Electrochemical Detection of Persulfate at the Modified Glassy Carbon Electrode with Nanocomposite Containing Nano‐Ruthenium Oxide/Thionine and Nano‐Ruthenium Oxide/Celestine Blue

The present study describes the fabrication of a sensitive amperometric sensor for the determination of persulfate. The immobilization surface was prepared by modifying a glassy carbon (GC) electrode with a nanocomposite containing ruthenium oxide (RuOx) nanoparticles and thionine (TH) or celestin blue (CB). The modified electrodes indicated excellent electrocatalytic activity toward persulfate reduction at a potential of +0.1 V. The proposed sensor showed detection limits of 1.46 µM for the GC/RuOx/TH modified electrode and 2.64 µM for the GC/RuOx/CB modified electrode. The sensitivities were obtained as 3 nA µM^?1 at a concentration range of 10 µM to 11 mM for the GC/RuOx/TH modified electrode and 1 nA µM^?1 at a concentration range of 10 µM to 6 mM for the GC/RuOx/CB modified electrodes.     

A Highly Sensitive and Selective Multiwall Carbon Nanotubes/Nafion/Au Microarrays Electrode for Dopamine Determination

This work presents the fabrication of Nafion (Nf) or Nafion/Multiwalled Carbon Nanotubes (Nf/MWCNTs) modified gold microarray (Au‐µA) and macro‐(Au‐M)electrode biosensors. The surface morphologies of the above electrodes were examined using SEM. The catalytic properties of the above electrodes towards dopamine were tested using square wave voltammetric technique. The Nf/MWCNT/Au‐µA electrode exhibited a wide range (0.1–1000 nM) of linearity among the other electrodes. The LOD of Nf/MWCNT/Au‐µA electrode was 50 pM for dopamine in the presence of 5000 µM ascorbic acid. Therefore, the Nf/MWCNT/Au‐µA biosensor was applied for the determination of dopamine in human serum.     

Selective and Simultaneous Determination of Dihydroxybenzene Isomers Based on Green Synthesized Gold Nanoparticles Decorated Reduced Graphene Oxide

In the present study, we report the simultaneous electrochemical determination of hydroquinone (HQ), catechol (CC) and resorcinol (RC) at gold nanoparticles (Au‐NPs) decorated reduced graphene oxide (RGO) modified electrode. An enhanced and well defined peak current response with a better peak separation of HQ, CC and RC is observed at RGO/Au‐NPs composite than that of RGO and Au‐NPs modified electrodes. The fabricated modified electrode shows a wide linear response in the concentration range of 3–90 µM, 3–300 µM and 15–150 µM for HQ, CC and RC, respectively. The detection limit of HQ, CC and RC is found as 0.15 µM, 0.12 µM and 0.78 µM, respectively.     

Electrochemical Sensor for Ultrasensitive Determination of Doxorubicin and Methotrexate Based on Cyclodextrin‐Graphene Hybrid Nanosheets

In this work, an electrochemical sensor based on a cyclodextrin‐graphene hybrid nanosheets modified glassy carbon electrode (CD‐GNs/GCE) was proposed for the ultrasensitive determination of doxorubicin and methotrexate. The peak currents of doxorubicin and methotrexate on the CD‐GNs/GCE increased 26.5 and 23.7 fold, respectively, compared to the results obtained on the bare GCE. Under optimized conditions, the linear response ranges for doxorubicin and methotrexate are 10 nM–0.2 µM and 0.1 µM–1.0 µM, with detection limits of 0.1 nM and 20 nM, respectively. The sensor showed the advantages of simple preparation, low cost, high sensitivity, good stability and reproducibility. These properties make the prepared sensor a promising tool for the determination of trace amounts of doxorubicin and methotrexate in biological, clinical and pharmaceutical fields.     

Highly Selective and Sensitive Triiodide PVC‐Based Membrane Electrode Based on a New Charge Transfer Complex of 2‐(((2‐(((E)‐1‐(2‐Hydroxyphenyl) Methylidine) Amino) Phenyl) Imino) Methyl) Phenol for Nano‐Level Monitoring of Triiodide

Abstract

A highly selective and sensitive triiodide sensor based on a 2‐(((2‐(((E)‐1‐(2‐hydroxy phenyl) methylidine) amino) phenyl) imino) methyl) phenol with iodine (CTC) as membrane carrier was developed. The electrode revealed a Nernstian behavior over a very wide triiodide‐ion concentration range (5.0×10^?8–1.0×10^?2 M), and relatively low detection limit (3.0×10^?8 M). The potentiometric response is independent of the pH of solution in the pH range of 3.0–10.0. The electrodes manifest advantages of low resistance, very fast response (<12 s), and most importantly, good selectivities relative to a wide variety of inorganic and organic anions, including iodide, bromide, chloride, fluoride, sulfite, sulfate, cyanide, thiocyanate, and acetate. In fact, the selectivity behavior of the proposed triiodide ion‐selective electrode shows great improvements compared to the previously reported electrodes for the triiodide ion. The proposed membrane sensor can be used for at least 6 months without any significant divergences in the potential. The electrode was successfully applied as an indicator electrode in the titration of triiodide with thiosulfate ion.     

A Simple Route of Modifying Copper Electrodes for the Determination of Methanol and Ethylene Glycol

Copper foil electrodes were modified in a stirred NaOH solution at room temperature. Measurements with scanning electron microscopy, energy‐dispersive X‐ray spectroscopy and X‐ray photoelectron spectroscopy confirmed the simultaneous structural transformation and chemical modification of the foil surface. The as‐prepared electrodes produced isolated anodic peaks in the cyclic voltammogram of methanol or ethylene glycol in alkaline solution. The highest anodic peak current was achieved at the electrode that was modified for 5 hours. Amperometric study illustrates that the modified electrode can detect lower than 100 µM methanol with a sensitivity of 15.8 µA/mM or 10 µM ethylene glycol with a sensitivity of 193 µA/mM. Importantly, the method is robust and the prepared electrodes show great reproducibility.     

Silver‐Palladium Nanoalloys Modified Carbon Ionic Liquid Electrode with Enhanced Electrocatalytic Activity Towards Formaldehyde Oxidation

Electrocatalysis of the oxidation of formaldehyde on silver‐palladium‐modified carbon ionic liquid electrode (AgPd/CILE) was investigated in 0.1 M NaOH. The electrochemical performance of the AgPd/CILE was compared with those of Pd/CILE and Ag/CILE. Ag plays an important role in the catalytic performance of AgPd nanocatalyst and yields an excellent antifouling effect. Amperometric measurements showed that AgPd/CILE is a promising sensor for the detection of formaldehyde in the range of 10.0 µM–70.0 mM with a sensitivity of 240.6 µA mM^?1 cm^?2 and a detection limit of 2 µM. The method is free from interference of methanol, ethanol and formic acid.     

A Sensitive and Selective Nitrite Detection in Water Using Graphene/Platinum Nanocomposite

A glassy carbon electrode modified with reduced graphene oxide and platinum nanocomposite film was developed simply by electrochemical method for the sensitive and selective detection of nitrite in water. The electrochemical reduction of graphene oxide (GO) efficiently eliminates oxygen‐containing functional groups. Pt nanoparticles were electrochemically and homogeneously deposited on the ErGO surface. Field emission scanning electron microscopy (FE‐SEM), Raman spectroscopy, attenuated total reflectance‐fourier transform infrared spectroscopy (ATR‐FTIR), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV) were used to examine the surface morphology and electrocatalytic properties of the Pt‐ErGO nanocomposite film‐modified electrode surface. The fabricated nitrite sensor showed good electrochemical performance with two linear ranges; one from 5 to 100 µM (R²=0.9995) and the other from 100 to 1000 µM (R²=0.9972) and a detection limit of 0.22 µM. The proposed sensor was successfully applied for the detection of nitrite in tap water samples which proves performance of the Pt‐ErGO nanocomposite films.     

Amperometric Biosensor for Choline Based on Gold Screen‐Printed Electrode Modified with Electrochemically‐Deposited Silica Biocomposite

A mediator‐free choline biosensor was developed using the electrochemically assisted sol‐gel deposition on gold screen‐printed electrodes. The addition of 12 mM of cationic surfactant CTAB in silica sol allowed enhancing the stability of the sensor. The modified electrode demonstrated catalytic activity and stable amperometric response to choline for over 3 weeks of exploitation with the sensitivity of 6 µA mM^?1 and LOD of 6 µM. The interference of ascorbic acid was reduced by pretreating the analyzed solution with MnO₂ powder. The application of the sensor with the purpose of identifying choline in the baby milk demonstrated satisfactory metrological characteristics.     

Development of a Carbon Paste Electrode Modified with Reduced Graphene Oxide and an Imidazole Derivative for Simultaneous Determination of Biological Species of N‐acetyl‐L‐cysteine,Uric Acid and Dopamine

In this work, the modified carbon paste electrode (CPE) with an imidazole derivative 2‐(2,3 dihydroxy phenyl) 4‐methyl benzimidazole (DHPMB) and reduced graphene oxide (RGO) was used as an electrochemical sensor for electrocatalytic oxidation of N‐acetyl‐L‐cysteine (NAC). The electrocatalytic oxidation of N‐acetyl‐L‐cysteine on the modified electrode surface was then investigated, indicating a reduction in oxidative over voltage and an intensive increase in the current of analyte. The scan rate potential, the percentages of DHPMB and RGO, and the pH solution were optimized. Under the optimum conditions, some parameters such as the electron transfer coefficient (α) between electrode and modifier, and the electron transfer rate constant) k_s) in a 0.1 M phosphate buffer solution (pH=7.0) were obtained by cyclic voltammetry method. The diffusion coefficient of species (D) 3.96×10^?5 cm² s^?1 was calculated by chronoamperometeric technique and the Tafel plot was used to calculate α (0.46) for N‐ acetyl‐L‐cysteine. Also, by using differential pulse voltammetric (DPV) technique, two linear dynamic ranges of 2–18 µM and 18–1000 µM with the detection limit of 61.0 nM for N‐acetyl‐L‐cysteine (NAC) were achieved. In the co‐existence system of N‐acetyl‐L‐cysteine (NAC), uric acid (UA) and dopamine (DA), the linear response ranges for NAC, UA, and DA are 6.0–400.0 µM, 5.0–50.0 µM and 2.0–20.0 µM, respectively and the detection limits based on (C=3s_b/m) are 0.067 µM, 0.246 µM and 0.136 µM, respectively. The obtained results indicated that DHPMB/RGO/CPE is applicable to separate NAC, uric acid (UA) and dopamine (DA) oxidative peaks, simultaneously. For analytic performance, the mentioned modified electrode was used for determination of NAC in the drug samples with acceptable results, and the simultaneous determination of NAC, UA and DA oxidative peaks was investigated in the serum solutions, too.     

Electrochemical Investigation of Metal Oxide Conducting Electrodes for Direct Detection of Sulfide

This study examined the performance of four conducting metal oxide electrodes for the direct electrochemical analysis of sulfide; the electrode materials studied were indium tin oxide (ITO), fluorine doped tin oxide (FTO), aluminum doped zinc oxide (AZO) and gallium doped zinc oxide (GZO). Cyclic voltammetry (CV) results obtained using the ITO, AZO, GZO and FTO electrodes showed direct electrooxidation peak potential of sulfide at 381, 507, 400, and 850 mV vs. Ag/AgCl, respectively; however, the less positive oxidation potential and high catalytic current response of the ITO electrode made it the electrode of choice for the direct oxidation of sulfide. The effects of different electrolytes and buffer solutions on the CV responses were also evaluated. A linear concentration range up to 350 µM and a detection limit of 8.0 µM were achieved. CV response was highly reproducible, remaining unaffected even after 50 measurements. The sensor was found to have good selectivity, with no interference from sulfite, sulfate or chloride ions. The present findings demonstrate that the bare ITO electrode can be used as the basis of an inexpensive, sensitive, selective and robust sulfide sensor.     

Anti‐cancer Herbal Drug Berberine – Sensitive Determination Using Boron‐doped Diamond Electrode

Determination of berberine, an isoquinoline plant alkaloid, with antibacterial, antiparasitic, antifungal, hypotensive and antitumoral effects, was proposed by introducing square wave voltammetry on boron‐doped diamond electrode. At optimized experimental parameters, in Britton‐Robinson buffer solution pH 5 berberine provides 3 oxidation peaks (+0.63; +1.14 and +1.34 V) and one reduction (+0.15 V) (vs. Ag/AgCl electrode), with good repeatability (relative standard deviation of 2.6 % and 1.9 % for 8 measurements at 0.5 and 10 µM concentration level, respectively). Calibration curve was linear in wade linear range from 0.1 to 50 µM with limit of detection of 0.04 µM. The proposed procedure was successfully applied for the determination of berberine in seed extract from Argemone mexicana with satisfactory recovery (102–102.6 %). The developed method may represent a sensitive alternative to highly toxic mercury electrodes, modified electrodes and chromatographic methods.     

Capacitive Chemical Sensor for Thiopental Assay Based on Electropolymerized Molecularly Imprinted Polymer

A novel capacitive sensor based on electropolymerized molecularly imprinted polymer (MIP) for thiopental detection is described. The molecularly imprinted film as a recognition element was prepared by electropolymerization of phenol on a gold electrode in the presence of thiopental (template). Cyclic voltammetry and capacitive measurements were used for characterization and evaluation of the polymeric film. The template molecules were removed from the modified electrode surface by washing with an ethanol:water solution. The sensor’s linear response range was between 3 and 20 µM, with a detection limit of 0.6 µM. The proposed sensor exhibited good selectivity, reproducibility. Satisfactory results were obtained in the direct detection of real samples.     

Green and Straightforward Modification of Graphite Electrode via In Situ Synthesis of Graphene Nanosheets for Quantifying Prazosin Hydrochloride in Urine Samples and Pharmaceutical Formulations

A sensitive electrochemical sensor based on in situ modification of graphite electrode via graphene nanosheets (GNs) was developed as a green method for prazosin hydrochloride (PRA) analyses. In this study, GNs were electrochemically synthesized on the surface of graphite electrode via in situ approach and used for the analyses. The proposed sensor showed several advantages such as high sensitivity, low LOD, and excellent repeatability. The oxidation peak current at the optimum analytical conditions using a GNs/graphite electrode at pH 6.0 was linearly dependent on PRA concentration in the range of 0.09–100 µM. A LOD of 0.02 µM and RSD of 3.8 % for 10 µM solution of PRA with a great recovery were obtained.     

Electrochemical Properties of Ag@iron Oxide Nanocomposite for Application as Nitrate Sensor

Ag@iron oxide nanocomposite powders were synthesized via a two‐step chemical method. Characterization by UV‐Vis, XRD, SEM‐EDX and TEM revealed they are composed of nanosized crystalline silver particles in strict contact with amorphous iron oxide(s). The electrochemical behavior of the synthesized Ag@iron oxide composite was investigated by cyclic voltammetry. Compared with the single phase‐modified electrodes, the Ag@iron oxide/SPCE electrode exhibits an enhanced cathodic current in response to the target analyte, due to a synergistic effect between Ag crystallites and amorphous iron oxide nanoparticles. An amperometric sensor for detection of nitrate based on Ag@iron oxide modified screen‐printed electrode (Ag@iron oxide/SPCE) has been fabricated, showing a good sensitivity (663 µA mM^?1 cm^?2) and a detection limit of 30 µM.     

Electropolymerized Diphenylamine on Functionalized Multiwalled Carbon Nanotube Composite Film and Its Application to Develop a Multifunctional Biosensor

Diphenylamine (DPA) monomers have been electropolymerized on the amino‐functionalized multiwalled carbon nanotube (AFCNT) composite film modified glassy carbon electrode (GCE) by cyclic voltammetry (CV). The surface morphology of PDPA‐AFCNT was studied using field‐emission scanning electron microscopy (FE‐SEM). The interfacial electron transfer phenomenon at the modified electrode was studied using electrochemical impedance spectroscopy (EIS). The PDPA‐AFCNT/GCE represented a multifunctional sensor and showed good electrocatalytic behavior towards the oxidation of catechol and the reduction of hydrogen peroxide. Rotating‐disk electrode technique was applied to detect catechol with a sensitivity of 1360 µA mM^?1 cm^?2 and a detection limit of 0.01 mM. Amperometric determination of hydrogen peroxide at the PDPA‐AFCNT film modified electrode results in a linear range from 10 to 800 µM, a sensitivity of 487.1 µA mM^?1 cm^?2 and detection limit of 1 µM. These results show that the nano‐composite film modified electrode can be utilized to develop a multifunctional sensor.     

Platinum Ultramicroelectrodes Modified with Electrogenerated Surfactant‐Templated Mesoporous Organosilica Films: Effect of Film Formation Conditions on Its Performance in Preconcentration Electroanalysis

Pt µdisc electrodes have been modified by mesoporous organosilica thin films by electrochemically assisted self‐assembly (EASA) of mercaptopropyltrimethoxysilane (MPTMS), tetraethoxysilane (TEOS), and the surfactant cetyltrimethylammonium bromide (CTAB). The EASA process involves the generation of hydroxide ions at the electrode/solution interface, upon the application of a cathodic current density, leading to TEOS and MPTMS polycondensation around the CTAB template and concomitant growing of a thiol‐functionalized mesoporous film onto the electrode surface. The experimental conditions (current density, deposition time, silane concentration and molar ratio between surfactant template and silane) were optimised to form a thin and permeable film likely to be used in preconcentration electroanalysis. The morphology of the film electrodes were characterised by scanning electron microscopy. The permeability properties of the modified Pt µdisc electrodes have been evidenced by cyclic voltammetry using Ru(NH₃)₆³⁺ as a redox probe. The best parameters identified for the film preparation are a current density of ? 8 mA cm^?2 applied for 15 s in a solution containing 110 mM of hydrolysed silane precursors and 70.4 mM of CTAB. Pt µdisc electrodes modified in these conditions were used for the open‐circuit preconcentration of Hg(II) species prior to their detection by anodic stripping voltammetry in a mercury‐free solution. In the optimized conditions, a sensitivity of 14.3 mA cm^?2 µM^?1 was obtained for the 0.02–0.08 µM concentration range. The analytical performance of such organosilica films could decay by up to two orders of magnitude for the materials prepared in conditions other than the optimized ones, highlighting the need for a fine control of the deposition parameters to elaborate sensors based on such modified ultramicroelectrodes.     

A Simple and Effective Way to Integrate Nile Blue Covalently onto Functionalized SWCNTs Modified GC Electrodes for Sensitive and Selective Electroanalysis of NADH

A simple and new way to assemble Nile blue (NB) covalently onto the surface of functionalized single‐walled carbon nanotubes (f‐SWCNTs) modified glassy carbon (GC) electrode (NB/f‐SWCNTs/GC electrode) was described. The NB/f‐SWCNTs/GC electrode catalyzes effectively the oxidation of NADH with a remarkably decreased overpotential (ca. 700 mV) compared with that at the bare GC. The reaction was found to obey a so‐called Michaelis–Menten kinetics and the related kinetic parameters were determined. This modified electrode possesses promising characteristics as NADH sensor; a wide linear dynamic range of 0.2 to 200 µM, low detection limit of 0.18 µM, fast response time (1–2 s), high sensitivity (24 µA cm⁻² mM⁻¹), anti‐interference ability and anti‐fouling.     

Electrochemical Determination of Phenolic Acids at a Zn/Al Layered Double Hydroxide Film Modified Glassy Carbon Electrode

A stable sensor for the determination of gallic acid (GA) and caffeic acid (CA) was fabricated by electrodeposition of Zn‐Al‐NO₃ layered double hydroxide film on a glassy carbon electrode (LDHf/GCE). A sensitive electrochemical method was achieved for the determination of GA and CA in a phosphate buffer solution (pH 3). The differential pulse voltammetry response of the LDHf/GCE to GA has a linear concentration range from 4 µM to 600 µM with a correlation coefficient of 0.9985 and the calculated detection limit of 1.6 µM at a signal‐to‐noise ratio of 3. The differential pulse voltammetry response of the LDHf/GCE to CA has a linear concentration range from 7 µM to 180 µM with a correlation coefficient of 0.9969 and the calculated detection limit of 2.6 µM at a signal‐to‐noise ratio of 3. The constructed sensor was applied to the determination of GA in commercial green tea samples.     

Carbon Nanotube‐Adsorbed Electrospun Nanofibrous Membranes as Coating for Electrochemical Sensors for Sulfhydryl Compounds

A new method to modify electrodes with carbon nanotubes (CNT) was developed. Multiwalled carbon nanotubes (MWNT) were adsorbed on the electrospun nylon‐6 nanofibrous membranes (Ny‐6‐NFM) and used as a coating to modify conventional glassy carbon electrodes. The modified electrode was designed for the amperometric detection of sulfhydryl compounds with the potential held at +0.3 V vs. Ag/AgCl. The modified electrode showed a linear response for cysteine up to 0.4 mM (R²=0.997), with a sensitivity of 5.1 µA/mM and a detection limit of 15 µM. Other sulfhydryl compounds showed similar results. After use, the Ny‐6‐NFM was easily peeled off, leaving the bare electrode surface back to its original electrochemical behaviour. This is the first attempt to use a disposable membrane functionalized with MWNT for electroanalytical purposes.