Cr(VI) of 12 mg/g and 250 mg/g for the clay and clay/HDTMABr, respectively. The reaction kinetics were studied and found to fit a pseudo-second-order model. The standard entropy (ΔS°), enthalpy (ΔH°), and Gibbs free energy (ΔG°) changes indicate that the chromium (VI) adsorption process is a physical, spontaneous, endothermic process. Cyclic voltammetry (CV) and the electrochemical impedance spectroscopy (EIS) are used for the electrochemical characterization of the raw clay and clay/HDTMABr in [Fe(CN)6]3-/4-/ 0.1 M KCl solution. The linear scan anodic stripping voltammetry (LSASV) is used for the reduction the Cr(VI) to Cr(III), indicating that Cr(VI) accumulates better at the surface of clay/HDTMABr compared to the bare graphite and the raw clay.

Ultra-thin silver nanowires’ synthesis in pore-confined space of mesoporous silica thin film

In the present work, we report a synthesis procedure for the preparation of vertically aligned mesoporous silica thin films containing long, nanometer-scale thin silver nanowires inside pores. The inter-channel nanowires had a fine crystalline structure and a diameter of no more than 2 nm. Despite the diameter being the edge of the theoretical possibility of synthesis, the nanowires were stable enough to be observed by transmission electron microscope and could be clearly observed. For the synthesis, we applied the idea of silica nanoreactors, and the procedure consists of two steps: fabrication of an initial organically-functionalized silica thin film containing silver ions distributed regularly inside vertically aligned pores and following thermal decomposition resulting in the decomposition of the organic anchoring groups and the formation of metallic crystalline nanowires from released silver atoms. Both the final nanocomposite and the initial material were studied by means of transition electron microscopy and electrochemical techniques: linear scan and differential pulse anodic stripping voltammetry. The crystallinity of silver nanowires inside silica mesopores was proved by electron diffraction. The spatial confinement realized by silica nanochannels facilitated the stabilization of relatively small and ultra-thin nanowires and the formation of a hexagonal P63/mmc silver crystalline structure instead of the more common Fm3m cubic.

Silver nanoparticle interactions with glycated and non-glycated human serum albumin mediate toxicity.

Introduction: Biomolecules bind to and transform nanoparticles, mediating their fate in biological systems. Despite over a decade of research into the protein corona, the role of protein modifications in mediating their interaction with nanomaterials remains poorly understood. In this study, we evaluated how glycation of the most abundant blood protein, human serum albumin (HSA), influences the formation of the protein corona on 40nm silver nanoparticles (AgNPs) and the toxicity of AgNPs to the HepG2 human liver cell line. Methods: The effects of glycation on AgNP-HSA interactions were quantified using circular dichroism spectroscopy to monitor protein structural changes, dynamic light scattering to assess AgNP colloidal stability, zeta potential measurements to measure AgNP surface charge, and UV-vis spectroscopy and capillary electrophoresis (CE) to evaluate protein binding affinity and kinetics. The effect of the protein corona and HSA glycation on the toxicity of AgNPs to HepG2 cells was measured using the WST cell viability assay and AgNP dissolution was measured using linear sweep stripping voltammetry. Results and Discussion: Results from UV-vis and CE analyses suggest that glycation of HSA had little impact on the formation of the AgNP protein corona with protein-AgNP association constants of ≈2x107 M-1 for both HSA and glycated HSA (gHSA). The formation of the protein corona itself (regardless of whether it was formed from HSA or glycated HSA) caused an approximate 2-fold decrease in cell viability compared to the no protein AgNP control. While the toxicity of AgNPs to cells is often attributed to dissolved Ag(I), dissolution studies showed that the protein coated AgNPs underwent less dissolution than the no protein control, suggesting that the protein corona facilitated a nanoparticle-specific mechanism of toxicity. Overall, this study highlights the importance of protein coronas in mediating AgNP interactions with HepG2 cells and the need for future work to discern how protein coronas and protein modifications (like glycation) may alter AgNP reactivity to cellular organisms.

In Situ Deposition of Gold Nanoparticles and L-Cysteine on Screen-Printed Carbon Electrode for Rapid Electrochemical Determination of As(III) in Water and Tea.

In this study, a screen-printed carbon electrode (SPCE) based on in situ deposition modification was developed for the sensitive, rapid, easy and convenient determination of As(III) in water and tea by linear sweep anodic stripping voltammetry (LSASV). The screen-printed carbon electrodes were placed in a solution consisting of As(III) solution, chlorauric acid and L-cysteine. Under certain electrical potential, the chloroauric acid was reduced to gold nanoparticles (AuNPs) on the SPCE. L-cysteine was self-assembled onto AuNPs and promoted the enrichment of As(III), thus enhancing the determination specificity and sensitivity of As(III). The method achieved a limit of determination (LOD) of 0.91 ppb (µg L-1), a linear range of 1~200 µg L-1, an inter-assay coefficient of variation of 5.3% and good specificity. The developed method was successfully applied to the determination of As(III) in tap water and tea samples, with a recovery rate of 93.8%~105.4%, and further validated by inductively coupled plasma mass spectrometry (ICP-MS). The developed method is rapid, convenient and accurate, holding great promise in the on-site determination of As(III) in tap water and tea leaves, and it can be extended to the detection of other samples.

An electrochemical sensor for capsaicin based on two-dimensional titanium carbide (MXene)-doped titania-Nafion composite film

Two-dimensional titanium carbide (called MXene) has been utilized to fabricate a highly sensitive electrochemical sensor for the determination of capsaicin. In the present work, Ti3C2Tx MXene was dispersed in the composite solution of sol–gel derived titania and Nafion. The as-prepared MXene-titania-Nafion composite solution was drop-cast on the surface of a glassy carbon (GC) electrode. Due to the electrostatic interaction between positively charged capsaicin at pH 1.0 and negatively charged MXene-titania-Nafion composite film, capsaicin was selectively adsorbed onto the present electrochemical sensor. The introduction of MXene in the titania-Nafion composite film on GC electrode significantly increased the oxidation current of capsaicin compared to that at a bare GC electrode and the titania-Nafion composite-modified GC electrode, which could be attributed to the synergistic effect of Ti3C2Tx MXene and mesoporous titania-Nafion composite film. The experimental parameters affecting the detection capability of capsaicin (i.e., pH, MXene loading amount and accumulation time) were optimized. Using the linear sweep adsorptive stripping voltammetry, the present electrochemical sensor based on the MXene-titania-Nafion composite film can detect capsaicin from 5.0 × 10−8 M to 2.5 × 10−5 M with a detection limit of 2.5 × 10−8 M (S/N = 3). Furthermore, the present electrochemical sensor exhibited good selectivity towards capsaicin against interfering species like glucose and organic acids. Recovery tests for spiked capsaicin in a real pepper sample showed good recoveries. Therefore, the present electrochemical sensor based on the MXene-titania-Nafion composite could be applied to the voltammetric determination of capsaicin in food and pharmaceuticals.

Electrochemical immunoassay of antibodies using freshly prepared and aged conjugates of silver nanoparticles

In this work, silver nanoparticles (AgNPs) were conjugated with immunoglobulins G using a simple passive adsorption method and the composition and properties of freshly prepared (Ab@AgNPs) and aged (Ab@AgNP/Ag2SNPs) conjugates were investigated for the first time by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and voltammetry. It was found that the state of the AgNPs in the conjugates changed during storage. In the freshly prepared Ab@AgNPs conjugates, silver is present in the metallic state only, while the aged Ab@AgNP/Ag2SNPs conjugates are characterized by the presence of a metallic core of AgNPs coated with a “corona” of Ag2S. This affects the selection of voltammetric conditions for recording an analytical signal from the silver label in the conjugates. The Ab@AgNPs and Ab@AgNP/Ag2SNPs conjugates were successfully tested in the electrochemical immunoassay of dog immunoglobulins as a model. A solid-phase indirect non-competitive assay was performed using a 96-well ELISA plate. To record intense analytical signals from the silver conjugates by linear scan anodic stripping voltammetry (LSASV) on a carbon composite electrode (CCE), they were preliminarily dissolved in acidic solutions. In the case of the Ab@AgNPs conjugate, a nitric acid solution (1 mol L−1) was used to dissolve silver conjugates, while in the case of Ab@AgNP/Ag2SNPs, a 1:1 mixture of 1 mol L−1 CH3COOH and 1 mol L−1 HNO3 was used. The CH3COOH dissolved the Ag2S “corona”, and HNO3 dissolved the silver core of the Ab@AgNP/Ag2SNPs conjugate.This work opens up the possibility of the prolonged use of silver conjugates in electrochemical immunoassay, which can be used in commercial test systems for immunological studies as an alternative to conjugates labelled with enzyme labels.

Electrochemical Synthesis of Nanocrystalline CuAg Coatings on Stainless Steel from Cyanide-Free Electrolyte

Herein we demonstrate a novel plating bath, free from cyanide, to plate a highly adherent nanocrystalline copper-silver (ncCuAg) coating on a stainless-steel substrate and its application as an antimicrobial coating. The microstructures, such as the grain size, texture, microstrain, and the crystalline preferential orientation of CuAg deposits, are systematically investigated by X-ray diffraction analysis. The range of 13.4–16.6 nm was discovered to be the crystallite size determined from the X-ray peak broadening (Scherrer’s formula). Both HRTEM, FESEM-EDS, XPS, and mapping analysis revealed that the ncCuAg coatings are composed of both Ag and Cu atoms. Electrochemical processes occurring during CuAg co-deposition were investigated by using linear sweep voltammetry (LSV), cyclic voltammetry (CV), and anodic linear stripping voltammetry (ALSV). Additionally, the coatings made of ncCuAg produced by these baths work well as antibacterial agents against gram-positive (Staphylococcus) and gram-negative bacteria (Escherichia coli).

An insight to the filtration mechanism of Pb(II) at the surface of a clay ceramic membrane through its preconcentration at the surface of a graphite/clay composite working electrode

The use of cyclic voltammetry (CV) and linear scan anodic stripping voltammetry (LSASV) to predict the selectivity of microfiltration ceramic membranes made from a lump of local clay towards Pb(II) ions filtration is described. The membranes were characterized by different techniques followed by CV analysis of the Fe(CN)63-/Fe(CN)64- redox couple and Pb(II) on bare graphite, raw clay, and clay-modified carbon paste electrode (clay-modified CPE). The effect of clay loading in the range of 1–10 % (w/w) on the electrodes is studied, where an enhanced peak current is observed for 5 % w/w clay. Moreover,adecreaseinthepeak current can be seen for bare graphite electrodes, suggesting that the clay mineral had played asubstantial role in the sieving of heavy metal ions through theceramic membrane. The electroactive surface area of 5% w/w raw clay towards Fe(II) ions was found to be in the order of 3.07 × 10-2 cm2 and higher than 5% w/w clay sintered to 1000 °C and bare graphite. CV analysis shows that both, 5 % w/w raw clay and 5 % w/w clay sintered to 1000 °C exhibited high peak currents towards Pb(II) ions. The mobility of the Pb(II) ions is found to increase when 5% w/w clay sintered to 1000 °C is utilized as membrane/electrode, leading to an increase in the amount of reduced Pb(II) ions on the surfaces of the clay membranes/electrodes. The study suggests successful filtration of Pb(II) ions through the proposed membrane/electrode and a much better accumulation than Fe(II) at the surface of the membrane/electrode before being subjected to filtration.

An Au(111)-dominant polycrystalline gold/gold nanoparticles/1,8-naphthyridine/glassy carbon electrode for anodic stripping voltammetry determination of As(III)

We report the fabrication of a 1,8-naphthyridine (Naph), gold nanoparticles and then Au(111)-dominant polycrystalline gold (Au(111)dpg) modified glassy carbon electrode (GCE) for linear sweep anodic stripping voltammetry (LSASV) determination of As(III). An ultrathin film of Naph was chemically bonded on a GCE by electroreduction of Naph in acidic solution. The bipyridine group of Naph on the Naph/GCE can capture gold nanoparticles (AuNPs) by coordination adsorption and can then direct an Au(111) oriented crystalline growth during gold staining in HAuCl4–NH2OH solution, due to the different affinities of Au(110), Au(100) and Au(111) facets to the pyridine unit in Naph. The prepared Au(111)dpg/AuNPs/Naph/GCE and the control electrodes were characterized by electrochemical methods, X-ray photoelectron spectroscopy, X-ray diffraction and scanning electron microcopy. LSASV determination of As(III) was performed on the Au(111)dpg/AuNPs/Naph/GCE with high performance. Sensitivity values of 11.6 µA ppb–1 (2.3∼75 ppb) and 3.1 µA ppb–1 (2.3∼75 ppb), as well as limit of detection values of 0.15 ppb and 0.52 ppb (S/N = 3) were obtained on the basis of the LSASV oxidation signals of As(0)→As(III) and As(III)→As(V), respectively. The Au(111)dpg/AuNPs/Naph/GCE was applied for As(III) determination in river water samples with satisfied results.

Enhancement of the Negative Capacitance Associated with the Dissolution of Silver by Salt Concentrations by Means of Anodic Stripping Voltammetry

The amount of anodically dissolved charge of silver by linear sweep stripping voltammetry has been observed to be smaller than that of the potentiostatically deposited charge. The imbalance in the charge is opposite to the participation in the double-layer capacitance. This can be explained in terms of the negative capacitive current, which is caused by dipoles of generated redox charge (Ag+) with counterions (NO3−). Lower concentrations of counterions may suppress the capacitance to retain the equality of the charge. This prediction is examined in this work by the oxidation of silver film at various concentrations of NO3− by anodic stripping voltammetry. The capacitance decreased with a decrease in the salt concentrations less than 0.05 mol dm−3. Low concentrations of salts prevent loss of the anodic charge in electroanalysis. This dependence was related with the lifespan of generated silver nitrate dipoles and is described theoretically.

A compact N-nitrosodiphenylamine imprinted sensor based on a Pd nanoparticles-MIP microsphere modified screen-printed graphene electrode

• A novel NDPhA imprinted sensor was firstly fabricated for sensitive and selective, determination of NDPhA. • NDPhA recognition sites were successfully furnished on PdNPs’ surface via 3D-imprinting technique. • The sensor is ready-to-use, cost-effective, flexibility, stability, and suited to large-scale production. Herein, we report the fabrication of a compact voltammetric sensor for the sensitive and selective determination of N -nitrosodiphenylamine (NDPhA) based on a screen-printed graphene electrode modified with a molecularly imprinted polymer coating on a palladium nanoparticle core (PdNPs@MIP/SPGrE). In addition, a novel approach for 3D-imprinting of NDPhA on the PdNPs surface is presented. PdNPs were first synthesized by chemical reduction using sodium borohydride. Then, Core-shell polymerization was achieved by successively coating the surface of PdNPs with poly(vinylpyrrolidone) and terminating with an MIP consisting of poly( N -Isopropylacrylamide)-co-trimethylolpropane trimethacrylate. Morphological, structural, and electrochemical characterization reveals that the as-prepared micro-sized spherical PdNPs@MIP has a uniform, high electro-catalytic activity and a specific surface area with many NDPhA imprinted sites. We constructed the compact NDPhA imprinted sensor by coating the SPGrE surface with PdNPs@MIP. Quantitative analysis was performed by linear sweep anodic stripping voltammetry (LSASV) using a deposition potential of +0.02 V for 60 s. The linear working ranges for NDPhA measurements were 0.01–0.1 μM (r 2 = 0.996) and 0.1–100 μM (r 2 = 0.992) with corresponding sensitivities of 51.935 and 0.821 (μA s) µM −1 , respectively. The system provides a good precision of %RSD 1.67% with an estimated detection limit (3S b , n = 3) of 0.0013 μM. The intraday and inter-day accuracy (%bias) of the certified reference material (CRM) are −0.74% and −1.01%, respectively. We demonstrate the successful application of the fabricated compact sensor to determine NDPhA in beverage and synthetic samples. The compact NDPhA imprinted sensor can provide an alternative approach to food quality control.

Anodic Stripping Voltammetric Analysis of Trace Arsenic(III) on a Au-Stained Au Nanoparticles/Pyridine/Carboxylated Multiwalled Carbon Nanotubes/Glassy Carbon Electrode.

A Au-stained Au nanoparticle (Aus)/pyridine (Py)/carboxylated multiwalled carbon nanotubes (C-MWCNTs)/glassy carbon electrode (GCE) was prepared for the sensitive analysis of As(III) by cast-coating of C-MWCNTs on a GCE, electroreduction of 4-cyanopyridine (cPy) to Py, adsorption of gold nanoparticles (AuNPs), and gold staining. The Py/C-MWCNTs/GCE can provide abundant active surface sites for the stable loading of AuNPs and then the AuNPs-initiated Au staining in HAuCl4 + NH2OH solution, giving a large surface area of Au on the Aus/Py/C-MWCNTs/GCE for the linear sweep anodic stripping voltammetry (LSASV) analysis of As(III). At a high potential-sweep rate of 5 V s−1, sharp two-step oxidation peaks of As(0) to As(III) and As(III) to As(V) were obtained to realize the sensitive dual-signal detection of As(III). Under optimal conditions, the ASLSV peak currents for oxidation of As(0) to As(III) and of As(III) to As(V) are linear with a concentration of As(III) from 0.01 to 8 μM with a sensitivity of 0.741 mA μM−1 and a limit of detection (LOD) of 3.3 nM (0.25 ppb) (S/N = 3), and from 0.01 to 8.0 μM with a sensitivity of 0.175 mA μM−1 and an LOD of 16.7 nM (1.20 ppb) (S/N = 3), respectively. Determination of As(III) in real water samples yielded satisfactory results.