Electrocatalytic Reduction and Determination of Iodate and Periodate at Silicomolybdate‐Incorporated‐Glutaraldehyde‐ Cross‐Linked Poly‐L‐lysine Film Electrodes

The present work describes reduction of iodate (IO₃^?), and periodate (IO₄^?) at silicomolybdate‐doped‐glutaraldehyde‐cross‐linked poly‐L ‐lysine (PLL‐GA‐SiMo) film coated glassy carbon electrode in 0.1 M H₂SO₄. In our previous study, we were able to prepare the PLL‐GA‐SiMo film modified electrode by means of electrostatically trapping SiMo₁₂O₄₀^4? mediator in the cationic film of PLL‐GA, and the voltammetric investigation in pure supporting indicated that the charge transport through the film was fast. Here, the electrocatalytic activity of PLL‐GA‐SiMo film electrode towards iodate and periodate was tested and subsequently used for analytical determination of these analytes by amperometry. The two electron reduced species of SiMo₁₂O₄₀^4? anion was responsible for the electrocatalytic reduction of IO₃^? at PLL‐GA‐SiMo film electrode while two and six electron reduced species were showed electrocatalytic activity towards IO₄^? reduction. Under optimized experimental conditions of amperometry, the linear concentration range and sensitivity are 2.5×10^?6 to 1.1×10^?2 M and 18.47 μA mM^?1 for iodate, and 5×10^?6 to 1.43×10^?4 M and 1014.7 μA mM^?1 for periodate, respectively.     

Iodate Sensing Electrodes Based on Phosphotungstate‐ Doped‐Glutaraldehyde‐Cross‐Linked Poly‐L‐lysine Coatings

Glassy carbon electrode modified with phosphotungstate‐doped‐glutaraldehyde‐cross‐linked poly‐L ‐lysine (PLL‐GA‐PW) film was employed for iodate determination. The PLL‐GA‐PW film electrode shows excellent electrocatalytic activity towards iodate reduction with significant reduction of overpotential. Under optimized experimental conditions, a linear range from 5×10^?8 to 2.27×10^?2 M with a sensitivity of 61.75 μA mM^?1 was obtained. Possible interfering species, in iodate determination, were evaluated and the applicability of proposed sensor for iodate estimation in table salt was also demonstrated. The PLL‐GA‐PW film electrode shows fast response, wider linear range, and good selectivity and stability.     

A Highly Selective Amperometric Hydrogen Peroxide Sensor Based on Silicomolybdate‐Doped‐Glutaraldehyde‐Cross‐Linked Poly‐L‐Lysine Film Modified Glassy Carbon Electrode

Silicomolybdate‐doped‐glutaraldehyde‐cross‐linked poly‐L ‐lysine (PLL‐GA‐SiMo) film modified glassy carbon electrode was prepared by means of electrostatically trapping the silicomolybdate anion in the cationic film. The PLL‐GA‐SiMo film was stable and the charge transport through the film was fast. The modified electrode shows excellent electrocatalytic activity towards hydrogen peroxide reduction with significant reduction of overpotential, however, not responded to potential interferrents such as dopamine, ascorbic acid and uric acid. This unique feature of PLL‐GA‐SiMo modified electrode allowed for the development of a highly selective method for the determination of H₂O₂ in the presence of interferents.     

Preparation,Characterization, and Bioelectrocatalytic Properties of Hemoglobin Incorporated Multiwalled Carbon Nanotubes‐Poly‐L‐lysine Composite Film Modified Electrodes Towards Bromate

The present work describes preparation of hemoglobin‐incorporated multiwalled carbon nanotubes‐poly‐L ‐lysine (MWCNT‐PLL)/Hb) composite modified electrode film modified glassy carbon electrode (GCE) and its electrocatalytic behavior towards reduction of bromate ( ) in 0.1 M acetate buffer (pH 5.6). The modified electrode has been successfully fabricated by immobilizing hemoglobin on MWCNT dispersed in poly‐L ‐lysine. The surface morphologies of MWCNT, PLL and Hb were characterized using atomic force microscopy (AFM). The voltammetric features suggested that the charge transport through the film was fast and the electrochemical behavior resembles that of surface‐confined redox species. Cyclic voltammetry was used to investigate the electrocatalytic behavior of the modified electrode towards bromate and was compared with that of the CNT‐modified as well as bare electrode. The analytical determination of bromate has been carried out in stirred solution at an optimized potential with a sensitivity of 7.56 μA mM^?1 and the calibration curve was linear between 1.5×0^?5 to 6.0×0^?3 M.     

Selective Detection of Ascorbic Acid Using Octacyanomolybdate‐Doped‐Glutaraldehyde‐Cross‐Linked Poly‐L‐Lysine Film Modified Glassy Carbon Electrode

The present work describes oxidation of ascorbic acid (AA) at octacyanomolybdate‐doped‐glutaraldehyde‐cross‐linked poly‐L ‐lysine (PLL‐GA‐Mo(CN) film modified glassy carbon electrode in 0.1 M H₂SO₄. The modified electrode has been successfully prepared by means of electrostatically trapping Mo(CN) mediator in the cationic film of glutaraldehyde‐cross‐linked poly‐L ‐lysine. The dependence of peak current of modified electrode in pure supporting indicates that the charge transfer in the film was a mixed process at low scan rates (5 to 200 mV s^?1), and kinetically restrained at higher scan rates (200 to 1000 mV s^?1). Cyclic voltammetry and rotating disk electrode (RDE) techniques are used to investigate the electrocatalytic oxidation of ascorbic acid and compared with its oxidation at bare and undoped PLL‐GA film coated electrodes. The rate constant of catalytic reaction k obtained from RDE analysis was found to be 9.5×10⁵ cm³ mol^?1 s^?1. The analytical determination of ascorbic acid has been carried out using RDE technique over the physiological interest of ascorbic acid concentrations with a sensitivity of 75 μA mM^?1. Amperometric estimation of AA in stirred solution shows a sensitivity of 15 μA mM^?1 over the linear concentration range between 50 and 1200 μM. Interestingly, PLL‐GA‐Mo(CN) modified electrode facilitated the oxidation of ascorbic acid but not responded to other electroactive biomolecules such as dopamine, uric acid, NADH, glucose. This unique feature of PLL‐GA‐Mo(CN) modified electrode allowed for the development of a highly selective method for the determination of ascorbic acid in the presence of interferents.     

Fe(CN)$\rm{ {_{6}^{4-}}}$‐Doped‐Glutaraldehyde‐Cross‐Linked Poly‐L‐Lysine Film Electrode. Part 1: Electrochemical Characterization and Its Electrocatalytic Activity Towards Oxidation of Ascorbic Acid

The present work describes preparation, characterization, and electrocatalytic behavior of a hexacyanoferrate‐doped‐glutaraldehyde‐cross‐linked poly‐L ‐lysine (PLL‐GA‐Fe(CN) film modified glassy carbon electrode. The modified electrode has been successfully prepared by electrostatically binding negatively charged Fe(CN) mediator into cross‐linked poly‐L ‐lysine cationic film. The dependence of the peak current of the modified electrode in pure supporting electrolyte (pH 6.8 phosphate buffer solution; PBS) shows that the charge transport in the film is fast and relatively unimpeded at lower scan rates. Cyclic voltammetry and rotating disk electrode (RDE) techniques are used to investigate the electrocatalytic activity of modified electrode towards oxidation of ascorbic acid. The rate constant (k), of catalytic reaction between electrogenerated Fe(CN) ions and ascorbic acid, obtained from RDE analysis was found to be 5.53×10⁵ cm³ mol^?1 s^?1. Finally, the PLL‐GA‐Fe(CN) film electrodes are successfully used for the individual estimation of ascorbic acid in the concentration range of physiological interest.     

Voltammetric Sensor for Sodium Nitroprusside Determination in Biological Fluids Using Films of Poly‐L‐Lysine

Sodium nitroprusside (NP), a commercial vasodilator, can be pre‐concentrated on vitreous carbon electrode modified by films of 97.5%: 2.5% poly‐L ‐lysine (PLL): glutaraldehyde (GA). This coating gives acceptable anion exchange properties whilst giving the required improvement of adhesion to the glassy carbon electrode surface. Linear response range and detection limit on nitroprusside in B‐R buffer pH 4.0, were 1×10^?6 to 2×10^?5 mol L^?1 and 1×10^?7 mol L^?1, respectively. The repeatability of the proposed sensor, evaluated in term of relative standard deviation, was measured as 4.1% for 10 experiments. The voltammetric sensor was directly applied to determination of nitroprusside in human plasma and urine samples and the average recovery for these samples was around 95–97% without any pre treatment.     

Electrocatalytic Oxidation and Determination of Dopamine in the Presence of Ascorbic Acid and Uric Acid at a Poly (4‐(2‐Pyridylazo)‐Resorcinol) Modified Glassy Carbon Electrode

A sensitive and selective electrochemical method for the determination of dopamine (DA) was developed using a 4‐(2‐Pyridylazo)‐Resorcinol (PAR) polymer film modified glassy carbon electrode (GCE). The PAR polymer film modified electrode shows excellent electrocatalytic activity toward the oxidation of DA in a phosphate buffer solution (PBS) (pH 4.0). The linear range of 5.0×10^?6–3.0×10^?5 M and detection limit of 2.0×10^?7 M were observed. Simultaneous detection of AA, DA and UA has also been demonstrated on the modified electrode. This work provides a simple and easy approach to selective detection of DA in the presence of AA and UA.     

Sol—Gel Derived Carbon Ceramic Electrode Bulk—Modified with Tris（1,10—phenanthroline—5,6—dione） iron （Ⅱ）Hexafluorophosphate and Its Use as an Amperometric Iodate Sensor

A surface‐renewable tris(1, 10‐phenanthroline‐5, 6‐dione) iron (D) hexafluorophosphate (FePD) modified carbon ceramic electrode was constructed by dispersing FePD and graphite powder in methyltrimethoxysilane (MTMOS) based gels. The FePD‐modified electrode presented pH‐dependent voltammetric behavior, and its peak currents were diffusion‐controlled in 0.1 mol/L Na₂SO₄ + H₂SO₄ solution (pH = 0.4). In the presence of iodate, dear electrocatalytic reduction waves were observed and thus the chemically modified electrode was used as an amperometric sensor for iodate in common salt. The linear range, sensitivity, detection limit and response time of the iodate sensor were 5 × 10^?6–1 × 10^?2 mol/L, 7.448 μA·L/ mmol, 1.2 × 10^?6 mol/L and 5 s, respectively. A distinct advantage of this sensor is its good reproducibility of surface‐renewal by simple mechanical polishing.     

Electrochemical Behavior of 8‐Azaguanine at DNA Langmuir–Blodgett Modified Glassy Carbon Electrode and Its Analytical Application

A highly sensitive electrochemical biosensor for the detection of trace amounts of 8‐azaguanine has been designed. Double stranded (ds)DNA molecules are immobilized onto a glassy carbon electrode surface with Langmuir–Blodgett technique. The adsorptive voltammetric behaviors of 8‐azaguanine at DNA‐modified electrode were explored by means of cyclic voltammetry and square wave voltammetry. Compared with bare glassy carbon electrode (GCE), the Langmuir–Blodgett film modified electrode can greatly improve the measuring sensitivity of 8‐azaguanine. Under the optimum experimental conditions, the Langmuir–Blodgett film modified electrode in pH 3.0 Britton–Robinson buffer solutions shows a linear voltammetric response in the range of 5.0×10^?8 to 1.0×10^?5 mol L^?1 with detection limit 9.0×10^?9 mol L^?1. The method proposed was applied successfully for the determination of 8‐azaguanine in diluted human urine with wonderful satisfactory.     

Electrocatalytic Oxidation and Determination of Cysteamine by Poly‐N,N‐dimethylaniline/Ferrocyanide Film Modified Carbon Paste Electrode

Functionalized poly‐N,N‐dimethylaniline film was prepared by adsorption of ferrocyanide onto the polymer forming at the surface of carbon paste electrode (CPE) in aqueous solution by using potentiostatic method. The electrocatalytic ability of poly‐N,N‐dimethylaniline/ferrocyanide film modified carbon paste electrode (PDMA/FMCPE) was demonstrated by oxidation of cysteamine. Cyclic voltammetry and chronoamperometry techniques were used to investigate this ability. Results showed that pH 7.00 is the most suitable for this purpose. It is found that the catalytic reaction rate constant, (k_h), is equal to 2.142×10³ M^?1 s^?1 by the data of chronoamperometry. The catalytic reduction peak current was linearly dependent on the cysteamine concentration and the linearity range obtained was 8.00×10^?5 M–1.14×10^?2 M. Detection limit was determined 7.97×10^?5 M (2σ). This method has been successfully employed for quantification of cysteamine in real sample.     

Electrocatalytic Reduction of Nitrite Ion on a Toluidine Blue Sol‐Gel Thin Film Electrode Derived from 3‐Aminopropyl Trimethoxy Silane

An organically modified sol‐gel electrode using 3‐aminopropyltrimethoxy silane for covalent immobilization of a redox mediator namely toluidine blue has been reported. Cyclic voltammetric characterization of the modified electrode in the potential range of 0.2 V to ?0.6 V exhibited stable voltammetric behavior in aqueous supporting electrolyte with a formal potential of ?0.265 V vs. SCE, corresponding to immobilized toluidine blue. The electrocatalytic activity of the modified electrode when tested towards nitrite ion exhibited a favorable response with the electrocatalytic reduction of nitrite occurring at a reduced potential of ?0.34 V. A good linear working range from 2.94×10^?6 M to 2.11×10^?3 M with a detection limit of 1.76×10^?6 M and quantification limit of 5.87×10^?6 M was obtained for nitrite determination. The stable and quick response (4 s) of the modified electrode towards nitrite under hydrodynamic conditions shows the feasibility of using the present sensor in flow systems. Significant improvements in the operational stability by overcoming the leachability problem and repeatability with a relative standard deviation of 1.8% of the TB thin film sensor have been obtained by the strategy of immobilization of the mediator in the sol‐gel matrix.     

Fabrication of Nanocomposite Containing Naphthoquinone and Nanogold Supported on Poly(2,6‐pyridinedicarboxylic acid) Film for Voltammetric Determination of N‐Acetyl‐L‐Cysteine

A modified electrode was fabricated by grafting of poly (2,6‐pyridinedicarboxylic acid) film (PDC) by electropolymerization of 2,6‐pyridinedicarboxylic acid on the glassy carbon electrode (GCE). Then, gold nanoparticles (NG) and 1,2‐naphthoquinone‐4‐sulfonic acid sodium (Nq) were immobilized on the PDC/GCE to prepare Nq/NG/PDC/GCE by immersing electrode into NG and Nq solution, respectively. The Nq species on NG/PDC/GCE could catalyze electrooxidation of N‐acetyl‐L ‐cysteine (NAC) with lowering the over potential by about 600 mV. This method used for detection of NAC in dynamic range from 4.0×10^?6 M to 1.30×10^?4 M with a detection of limit (2σ) 8.0×10^?7 M.     

Electrocatalytic Oxidation of Acyclovir on Poly(p‐Aminobenzene Sulfonic Acid) Film Modified Glassy Carbon Electrode

Acyclovir is an antiviral effective drug active compound. A glassy carbon electrode (GCE) was modified with an electropolymerized film of p‐aminobenzene sulfonic acid (p‐ABSA) in phosphate buffer solution (PBS). The polymer film‐modified electrode was used to electrochemically detect acyclovir. Polymer film showed excellent electrocatalytic activity for the oxidation of acyclovir. The anodic peak potential value of the acyclovir at the poly(p‐ABSA) modified glassy carbon electrode was 950 mV obtained by DPV. A linear calibration curve for DPV analysis was constructed in the acyclovir concentration range 2×10^?7–9×10^?6 mol L^?1. Limit of detection (LOD) and limit of quantification (LOQ) were obtained as 5.57×10^?8 and 1.85×10^?7 mol L^?1 respectively. The proposed method exhibits good recovery and reproducibility.     

Anodic Stripping Voltammetric Determination of Mercury(II) in Water Using a 4‐Tert‐Butyl‐1‐(Ethoxycarbonylmethoxy)Thiacalix[4]Arene Modified Glassy Carbon Electrode

A glassy carbon electrode coated the film of 4‐tert‐butyl‐1‐(ethoxycarbonylmethoxy)thiacalix[4]arene is designed for the determination of trace amounts of Hg²⁺. Compared with bare glassy carbon electrode, the modified electrode can improve the measuring sensitivity of Hg²⁺. Under the optimum experimental condition, the modified electrode in 0.1 mol L^?1 H₂SO₄ + 0.01 mol L^?1 KCl solution shows a linear voltammetric response in the range of 8.0 × 10^?9 ～ 3.0 × 10^?6 mol L^?1 with detection limit 5.0 × 10^?9 mol L^?1 for Hg²⁺. The high sensitivity, selectivity, and stability of modified electrode also prove its practical application for a simple, rapid and economical determination of Hg²⁺ in water samples.     

Electrochemical Behavior of Herbal Antitumor Drug Aloe‐Emodin at Carbon‐Coated Nickel Magnetic Nanoparticles Modified Glassy Carbon Electrode

The electrochemical behavior of aloe‐emodin (AE), an important herbal antitumor drug, was investigated at a carbon‐coated nickel magnetic nanoparticles modified glassy carbon electrode (CNN/GCE). A couple of well‐defined redox peaks was obtained. Some electrochemical parameters of AE at a CNN/GCE, such as the charge number, exchange current density, standard heterogeneous rate constant, were measured. The square wave voltammetry (SWV) response of AE was linear with the concentration over two concentration intervals viz. 6.24×10^?9?1.13×10^?6 M and 1.13×10^?6?1.23×10^?5 M, with a detection limit of 2.08 nM. A fast, simple and sensitive detection and analysis of AE was developed.     

Highly Selective and Sensitive Copper(II) Membrane Sensors Based on 6‐Methyl‐4‐(1‐phenylmethylidene)amino‐3‐thioxo‐1,2,4‐triazin‐5‐one as a New Neutral Ionophore

A new Cu(II) ion‐selective PVC membrane sensor based on 6‐methyl‐4‐(1‐phenylmethylidene)amino‐3‐thioxo‐1,2,4‐triazin‐5‐one (MATTO) as an excellent sensing material was developed. The electrode exhibits a Nernstian slope of 29.2±0.4 mV per decade over a very wide concentration range between 1.0×10^?1 and 1.0×10^?6 M, with a detection limit of 4.8×10^?7 M (30.5 ng/mL). The sensor possesses the advantages of short conditioning time, fast response time (<10 s), and especially, very good selectivity towards transition and heavy metal, and some mono, di and trivalent cations. The proposed electrode was successfully applied to the determination of copper in wastewater of copper electroplating samples and as an indicator electrode in potentiometric titration of Cu(II) ions with EDTA.     

Sensitive amperometric pyridoxine sensor based on self‐assembled Prussian blue nanoparticle‐modified poly(o‐phenylenediamine)/glassy carbon electrode

Prussian blue nanoparticles (PBNPs) were prepared by a self‐assembly process on a glassy carbon electrode (GCE) modified with poly(o‐phenylenediamine) (PoPD) film. The stepwise fabrication process of PBNP‐modified PoPD/GCE was characterized using scanning electron microscopy and electrochemical impedance spectroscopy. The prepared PBNPs showed an average size of 70 nm and a homogeneous distribution on the surface of the modified electrode. The PBNPs/PoPD/GCE showed electrocatalytic activity towards the oxidation of pyridoxine (PN) and was used as an amperometric sensor. The modified electrode exhibited a linear response for PN oxidation over the concentration range 3–38.5 μM with a detection limit of ca 6.10 × 10^?7 M (S/N = 3) and sensitivity of 2.79936 × 10³ mA M^?1 cm^?2 using an amperometric method. The mechanism and kinetics of the catalytic oxidation reaction of PN were investigated using cyclic voltammetry and chronoamperometry. The values of α, k_cat and D were estimated as 0.36, 1.089 × 10² M^?1 s^?1 and 8.9 × 10^?5 cm² s^?1, respectively. This sensor also exhibited good anti‐interference and selectivity. Copyright © 2016 John Wiley & Sons, Ltd.     

Electrochemical Properties of the Oxo‐Manganese‐Phenanthroline Complex Immobilized on Ion‐Exchange Polymeric Film and Its Application as Biomimetic Sensor for Sulfite Ions

A biomimetic sensor containing the oxo‐bridged dinuclear manganese‐phenanthroline complex incorporated into a cation‐exchange polymeric film deposited onto glassy carbon electrode for detection of sulfite was studied. Cyclic voltammetry at the modified electrode in universal buffer showed a two electron oxidation/reduction of the couple Mn^IV(μ‐O)₂Mn^IV/Mn^III(μ‐O)₂Mn^III. The sensor exhibited electrocatalytic property toward sulfite oxidation with a decrease of the overpotential of 450 mV compared with the glassy carbon electrode. A plot of the anodic current versus the sulfite concentration for potential fixed (+0.15 V vs. SCE) at the sensor was linear in the 4.99×10^?7 to 2.49×10^?6 mol L^?1 concentration range and the concentration limit was 1.33×10^?7 mol L^?1. The mediated mechanism was derived by Michaelis? Menten kinetics. The calculated kinetics values were Michaelis? Menten rate constant= =1.33 µmol L^?1, catalytic rate constant=6.06×10^?3 s^?1 and heterogeneous electro‐chemical rate constant=3.61×10^?5 cm s^?1.     

Selective Detection of Dopamine Using Glassy Carbon Electrode Modified by a Combined Electropolymerized Permselective Film of Polytyramine and Polypyrrole‐1‐propionic Acid

A sensitive and selective electrochemical method for the determination of dopamine using a combined electropolymerized permselective film of polytyramine and polypyrrole‐1‐propionic acid on a glassy carbon (GC) electrode was developed. The formation of a “layer‐by‐layer” film has allowed for selective detection of dopamine in the presence of 3,4‐dihydroxyphenylalanine (L‐DOPA), DOPAC, ascorbic acid, uric acid, epinephrine and norepinephrine. The modified electrodes exhibited a detection limit of 100 nM with linearity ranging from 5×10^?6 to 5×10^?5 M. No cleaning step was required during the course of repeated measurement.