Determination of Cu2+ in Drinking Water Based on Electrochemiluminescence of Ru(phen)32+ and Cyclam

A convenient and simple electrochemiluminescence (ECL) method was employed to detect trace amounts of Cu²⁺ in drinking water. This method is based on the inhibitory effect of Cu²⁺ on the ECL of Ru(phen)₃²⁺ and 1,4,8,11‐tetraazacyclotetradecane (cyclam) system. ECL intensity of Ru(phen)₃²⁺ was considerably enhanced by the addition of cyclam because of the ECL reaction between them. The ECL intensity of Ru(phen)₃²⁺/cyclam system rapidy decreased with the addition Cu²⁺ because of the formation of chelate complex [Cu(cyclam)]²⁺. Good linear response (R ²=0.9948) was obtained at Cu²⁺ concentration of 1.0×10⁻⁹−1.0×10⁻⁵ mol ⋅ L⁻¹ at glassy carbon electrode in 0.1 mol ⋅ L⁻¹ phosphate buffer (pH 9.0). Observed detection limit of 4.8×10⁻¹⁰ mol ⋅ L⁻¹ satisfied the maximum contaminant level goal (MCLG) for Cu²⁺ set by the US Environmental Protection Agency (US EPA). Applicability of the proposed method was verified by the good reproducibility and stability of the method when applied to determine Cu²⁺ in tap water and simulated wastewater. Thus, a novel ECL detection method was developed for Cu²⁺ detection.     

Novel Potentiometric Solid-contact Electrode for the Determination of Fe2+ Ions via MWCNTs-Gemifloxacin Composite

A novel electrode was fabricated for the quantitation of Fe²⁺ ion. It was based on the covalent attachment of the gemifloxacin molecule (the recognition element) to the surface of MWCNTs to be incorporated as an electroactive material. Linear response of Fe²⁺ ions was found in the concentration range of 1×10⁻² mol L⁻¹ to 1×10⁻⁸ mol L⁻¹ with a Nernstian slope of 30.37 ±0.3 (mV/decade) and attained a stable response within 5 s. The sensor exhibited LOD value of 4.8×10⁻⁹ mol L⁻¹. It was applied in the monitoring of Fe²⁺ concentration in multi-vitamins tablets, tap water and milk samples with acceptable recovery ranged from 94.00 % to 102.00 %.     

Application of Double Deposition and Stripping Steps System for Minimization of Interferences of Peaks’ Overlapping in Anodic Stripping Voltammetry

An anodic stripping voltammetric procedure for the determination of bismuth in the presence of excess of Cu²⁺ ions at two ex situ plated gold film electrodes was described. The procedure is based on utilization of two deposition and two stripping steps system. The presented procedure ensures increasing the sensitivity of Bi³⁺ determination and minimization of interferences related to peaks’ overlapping. The calibration graph for bismuth determination was linear from 2.5×10⁻⁹ to 2×10⁻⁸ mol L⁻¹ for deposition time of 300 s at both working electrodes while detection limit was 7.7×10⁻¹⁰ mol L⁻¹.     

A new Approach for the Voltammetric Sensing of the Phytoestrogen Genistein at a Non-modified Boron-doped Diamond Electrode

An effective electrochemical sensor was constructed using an unmodified boron-doped diamond electrode for determination of genistein by square-wave voltammetry. Cyclic voltammetric investigations of genistein with HClO₄ solution indicated that irreversible behavior, adsorption-controlled and well-defined two oxidation peaks at about +0.92 (P_A1) & +1.27 V (P_A2). pH, as well as supporting electrolytes, are important in genistein oxidations. Quantification analyses of genistein were conducted using its two oxidation peaks. Using optimized experiments as well as instrumental conditions, the current response with genistein was proportionately linear in the concentrations range of 0.1 to 50.0 μg mL⁻¹ (3.7×10⁻⁷−1.9×10⁻⁴ mol L⁻¹), by the detection limit of 0.023 μg mL⁻¹ (8.5×10⁻⁸ mol L⁻¹) for P_A1 and 0.028 μg mL⁻¹ (1.1×10⁻⁷ mol L⁻¹) for P_A2 in 0.1 mol L⁻¹ HClO₄ solution (in the open circuit condition at 30 s accumulation time). Ultimately, the developed method was effectively applied to detect genistein in model human urine samples by using its second oxidation peak (P_A2).     

Graphdiyne and Ionic Liquid Composite Modified Gold Electrode for Sensitive Voltammetric Analysis of Rutin

It is significant to develop a point-of-care testing (POCT) method for rapid detection of medicinal molecules. In this paper, a graphdiyne (GDY)-ionic liquid (IL) composite was prepared via one-step facile ultrasound preparation process and then modified on gold (Au) electrode surface by simple casting method. Scanning electron microscopy and transmission electron microscopy were used to characterize the morphology of GDY-IL composite. Cyclic voltammetric results proved that GDY-IL composite on the electrode surface could effectively improve electron transfer rate, which meant that GDY-IL composite had high conductivity with big surface area. Finally, the modified electrode exhibited excellent performances for rutin detection with wider linear range (8.0×10⁻⁹ mol L⁻¹–2.0×10⁻⁶ mol L⁻¹ and 2.0×10⁻⁶ mol L⁻¹–1.5×10⁻⁴ mol L⁻¹) and lower detection limit (2.7 nmol L⁻¹, 3S₀/S). The Nafion/GDY-IL/Au electrode showed good sensitivity and high selectivity, which was satisfactory in analytical application to real samples. Therefore, the GDY-IL composite modified electrode has the potential applications in the POCT for electrochemical analysis of various medicinal molecules.     

Amperometric detection of indapamide on glassy carbon electrode

This work describes the development of a fast, precise and reliable voltammetric method for the quantification of indapamide, an orally active diuretic sulfonamide used for hypertensive treatment. This compound acts inhibiting sodium reabsorption and increasing the elimination of water. This characteristic was responsible for its banishment by the International Olympic Committee since 1999. The study begins by finding an adequate potential range (−0.20 to 0.30 V) to avoid poisoning the working glassy carbon electrode (GCE) in phosphate buffer 0.10 mol L⁻¹ (pH=12.0). Utilizing flow injection analysis, linear responses between 2.0 × 10⁻⁶ mol L⁻¹ to 2.5 × 10⁻⁵ mol L⁻¹ of indapamide (R²=0.995), and detection limit (LOD) 3.0 × 10⁻⁷ mol L⁻¹ were obtained. This method was applied for the quantification of indapamide in tablets and in synthetic urine. The same flow system was used for the analysis of commercial drugs and the response obtained corresponded to 98 % of the concentration indicated on the drug label. These tablets were also analyzed by high performance liquid chromatography (HPLC), obtaining a recovery of 103 % and LOD 4.0 × 10⁻⁷ mol L⁻¹. The velocity of analysis using flow methods compares advantageously to the classical chromatographic methods. For synthetic urine, linear responses were obtained in samples spiked in the region from 5.0 × 10⁻⁶ mol L⁻¹ to 30 × 10⁻⁶ mol L⁻¹ (R²=0.991) and LOD 3.0 × 10⁻⁷ mol L⁻¹.     

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.     

A Simple,sensitive, and selective electrochemical aptasensor for cortisol based on rGO-AuNPs

Cortisol is a steroid hormone naturally produced by the adrenal glands. It participates in and controls several processes in the body and is considered an important physiological biomarker. Due to its very low concentrations in body fluids, its detection requires high sensitivity and specificity. Here, we present a simple electrochemical biosensor based on reduced graphene oxide (rGO) modified with gold nanoparticles (AuNPs) for the immobilization of the cortisol-specific aptamer (Ap) (MCH-Ap-AurGO/GCE). Important analytical parameters for identifying the target analyte were optimized, such as conditions and amount of immobilized Ap, the influence of the concentration and nature of the supporting electrolyte, pH of the medium, and incubation time. The optimized conditions for the aptasensor were: concentration of Ap 1.0 × 10⁻⁶ mol L⁻¹, support electrolyte Tris/HCl 50 mmol L⁻¹, MgCl₂ 10 mmol L⁻¹, and NaCl 10 mmol L⁻¹, at pH 5.0 and incubation time of 15 min. A linear response range was obtained from 1 × 10⁻¹⁸ up to 1 × 10⁻¹¹ mol L⁻¹ of cortisol with a detection limit (LOD) of 1.0 × 10⁻¹⁸ mol L⁻¹. A curve adjusted for operational purposes in the saliva sample was fitted for the concentration range between 0.5 × 10⁻¹⁴ and 1 × 10⁻¹¹ mol L⁻¹, with a linear regression equation ΔRtc/Rtc₁ = 2.70 + 0.17 × log([Cortisol]). The aptasensor demonstrated a great potential for detecting cortisol in a simple, fast, and highly sensitive way, opening its path for application in real samples, which present levels below the concentration in which cortisol is commonly found in body fluids.     

Determination of Cr(VI) by Catalytic Adsorptive Stripping Voltammetry with Application of Nitrilotriacetic Acid as a Masking Agent

A selective and sensitive method for determination of traces of Cr(VI) in the presence of a large excess of Cr(III) by differential pulse catalytic adsorptive stripping voltammetry is presented. For minimization of Cr(III) interference nitrilotriacetic acid was used as a masking agent. The determinations were performed in a flow system. The calibration plot was linear from 1×10⁻¹⁰ to 1×10⁻⁸ mol L⁻¹ for accumulation time 60 s. The relative standard deviation for 3×10⁻⁹ mol L⁻¹ Cr(VI) was 4.1% (n=5). The detection limit for an accumulation time of 60 s was 4×10⁻¹¹ mol L⁻¹. The influence of common foreign ions is also presented. The performance of the method was verified by analysis of certified reference material for Cr(VI) and comparing the results of analyses of natural water samples with those obtained by another accepted electrochemical method.     

A comparison study of adsorptive transfer voltammetry and solution phase voltammetry for the determination of caffeic acid

This study reports a comparison of adsorptive transfer and solution phase voltammetric methods for the study of caffeic acid. For this purpose, a platform was prepared by the modification of glassy carbon electrodes (GCEs) with MWCNTs and samarium nanoparticles (SmNPs) by means of an ultrasonic bath. The surface morphology of the platform was characterized using SEM, EDX and XRD. The adsorptive transfer voltammetric method was based on the adsorption of caffeic acid (CFA) at the surface of the modified electrode by keeping it into a solution of CFA. Afterwards, the modified electrode was transferred with the adsorbed species in a cell containing only 0.1 mol L⁻¹ phosphate buffer solution (PBS) for the analysis. The current response of CFA was found to be linear over a concentration from 5.0 × 10⁻¹⁰ mol L⁻¹ to 1.0 × 10⁻⁷ mol L⁻¹. The values of the limit of detection (LOD) and limit of quantification (LOQ) were 2.0 × 10⁻¹⁰ mol L⁻¹ and 6.67 × 10⁻¹⁰ mol L⁻¹, respectively. The adsorptive transfer method using the modified electrode (SmNPs/MWCNTs/GCE) has successfully been applied to food samples for determining CFA. The solution phase voltammetry was carried out by dipping the electrode into a voltammetric cell containing CFA. The plot of peak currents was linear over the concentration range of 5.0 × 10⁻⁹ mol L⁻¹ –8.0 × 10⁻⁸ mol L⁻¹. The values of LOD and LOQ were 2.0 × 10⁻⁹ mol L⁻¹ and 6.67 × 10⁻⁹ mol L⁻¹ for CFA using a classical solution phase voltammetry at the proposed platform. It was shown that the LOD obtained at adsorptive transfer voltammetry was 10-fold lower when compared to classical solution phase voltammetry.     

Amperometric Tyrosinase Biosensor Based on Carbon Black Paste Electrode for Sensitive Detection of Catechol in Environmental Samples

In this work, a renewable tyrosinase-based biosensor was developed for the detection of catechol, using a carbon black paste electrode, without any mediator. The effect of pH, type of electrolyte, and amount of tyrosinase enzyme were explored for optimum analytical performance. The best-performing biosensor in amperometric experiments at potential −0.2 V vs. Ag/AgCl (3 mol L⁻¹ KCl) was obtained using a 0.1 mol L⁻¹ phosphate buffer solution (pH 7.0) as electrolyte. Under optimized conditions, the proposed biosensor had two concentration linear ranges from 5.0×10⁻⁹ to 4.8×10⁻⁸ and from 4.8×10⁻⁸ to 8.5×10⁻⁶ mol L⁻¹ and a limit of detection of 1.5×10⁻⁹ mol L⁻¹. The apparent Michaelis-Menten constant ( ) was calculated by the amperometric method, and the obtained value was 1.2×10⁻⁵ mol L⁻¹ whose result was similar when compared with other studies previously. The biosensor was applied in river water samples, and the results were very satisfactory, with recoveries near 100 %. In addition, the response of this biosensor for different compounds, taking into account their molecular structures was investigated and the results obtained showed no interference with the response potential of catechol. The electrochemical biosensor developed in this work can be considered highly advantageous because it does not require the use of a mediator (direct detection) for electrochemical response, and also because it is based on a low-cost materials that can be used with success to immobilise other enzymes and/or biomolecules.     

A sensitive DNA biosensor based on the distance dependent quenching of Silica@Ru(bpy)32+-chitosan-GO electrochemiluminescence by Ferrocene@Gold nanoparticles

A sensitive electrochemiluminescence (ECL) biosensor for the specific DNA sequence of hepatitis C virus (HCV) was developed based on the efficient quenching effect of the ferrocene cluster functionalized gold nanoparticles (Fc@AuNPs) on the ECL of electrodeposited silica@Ru(bpy)₃²⁺-chitosan-graphene oxide nanocomposite (SiO₂@Ru−CS−GO). Graphene oxide (GO) can accelerate electron transfer rate, thus improving the ECL of Ru(bpy)₃²⁺ on electrode surface. The molecular beacons (MB) was fixed to SiO₂@Ru−CS−GO by glutaraldehyde (GA) using the Schiff reaction between amino groups of chitosan (CS) and MB. The ECL of SiO₂@Ru−CS−GO was depressed greatly by the Fc@AuNPs labelled at the end of MB, then, a stronger ECL was observed when the distance between Fc@AuNPs and SiO₂@Ru−CS−GO increased after the hybridization of target DNA with MB. Under optimum conditions, the restored ECL intensity increased linearly with the target DNA concentration in the range of 1.0×10⁻¹⁶∼1.0×10⁻¹⁰ mol ⋅ L⁻¹, and the limit of detection (LOD) is 1.4×10⁻¹⁷ mol ⋅ L⁻¹. The proposed method exhibits acceptable stability and reproducibility. In general, the constructed HCV biosensor can be used for the sensitive detection of HCV in human serum, suggesting potential application prospects in bioanalysis.     

A New Approach for Decreasing the Detection Limit of Gentamicin Ion‐selective Electrodes by Incorporation of Multiwall Carbon Nanotubes (MWCNTs)/Lipophilic Anionic Additives

Two novel carbon paste electrodes based on gentamicin‐reineckate (GNS‐RN)/multiwall carbon nanotubes (MWCNTs)/sodium tetraphenyl borate (NaTPB) or potassium tetraphenylborate (KTPB) for potentiometric determination of gentamicin sulfate were constructed. Our endeavors of lowering the detection limit for gentamicin ion‐selective electrodes were described. The paper focused on gentamicin carbon paste electrodes based on GNS‐RN as electroactive material, o ‐nitrophenyloctyl ether (o ‐NPOE) as plasticizer and incorporation of MWCNTs and lipophilic anionic additives (NaTPB and KTPB) which lower the detection limit of the electrodes showing best results for determination of gentamicin ion. The characteristics of the electrodes, GNS‐RN+NaTPB+MWCNTs (sensor 1) and GNS‐RN+KTPB+ MWCNTs (sensor 2), were measured, showing favorable features as they provided measurements of the potential with near‐Nernstian slopes of 29.6±0.3 and 29.1±0.3 mV/decade over the concentration range of 1.0×10⁻⁶–1.0×10⁻² mol L⁻¹ and pH ranges 3.0–8.2 and 3.0–8.0 in short response times (6.5 sec). Importantly, the electrodes had low detection limits of 3.0×10⁻⁷and 3.4×10⁻⁷ mol L⁻¹ for the two sensors, respectively. The sensors showed high selectivity for gentamicin ion with respect to a large number of interfering species. The electrodes were successfully applied for the potentiometric determination of GNS ions in pure state, pharmaceutical preparations and human urine with high accuracy and precision. The results of this study were compared with some previously published data using other analytical methods.     

A Graphene Oxide‐DNA Electrochemical Sensor Based on Glassy Carbon Electrode for Sensitive Determination of Methotrexate

Methotrexate (MTX) was used as an anti‐cancer drug, but its excessive use can cause serious side effects, it was necessary to monitor MTX in vivo. In this report, DNA was immobilized on a glassy carbon electrode (GCE) modified with graphene oxide (GO) to develop an electrochemical sensor for sensitive determination of MTX for the first time. The adsorptive voltammetric behaviors of MTX on DNA sensor were investigated using differential pulse voltammetry (DPV). The peak current response of guanine in DNA was used as a determination signal of MTX in acetate buffer solution pH 4.6. Voltammetric investigations revealed that the proposed method could determine MTX in the concentration range from 5.5×10⁻⁸ to 2.2×10⁻⁶ mol L⁻¹ with a lower detection limit of 7.6×10⁻9 mol L⁻¹ (S/N=3). The method was applied to detect MTX in human blood serum and diluted urine samples with excellent recoveries of 97.4–102.5 %. Compared with the previous studies, the DNA/GO/GCE electrode constructed by us based on the change rate of guanine current (R%) in DNA, proportionally reflecting the MTX concentration, is simple and sensitive .     

Sensitive Voltammetric Determination of Methyl Parathion Using a Carbon Paste Electrode Modified with Mesoporous Zirconia

A mesoporous zirconia modified carbon paste electrode was developed for electrochemical investigations of methyl parathion (MP, Phen‐NO₂). The significant increase of the peak currents and the improvement of the redox peak potential indicate that mesoporous zirconia facilitates the electronic transfer of MP. The oxidation peak current was proportional to the MP concentration in the range from 1.0×10⁻⁸ to 1.0×10⁻⁵ mol L⁻¹ with a detection limit of 4.6×10⁻⁹ mol L⁻¹ (S/N=3) after accumulation under open‐circuit for 210 s. The proposed method was successfully applied to the determination of MP in apple samples.     

Voltammetry and EQCM Investigation of Glutathione Monolayer and Its Complexation with Cu2+

The glutathione (GSH) self‐assembled monolayer and its compexlation with Cu²⁺ were studied by using voltammetry and EQCM. It was found that the monolayer could rearrange during the redox process of Cu²⁺/Cu⁺. The protonating, or not, of the carboxyl terminates of the adsorpted GSH molecules influence the compexlation interaction significantly for they are the key binding sites. The GSH monolayer had the capacity to accumulate Cu²⁺ and the monolayer modified gold electrode was employed to detect the low levels of Cu²⁺ with a limit of 1.0×10^?10 mol L^?1.     

Electrochemical Sensor Based on Multiwalled Carbon Nanotube,Alizarine Red S and Chitosan for Simultaneous Determination of Oxomemazine Hydrochloride,Paracetamol and Guaifenesin

A simple and highly sensitive sensor has been used for the determination of oxomemazine hydrochloride (OXO) in presence of paracetamol (PAR) and guaifenesin (GU). Carbon paste electrode was modified with multiwalled carbon nanotube (MWCNT), alizarine red S (AZ) and chitosan (CH). Scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and differential pulse voltammetry (DPV) were used to characterize the nanostructure and performance of the sensor. Under the optimized experimental conditions OXO gave linear response over the range of 2.00×10⁻⁶–1.00×10⁻⁴ mol L⁻¹. The detection limit was found to be 4.35×10⁻⁷ mol L⁻¹. The practical application of the modified electrode was demonstrated by measuring the concentration of OXO in pharmaceutical samples and urine. This revealed that suggested sensor shows excellent analytical performance for the determination of OXO in terms of a very low detection limit, high sensitivity and selectivity.     

A Potentiometric Sensor for Cd2+ Based on Carbon Nanotube Paste Electrode Constructed from Room Temperature Ionic Liquid,Ionophore and Silica Nanoparticles

A novel and effective potentiometric sensor for the rapid determination of Cd²⁺ based on carbon paste electrode consisting of the room temperature ionic liquid 1‐butyl‐3‐methylimidazolium hexafluorophosphate, multiwalled carbon nanotubes, silica nanoparticles and ionophore was constructed. The prepared composite has a low potential drift, high selectivity and fast response time, which leads to a more stable potential signal. A linear dynamic range of 4.50×10^?9–1.00×10^?1 mol L^?1 with a detection limit of 2.00×10^?9 mol L^?1 was obtained. The modified electrode was successfully applied to the accurate determination of trace amounts of Cd²⁺ in environmental and biological samples.     

Isoniazid-sensing Behavior of a Hybrid Silsesquioxane and Cobalt Pentacyanonitrosylferrate-based Nanocomposite

A novel silsesquioxane and cobalt nitroprusside compound was prepared from octa(aminopropyl)silsesquioxane, resulting in a nanocomposite (ACCoN), which was then characterized by different spectroscopic techniques. The cyclic voltammograms of the ACCoN-modified graphite paste electrode indicated a redox pair with a formal potential (E^θ′)=0.38 V, assigned to the Co^(II)Fe^(II)(CN)₅NO/Co^(II)Fe^(III)(CN)₅NO redox couple. The ACCoN-modified graphite paste electrode was sensitive to isoniazid concentrations, presenting a linear response at a concentration range from 6.0×10⁻⁷ to 1.0×10⁻⁵ mol L⁻¹, with limit of detection and amperometric sensitivity of 5.53×10⁻⁷ mol L⁻¹ and 0.17 A/mol L⁻¹, respectively.     

Study on Cd2+ Determination Using Bud-like Poly-L-Tyrosine/Bi Composite Film Modified Glassy Carbon Electrode Combined with Eliminating of Cu2+ Interference by Electrodeposition

A bud-like poly-L-tyrosine/Bi modified glassy carbon electrode (p-Tyr/Bi/GC) was prepared by CV and in situ Bi plating, whose conductivity and membrane morphology were characterized by CV, EIS and SEM, respectively. The p-Tyr membrane can effectively promote the enrichment of Cd²⁺. The optimal Tyr concentration and scanning number for p-Tyr/GC preparation were 2.0 mmol ⋅ L⁻¹ and 35, while the optimal Bi³⁺ concentration, pH and Cd²⁺ accumulation potential in test medium were 3.0 μmol ⋅ L⁻¹, 6.5 and −1.3 V, respectively. The linear equation of p-Tyr/Bi/GC's response to Cd²⁺ (1.0 nmol ⋅ L⁻¹ to 2.0 μmol ⋅ L⁻¹) was i_p (μA) = −0.6809 + 100.2c (μmol ⋅ L⁻¹) (R² = 0.9985) with a detection limit of 0.11 nmol ⋅ L⁻¹ (3S/N). The elimination of interference caused by Cu²⁺ in sample was studied by electrodeposition. The p-Tyr/Bi/GC electrode was successfully used for detecting Cd in rice samples with good reliability and accuracy. The developed Cd²⁺ sensor exhibits high sensitivity, wide linear range and low detection limit, especially the designed method of eliminating Cu²⁺ interference has the characteristics of high selectivity, simple operation and wide application range.