Simultaneous determination of phenylhydrazine and hydrazine by a nanostructured electrochemical sensor

In the present paper, the use of a nanostructured electrochemical sensor was described for simultaneous determination of phenylhydrazine (PhH) and hydrazine (HZ). This electrochemical sensor was prepared by a simple and rapid method by modification of carbon paste electrode with a derivative of hydroquinone and TiO₂ nanoparticles. The modified electrode showed an excellent character for electrocatalytic oxidation of PhH. Using differential pulse voltammetry, a highly selective and simultaneous determination of PhH and HZ has been explored at the modified electrode. Differential pulse voltammetry peak currents of PhH and HZ increased linearly with their concentration at the ranges of 2.0 × 10^? 6 to 1.0 × 10^? 3 M and 7.5 × 10^? 5–1.0 × 10^? 3 M, respectively and the detection limits for PhH and HZ were 7.5 × 10^? 7 M and 9.0 × 10^? 6 M, respectively.     

Electrochemical oxidation of adenosine-5′-triphosphate on a chitosan–graphene composite modified carbon ionic liquid electrode and its determination

In this paper a new electrochemical method was proposed for the determination of adenosine-5′-triphosphate (ATP) based on a chitosan (CTS) and graphene (GR) composite film modified carbon ionic liquid electrode (CTS–GR/CILE). CILE was fabricated by using ionic liquid 1-butyl-3-methylimidazolium dihydrogen phosphate ([BMIM]H₂PO₄) as the binder, which was further modified by GR and CTS composite. The modified electrode exhibited an excellent electrocatalytic activity toward the oxidation of ATP with the increase of the oxidation peak current and the decrease of the oxidation peak potential. The electrochemical parameters of ATP on CTS–GR/CILE were calculated with the electron transfer coefficient (α) as 0.329, the electron transfer number (n) as 2.15, the apparent heterogeneous electron transfer rate constant (ks) as 3.705 × 10^? 5 s^? 1 and the surface coverage (Γ_T) as 9.33 × 10^? 10 mol cm^? 2. Under the optimal conditions the oxidation peak current was proportional to ATP concentration in the range from 1.0 × 10^? 6 to 1.0 × 10^? 3 M with the detection limit of 0.311 μM (S/N = 3). The proposed electrode showed excellent reproducibility, stability, anti-interference ability and further successfully applied to the ATP injection sample detection.     

Preparation and characterization of copper nanoparticles/zinc oxide composite modified electrode and its application to glucose sensing

We report a new method for selective detection of d(+)-glucose using a copper nanoparticles (Cu-NPs) attached zinc oxide (ZnO) film coated electrode. The ZnO and Cu-NPs were electrochemically deposited onto indium tin oxide (ITO) coated glass electrode and glassy carbon electrode (GCE) by layer-by-layer. In result, Cu-NPs/ZnO composite film topography was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. SEM and AFM confirmed the presence of nanometer sized Cu-NPs/ZnO composite particles on the electrode surface. In addition, X-ray diffraction pattern revealed that Cu-NPs and ZnO films were attached onto the electrode surface. Indeed, the Cu-NPs/ZnO composite modified electrode showed excellent electrocatalytic activity for glucose oxidation in alkaline (0.1 M NaOH) solution. Further, we utilized the Cu-NPs/ZnO composite modified electrode as an electrochemical sensor for detection of glucose. This glucose sensor showed a linear relationship in the range from 1 × 10^? 6 M to 1.53 × 10^? 3 M and the detection limit (S/N = 3) was found to be 2 × 10^? 7 M. The Cu-NPs/ZnO composite as a non-enzymatic glucose sensor presents a number of attractive features such as high sensitivity, stability, reproducibility, selectivity and fast response. The applicability of the proposed method to the determination of glucose in human urine samples was demonstrated with satisfactory results.     

Multi-walled carbon nanotube modified carbon paste electrode as an electrochemical sensor for the determination of epinephrine in the presence of ascorbic acid and uric acid

A biocompatible electrochemical sensor for selective detection of epinephrine (EP) in the presence of 1000-fold excess of ascorbic acid (AA) and uric acid (UA) was fabricated by modifying the carbon paste electrode (CPE) with multi-walled carbon nanotubes (MWCNTs) using a casting method. The electro-catalytic activity of the modified electrode for the oxidation of EP was investigated. The current sensitivity of EP was enhanced to about five times upon modification. A very minimum amount of modifier was used for modification. The voltammetric response of EP was well resolved from the responses of AA and UA. The electrochemical impedance spectroscopic (EIS) studies reveal the least charge transfer resistance for the modified electrode. The AA peak that is completely resolved from that of EP at higher concentrations of AA and the inability of the sensor to give an electrochemical response for AA below a concentration of 3.0 × 10^? 4 M makes it a unique electrochemical sensor for the detection of EP which is 100% free from the interference of AA. Two linear dynamic ranges of 1.0 × 10^? 4–1.0 × 10^? 5 and 1.0 × 10^? 5–5.0 × 10^? 7 M with a detection limit of 2.9 × 10^? 8 M were observed for EP at modified electrode. The practical utility of this modified electrode was demonstrated by detecting EP in spiked human blood serum and EP injection. The modified electrode is highly reproducible and stable with anti fouling effects.     

Study on electrochemical behaviors and the reaction mechanisms of dopamine and epinephrine at the pre-anodized inlaying ultrathin carbon paste electrode with nichrome as a substrate

In this paper, nichrome was adopted as a substrate, to fabricate the pre-anodized inlaying ultrathin carbon paste electrode (PAIUCPE). The electrochemical behaviors of dopamine (DA) and epinephrine (EP) at the electrode were investigated by cyclic voltammetry (CV). The reaction mechanisms of DA and EP have also been put forward. It was found that the electrode showed an excellent electrochemical behavior for electrode reaction of DA and EP. The cathodic potential difference of DA and EP was about 370 mV and the simultaneous determination of DA and EP was achieved based on it. The reduction peak current was proportional to the DA and EP concentrations in the range of 8.0 × 10^? 7–3.0 × 10^? 4 M and 2.0 × 10^? 6–1.5 × 10^? 4 M with the detection limits of 1.70 × 10^? 7 M and 3.27 × 10^? 7 M, respectively. Because the oxidation of ascorbic acid (AA) is an irreversible reaction at the PAIUCPE, the interferences of AA for determining DA and EP were eliminated. The method has been successfully applied to the determination of DA and EP in hydrochloride injection with satisfactory results.     

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%.     

Potentiometric detection of silver (I) ion based on carbon paste electrode modified with diazo-thiophenol-functionalized nanoporous silica gel

For the first time, triazene compound functionalized silica gel was incorporated into carbon paste electrode for the potentiometric detection of silver (I) ion. A novel diazo-thiophenol-functionalized silica gel (DTPSG) was synthesized, and the presence of DTPSG acted as not only a paste binder, but also a reactive material. The electrode with optimum composition, exhibited an excellent Nernstian response to Ag⁺ ion ranging from 1.0 × 10^? 6 to 1.0 × 10^? 1 M with a detection limit of 9.5 × 10^? 7 M and a slope of 60.4 ± 0.2 mV dec^? 1 over a wide pH range (4.0–9.0) with a fast response time (50 s) at 25 °C. The electrode also showed a long-time stability, high selectivity and reproducibility. The response mechanism of the proposed electrode was investigated by using AC impedance. Moreover, the electrode was successfully applied for the determination of silver ions in radiology films, and for potentiometric titration of the mixture solution of Cl^? and Br^? ions.     

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.     

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.     

Iodide selective membrane electrodes based on a Molybdenum–Salen as a neutral carrier

A new polymeric membrane electrode (PME) and a coated platinum disk electrode (CPtE) based on Schiff base complex of Mo(VI) as a suitable carrier for I^? ion were described. The influence of membrane composition, pH and possible interfering anions were investigated on the response properties of the electrodes. The electrodes exhibited a Nernstian slope of 63.0 ± 0.5 (CPtE) and 60.3 ± 0.4 (PME) mV decade^? 1 in I^? ion over a wide concentration range from 7.9 × 10^? 7 to 1.0 × 10^? 1 M for CPtE and 9.1 × 10^? 6 to 1.0 × 10^? 1 M I^? for PME. The potentiometric response of the electrodes was independent of the pH of the test solution in the pH range 2.0–8.5 with a fast response time (< 10 s). The process of transfer of iodide across the membrane interface was investigated by use of the AC impedance technique. The proposed sensors were successfully applied to direct determination of iodide in samples containing interfering anions, waste water and as indicator electrodes in precipitation titrations.     

A new silver(I)-selective electrode based on derivatized MWCNTs@SiO2 nanocomposites as a neutral carrier

For the first time a novel carbon paste electrode (CPE) for the detection of trace silver(I) was designed by using derivatized silica-coated multi-walled carbon nanotubes (MWCNTs@SiO₂) nanocomposites as a neutral carrier. This proposed electrode, with optimum composition, exhibits a wide dynamic range of 8.6 × 10^? 8 to 1.0 × 10^? 1 M toward silver(I) with a detection limit of 8.0 × 10^? 8 M and a Nernstian slope of 60.8 ± 0.2 mV dec^? 1. Meanwhile, it also shows a good selectivity and a relatively fast response time (~ 20 s), a long lifetime (1 month) and a wide pH range (4.0–9.0). Finally, the developed CPEs were successfully applied in the potentiometric titration of potassium bromide and determination of Cl^? ions in different water samples.     

Highly selective determination of perchlorate by a novel potentiometric sensor based on a synthesized complex of copper

In this paper, a highly selective poly (vinyl chloride) (PVC) membrane electrode based on (1, 9-dibenzyl-1, 3, 7, 9, 11, 15-hexaaza cyclohexa decane) copper(II) perchlorate; [Cu((benzyl)₂[16]aneN₆)](ClO₄)₂; as a synthesized ionophore, for perchlorate-selective electrode is reported. The influence of membrane composition, pH and possible interfering anions were investigated on the response properties of the electrode. The sensor responds to perchlorate ion in linear range from 1.0 × 10^? 6 to 1.0 × 10^? 1 M with a slope ? 59.4 ± 0.3 mV per decade. The limit of detection of the electrode was 4.0 × 10^? 7 M ClO₄^–. Selectivity coefficients indicate a good discriminating ability towards ClO₄^– ion in comparison to other anions. The proposed sensor has a fast response time of about 7 s and can be used for at least 2 months without any considerable divergence in potential. Due to importance of analysis of perchlorate in water samples, this selective electrode was applied as potentiometric sensor in determination of perchlorate ion in real samples.     

Ho3+ carbon paste sensor based on multi-walled carbon nanotubes: Applied for determination of holmium content in biological and environmental samples

For the first time a novel multi-walled carbon nanotubes (MWCNTs) modified Ho³⁺ carbon paste sensor is introduced. The electrode with a composition containing 20% paraffin oil, 60% graphite powder, 15% N-(1-thia-2-ylmethylene)-1,3-benzothiazole-2-amine (TBA) as an ionophore, and 5% MWCNTs, exhibits a stable potential response to Ho³⁺ ions with a nice Nernstian behavior (19.3 ± 0.3 mV decade^? 1) in a wide dynamic linear concentration range of Ho³⁺ ions (1 × 10^? 8–1.0 × 10^? 2 M). In the absence of MWCNTs, sensitivity of the Ho³⁺ sensor was relatively poor. The proposed modified Ho³⁺ sensor shows very low detection limit (7.0 × 10^? 9 M) and a fast response time (13 s). It has a long life time (more than 2 months) and its response is independent of pH in the range of 3.8–7.5. In term of selectivity, Ho³⁺ sensor has a good selectivity over all lanthanide members and common alkali and alkaline earth metal ions. The Ho³⁺ sensor was applied for the determination of Ho³⁺ ion concentration in water, holmium alloys and synthetic human serum.     

Determination of benzalkonium chloride preservative in pharmaceutical formulation of eye and ear drops using new potentiometric sensors

A novel approach for determination of low concentrations of the preservative, benzalkonium chloride (BCCl), in pharmaceutical formulation constitutes is presented. New chemically modified carbon paste electrodes (CMCPEs) are developed. The first is based on an ion-association of BCCl with phosphomolybdic acid (PMA) as the ion-exchanger (BC–PM) dissolved in the mixed plasticizers dibutyl phthalate (DBP) and dioctyl sebacate (DOS) encoded sensor A. In the other electrode, encoded sensor B, the plasticizers DBP and dioctyl phthalate (DOP) are more suitable solvent mediators for the paste. These electrodes exhibit a Nernstian slope of 58.2 ± 0.6 and 62.3 ± 0.7 mV/decade in concentration range 1.3 × 10^? 7–1.7 × 10^? 4 M and 2.5 × 10^? 7–1.7 × 10^? 4 M with the limit of detection of 1.0 × 10^? 7 M and 1.6 × 10^? 7 for sensors A and B, respectively. The sensors have short and stable response time 5–8 s, good reproducibility and can be used in pH range of 5.7–8.6. The present electrodes show good discrimination of BCCl from several inorganic, organic ions and some common drug excipients. These characteristics of the electrodes make them useful in successful determination of BCCl in its pharmaceutical preparations (eye and ear drops) and aqueous solutions. The results obtained were satisfactory with excellent percentage recovery comparable and sometimes better than those obtained by other routine methods for the assay.     

Determination of zinc(II) ions in waste water samples by a novel zinc sensor based on a new synthesized Schiff's base

A highly selective and sensitive zinc ion-selective membrane electrode based on N,N′-phenylenebis (salicylideaminato) (L) as a new carrier is reported. The membrane is composed of poly (vinyl chloride) (PVC), o-nitrophenyl octyl ether (NPOE) as plasticizer, potassium tetrakis(p-chlorophenyl) borate (KTpClPB) as lipophilic ionic additive, and L as sensing material. The proposed electrode displays a Nernstian response to Zn²⁺ ions over a wide concentration range of 5.0 × 10^? 7–1.0 × 10^? 1 M with the slope of 29.4 ± 0.2 mV per decade and a detection limit of 2.6 × 10^? 7 M. The sensor has a relatively fast response time of < 10 s and it can be used in the pH range of 3.0–7.0 for at least 2 months without any significant divergency in potential. The selectivity coefficients for mono-, di-, and trivalent cations indicate the good selectivity of sensor for Zn²⁺ ions over a large number of interfering cations. As a result the proposed electrode was applied to Zn²⁺ ions determination in mixture solutions and wastewater samples.     

Optical sensor based on 1,3-di(2-methoxyphenyl)triazene for monitoring trace amounts of mercury(II) in water samples

A new optical sensor for highly sensitive and selective determination of mercury(II) ion in aqueous solutions is developed. The mercury sensing membrane was prepared by incorporating 1,3-di(2-methoxyphenyl)triazene (MPT) as chromoionophore in the plasticized PVC membrane containing tris(2-ethylhexyl)phosphate (TEHP) as plasticizer. The proposed sensor displays a wide linear range of 9.0 × 10^?10–2.5 × 10^?7 M with a low detection limit of 2.0 × 10^?10 M in aqueous solutions at pH 4.0. This sensor has a relatively fast response time of less than 5 min. In addition to high stability and reproducibility, it shows a unique selectivity towards Hg²⁺ ion with respect to common coexisting cations. The sensor can readily be regenerated by exposure to a solution of sodium iodide (0.01 M). The proposed optode was applied to the determination of Hg²⁺ in water samples.     

Electrocatalytical oxidation and sensitive determination of acetaminophen on glassy carbon electrode modified with graphene–chitosan composite

The electrochemical behaviors of acetaminophen (ACOP) on a graphene–chitosan (GR–CS) nanocomposite modified glassy carbon electrode (GCE) were investigated by cyclic voltammetry (CV), chronocoulometry (CC) and differential pulse voltammetry (DPV). Electrochemical characterization showed that the GR–CS nanocomposite had excellent electrocatalytic activity and surface area effect. As compared with bare GCE, the redox signal of ACOP on GR–CS/GCE was greatly enhanced. The values of electron transfer rate constant (k_s), diffusion coefficient (D) and the surface adsorption amount (Γ^?) of ACOP on GR–CS/GCE were determined to be 0.25 s^? 1, 3.61 × 10^? 5 cm² s^? 1 and 1.09 × 10^? 9 mol cm^? 2, respectively. Additionally, a 2e^?/2H⁺ electrochemical reaction mechanism of ACOP was deduced based on the acidity experiment. Under the optimized conditions, the ACOP could be quantified in the range from 1.0 × 10^? 6 to 1.0 × 10^? 4 M with a low detection limit of 3.0 × 10^? 7 M based on 3S/N. The interference and recovery experiments further showed that the proposed method is acceptable for the determination of ACOP in real pharmaceutical preparations.     

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.     

Electrocatalytic determination of dopamine in the presence of uric acid using an indenedione derivative and multiwall carbon nanotubes spiked in carbon paste electrode

In the present study, a modified carbon paste electrode (CPE) containing multi-wall carbon nanotubes and an indenedione derivative(IMWCNT?CPE) was constructed and was successfully used for dopamine(DA) electrocatalytic oxidation and simultaneous determination of DA and uric acid (UA). Cyclic voltammograms of the IMWCNT?CPE show a pair of well-defined and reversible redox. The obtained results indicate that the peak potential of DA oxidation at IMWCNT?CPE shifted by about 65 and 185 mV toward the negative values compared with that at a MWCNT and indenedione modified CPE, respectively. The electron transfer coefficient, α, and the heterogeneous electron transfer rate constant, k′, for the oxidation of DA at IMWCNT?CPE were calculated 0.4 ± 0.01 and (1.13 ± 0.03) × 10^? 3 cm s^? 1, respectively. Furthermore, differential pulse voltammetry (DPV) exhibits two linear dynamic ranges of 1.9–79.4 μM, and 79.4–714.3 μM and a detection limit of 0.52 μM for DA determination. Then IMWCNT?CPE was applied to the simultaneous determination of DA and UA with DPV. Finally, the activity of the modified electrode was also investigated for determination of DA and UA in real samples, such as injection solution of DA and urine, with satisfactory results.