Visible LED light photoelectrochemical sensor for detection of L-Dopa based on oxygen reduction on TiO2 sensitized with iron phthalocyanine

The present work describes the development of a new strategy to photoelectrochemical detection of L-Dopa at low potential based on oxygen reduction on TiO₂ sensitized with iron phthalocyanine (FePc/TiO₂). The FePc/TiO₂ composite shows a photocurrent 10-fold higher than that of pure TiO₂ nanoparticles and it was 4-fold higher than that of FePc exploiting visible light. The band gaps of pure TiO₂ nanoparticles, FePc and FePc/TiO₂, calculated according to the Kubelka–Munk equation, were 3.22 eV, 3.11 eV and 2.82 eV, respectively. The FePc/TiO₂ composite showed a low charge transfer resistance in comparison to the photoelectrode modified with FePc or TiO₂. Under optimized conditions, the photoelectrochemical sensor shows a linear response range from 20 up to 190 μmol L^− 1 with a sensitivity of 31.8 μA L mmol^− 1 and limit of detection of 1.5 μmol L^− 1 for the detection of L-Dopa.     

Sensitive Nonenzymatic Electrochemiluminescence Determination of Hydrogen Peroxide in Dental Products using a Polypyrrole/Polyluminol/Titanium Dioxide Nanocomposite

A layer-by-layer assembled of a polypyrrole and polyluminol was synthesized through the electrodeposition of pyrrole and luminol in acidic medium on a graphite electrode. The electrode was then modified by casting titanium dioxide (TiO₂) nanoparticles on its surface for enhancing electrochemiluminescence of luminol. The properties of this electrochemiluminescence sensor were studied by cyclic voltammetry, electrochemical impedance spectroscopy, field emission scanning electron microscopy, and energy dispersive X-ray spectroscopy. The results demonstrated that the modification of this electrochemiluminescence sensor shows sensitive response for the determination of hydrogen peroxide. Figures of merit include broad linearity from 1?pmol L^?1 to 4?µmol L^?1 (R²?=?0.996) with a limit of detection as low as 0.40?pmol L^?1 at a signal-to-noise ratio of three and good reproducibility with relative standard deviation of 4% for the determination of a 400?nmol L^?1 hydrogen peroxide solution (n?=?4), along with favorable long-term stability. The presence of glucose, citric acid, uric acid, dopamine, and ascorbic acid at concentrations as high as 100?nmol L^?1 of H₂O₂ did not produce any electrochemiluminescence signals, which demonstrates the selective nature of this modified electrode. The sensor was also used for the determination of H₂O₂ in mouthwash formulations and dental whitelight gels.     

Synthesis of Functionalized MWCNTs Decorated with Copper Nanoparticles and Its Application as a Sensitive Sensor for Amperometric Detection of H2O2

Functionalized‐multiwall carbon nanotubes decorated with redox active copper nanoparticles have been fabricated for sensitive enzyme‐less H₂O₂ detection. The new nanocomposite was characterized by Transmission electron microscopy, energy dispersive X‐ray analysis and cyclic voltammetry. The response of the modified electrode to H₂O₂ was examined using amperometry at ?0.45 V vs. Ag/AgCl in a buffer solution at pH 10.0. The developed sensor displayed linear concentration ranges of 0.5–10.0 and 10.0–10000.0 µmol L^?1 with a detection limit of 0.3 µmol L^?1. The proposed sensor displayed good selectivity for H₂O₂ detection in the presence of common interferences such as ascorbic acid.     

Electrochemical Detection of Nitrite in Meat and Water Samples Using a Mesoporous Carbon Ceramic SiO2/C Electrode Modified with In Situ Generated Manganese(II) Phthalocyanine

Mesoporous carbon ceramic SiO₂/50 wt % C (S_BET=170 m² g^?1), where C is graphite, were prepared by the sol‐gel method. The materials were characterized using N₂ sorption isotherms, scanning electron microscopy, and conductivity measurements. The matrix was used as support for the in situ immobilization of Mn(II) phthalocyanine (MnPc) on their surface. XPS was used to determine the Mn/Si atomic ratios of the MnPc‐modified materials. Pressed disk electrodes were prepared with the MnPc‐modified matrix, and tested as an electrochemical sensor for nitrite oxidation. The linear response range, sensitivity, detection limit and quantification limit were 0.79–15.74 µmol L^?1, 17.31 µA L µmol^?1, 0.02 µmol L^?1 and 0.79 µmol L^?1, respectively, obtained using cyclic voltammetry. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation was 1.7 % for 10 measurements of a solution of 12.63 µmol L^?1 nitrite. The sensor employed to determine nitrite in sausage meat, river and lake water samples showed to be a promising tool for this purpose.     

A Highly Sensitive and Selective Enzymatic Biosensor Based on Direct Electrochemistry of Hemoglobin at Zinc Oxide Nanoparticles Modified Activated Screen Printed Carbon Electrode

A sensitive enzymatic biosensor has been developed for the detection of hydrogen peroxide (H₂O₂), nitrite ( ) and trichloroacetic acid (TCA) by using hemoglobin (Hb) immobilized on activated screen printed carbon electrode (ASPCE) and zinc oxide (ZnO) composite. A pair of well defined redox peaks is observed with a heterogeneous electron transfer rate constant (K_s) of 5.27 s^?1 for Hb at ASPCE/ZnO. The biosensor exhibits the detection of H₂O₂, TCA and in the concentration range of 0.5–129.5 µmol L^?1, 2.5–72.5 mmol L^?1 and 0.2–674 µmol L^?1 with the detection limit of 0.083 µmol L^?1, 0.12 mmol L^?1 and 0.069 µmol L^?1, respectively.     

Alumina Polished Glassy Carbon Electrode as a Simple Electrode for Lower Potential Electrochemical Detection of Dopamine in its Sub‐micromolar Level

The electrochemical behaviour of dopamine (DA) at a cleaned and alumina polished glassy carbon electrode (GCE) was studied using cyclic voltammetry (CV). The CV studies revealed that alumina polished GCE (AGCE) shows an enhanced oxidation peak current response with 217 mV negative potential shift towards DA than that of cleaned GCE. The differential pulse voltammetry result shows that the AGCE detects the DA in the linear concentration ranges from 0.15 to 25.25 µmol L^?1. The limit of detection was calculated as 0.046 µmol L^?1 with a sensitivity of 3.74 µA µmol L^?1 cm^?2 for the determination of DA. The fabricated AGCE shows a satisfactory selectivity, practicality along with appreciable repeatability and reproducibility.     

Design of a New Carbon Paste Electrode Modified with TiO2 Nanoparticles to Use in an Electrochemical Study of Codeine and Simultaneous Determination of Codeine and Acetaminophen in Human Plasma Serum Samples

A new electrochemical sensor was fabricated via TiO₂ nanoparticles onto a carbon paste electrode. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) studied the response of the modified electrode toward codeine. The effects of pH, modifier amount, pulse amplitude, and scan rate of potential have been examined. Using DPV, we could measure simultaneously codeine and acetaminophen in one mixture. The detection limits of 0.018 and 0.050 µmol L^?1 were achieved for codeine and acetaminophen, respectively. The electrooxidation pathway, transfer coefficient, and standard rate constant, are estimated. The proposed voltammetric sensor was successfully applied to determination of codeine and acetaminophen in human plasma serum samples.     

Synthesis,characterization, and electrocatalysis of a dinuclear cobalt(III) thioxanthate complex

This study reports on the synthesis, characterization, and performance of a new dinuclear cobalt(III) thioxanthate complex of [Co₂(μ-SC₂H₄OH)₂(HOC₂H₄SCS₂)₄] as an electrocatalyst for trichloroacetic acid (TCA) and bromate reduction. Its structure was characterized by X-ray crystallography and elemental analysis. The structure contains two different anions of 2-sulfanylethanol thioxanthate and 2-sulfanylethanol. The electrochemical behavior and the electrocatalysis of the cobalt complex bulk-modified carbon paste electrode have been studied by cyclic voltammetry. It shows good electrocatalytic activities toward the reduction of TCA and bromate. The values for the detection limit and the sensitivity are 0.06 µmol L^?1 and 19.40 µA µmol L^?1 for TCA detection and 0.01 µmol L^?1 and 177.6 µA µmol L^?1 for bromate detection, respectively. This modified electrode exhibits good reproducibility, high stability, low detection limit and technical simplicity, and allows a possibility for rapid preparation, which is important for practical applications.     

Ti/TiO2 Electrode Preparation Using Laser Anneal and Its Application to Determination of Chemical Oxygen Demand

A method for Ti/TiO₂ photoelectrode preparation using laser calcination instead of oven calcination process was introduced. The prepared TiO₂ film was investigated by X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS) and amperometry, and it was found that the prepared electrode mainly consisted of anatase TiO₂ nanoparticles on its surface and exhibited a superior photocatalytic activity. The electrode was employed as a sensor to measure chemical oxygen demand (COD) of the wastewater. The measuring principle was based on the photocurrent responses of the electrode which were proportional to the COD values. Under the optimized experimental conditions, the linear range was 50–2000 mg L⁻¹, and the detection limit was 16 mg L⁻¹ (S/N=3). This method was characterized by short analysis time, simplicity, low environmental impact and long lifetime of the sensor. Additionally, the COD values obtained from the proposed and conventional methods agreed well as demonstrated by the high significant correlation between the two sets of COD values (R=0.9895, n=25).     

Tapioca Biofilm Containing Nitrogen‐doped Titanium Dioxide Nanoparticles for Electrochemical Detection of 17‐β Estradiol

A novel sensor architecture based on thin film of tapioca decorated within nitrogen‐doped titanium dioxide (N‐TiO₂) nanoparticles is reported. The nanostructures were characterized by scanning electron microscope, transmission electron microscope, X‐rays diffraction and voltammetric techniques. The proposed electrode was used for detection of low concentrations of 17‐β estradiol in without purification step, which was investigated by using linear sweep adsorptive stripping voltammetry. Under optimal conditions, the analytical curve was linear over a 17β‐estradiol concentration range of 9.9×10⁻⁶ to 1.4×10⁻⁵ mol L⁻¹, with a detection limit of 1.7×10⁻⁷ mol L⁻¹. The tapioca and N‐TiO₂ nanoparticles homogeneous film was applied for detection of 17‐β‐estradiol in tap water and synthetic urine samples, which presented satisfactory results.     

Selective and Sensitive Determination of Uranyl Ions in Complex Matrices by Ion Imprinted Polymers‐Based Electrochemical Sensor

We report on the design of a UO₂²⁺‐selective electrode based on the use of UO₂²⁺ imprinted polymer nanoparticles (IP‐NPs), and its application for the differential pulse adsorptive cathodic stripping voltammetry determination of uranyl ions. A carbon paste electrode was modified with the IP‐NPs, and differential pulse adsorptive cathodic stripping voltammetry was applied as the detection technique after open‐circuit sorption of UO₂²⁺ ions. The modified electrode responses to UO₂²⁺ was linear in the 0.1 µg L^?1 to 10 µg L^?1 and in the 0.01 mg L^?1 to 10 mg L^?1. The method detection limit of the sensor was 0.03 µg L^?1.     

Determination of trace molybdenum in biological and water samples by graphite furnace atomic absorption spectrometry after separation and preconcentration on immobilized titanium dioxide nanoparticles

A new method has been developed for the determination of trace molybdenum based on separation and preconcentration with TiO₂ nanoparticles immobilized on silica gel (immobilized TiO₂ nanoparticles) prior to its determination by graphite furnace atomic absorption spectrometry (GFAAS). The optimum experimental parameters for preconcentration of molybdenum, such as pH of the sample, sample flow rate and volume, eluent and interfering ions, have been investigated. Molybdenum can be quantitatively retained by immobilized TiO₂ nanoparticles at pH 1.0 and separated from the metal cations in the solution, then eluted completely with 0.5 mol L^?1 NaOH. The detection limit of this method for Mo was 0.6 ng L^?1 with an enrichment factor of 100, and the relative standard deviation (RSD) was 3.4% at the 10 ng mL^?1 Mo level. The method has been applied to the determination of trace amounts of Mo in biological and water samples with satisfactory results.     

Voltammetric Determination of 4‐Nitrophenol and 5‐Nitrobenzimidazole Using Different Types of Silver Solid Amalgam Electrodes – A Comparative Study

The voltammetric behavior of two genotoxic nitro compounds (4‐nitrophenol and 5‐nitrobenzimidazole) has been investigated using direct current voltammetry (DCV) and differential pulse voltammetry (DPV) at a polished silver solid amalgam electrode (p‐AgSAE), a mercury meniscus modified silver solid amalgam electrode (m‐AgSAE), and a mercury film modified silver solid amalgam electrode (MF‐AgSAE). The optimum conditions have been evaluated for their determination in Britton‐Robinson buffer solutions. The limit of quantification (L_Q) for 5‐nitrobenzimidazole at p‐AgSAE was 0.77 µmol L^?1 (DCV) and 0.47 µmol L^?1 (DPV), at m‐AgSAE it was 0.32 µmol L^?1 (DCV) and 0.16 µmol L^?1 (DPV), and at MF‐AgSAE it was 0.97 µmol L^?1 (DCV) and 0.70 µmol L^?1 (DPV). For 4‐nitrophenol at p‐AgSAE, L_Q was 0.37 µmol L^?1 (DCV) and 0.32 µmol L^?1 (DPV), at m‐AgSAE it was 0.14 µmol L^?1 (DCV) and 0.1 µmol L^?1 (DPV), and at MF‐AgSAE, it was 0.87 µmol L^?1 (DCV) and 0.37 µmol L^?1 (DPV). Thorough comparative studies have shown that m‐AgSAE is the best sensor for voltammetric determination of the two model genotoxic compounds because it gives the lowest L_Q, is easier to prepare, and its surface can be easily renewed both chemically (by new amalgamation) and/or electrochemically (by imposition of cleaning pulses). The practical applicability of the newly developed methods was verified on model samples of drinking water.     

A Novel Sensor Based on Manganese azo‐Macrocycle/Carbon Nanotubes to Perform the Oxidation and Reduction Processes of Two Diphenol Isomers

The present work describes the development of a selective and sensitive voltammetric sensor for simultaneous determination of catechol (CC) and hydroquinone (HQ), based on a glassy carbon (GC) electrode modified with manganese phthalocyanine azo‐macrocycle (MnPc) adsorbed on multiwalled carbon nanotubes (MWCNT). Scanning electron microscopy and scanning electrochemical microscopy were used to characterize the composite material (MnPc/MWCNT) on the glassy carbon electrode surface. The modified electrode showed excellent electrochemical activity towards the simultaneous oxidation and reduction of CC and HQ. On the MnPc/MWCNT/GC electrode, both CC and HQ can generate a pair of quasi‐reversible and well‐defined redox peaks. Under optimized experimental and operational conditions, the cathodic peak currents were linear over the range 1–600 µmol L^?1 for both CC and HQ, with limits of detection of 0.095 and 0.041 µmol L^?1, respectively. The anodic peak currents were also linear over the range 1–600 µmol L^?1 for both CC and HQ, with limits of detection of 0.096 and 0.048 µmol L^?1, respectively. The proposed method was effectively applied for the simultaneous detection of hydroquinone and catechol in water samples and the results were in agreement with those obtained by a comparative method described in the literature.     

Electrochemical Determination of the KRAS Genetic Marker for Colon Cancer with Modified Graphete and Graphene Paste Electrodes

The determination of KRAS was performed using electrochemical sensing devices based on graphite and graphene pastes, modified with a phthalocyanine-boron dipyrromethene (BODIPY) and azulenes dyes. The limits of quantification for KRAS were 1.54?×?10^?4?µg/mL using the sensor based on the phthalocyanine-BODIPY dye and graphite, 2.64?×?10^?7?µg/mL using the sensor based on 2,6-bis((E)-2-(furan-2-yl)vinyl)-4-(4,6,8-trimethylazulen-1-yl)pyridine/TiO₂Pt/reduced graphene oxide, and 3.84?×?10^?3?µg/mL using the sensor based on 2,6-bis((E)-2-(thiophen-3-yl)vinyl)-4-(4,6,8-trimethylazulen-1-yl)pyridine/TiO₂Pt/reduced graphene oxide. Recovery measurements demonstrated the suitable analytical performance of these sensors for the early detection of colon cancer by the analysis of whole blood samples.     

Determination of Antimony(III) by Differential Pulse Voltammetry Using a Gold Nanoparticle–Ionic Liquid–Graphene-Modified Selenium-Doped Carbon Paste Electrode

A simple and sensitive differential pulse stripping voltammetric method was developed for the determination of antimony(III) using a selenium-doped carbon paste electrode modified with an ionic liquid, graphene, and gold nanoparticles. The conditions, including the mass of graphene, concentration of hydrochloric acid, deposition potential, and deposition time were optimized by single-factor experiments. Under the optimal conditions, a linear equation of I_Sb(III) (µA)?=??16.9882???11.0929 c (µmol/L) (R?=?0.9965) and a detection limit of 2.7?×?10^?8?mol/L were obtained for 8.0?×?10^?8 to 4.8?×?10^?6?mol/L antimony(III). The response shows that the sensor enhances the sensitivity of antimony due to the high conductivity and large surface areas of the ionic liquid, graphene, and gold nanoparticles. This electrode may provide a new sensing platform for the determination of antimony.     

Development of an Amperometric Sensor Highly Selective For Dopamine and Analogous Compounds Determination Using Bis(2,2′‐Bipyridil) Copper(II) Chloride Complex

The use of [Cu(bipy)₂]Cl₂?6H₂O as a biomimetic catalyst in the construction of an amperometric sensor for dopamine determination is reported. The sensor was prepared modifying a glassy carbon electrode with a Nafion membrane doped with [Cu(bipy)₂]Cl₂?6H₂O complex. The sensor presented a higher response in 0.25 mol L^?1 phosphate buffer solution (pH 7.0), with an applied potential of ?50 mV (vs. SCE). In the optimized operational conditions, a linear response range between 35 and 240 μmol L^?1, with a sensitivity of 2.02±0.07 nA l μmoL^?1 cm^?2 and detection limit of 8.0 μmol L^?1 were typically observed for the sensor. The response time presented for this sensor was 0.5 s, presenting the same response for at least 40 successive measurements, with good repeatability (3.0%) expressed as relative standard deviation for n=6. The difference of the response between four sensor preparations was 4%. A detailed investigation about the sensor response for other sixteen phenolic compounds and interfering species were carried out. The sensor was applied in the determination of dopamine in pharmaceutical preparation with success.     

Synergistic Effect of Graphene and Multiwalled Carbon Nanotubes on a Glassy Carbon Electrode for Simultaneous Determination of Uric Acid and Dopamine in the Presence of Ascorbic Acid

A poly(diallyldimethylammonium chloride)-graphene-multiwalled carbon nanotube modified glassy carbon electrode was fabricated and evaluated by cyclic voltammetry and differential pulse voltammetry. The modified electrode offered high sensitivity, selectivity, excellent long-term stability, and electrocatalytic activity for uric acid and dopamine. This sensor showed wide linear dynamic ranges of 5.0 to 350.0 µmol L^?1 for uric acid and 10.0 to 400.0 µmol L^?1 for dopamine in the presence of 500 µmol L^?1 ascorbic acid. The limits of detection were 0.13 for uric acid and 0.55 µmol L^?1 for dopamine. This functionalized electrode has potential application in bioanalysis and biomedicine.     

Enhanced Electrochemiluminescence of TiO2 Nanoparticles Modified Electrode by Nafion Film and Its Application in Selective Detection of Dopamine

In this work, a simple and effective approach to obtain stable, nontoxic and strong electrochemiluminescence (ECL) interfaces is provided by coating TiO₂ nanoparticles (NPs) modified glassy carbon electrode (GCE) surfaces with Nafion. Unlike a decrease of the current resulting from the blocked diffusion usually displayed in electrochemical processes by Nafion coating, a Nafion/TiO₂ NPs modified electrode not only shows a highly stable ECL, but also shows an 8‐fold increase of ECL intensity and a reduction of the overpotential of ca. 300 mV in the presence of K₂S₂O₈ as co‐reactant, compared with those of bare TiO₂ NPs modified electrodes. The roles of Nafion coating on TiO₂ NPs in the ECL process are proposed to be twofold: to provide refuge for the free radicals and to enhance the electron‐hole recombination. Benefiting from its excellent ECL performance, the cationic exchange function of Nafion and the susceptible to being oxidized performance of dopamine (DA) by holes, the Nafion/TiO₂ composite electrode could be used to sensitively and selectively detect DA with a detection limit of 1.0×10^?11 M and a linear range of 1.0×10^?11–6.0×10^?7 M. The coexisting anionic species such as excess ascorbic acid show little interference on DA detection.     

Sensitive and Selective Detection of Dopamine Using a DNA Immobilized Ethylenedidamine/Polyglutamic Modified Electrode

DNA was attached on the surface of an ethylenedidamine/polyglutamic(En/PGA) modified glassy carbon electrode (GCE) to create a novel voltammetric sensor (DNA/En/PGA/GCE) for dopamine (DA). This modified electrode exhibited a linear voltammetric response for DA in the range from 1.0×10^?7 mol L^?1 to 1×10^?5 mol L^?1, with a detection limit of 2×10^?8 mol L^?1. The detection of DA was found to be unaffected by the presence of ascorbic acid, uric acid, serotonin and folic acid. The method proposed was applied to detect DA in pharmaceutical dosage and human blood serum with good satisfactory results.