An electropolymerized Nile Blue sensing film-based nitrite sensor and application in food analysis

This paper reports a poly-Nile Blue (PNB) sensing film based electrochemical sensor and the application in food analysis as a possible alternative for electrochemical detection of nitrite. The PNB-modified electrode in the sensor was prepared by in situ electropolymerization of Nile Blue at a prepolarized glassy carbon (GC) electrode and then characterized by cyclic voltammetry (CV) and pulse voltammetry in phosphate buffer (pH 7.1). Several key operational parameters affecting the electrochemical response of PNB sensing film were examined and optimized, such as polarization time, PNB film thickness and electrolyte pH values. As the electroactive PNB sensing film provides plenty of active sites for anodic oxidation of nitrite, the nitrite sensor exhibited high performance including high sensitivity, low detection limit, simple operation and good stability at the optimized conditions. The nitrite sensor revealed good linear behavior in the concentration range from 5.0 × 10⁻⁷ mol L⁻¹ to 1.0 × 10⁻⁴ mol L⁻¹ for the quantitative analysis of nitrite anion with a limit of detection of 1.0 × 10⁻⁷ mol L⁻¹. Finally, the application in food analysis using sausage as testing samples was investigated and the results were consistent with those obtained by standard spectrophotometric method.     

Simultaneous determination of hydroquinone and catechol at PASA/MWNTs composite film modified glassy carbon electrode

A poly-amidosulfonic acid and multi-wall carbon nanotubes composite (PASA/MWNTs) modified electrode has been constructed by electropolymerization on glassy carbon electrode (GCE). The electrochemical behaviors of hydroquinone (HQ) and catechol (CC) were investigated using cyclic and differential pulse voltammetries (DPVs) at the prepared electrode. Separation of the reductive peak potentials for HQ and CC was about 120 mV in pH 6.0 phosphate buffer solution (PBS), which makes it suitable for simultaneous determination of these compounds. In the presence of 1.0 × 10⁻⁴ mol L⁻¹ isomer, the reductive peak currents of DPV are proportional to the concentration of HQ in the range of 6.0 × 10⁻⁶ to 4.0 × 10⁻⁴ mol L⁻¹, and to that of CC in the range of 6.0 × 10⁻⁶ to 7.0 × 10⁻⁴ mol L⁻¹. When simultaneously changing the concentration of both HQ and CC, the linear concentration range of HQ (or CC) is 6.0 × 10⁻⁶ to 1.0 × 10⁻⁴ mol L⁻¹ (or 6.0 × 10⁻⁶ to 1.8 × 10⁻⁴ mol L⁻¹), and the corresponding detection limits are 1.0 × 10⁻⁶ mol L⁻¹. The proposed method has been applied to simultaneous determination of HQ and catechol in water sample, and the results are satisfactory.     

Bifunctional sensor of nitric oxide and oxygen based on hematite nanotubes embedded in chitosan matrix

A novel hybrid bifunctional sensing platform for simultaneous determination of NO and O₂ has been developed, whereby hematite nanotubes are immobilized into the chitosan matrix onto a gold electrode (labeled as HeNTs-Chi/Au). The HeNTs distributed in porous-structured chitosan matrix not only offer abundant active sites for bifunctional sensing of NO and O₂, but also facilitate oxidation of NO and reduction of O₂ dramatically. Straight calibration curves are achieved in analyte concentration ranges of 5.0 × 10⁻⁸ to 1.25 × 10⁻⁶ mol L⁻¹ for NO and 2.5 × 10⁻⁷ to 6.0 × 10⁻⁶ mol L⁻¹ for O₂. Also, the detection limits are low of 8.0 × 10⁻⁹ mol L⁻¹ for NO and 5.0 × 10⁻⁸ mol L⁻¹ for O₂. Such an efficient bifunctional sensor for NO and O₂ offers great potential in quantitation of NO levels in biological and medical systems, since NO level is highly regulated by various reactive oxygen species.     

A novel poly(taurine) modified glassy carbon electrode for the simultaneous determination of epinephrine and dopamine

A novel taurine modified glassy carbon electrode was prepared by electropolymerization method. The electrochemical behaviors of epinephrine (EP) and dopamine (DA) at the modified electrode were studied by cyclic voltammetry. The modified electrode exhibited enhanced sensitivity and excellent electrochemical discrimination to DA and EP. The cathodic peaks of the two species were well-separated with a potential difference of about 390 mV, so the poly(taurine) modified electrode was used for simultaneous voltammetric measurement of EP and DA by differential pulse voltammetry. Under the optimum conditions, the cathodic peak currents were linear to concentrations of EP and DA in the range of 2.0 × 10⁻⁶ to 6.0 × 10⁻⁴ mol L⁻¹ and 1.0 × 10⁻⁶ to 8.0 × 10⁻⁴ mol L⁻¹, respectively. The detection limits for EP and DA were 3.0 × 10⁻⁷ and 1.0 × 10⁻⁷ mol L⁻¹, respectively. Because the oxidation of ascorbic acid (AA) is an irreversible reaction at modified electrode, the interference of AA for determining EP and DA was eliminated. The modified electrode has been satisfactorily used for the simultaneous determination of EP and DA in pharmaceutical injections.     

Enhanced sensitivity for Cu(II) by a salicylidine-functionalized polysiloxane carbon paste electrode

A new approach for decreasing the detection limit for a copper(II) ion-selective electrode (ISE) is presented. The ISE is designed using salicylidine-functionalized polysiloxane in carbon paste. This work describes the attempts to develop the electrode and measurements of its characteristics. The new type of renewable three-dimensional chemically modified electrode could be used in a pH range of 2.3–5.4, and its detection limit is 2.7 × 10⁻⁸ mol L⁻¹ (1.2 μg L⁻¹). This sensor exhibits a good Nernstian slope of 29.4 ± 0.5 mV/decade in a wide linear concentration range of 2.3 × 10⁻⁷ to 1.0 × 10⁻³ mol L⁻¹ of Cu(II). It has a short response time (8 s) and noticeably high selectivity over other Cu(II) selective electrodes. Finally, it was satisfactorily used as an indicator electrode in complexometric titration with EDTA and determination of copper(II) in miscellaneous samples such as urine and various water samples.     

C60 trianion-mediated electrocatalysis and amperometric sensing of hydrogen peroxide

Heterogeneous electrocatalytic reduction of hydrogen peroxide (H₂O₂) by C₆₀ is reported for the first time. C₆₀ is embedded in tetraoctylammonium bromide (TOAB) film and is characterized by scanning electron microscopy and cyclic voltammetry. Electrocatalytic studies show that the trianion of C₆₀ mediates the electrocatalytic reduction of H₂O₂ in aqueous solution containing 0.1 M KCl. Application of such film modified electrode as an amperometric sensor for H₂O₂ determination is also examined. The sensor shows a fast response within 1 s and a linear response is obtained (R = 0.9986) in the concentration range from 3.33 × 10⁻⁵ to 2.05 × 10⁻³ mol L⁻¹ for H₂O₂, with the detection limit of 2 × 10⁻⁵ mol L⁻¹ and the sensitivity of 1.65 μA mM⁻¹. A good repeatability and stability is shown for the sensor during the experiment.     

Electrochemical behavior and voltammetric determination of tryptophan based on 4-aminobenzoic acid polymer film modified glassy carbon electrode

Herein, a novel electrochemical method was developed for the determination of tryptophan based on the poly(4-aminobenzoic acid) film modified glassy carbon electrode (GCE). The electrochemical behaviors of tryptophan at the modified electrode were investigated. It was found that the oxidation peak current of tryptophan at the modified GCE was greatly improved compared with that at the bare GCE. The effects of supporting electrolyte, pH value, scan rate, accumulation potential and time were examined. The oxidation peak current of tryptophan was proportional to its concentration over the range from 1.0 × 10⁻⁶ to 1.0 × 10⁻⁴ mol L⁻¹. The limit of detection was evaluated to be 2.0 × 10⁻⁷ mol L⁻¹. The proposed method was sensitive and simple. It was successfully employed to determine tryptophan in pharmaceutical samples.     

Luminescent CuS nanotubes as silver ion probes

CuS nanotubes (NTs) made up of nanoparticles were successfully prepared in large quantities in an O/W microemulsion system under low temperature. Based on the characteristics of synchronous fluorescence spectroscopy (SFS), a new method with high sensitivity and selectivity was developed for rapid determination of silver ion with functional copper sulphide (CuS) nanotubes as a fluorescence probe. Under optimal conditions, functional copper sulphide displayed a calibration response for silver ion over a wide concentration range from 1.0 × 10⁻¹⁰ to 1.0 × 10⁻⁸ mol L⁻¹. The limit of detection was 0.5 × 10⁻¹⁰ mol L⁻¹ and the relative standard deviation of eight replicate measurements for the highest concentration (1 × 10⁻⁸ mol L⁻¹) was 3%. Compared with several fluorescence methods, the proposed method had a wider linear range and improved the sensitivity. Furthermore, the concentration dependence of the synchronous fluorescence intensity is effectively described by a Langmuir-type binding isotherm.     

Voltammetric determination of hypoxanthine based on the enhancement effect of mesoporous TiO2-modified electrode

A mesoporous TiO₂ was synthesized according to the reported method, and then used to modify the carbon paste electrode (CPE). The electrochemical behavior of hypoxanthine was investigated with great detail. Compared with the unmodified CPE, the mesoporous TiO₂-modified CPE greatly enhances the oxidation signal of hypoxanthine. Due to huge surface area, well-defined and special mesopores, the mesoporous TiO₂-modified CPE shows considerable enhancement effect toward hypoxanthine. Based on this, a sensitive, rapid and convenient electrochemical method was developed for the determination of hypoxanthine. The linear range is over the range from 2.0 × 10⁻⁷ to 5.0 × 10⁻⁵ mol L⁻¹, and the limit of detection is estimated to be 5.0 × 10⁻⁸ mol L⁻¹. The relative standard deviation (RSD) for 10 mesoporous TiO₂-modified CPEs is 5.7%. Finally, this sensing method was successfully used to determine hypoxanthine in human blood serum samples.     

Anion recognition using newly synthesized hydrogen bonding disubstituted phenylhydrazone-based receptors: poly(vinyl chloride)-based sensor for acetate

A potentiometric acetate-selective sensor, based on the use of butane-2,3-dione,bis[(2,4-dinitrophenyl)hydrazone] (BDH) as a neutral carrier in poly(vinyl chloride) (PVC) matrix, is reported. Effect of various plasticizers and cation excluder, cetryaltrimethylammonium bromide (CTAB) was studied. The best performance was obtained with a membrane composition of PVC:BDH:CTAB ratio (w/w; mg) of 160:8:8. The sensor exhibits significantly enhanced selectivity toward acetate ions over a wide concentration range 5.0 × 10⁻⁶ to 1.0 × 10⁻¹ M with a lower detection limit of 1.2 × 10⁻⁶ M within pH range 6.5–7.5 with a response time of <15 s and a Nernstian slope of 60.3 ± 0.3 mV decade⁻¹ of activity. Influences of the membrane composition, and possible interfering anions were investigated on the response properties of the electrode. Fast and stable response, good reproducibility and long-term stability are demonstrated. The sensor has a response time of 15 s and can be used for at least 65 days without any considerable divergence in their potential response. Selectivity coefficients determined with the separate solution method (SSM) and fixed interference method (FIM) indicate that high selectivity for acetate ion. The proposed electrode shows fairly good discrimination of acetate from several inorganic and organic anions. It was successfully applied to direct determination of acetate within food preservatives. Total concentration of acetic acid in vinegar samples were determined by direct potentiometry and the values agreed with those mentioned by the manufacturers.     

Flow injection determination of ketotifen fumarate using PVC membrane selective electrodes

In this study a PVC membrane electrode for determination of ketotifen fumarate is reported, where ketotifen tetraphenylborate (Keto-TPB) was used as ion exchanger. The electrode has linear range of 5.6 × 10^− 6–1.0 × 10^− 2 and 1.0 × 10^− 5–1.0 × 10^− 2 mol/L, with detection limits 2.37 × 10^− 6and 4.60 × 10^− 6 mol/L in batch and flow injection analysis (FIA), respectively. The electrodes show a Nernstian slope value (58.40 and 61.50 mV/decade in batch and FIA, respectively), and the response time is very short (≤ 10 s). The potential is nearly stable over the pH range 2.0–8.0. Selectivity coefficient values towards different inorganic cations, sugars and amino acids reflect high selectivity of the prepared electrodes. These are used for determination of Ketotifen using potentiometric titration and standard addition methods in pure samples and its pharmaceutical preparations (Zaditen tablets and syrup). The average recovery values are 99.5 and 99.2% with RSD 1.4 and 1.2% for potentiometric titrations and standard addition methods, respectively. The electrode response at different temperatures was also studied.     

Surface-enhanced oxidation and detection of Sunset Yellow and Tartrazine using multi-walled carbon nanotubes film-modified electrode

The insoluble multi-walled carbon nanotubes (MWNT) was successfully dispersed into water in the presence of hydrophobic surfactant. After that, MWNT film-coated glassy carbon electrode (GCE) was achieved via dip-coating and evaporating water. Owing to huge surface area, high sorption capacity and subtle electronic properties, MWNT film exhibits highly efficient accumulation efficiency as well as considerable surface enhancement effects to Sunset Yellow and Tartrazine. As a result, the oxidation peak currents of Sunset Yellow and Tartrazine remarkably increase at the MWNT film-modified GCE. Based on this, a novel electrochemical method was developed for the simultaneous determination of Sunset Yellow and Tartrazine. The limits of detection are 10.0 ng mL⁻¹ (2.2 × 10⁻⁸ mol L⁻¹) and 0.1 μg mL⁻¹ (1.88 × 10⁻⁷ mol L⁻¹) for Sunset Yellow and Tartrazine. Finally, the proposed method was successfully used to detect Sunset Yellow and Tartrazine in soft drinks.     

Non-extraction flow injection determination of cationic surfactants using eriochrome black-T

A new, rapid, sensitive, non-extraction batch, and flow injection spectrophotometric method for the determination of cationic surfactants (CSs) such as cetyltrimethyl ammonium bromide (CTAB), tetra-n-butyl ammonium chloride (TBAC) and cetylpyridinium chloride (CPC) is proposed. The method is based on the interaction of cationic surfactants with eriochrome black-T to form an ion-association complex. This complex has strong absorbance at 708 nm. The effects of chemical parameters and FIA variables on the determination of cationic surfactants were studied in detail, especially for CTAB. Under optimum conditions, the two linear calibration ranges of the method are 3.0 × 10⁻⁶ to 5.0 × 10⁻³ mol L⁻¹ CTAB, CPB and DTAB for the batch spectrophotometric method and 2.0 × 10⁻⁶ to 2.0 × 10⁻⁴ mol L⁻¹ CTAB, CPB and TBC for the flow injection spectrophotometric method. The sample throughput was 35 ± 5 samples h⁻¹ at room temperature. The relative standard deviations for 10 replicates of analysis of (2.0, 0.6 and 0.2) × 10⁻⁴ mol L⁻¹ CTAB were 1.2, 1.3, and 0.8%, respectively. In addition, the influence of potential interfering substances on the determination of cationic surfactants was studied. The proposed method is simple and rapid, using no toxic organic solvents. It was applied to the determination of trace CS in industrial wastewater with satisfactory results.     

A new potentiometric ibuprofenate ion sensor immobilized in a graphite matrix for determination of ibuprofen in tablets

The characteristics, performance, and application of an electrode, namely, Pt|Hg|Hg₂(IBP)₂|Graphite, where IBP stands for ibuprofenate ion, are described. This electrode responds to IBP with sensitivity of (58.6 ± 0.9) mV decade^− 1 over the range 5.0 × 10^− 5–1.0 × 10^− 1 mol L^− 1 at pH 6.0–9.0 and a detection limit of 3.8 × 10^− 5 mol L^− 1. The electrode is easily constructed at a relatively low cost with fast response time (within 15–30 s) and can be used for a period of 5 months without any considerable divergence in potentials. The proposed sensor displayed good selectivity for ibuprofen in the presence of several substances, especially concerning carboxylate and inorganic anions. It was used for the direct assay of ibuprofen in commercial tablets by means of the standard additions method. The analytical results obtained by using this electrode are in good agreement with those given by the United States Pharmacopeia procedure.     

Effect of various additives on the performance of a newly developed PVC based potentiometric sensor for anionic surfactants

A new poly(vinyl chloride) PVC membrane electrode to determine monomer concentrations of dodecylbenzenesulphonate ions (DBS⁻) based on a neutral ion-pair carrier complex of dodecyltrimethylammonium–dodecylbenzenesulphonate (DTA⁺–DBS⁻), is reported here. The electrode exhibits a slope of 51.25 mV per decade for DBS⁻ ions. The DBS⁻ ion selective electrode (ISE) can determine monomer units down to concentrations as low as 3.32 × 10⁻⁴ M. The effect of three kinds of additives, i.e. alcohols, glycols and triblock polymers on the performance of the surfactant selective electrode is studied systematically. The effect of foreign anions along with primary ions on the performance of ion-selective electrode is investigated in terms of potentiometric selectivity coefficients, which were determined using the fixed interference method (FIM) at 1.0 × 10⁻² M concentration of foreign anions. The sensor responds well to the surfactant ions in the presence of additives at lower concentration. The Gibbs free energy of micelle formation (ΔG_m) of sodium dodecylbenzenesulphonate (SDBS) in the presence of various additives is calculated and found to vary differently with respect to the increase in the amount of additives. The sensor worked in the acidic pH range with a short response time of 30 s. The lifetime of the sensor is more than three months. The sensor was further used to determine the amount of DBS⁻ in local detergents. This method of determining anionic surfactants was found to be quite accurate when compared with classical methods.     

Potentiometric Membrane Sensor for Determination of Saccharin

A potentiometric poly(vinyl chloride) membrane sensor for determination of saccharin is described. It is based on the use of Aliquat 336S-saccharinateion-pair as an electroactive material in plasticized PVC membranes with o-nitrophenyloctylether or dioctylphthalate. The sensor is conditioned for at least two days in 0.1 mol L⁻¹ sodium saccharinate before use. It exhibits fast, stable and Nernstian response for saccharinate ions over the concentration range of 1.0 × 10⁻¹–5.0 × 10⁻⁵ mol L⁻¹ and pH range of 4.5–11. The sensor is used for determination of saccharin in some dosage forms. Results with an average recovery of 101% and a mean standard deviation of 0.2% are obtained which is compared favourably with data obtained using the British pharmacopoeia method. The sensor shows reasonable selectivity towards saccharin in presence of many anions and natural sweeteners.     

Voltammetric determination of N-acetylcysteine using a carbon paste electrode modified with copper(II) hexacyanoferrate(III)

The preparation and electrochemical characterization of a carbon paste electrode modified with copper(II) hexacyanoferrate(III) (CuHCF) as well as its behavior as electrocatalyst toward the oxidation of N-acetylcysteine were investigated. The electrochemical behavior of the modified electrode and the electrooxidation of N-acetylcysteine were explored using sweep linear voltammetry. The best voltammetric response was observed for a paste composition of 20% (w/w) copper(II) hexacyanoferrate(III) complex, acetate buffer solution at pH of 6.0 as the electrolyte and scan rate of 10 mV s^− 1. A linear voltammetric response for N-acetylcysteine was obtained in the concentration range from 1.2 × 10^− 4 to 8.3 × 10^− 4 mol L^− 1, with a detection limit of 6.3 × 10^− 5 mol L^− 1. The proposed electrode is useful for the quality control and routine analysis of N-acetylcysteine in pharmaceutical formulations.     

Sensitive detection of potassium ion using Prussian blue nanotube sensor

A model K⁺ sensor using Prussian blue nanotubes is fabricated by electrochemical deposition of Prussian blue (PB) within the nanochannels of a porous metal-coated membrane with partially covered pore openings. The PB nanotube sensor exhibits excellent stability giving reproducible peak potentials up to 500 measurement cycles, a very low detection limit of 2.0 × 10⁻⁸ M and extremely wide logarithmic linear ranges between 5.0 × 10⁻⁸–7.0 × 10⁻⁴ M and 7.0 × 10⁻⁴–1.0 M. Negligible interferences by Na⁺, Mg²⁺ and Ca²⁺ are observed and a rapid analysis time of 30 s is readily achieved. The ease of electrodeposition, high stability of PB nanotubes and outstanding analytical performance which surpasses conventional PB voltammetric and potentiometric sensors demonstrates potential sensing applications including ion sensors and biosensors using PB and other metal hexacyanoferrate nanotubes.     

Influence of the surfactant bromide of cetyltrimetyl ammonium in the determination of chlorogenic acid in instant coffee and mate tea samples

In this study, two quantitative differential-pulse polarography (DPP) and square-wave voltammetry (SWV) methods were developed to determine total chlorogenic acid (CGA). Studies on this compound involve its reduction at a hanging mercury drop electrode in micellar media—a simple, fast, reliable, and sensitive method. The use of surfactant cationic cetyltrimethylammonium bromide (CTAB) was pivotal to the development of these methods, allowing for satisfactory changes in CGA reduction. The supporting electrolyte which provided the best-defined CGA determination was 0.04-mol L⁻¹ phosphate buffer at pH 6.0 in the presence of CTAB. Based on this use and under optimized conditions, the two new DPP and SWV methods for CGA analysis had detection limits of 2.36 × 10⁻⁷ and 1.34 × 10⁻⁹ mol L⁻¹, respectively, for a pure standard. Analysis of the standard in the presence of treated instant coffee and mate tea samples allowed for good average recovery rates, ranging from 97.06% to 105.90%.     

A new hydrogen peroxide biosensor based on gold nanoelectrode ensembles/multiwalled carbon nanotubes/chitosan film-modified electrode

Gold nanoelectrode ensembles were produced by electrodeposition using multiwalled carbon nanotubes (MWNTs) as template. A new third generation amperometric biosensor for hydrogen peroxide was developed based on adsorption of horseradish peroxidase (HRP) at the glassy carbon (GC) electrode modified with Au nanoelectrode ensembles/multiwalled carbon nanotubes/chitosan film. The resulting HRP biosensor offered an excellent detection for hydrogen peroxide at −0.11 V with a linear response range of 2.08 × 10⁻⁷ to 7.6 × 10⁻³ M with a correlation coefficient of 0.998, and response time <5 s. The detection limit was 1.02 × 10⁻⁷ M at 3σ. The biosensor displays rapid response, expanded linear response range, and excellent repeatability. The simple and fast fabrication of the sensor makes it superior to other techniques.