Application of ionic liquid–TiO2 nanoparticle modified carbon paste electrode for the voltammetric determination of benserazide in biological samples

An ionic liquid–TiO₂ nanoparticle modified carbon paste electrode (IL–TiO₂/CPE) was used as a fast and sensitive tool for the investigation of the electrochemical oxidation of benserazide using voltammetry. This modified electrode has been fabricated using hydrophilic ionic liquid (n-hexyl-3-methylimidazolium hexafluoro phosphate) as a binder. The modified electrode offers a considerable improvement in voltammetric sensitivity toward benserazide, compared to the bare electrode. Using differential pulse voltammetry (DPV), the electrocatalytic oxidation peak current of benserazide shows a linear calibration curve in the range of 1.0–600 μmol L^? 1 benserazide. The limit of detection was equal to 0.4 μmol L^? 1. The relative standard deviation (RSD%) for eight successive assays of 10 μmol L^? 1 benserazide was 1.1%. Finally, the proposed method was successfully applied to the determination of benserazide in real samples such as blood serum and urine.     

Designing and synthesis of bis(2,4-dihydroxybenzylidene)-1,6-diaminohexane and its efficient application as neutral carrier for preparation of new copper selective electrode

A new copper carbon paste electrode (CPE) based on incorporation bis(2, 4-dihydroxybenzyliden)-1,6-diaminohexane (DHBDAH) in graphite powder matrix has been described. The influence of variables including an amount of graphite, sodium tetraphenylborate (NaTPB), DHBDAH and nujol on the Cu²⁺ carbon paste electrode response was studied and optimized. The optimum carbon paste composition was set as follows, graphite powder: NaTPB: Nujol: DHBDAH with amount of 150:2.3:30:4 mg, respectively. At the optimum conditions, the potential response is linear over the concentration range of 5.0 × 10^? 8 to 1.0 × 10^? 1 mol L^? 1 with a Nernstian slope of 29.5 ± 1.1 mV per decade of Cu²⁺ ion concentration. The good performance of electrode such as low detection limit of (LOD) (4 × 10^? 8 mol L^? 1), wide applicable pH range (2.5–5.5), fast response time (?10 s) and adequate shelf life (69 days) indicate the utility of the proposed electrode for evaluation of Cu²⁺ ion content in various analysis. Due to moderate potentiometric selectivity coefficients of proposed electrode obtained by fixed interference method (FIM) and separate solution method (SSM), the proposed electrode successfully can be applied for the determination of Cu²⁺ ions content in some real samples.     

Voltammetric sensor based on carbon paste electrode modified with molecular imprinted polymer for determination of sulfadiazine in milk and human serum

A new sensitive voltammetric sensor for determination of sulfadiazine is described. The developed sensor is based on carbon paste electrode modified with sulfadiazine imprinted polymer (MIP) as a recognition element. For comparison, a non-imprinted polymer (NIP) modified carbon paste electrode was prepared. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods were performed to study the binding event and electrochemical behavior of sulfadiazine at the modified carbon paste electrodes. The determination of sulfadiazine after its extraction onto the electrode surface was carried out by DPV at 0.92 V vs. Ag/AgCl owing to oxidation of sulfadiazine. Under the optimized operational conditions, the peak current obtained at the MIP modified carbon paste electrode was proportional to the sulfadiazine concentration within the range of 2.0 × 10^? 7–1.0 × 10^? 4 mol L^? 1 with a detection limit and sensitivity of 1.4 × 10^? 7 mol L^? 1 and 4.2 × 10⁵ μA L mol^? 1, respectively. The reproducibility of the developed sensor in terms of relative standard deviation was 2.6%. The sensor was successfully applied for determination of sulfadiazine in spiked cow milk and human serum samples with recovery values in the range of 96.7–100.9%.     

A comparative study on fabrication of Mn2 + selective polymeric membrane electrode and coated graphite electrode

Poly(vinyl chloride)-based membranes of two ligands 2,4-bis(2-acetoxybenzylamino)-6-phenyl-1,3,5-triazine (L₁) and N2,N4-di(cyanoethyl)-2,4-bis(2-acetoxybenzylamino)-6-phenyl-1,3,5-triazine (L₂) were fabricated and explored as Mn^2 + ion selective electrodes. The performance of the polymeric membranes electrodes of ionophores with different plasticizers (dibutylphthalate, benzoic acid, o-nitrophenyloctyl ether, 1-chloronapthalene and tri-n-butylphosphate) and anion excluders (sodium tetraphenylborate and potassium tetrakis p-(chloro phenyl)borate) was looked in to and the better results were obtained with the membrane having composition L₂: NaTPB: DBP: PVC as 6: 3: 56: 35 (w/w; mg). The coated graphite electrode (CGE) with same composition was also fabricated and investigated as Mn^2 + selective electrode. It was found that CGE showed better response characteristics than PME. The potentiometric response of CGE was independent of pH in the range 3.0–9.0 exhibiting the Nernstian slope 29.5 ± 0.3 mV decade^? 1 of activity and working concentration range 4.1 × 10^? 7–1.0 × 10^? 1 mol L^? 1 with a limit of detection 6.7 × 10^? 8 mol L^? 1. The electrode showed a fast response time of 12 s with a shelf life of 105 days. The proposed CGE could be successfully used for the determination of Mn^2 + ions in different water, soil, vegetables and medicinal plants also used as an indicator electrode in potentiometric titration with EDTA.     

A highly sensitive and selective electrochemical sensor for determination of Cr(VI) in the presence of Cr(III) using modified multi-walled carbon nanotubes/quercetin screen-printed electrode

A novel screen-printed carbon electrode modified with quercetin/multi-walled carbon nanotubes was fabricated for determination of Cr(VI) in the presence of excess of Cr(III) without any pretreatment. The method is based on accumulation of the quercetin–Cr(III) complex generated in situ from Cr(VI) at the modified electrode surface in an open circuit followed by differential pulse voltammetry detection. The new method allowed selective determination of Cr(VI) in the presence of Cr(III). The influence of various parameters affecting the adsorptive stripping voltammetry performance was investigated. Under the optimum conditions, the calibration plot was found to be linear in the Cr(VI) concentration range from 1.0 to 200 μmol^? 1 with a limit of detection(S/N = 3) of 0.3 μmol L^– 1. The relative standard deviation (RSD%) of seven replicates of the current measurements for a 50 μmol^? 1 of Cr(VI) solution was 3.0%. The developed electrode displayed a very low or no sensitivity to alkali, alkali-earth and transition metal cations and was successfully applied for the determination of Cr(VI) in drinking water samples.     

Determination of Pb2+ ions by a modified carbon paste electrode based on multi-walled carbon nanotubes (MWCNTs) and nanosilica

A novel carbon paste ion selective electrode for determination of trace amount of lead was prepared. Multi-walled carbon nanotubes (MWCNTs) and nanosilica were used for improvement of a lead carbon paste sensor response. MWCNTs have a good conductivity which helps the transduction of the signal in carbon paste electrode. The electrode composition of 20 wt% paraffin oil, 57% graphite powder, 15% ionophore (thiram), 5% MWCNTs, and 3% nanosilica showed the stable potential response to Pb²⁺ ions with the Nernstian slope of 29.8 (±0.2) mV decade^?1 over a wide linear concentration range of 10^?7–10^?2 mol L^?1. The electrode has fast response time, and long term stability (more than 2 months). The proposed electrode was used to determine the concentration of lead ions in waste water and black tea samples.     

Electrochemical sensor for ranitidine determination based on carbon paste electrode modified with oxovanadium (IV) salen complex

The preparation and electrochemical characterization of a carbon paste electrode modified with the N,N-ethylene-bis(salicyllideneiminato)oxovanadium (IV) complex ([VO(salen)]) as well as its application for ranitidine determination are described. The electrochemical behavior of the modified electrode for the electroreduction of ranitidine was investigated using cyclic voltammetry, and analytical curves were obtained for ranitidine using linear sweep voltammetry (LSV) under optimized conditions. The best voltammetric response was obtained for an electrode composition of 20% (m/m) [VO(salen)] in the paste, 0.10 mol L^? 1 of KCl solution (pH 5.5 adjusted with HCl) as supporting electrolyte and scan rate of 25 mV s^? 1. A sensitive linear voltammetric response for ranitidine was obtained in the concentration range from 9.9 × 10^? 5 to 1.0 × 10^? 3 mol L^? 1, with a detection limit of 6.6 × 10^? 5 mol L^? 1 using linear sweep voltammetry. These results demonstrated the viability of this modified electrode as a sensor for determination, quality control and routine analysis of ranitidine in pharmaceutical formulations.     

Accumulation and trace measurement of paraquat at kaolin-modified carbon paste electrode

The carbon paste electrode modified by kaolin (KCPE) has been utilized for the determination of pesticides with high sensitivity based on their redox behavior. The experiment is performed on the use of cyclic and square wave voltammetry. Experimental conditions were optimized by varying the accumulation time, kaolin loading and measuring solution pH. Square wave voltammetric response showed a linear calibration curve in the range from 3.9 × 10^? 9 to 9 × 10^? 5 mol L^? 1 with a detection limit of 2 × 10^? 10 mol L^? 1 at kaolin-modified carbon paste electrode. As a result, it was found that there was feasibility in the use of kaolin to improve the carbon paste electrode properties.     

Characterization of carbon nanotubes decorated with NiFe2O4 magnetic nanoparticles as a novel electrochemical sensor: Application for highly selective determination of sotalol using voltammetry

A magnetic nano‐composite of multiwall carbon nanotube, decorated with NiFe₂O₄ nanoparticles, was synthesized with citrate sol–gel method. The multiwall carbon nanotubes decorated with NiFe₂O₄ nanoparticles (NiFe₂O₄–MWCNTs) were characterized with different methods such as Fourier transform infrared spectroscopy (FT‐IR), transmission electron microscopy (TEM), atomic force microscopy (AFM), vibrating sample magnetometer (VSM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The new nano-composite acts as a suitable electrocatalyst for the oxidation of sotalol at a potential of 500 mV at the surface of the modified electrode. Linear sweep voltammetry exhibited two wide linear dynamic ranges of 0.5–1000 μmol L^? 1 sotalol with a detection limit of 0.09 μmol L^? 1. The modified electrode was used as a novel electrochemical sensor for the determination of sotalol in real samples such as pharmaceutical, patient and safe human urine.     

Amperometric choline biosensors based on multi-wall carbon nanotubes and layer-by-layer assembly of multilayer films composed of Poly(diallyldimethylammonium chloride) and choline oxidase

A layer-by-layer deposition technique combined with Multi-wall carbon nanotubes (MWCNTs) was employed for fabricating choline sensors. The terminals and side-walls were linked with oxygen-containing groups when MWCNTs were treated with concentrated acid mixtures. A film of MWCNTs was initially prepared on the platinum electrode surface. Based on the electrostatic interaction between positively charged polyallylamine (PAA) and negatively charged MWCNTs and poly(vinyl sulfate) (PVS), a polymer film of (PVS/PAA)₃ was alternately adsorbed on the modified electrode continuously to be used as a permselective layer. Then poly(diallyldimethylammonium) (PDDA) and choline oxidase(ChOx) multilayer films were assembled layer-by-layer on the pretreated electrode, so an amplified biosensor toward choline was constructed. The choline sensor showed a linear response range of 5 × 10^? 7 to 1 × 10^? 4 M with a detection limit of 2 × 10^? 7 M estimated at a signal-to-noise ratio of 3, and a sensitivity of 12.53 μA/mM with a response time of 7.6 s in the presence of MWCNTs. Moreover, it exhibited excellent reproducibility, long-term stability as well as good suppression of interference. This protocol could be used to immobilize other enzymes for biosensor fabrication.     

Application of graphene–pyrenebutyric acid nanocomposite as probe oligonucleotide immobilization platform in a DNA biosensor

A stable and uniform organic–inorganic nanocomposite that consists of graphene (GR) and pyrenebutyric acid (PBA) was obtained by ultrasonication, which was characterized by scanning electron microscopy (SEM) and UV–vis absorption spectra. The dispersion was dropped onto a gold electrode surface to obtain GR–PBA modified electrode (GR–PBA/Au). Electrochemical behaviors of the modified electrode were characterized by cyclic voltammetry and electrochemical impedance spectroscopy using [Fe(CN)₆]^3 ?/4 ? as the electroactive probe. A novel DNA biosensor was constructed based on the covalent coupling of amino modified oligonucleotides with the carboxylic group on PBA. By using methylene blue (MB) as a redox-active hybridization indicator, the biosensor was applied to electrochemically detect the complementary sequence, and the results suggested that the peak currents of MB showed a good linear relationship with the logarithm values of target DNA concentrations in the range from 1.0 × 10^? 15 to 5.0 × 10^? 12 M with a detection limit of 3.8 × 10^? 16 M. The selectivity experiment also showed that the biosensor can well distinguish the target DNA from the non-complementary sequences.     

Flow-based method for epinephrine determination using a solid reactor based on molecularly imprinted poly(FePP–MAA–EGDMA)

A solid phase reactor based on molecularly imprinted poly(iron (III) protoporphyrin-methacrylic acid-ethylene glycol dimethacrylate) (MIP–MAA) has been synthesized by bulk method and applied as an selective material for the epinephrine determination in the presence of hydrogen peroxide. In order to prove the selective behaviour of MIP, two blank polymers named non-imprinted polymer (NIP1), non-imprinted polymer in the absence of hemin (NIP2) as well as a poly(iron (III) protoporphyrin-4-vynilpyridine-ethylene glycol dimethacrylate) (MIP–4VPy) were synthesized. The epinephrine-selective MIP–MAA reactor was used in a flow injection system, in which an epinephrine solution (120 μL) at pH 8.0 percolates in the presence of hydrogen peroxide (300 μmol L^? 1) through MIP–MAA. The oxidation of epinephrine by hydrogen peroxide is increased by using MIP–MAA, being the product formed monitored by amperometry at 0.0 V vs. Ag/AgCl. The MIP–MAA showed better selective behaviour than NIP1, NIP2 and MIP–4VPy, demonstrating the effectiveness of molecular imprinting effect. Highly improved response was observed for epinephrine in detriment of similar substances (phenol, ascorbic acid, methyl-l-DOPA, p-aminophenol, catechol, l-DOPA and guaiacol). The method provided a calibration curve ranging from 10 to 500 μmol L^? 1 and a limit of detection of 5.2 μmol L^? 1. Kinetic data indicated a value of maximum rate V_max (0.993 μA) and apparent Michaelis–Menten constant of K_m^app(725.6 μmol L^? 1). The feasibility of biomimetic solid reactor was attested by its successful application for epinephrine determination in pharmaceutical formulation.     

Direct electrodeposition of gold nanotube arrays of rough and porous wall by cyclic voltammetry and its applications of simultaneous determination of ascorbic acid and uric acid

Gold nanotube arrays of rough and porous wall has been synthesized by direct electrodeposition with cyclic voltammetry utilizing anodic aluminum oxide template (AAO) and polycarbonate membrane (PC) during short time (only 3 min and 2 min, respectively). The mechanism of the direct electrodeposition of gold nanotube arrays by cyclic voltammetry (CV) has been discussed. The morphological characterizations of the gold nanotube arrays have been investigated by scanning electron microscopy (SEM). A simultaneous determination of ascorbic acid (AA) and uric acid (UA) by differential pulse voltammetry (DPV) was constructed by attaching gold nanotube arrays (using AAO) onto the surface of a glassy carbon electrode (GCE). The electrochemical behavior of AA and UA at this modified electrode has been studied by CV and differential pulse voltammetry (DPV). The sensor offers an excellent response for AA and UA and the linear response range for AA and UA were 1.02 × 10^? 7–5.23 × 10^? 4 mol L^? 1 and 1.43 × 10^? 7–4.64 × 10^? 4 mol L^? 1, the detection limits were 1.12 × 10^? 8 mol L^? 1 and 2.24 × 10^? 8 mol L^? 1, respectively. This sensor shows good regeneration, stability and selectivity and has been used for the determination of AA and UA in real human urine and serum samples with satisfied results.     

Preparation and study of a naproxen ion-selective electrode

Naproxen membrane electrodes based on different plasticizers and quaternary ammonium salt tetraoctylammonium (S)-6-methoxy-α-methyl-2-naphthaleneacetate (NAP–TOA) were prepared. The electrode response to naproxen has the sensitivity of ? 59.2 mV decade^? 1 over the linear range of 10^? 4–10^? 1 mol L^? 1 and limit of detection 1.80 × 10^? 5 mol L^? 1. This electrode has a response time 15–20 s and can be used in the pH range 5.5–9.5. The selective coefficients were determined in relation to some organic and inorganic anions and excipients of pharmaceuticals. The notable property and attractive quality of the naproxen electrode are low cost, comfortable application and very long lifetime—about 20 months. The electrode was successfully applied for determination of naproxen in urine samples and pharmaceuticals by the calibration curve method and standard addition method. The obtained results are comparable and sometimes better than those obtained by pharmacopoeial method.     

Quantitative monitoring of terbium ion by a Tb3+ selective electrode based on a new Schiff's base

Solution study showed N,N′-bis(5-nitrosalicylidene)-2-aminobenzylamin (L) trends toward Tb³⁺ ion. Then, it was used as a suitable ionophore in construction of terbium ion selective electrode. The electrode with composition of 30% PVC, 65% solvent mediator (NB), 3% ionophore (L) and 2% anionic additive (NaTPB) shows the best potentiometric response characteristics. It displays a Nernstian behavior (20.1 mV decade^?1) over the concentration range 1.0 × 10^? 6 to 1.0 × 10^? 2 mol L^?1. The detection limit of the electrode is 6.3 × 10^? 7 mol L^?1. It has a very short response time (~ 10 s) and a useful working pH range of 2.6–9.4 for at least 2 months. The proposed membrane sensor shows excellent discriminating ability towards Tb³⁺ ions with regard to several alkali, alkaline earth, transition and heavy metal ions. To investigate the analytical applicability of the sensor, it was successfully applied to the determination of terbium in certified reference material.     

Determination of ultratrace levels of lead (II) in water samples using a modified carbon paste electrode based on a new podand

A new podand of 1,1′-thiobis(naphthalene-2,1-diyl)bis(2-aminobenzoate) (TNBA) was synthesized and used as a suitable carrier for construction of Pb²⁺ modified carbon paste electrode (CPE). The effects of various plasticizers; 2-nitrophenyloctylether (o-NPOE), dioctyl pththalate (DOP), dibutyl phthalate (DBP) and paraffin oil were studied. The best performance was obtained with a matrix composition of CPE with a DOP/graphite powder/TNBA weight percent ratio of 35/60.5/4.5. The sensor exhibits significantly enhanced selectivity toward Pb²⁺ ion over the concentration range 8.0 × 10^? 8 to 1.0 × 10^? 2 mol L^? 1 with a lower detection limit of 5.0 × 10^? 8 mol L^? 1 and a Nernstian slope of 29.0 ± 0.2 mV decade^? 1 of lead activity. It has a fast response time of 8 s with a working pH range from 3.5 to 7. The interaction between TNBA and Pb²⁺ was studied spectrophotometrically and it exhibits that the stoichiometry of the complex is 1:1 in acetonitrile solution. Finally, the electrode was satisfactorily used as an indicator electrode in complexometric titration of Pb²⁺ with EDTA and in direct determination of lead in various water samples.     

Selective determination of sucrose based on electropolymerized molecularly imprinted polymer modified multiwall carbon nanotubes/glassy carbon electrode

A novel and selective electrochemical sensor was successfully developed for the determination of sucrose by integrating electropolymerization of molecularly imprinted polymer with multiwall carbon nanotubes. The sensor was prepared by electropolymerizing of o-phenylenediamine in the presence of template, sucrose, on a multiwall carbon nanotube-modified glassy carbon electrode. The sensor preparation conditions including sucrose concentration, the number of CV cycles in the electropolymerization step, pH of incubation solution, extraction time of template from the imprinted film and the incubation time were optimized using response surface methodology (RSM). A mixture of acetonitrile/acetic acid was used to remove the template. Hexacyanoferrate(II) was used as a probe to characterize the sensor using electrochemical impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry. Capturing of sucrose by the modified electrode causes decreasing the response of the electrode to hexacyanoferrate(II). Calibration curve was obtained in the sucrose concentration range of 0.01–10.0 mmol L^? 1 with a limit of detection 3 μmol L^? 1. This sensor provides an efficient way for eliminating interferences from compounds with similar structures to sucrose. The sensor was successfully used to determine sucrose in sugar beet juices with satisfactory results.     

Nickel analysis in real samples by Ni2 + selective PVC membrane electrode based on a new Schiff base

A newly synthesized Schiff base 3-aminoacetophenonesemicarbazone (AAS) has been used for the preparation of Ni^2 + selective PVC membrane electrode. The proposed electrode exhibits a Nernstian response over the nickel concentration range of 1.0 × 10^? 7 to 1.0 × 10^? 2 mol L^? 1 with a slope of 30.0 ± 0.3 mV/decade of concentration. The limit of detection as determined from the intersection linear segment of the calibration plot is 5.1 × 10^? 8 mol L^? 1. The electrode shows good selectivity towards nickel with respect to several alkali, alkaline earth, transition and heavy metal ions. The response time of the electrode is very fast (≥ 10 s) and can be used for 17 weeks in the pH range of 2.0–9.8. The electrode can also be used in partially non-aqueous media having up to 20% (v/v) methanol, ethanol or acetone content with no significant change in the value of slope or working concentration range. To investigate the analytical applicability of the electrode, it was successfully applied as an indicator electrode in Ni^2 + ion potentiometric titration with EDTA, and in direct determination of nickel(II) in real samples.     

Hexadecylpyridinium surfactant modified zeolite A as an active component of a polymeric membrane sulfite selective electrode

Zeolite A was synthesized from waste porcelain and modified by hexadecylpyridinium surfactant to change the cation exchanger property of the raw zeolite to anion exchanger property in the obtained surfactant modified zeolite (SMZ). The SMZ was used as an active ingredient component of a membrane selective sulfite electrode. The electrode was fully characterized in terms of composition, response time, thermal stability and usable pH range. The sensor showed suitable response to sulfite in the concentration range of 8.0 × 10^? 7 to 1.0 × 10^? 1 mol L^? 1, with a detection limit of 5.0 × 10^? 7 mol L^? 1 and a slope of ? 29.5 ± 0.8 mV per decade of sulfite concentration.     

Ferrocene adsorbed into the porous octakis(hydridodimethylsiloxy)silsesquioxane after thermolysis in tetrahydrofuran media: An applied surface for ascorbic acid determination

Octakis(hydridodimethylsiloxi)silsesquioxane (Q₈M₈^H) was synthesized and Ferrocene was adsorbed in a polymeric net through electrostatic interactions, with anion forming after the cleavage of any siloxy groups (ESFc). The nanostructured materials (Q₈M₈^H and EsFc) were characterized by Fourier transform infrared spectra (FT-IR), nuclear magnetic resonance (NMR), X-ray diffraction (XRD), Thermogravimetric analyses and Voltammetric technique The cyclic voltammograms of the graphite paste electrode modified with ESFc showed one redox couple with E⁰′ = 0.320 V (1.0 mol L^?1 NaCl, v = 50 mV s^?1), with a diffusion-controlled process and the redox process shows electrocatalytic activity for the oxidation of ascorbic acid.