Stripping voltammetric determination of silver(I) at carbon paste electrode modified with 3-amino-2-mercapto quinazolin-4(3H)-one

A differential pulse anodic stripping voltammetric method was developed for the determination of Ag(I) at a 3-amino-2-mercapto quinazolin-4(3H)-one modified carbon paste electrode. The analysis procedure consisted of an open circuit accumulation step in stirred sample solution for 12 min. This was followed by medium exchange to a clean solution where the accumulated Ag(I) was reduced for 15 s in −0.6 V. Subsequently an anodic potential scan was effected from −0.2 to +0.2 V to obtain the voltammetric peak. The detection limit of silver(I) was 0.4 μg L⁻¹ and R.S.D. for 10, 100 and 200 μg L⁻¹ silver(I) were 2.4, 1.8 and 1.3%, respectively. The calibration curve was linear for 0.9-300 μg L⁻¹ silver(I). Many coexisting ions had little or no effect on the determination of silver(I). The procedure was applied to determination of silver(I) in X-ray photographic films and natural waters. In X-ray photographic film samples, the results have compared to those obtained by atomic absorption spectroscopy.     

Determination of l-histidine by modified carbon paste electrode using tetra-3,4-pyridinoporphirazinatocopper(II)

This paper describes a potentiometric method for determination of l-histidine (l-his) in aqueous media, using a carbon paste electrode modified with tetra-3,4-pyridinoporphirazinatocopper(II) (Cu (3,4tppa)). The electrode exhibits linear response to the logarithm of the concentration of l-histidine from 2.4 × 10⁻⁵ to 1.0 × 10⁻² M, with a response slope of −49.5 ± 1 mV and response time of about 1.5 min. The detection limit according to IUPAC recommendation was 2.0 × 10⁻⁵ M. The proposed electrode shows a good selectivity for l-his over a wide variety of anions. This chemically modified carbon paste electrode was successfully used for the determination of l-his in a synthetic serum and RANDOX control serum solutions.     

5,10,15-Tris(pentafluorophenyl)corrole as highly selective neutral carrier for a silver ion-sensitive electrode

A new highly selective silver(I) electrode was prepared with a PVC membrane using 5,10,15-tris(pentafluorophenyl)corrole as an electroactive material, 2-nitrophenyl octyl ether (o-NPOE) as a plasticizer and sodium tetraphenylborate (NaTPB) as an additive in the percentage ratio of 3:3:62:32 (corrole:NaTPB:o-NPOE:PVC, w:w). The electrode exhibited linear response with a near Nernstian slope of 54.8 mV/decade within the concentration range of 5.1 × 10⁻⁶ to 1.0 × 10⁻¹ M silver ions, with a working pH range from 4.0 to 8.0, and a fast response time of <30 s. Selectivity coefficients for Ag(I) relative to a number of interfering ions were investigated. The electrode is highly selective for Ag(I) ions over a large number of mono-, bi-, and tri-valent cations. Common interferents like Hg²⁺ and Cd²⁺ show very low interfering effect on the silver assay, which is valuable property of the proposed electrode. Several electroactive materials and solvent mediators have been compared and the experimental conditions were optimized. The sensor was applied to the determination of silver in real ore samples with satisfied results.     

Preparation of a carbon ceramic electrode modified by 4-(2-pyridylazo)-resorcinol for determination of trace amounts of silver

A 4-(2-pyridylazo)-resorcinol (PAR)-modified carbon ceramic electrode (CCE) prepared by the sol-gel technique has been reported for the first time in this paper. By immersing the CCE in aqueous solution of PAR (0.001 mol L⁻¹), after a short period of time, a thin film of PAR was rapidly formed on the surface of the electrode due to its strong adsorption properties. A differential pulse anodic stripping voltammetric (DPASV) method was developed for determination of Ag(I) at the modified carbon ceramic electrode. The analysis procedure consisted of an open circuit accumulation step in a sample solution which was continuously stirred for 12 min. This was followed by replacing the medium with a clean solution where the accumulated Ag(I) was reduced for 15 s in −0.6 V. Then, the potential was scanned from −0.2 to +0.2 V to obtain the voltammetric peak. The detection limit of silver(I) was 0.123 μg L⁻¹, and for seven successive determinations of 10, 100 and 200 μg L⁻¹ Ag(I), the relative standard deviations were 2.1, 1.4 and 1.03%, respectively. The calibration curve was linear for 0.5-300 μg L⁻¹ silver(I). The procedure was applied to determine silver(I) in X-ray photographic films and super-alloy samples.     

Stripping voltammetry of silver ions at polythiophene-modified platinum electrodes

The present work describes the development of a modified platinum electrode for stripping voltammetric determination of silver. The deposition of films based on electropolymerisation of the monomer thiophene was carried out by cycling the potential towards positive values between 0 and 1.6 V.The preconcentration process of silver ions was initiated on the surface of the modified electrode by complexing silver with polythiophene (PTH) when a negative potential (−0.5 V) was applied; then the reduced products was oxidized by means of differential pulse stripping voltammetry and the peak was observed at 0.17 V. Parameters such as pH, supporting electrolyte and number of electropolymerisation cycles were studied. A linear relation between current peak and concentration of Ag(I) was obtained in the range 0.07-1.0 mg L⁻¹. The detection limit for Ag(I) was evaluated to be 0.06 mg L⁻¹. The reproducibility was tested carrying out 11 measurements at different electrodes and the relative standard deviation was 1.5%. The interference of several metals was investigated and showed negligible effect on the electrode response.     

Determination of benorilate in pharmaceutical formulations and its metabolite in urine at carbon paste electrode modified by silver nanoparticles

Benorilate was determined by the differential pulse voltammetry (DPV) using a carbon paste electrode modified by silver nanoparticles in 1.25 × 10⁻³ mol l⁻¹ KH₂PO₄ and Na₂HPO₄ buffer solution (pH = 6.88, 25 °C) .The anodic peak potential was +0.970 V (versus SCE). A good linear relationship was realized between the anodic peak currents and benorilate concentrations in the range of 1.0 × 10⁻⁷ to 2.5 × 10⁻⁴ mol l⁻¹ with the detection limit of 1.0 × 10⁻⁸ mol l⁻¹. The recovery was 95.2-103.6% with the relative standard deviation of 3.6% (n = 9). The pharmaceutical preparations, benorilate tablets samples and its metabolite (salicylic acid) in urine were determined with the desirable results.     

A selective modified carbon paste electrode for determination of cyanide using tetra-3,4-pyridinoporphyrazinatocobalt(II)

A chemically modified carbon paste electrode with 3,4-tetra pyridinoporphirazinatocobalt(II) (Co(3,4 tppa) was applied to the determination of free cyanide ion. The electrode has a linear range between 1.5 × 10⁻⁵ M and 1.0 × 10⁻² M with a Nernstian slope of 60 ± 1.5 mV/decade and its detection limit is 9 × 10⁻⁶ M. The response time of electrode is 5 min. The proposed electrode was applied successfully for the determination of cyanide in commercially available spring water. Some anions, such as SCN⁻, I⁻, Cl⁻, Br⁻ and oxalate that are usually serious interfering species for most of cyanide selective electrodes, did not have any interfering effect for this proposed electrode.     

Electrochemical detection of DNA hybridization based on polypyrrole/ss-DNA/multi-wall carbon nanotubes paste electrode

A sensitive electrochemical detection of DNA hybridization using a paste electrode assembled by multi-wall carbon nanotubes (MWNT) and immobilizing DNA probe within electropolymerized polypyrrole (ppy) was developed. The detection approach relied on entrapping of DNA probe within electropolymerized ppy film on the MWNT paste electrode and monitoring the current change generated from an electroactive intercalator of ethidium bromide (EB) after DNA hybridization. As a consequence of DNA hybridization, significant changes in the current of EB intercalated with double-stranded DNA (ds-DNA) on the MWNT paste electrode were observed. Based on the response of EB, only the complementary DNA sequence gave an obvious current signal compared with the five-point mismatched and non-complementary sequences. The oxidation peak current was linearly related to the logarithm of the concentration of the complementary DNA sequence from 1.0 × 10⁻¹⁰ to 1.0 × 10⁻⁸ M with a detection limit of 8.5 × 10⁻¹¹ M. This work demonstrates that the incorporation of MWNT paste electrode with electropolymerization is a promising strategy of functional interfaces for the immobilization of biological recognition elements.     

Voltammetric behavior of copper(I)oxide modified carbon paste electrode in the presence of cysteine and ascorbic acid

The electrochemical behavior of a copper(I)oxide (Cu₂O) modified carbon paste electrode (MCPE) was investigated in different buffer solutions and in the presence of ascorbic acid (AA) and cysteine (RS). Working conditions such as pH, mineral oil, and modifier ratio were optimized. Voltammetric results revealed that RS forms rather stable complexes with Cu(I) which has a high electrocatalytic reduction peak current at −0.65 V versus SCE in borate buffer (pH 9.2). In the case of AA, a complexation occurred with Cu(II) species at the electrode surface, rather than Cu(I). The electrocatalytic reduction peak current of the Cu(II)-AA complex was observed at −0.07 V in phosphate buffer at pH 6.9. Linear responses were observed in the range 2.0×10⁻⁹ to 3.0×10⁻⁸ M with a 0.9954 correlation coefficient for RS and 1.0×10⁻⁹ to 2.0×10⁻⁸ M with a 0.9961 correlation coefficient for AA.     

A novel nonenzymatic hydrogen peroxide sensor based on multi-wall carbon nanotube/silver nanoparticle nanohybrids modified gold electrode

A novel strategy to fabricate hydrogen peroxide (H₂O₂) sensor was developed based on multi-wall carbon nanotube/silver nanoparticle nanohybrids (MWCNT/Ag nanohybrids) modified gold electrode. The process to synthesize MWCNT/Ag nanohybrids was facile and efficient. In the presence of carboxyl groups functionalized multi-wall carbon nanotubes (MWCNTs), silver nanoparticles (Ag NPs) were in situ generated from AgNO₃ aqueous solution and readily attached to the MWCNTs convex surfaces at room temperature, without any additional reducing reagent or irradiation treatment. The formation of MWCNT/Ag nanohybrids product was observed by transmission electron microscope (TEM), and the electrochemical properties of MWCNT/Ag nanohybrids modified gold electrode were characterized by electrochemical measurements. The results showed that this sensor had a favorable catalytic ability for the reduction of H₂O₂. The resulted sensor could detect H₂O₂ in a linear range of 0.05-17 mM with a detection limit of 5 × 10⁻⁷ M at a signal-to-noise ratio of 3. The sensitivity was calculated as 1.42 μA/mM at a potential of −0.2 V. Additionally, it exhibited good reproducibility, long-term stability and negligible interference of ascorbic acid (AA), uric acid (UA), and acetaminophen (AP).     

Sensitive electrochemical sensor of tryptophan based on Ag@C core–shell nanocomposite modified glassy carbon electrode

We here reported a simple electrochemical method for the detection of tryptophan (Trp) based on the Ag@C modified glassy carbon (Ag@C/GC) electrode. The Ag@C core–shell structured nanoparticles were synthesized using one-pot hydrothermal method and characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), and Fourier transform-infrared spectroscopy (FTIR). The electrochemical behaviors of Trp on Ag@C/GC electrode were investigated and exhibited a direct electrochemical process. The favorable electrochemical properties of Ag@C/GC electrode were attributed to the synergistic effect of the Ag core and carbon shell. The carbon shell cannot only protect Ag core but also contribute to the enhanced substrate accessibility and Trp-substrate interactions, while nano-Ag core can display good electrocatalytic activity to Trp at the same time. Under the optimum experimental conditions the oxidation peak current was linearly dependent on the Trp concentration in the range of 1.0 × 10⁻⁷ to 1.0 × 10⁻⁴ M with a detection limit of 4.0 × 10⁻⁸ M (S/N = 3). In addition, the proposed electrode was applied for the determination of Trp concentration in real samples and satisfactory results were obtained. The technique offers enhanced sensitivity and may trigger the possibilities of the Ag@C nanocomposite towards diverse applications in biosensor and electroanalysis.     

Organically nanoporous silica gel based on carbon paste electrode for potentiometric detection of trace Cr(III)

A new ion-selective electrode (ISE) for the detection of trace chromium(III) was designed by using 2-acetylpyridine and nanoporous silica gel (APNSG)-functionalized carbon paste electrode (CPE). The presence of APNSG acted as not only a paste binder, but also a reactive material. With 7.5 wt% APNSG proportions, the developed electrode exhibited wide dynamic range of 1.0 × 10⁻⁸ to 1.0 × 10⁻³ M toward Cr(III) with a detection limit of 8.0 × 10⁻⁹ M and a Nernstian slope of 19.8 ± 0.2 mV decade⁻¹. The as-prepared electrode displayed rapid response (∼55 s), long-time stability, and high sensitivity. Moreover, the potentiometric responses could be carried out with wide pH range of 1.5-5.0. In addition, the content of Cr(III) in food samples, e.g. coffee and tea leaves, has been assayed by the developed electrode, atomic absorption spectrophotometer (AAS) and atomic emission spectrometer (ICP-AES), respectively, and consistent results were obtained. Importantly, the response mechanism of the proposed electrode was investigated by using AC impedance and UV-vis spectroscopy.     

Stripping voltammetric determination of silymarin in formulations and human blood utilizing bare and modified carbon paste electrodes

Silymarin is one of the most powerful natural substances that have the ability to protect and rebuild the liver cells damaged by alcohol and other toxic substances. Silymarin showed two irreversible anodic peaks in buffered solutions (pH 2.5-8.0) at either the bare carbon paste electrode or the montmorillonite-Ca modified carbon paste one. These two peaks have been attributed to oxidation of the two phenolic OH groups at positions C-20 and C-7 of silymarin molecule. A square-wave adsorptive anodic stripping voltammetry method was optimized for determination of silymarin utilizing the bare and the modified carbon paste electrodes. The method was fully validated and successfully applied for the determination of silymarin in commercial formulations and human serum without prior extraction utilizing both carbon paste electrodes. Limits of quantitation of 1 × 10⁻⁷ and 7 × 10⁻⁹ mol L⁻¹ silymarin have been achieved in bulk form or in formulations while 2 × 10⁻⁷ and 8 × 10⁻⁹ mol L⁻¹ silymarin were achieved in spiked human serum utilizing the bare carbon paste electrode and the modified one, respectively. The two electrodes exhibited excellent selectivity towards silymarin even in the presence of 10²to 10³-fold excess of its co-formulated drugs, common excipients, and common metal ions. The pharmacokinetic parameters of silymarin in plasma of healthy human volunteers were estimated following the administration of a single oral dose of 120 mg silymarin utilizing the modified carbon paste electrode. The estimated pharmacokinetic parameters were favorably compared with those reported in literature.     

Use of organofunctionalized nanoporous silica gel to improve the lifetime of carbon paste electrode for determination of copper(II) ions

A new functionalized nanoporous silica gel with dipyridyl group (DPNSG) was synthesized. Then, the potentiometric response of the copper(II) ion was investigated at a carbon paste electrode chemically modified with this newly designed functionalized nanoporous silica gel. The electrodes with DPNSG proportions of 15.0% (w/w) demonstrated very stable potentials. Calibration plots with Nernstian slopes for Cu²⁺ were observed, 28.4 (±1.0) mV decade⁻¹, over a wide linear concentration range (1.0 × 10⁻⁷ to 1.0 × 10⁻² M). The electrode exhibited a detection limit of 8.0 × 10⁻⁸ M. Moreover, the selectivity coefficients measured by the match potential method in acetate buffer, pH 5.5, were investigated. The electrode presented a response time of ∼50 s, high performance, high sensitivity in a wide range of cation activities and good long-term stability (more than 9 months). The method was satisfactory and was used to determine the copper ion concentration in waste waters, contaminated by this metal.     

Sensitive DNA biosensor improved by Luteolin copper(II) as indicator based on silver nanoparticles and carbon nanotubes modified electrode

A novel and sensitive electrochemical DNA biosensor has been developed for the detection of DNA hybridization. The biosensor was proposed by using copper(II) complex of Luteolin C₃₀H₁₈CuO₁₂ (CuL₂) as an electroactive indicator based on silver nanoparticles and multi-walled carbon nanotubes (Ag/MWCNTs) modified glassy carbon electrode (GCE). In this method, the 4-aminobenzoic acid (4-ABA) and Ag nanoparticles were covalently grafted on MWCNTs to form Ag/4-ABA/MWCNTs. The proposed method dramatically increased DNA attachment quantity and complementary ssDNA detection sensitivity for its large surface area and good charge-transport characteristics. DNA hybridization detection was performed using CuL₂ as an electroactive indicator. The CuL₂ was synthesized and characterized using elemental analysis (EA) and IR spectroscopy. Cyclic voltammetry (CV) and fluorescence spectroscopy were used to investigate the interaction between CuL₂ and ds-oligonucleotides (dsDNA). It was revealed that CuL₂ presented high electrochemical activity on GCE, and it could be intercalated into the double helices of dsDNA. The target ssDNA of the human hepatitis B virus (HBV) was quantified in a linear range from 3.23 × 10⁻¹² to 5.31 × 10⁻⁹ M (r = 0.9983). A detection limit of 6.46 × 10⁻¹³ M (3σ, n = 11) was achieved.     

Preparation of silver hexacyanoferrate nanoparticles and its application for the simultaneous determination of ascorbic acid, dopamine and uric acid

A silver hexacyanoferrate nanoparticles/carbon nanotubes modified glassy carbon electrode was fabricated and then successfully used for the simultaneous determination of ascorbic acid, dopamine and uric acid by cyclic voltammetry. A detailed investigation by transmission electron microscopy (TEM) and electrochemistry was performed in order to elucidate the preparation process and properties of the nanocomposites. The size of silver hexacyanoferrate nanoparticles was examined by TEM around 27 nm. Linear calibration plots were obtained over the range of 4.0 × 10⁻⁶-7.8 × 10⁻⁵, 2.4 × 10⁻⁶-1.3 × 10⁻⁴ and 2.0 × 10⁻⁶-1.5 × 10⁻⁴ mol L⁻¹ with detection limits of 4.2 × 10⁻⁷,1.4 × 10⁻⁷ and 6.0 × 10⁻⁸ mol L⁻¹ for ascorbic acid, dopamine and uric acid, respectively. The practical analytical utilities of the modified electrode were demonstrated by the determination of ascorbic acid, dopamine and uric acid in urine and human blood serum samples.     

Accumulation and trace measurement of chloroquine drug at DNA-modified carbon paste electrode

The voltammetric behaviour of chloroquine was investigated at carbon paste and dsDNA-modified carbon paste electrodes in different buffer systems over a wide pH range using cyclic and differential pulse voltammetry. Chloroquine was oxidized in the pH range 2.0-11.0 yielding one irreversible main oxidation peak. A second peak was also observed only in the pH range 5.0-7.0. The modification of the carbon paste surface with dsDNA allowed a preconcentration process to take place for chloroquine such that higher sensitivity was achieved as compared with the bare surface. The response was characterized with respect to solution pH, ionic strength, accumulation time and potential, chloroquine concentration, and other variables. Stripping voltammetric response showed a linear calibration curve in the range 1.0 × 10⁻⁷ to 1.0 × 10⁻⁵ mol l⁻¹ with a detection limit of 3.0 × 10⁻⁸ mol l⁻¹ at the dsDNA-modified electrode. Application of the modified electrode to serum, without sample pretreatment, resulted in good recovery higher than 95% and the higher standard deviation was 3.0%.     

Voltammetric studies of sumatriptan on the surface of pyrolytic graphite electrode modified with multi-walled carbon nanotubes decorated with silver nanoparticles

Multi-walled carbon nanotube decorated with silver nanoparticles (AgNPs-MWCNT) is used as an effective strategy for modification of the surface of pyrolytic graphite electrode (PGE). This modification procedure improved colloidal dispersion of the decorated MWCNTs in water, affording uniform and stable thin films for altering the surface properties of the working electrode. Robust electrode for sensing applications is obtained in a simple solvent evaporation process. The electrochemical behavior of sumatriptan (Sum) at the bare PGE and AgNPs-MWCNT modified PGE is investigated. The results indicate that the AgNPs-MWCNT modified PGE significantly enhanced the oxidation peak current of Sum. A remarkable enhancement in microscopic area of the electrode together with strong adsorption of Sum on the surface of the modified electrode resulted in a considerable increase in the peak current of Sum. Experimental parameters, such as scan rate, pH, accumulation conditions and amount of the modifier used on the PGE surface are optimized by monitoring the CV responses toward Sum. It is found that a maximum current response can be obtained at pH 7.4 after accumulation at open circuit for 150 s. Further experiments demonstrated that the oxidative peak currents increased linearly with Sum concentration in the range of 8.0 × 10⁻⁸-1.0 × 10⁻⁴ mol L⁻¹ with a detection limit of 4.0 × 10⁻⁸ mol L⁻¹. The modified electrode showed high sensitivity, selectivity, long-term stability and remarkable voltammetric reproducibility in response to Sum. These excellent properties make the prepared sensor suitable for the analysis in pharmaceutical and clinical preparations. The modified electrode was successfully applied for the accurate determination of trace amounts of Sum in pharmaceutical preparations.     

Electrochemical behaviors of guanosine on carbon ionic liquid electrode and its determination

The electrochemical behaviors of guanosine on the ionic liquid of N-butylpyridinium hexafluorophosphate (BPPF₆) modified carbon paste electrode (CPE) was studied in this paper and further used for guanosine detection. Guanosine showed an adsorption irreversible oxidation process on the carbon ionic liquid electrode (CILE) with the oxidation peak potential located at 1.12 V (vs. SCE) in a pH 4.5 Britton-Robinson (B-R) buffer solution. Compared with that on the traditional carbon paste electrode, small shift of the oxidation peak potentials appeared but with a great increment of the oxidation peak current on the CILE, which was due to the presence of ionic liquid in the modified electrode adsorbed the guanosine on the surface and promoted the electrochemical response. The electrochemical parameters such as the electron transfer coefficient (α), the electron transfer number (n), and the electrode reaction standard rate constant (k_s) were calculated as 0.74, 1.9 and 1.26 × 10⁻⁴ s⁻¹, respectively. Under the optimal conditions the oxidation peak current showed a good linear relationship with the guanosine concentration in the range from 1.0 × 10⁻⁶ to 1.0 × 10⁻⁴ mol/L by cyclic voltammetry with the detection limit of 2.61 × 10⁻⁷ mol/L (3σ). The common coexisting substances showed no interferences to the guanosine oxidation. The CILE showed good ability to distinguish the electrochemical response of guanosine and guanine in the mixture solution. The urine samples were further detected by the proposed method with satisfactory results.     

Potentiometric stripping analysis of methyl and ethyl parathion employing carbon nanoparticles and halloysite nanoclay modified carbon paste electrode

Carbon nanoparticles (CNPs) and halloysite nanoclay (HNC) modified carbon paste electrode (HNC–CNP–CPE) was developed for the determination of methyl parathion (MP) and ethyl parathion (EP). The electrochemical behavior of these molecules was investigated employing cyclic voltammetry (CV), chronocoulometry (CC), electrochemical impedance spectroscopy (EIS) and potentiometric stripping analysis (PSA). After optimization of analytical conditions employing this electrode at pH 5.0 in acetate buffer (0.1 M), the peak currents were found to vary linearly with its concentration in the range of 1.55 × 10⁻⁹ to 3.67 × 10⁻⁶ M and 1.21 × 10⁻⁹ to 4.92 × 10⁻⁶ M for MP and EP, respectively. The detection limits (S/N = 3) of 4.70 × 10⁻¹⁰ M and 3.67 × 10⁻¹⁰ M were obtained for MP and EP, respectively, using PSA. The prepared modified electrode showed several advantages such as simple preparation method, high sensitivity, very low detection limits and excellent reproducibility. The proposed method was employed for the determination of MP and EP in fruits, vegetables, water and soil samples.