Nano TiO2 Modified Carbon‐ceramic Electrode and Its Application for Electrocatalytic Oxidation of NADH

The electrocatalytic oxidation of nicotinamide adenine dinucleotide (NADH) was studied on nanoTiO₂ modified sol‐gel electrode, using cyclic voltammetry, chronoamperometry and differential pulse voltammetry as diagnostic techniques. It is demonstrated that TiO₂ nanoparticles on sol‐gel network catalyze the oxidation of NADH in the absence of any electron transfer mediators. Effect of various parameters such as pH, scan rate, TiO₂ percentage on the response of modified electrode was studied. In addition, scanning electron microscopy (SEM) was used to characterize the surface morphology of the spots. A dynamic range between 0.5–50 μM with detection limit of 0.35 μM was obtained with DPV studies. This method was successfully used for determination of NADH in cucumber cotyledons samples. The electrode showed relatively good stability over more than 2 months.     

Efficient Electrocatalytic Detection of Epinephrine at Gold Electrodes Modified with Self‐Assembled Metallo‐Octacarboxyphthalocyanine Complexes

Electrocatalysis of epinephrine at gold electrode pre‐modified with the self‐assembled monolayer of cysteamine and subsequently integrated with novel metallo‐octacarboxyphthalocyanine (MOCPc where M=Fe, Co and Mn) complexes (Au‐Cys‐MOCPc) was investigated. The electrodes showed response to the presence of epinephrine. The oxidation peak potential (E_p/V vs. Ag|AgCl, sat'd KCl) and charge transfer resistance (R_ct (kΩ)) in epinephrine solution depend markedly on the central metal of the phthalocyanine cores: Au‐Cys‐FeOCPck_ch=4.1×10⁷ M^?1 s^?1) which is higher than that of the Au‐cys‐CoOCPc or Au‐cys‐MnOCPc electrode. Mechanism, recognizing the mediation of the electrocatalytic process by the central M(II)/M(III) redox processes was proposed. Epinephrine electro‐oxidation at the Au‐cys‐FeOCPc electrode was studied in more details for the response characteristics. The diffusion coefficient of epinephrine was evaluated as (2.62±0.23)×10^?9 cm² s^?1. It was established that Au‐Cys‐FeOCPc is suitable for sensitive determination of epinephrine in physiological pH (7.40) conditions showing linear concentration range of up to 300 nM, with excellent sensitivity (0.53±0.01 nA nM^?1), and very low limits of detection (13.8 nM) and quantification (45.8 nM). The peak separation between ascorbic acid and epinephrine is large enough (190 mV) to permit simultaneous determination of both epinephrine and ascorbic acid in physiological pH 7.4 conditions using the Au‐cys‐FeOCPc electrode. Au‐cys‐FeOCPc electrode was successfully used for the determination of epinephrine in epinephrine hydrochloric acid injection with recovery of ca. 98.4%.     

EQCM and Fluoroelectrochemical Studies on the Catalytic Oxidation of NADH at a Pencil 8B‐Scrawled Gold Electrode with High Detection Sensitivity

We report for the first time the effective catalytic electrooxidation of nicotinamide adenine dinucleotide (NADH) on the pencil 8B‐scrawled gold electrode of an electrochemical quartz crystal microbalance (EQCM). The EQCM allowed us to quantitatively evaluate the catalytic activity of the pencil‐scrawled Au electrode. With increasing the mass of modified pencil powders, the peak potential for NADH oxidation shifted negatively, with maximum shift of ?0.35 V at saturated pencil modification; the NADH‐oxidation peak current density (j_p) was also notably increased, and the j_p at saturated pencil modification was found to be larger than those at conventional pencil 8B and bare Au electrodes. Sensitive amperometric detection of NADH was achieved at the gold electrode with saturated pencil modification, with low detection potential (0.4 V versus SCE), low detection limit (0.08 μmol L^?1) and wide linear range (0.2–710 μmol L^?1). The fluoroelectrochemical measurements of NADH at bare and pencil‐modified gold electrodes were also conducted with satisfactory results. The convenient and low‐cost modification of pencil powders on the Au electrode may have presented a new functional surface of the EQCM, which is recommended for wider applications to bioelectrochemical studies, especially in view of the EQCM's capability of providing abundant in situ information in relevant processes.     

NADH Electrocatalytic Oxidation on Gold Nanoparticle‐Modified PVC/TTF‐TCNQ Composite Electrode. Application as Amperometric Sensor

We herein report on the electrocatalytic activity towards the oxidation of NADH of a PVC/TTF‐TCNQ composite electrode modified with gold nanoparticles. This electrocatalytic property allows proposing this system as a new alternative for amperometric determination of NADH, without need to add another mediator. The sensor shows a linear response to NADH over a concentration range from 5.0×10^?6 M up to 5.0×10^?4 M, with a sensitivity of 11.22±0.5 mA M^?1 and a detection limit (S/N=3) of 4.0×10^?6 M for measurements in batch and similar data in FIA.     

Low Potential Detection of NADH at Titanium‐Containing MCM‐41 Modified Glassy Carbon Electrode

Titanium‐containing MCM‐41 (Ti‐MCM‐41) modified glassy carbon electrode (GCE) can exhibit an excellent electrocatalytic activity towards the oxidation of β‐Nicotinamide adenine dinucleotide (NADH). A dramatic decrease in the over‐voltage of NADH oxidation reaction is observed at 0.28 V (vs. SCE). The modified electrode is found to be stable and reproducible. The electrode shows a linear response for a wide range of 10–1200 μM NADH and the detection limit is 8.0 μM. Ti‐MCM‐41 mesoporous molecular sieves provide an efficient matrix for development of NADH biosensors and the prepared electrode not only can be used to detect the concentration of NADH in biochemical reaction, but also as the potential matrix of the construction of dehydrogenases biosensor.     

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.     

Voltammetric Determination of 2′‐Deoxyadenosine and Adenine in Urine of Patients with Hepatocellular Carcinoma Using Fullerene‐C60‐modified Glassy Carbon Electrode

A fullerene‐C₆₀‐modified glassy carbon electrode has been examined for the simultaneous determination of 2′‐deoxyadenosine (2′‐dAdo) and adenine in human blood and urine using Osteryoung square‐wave voltammetry (OSWV) at pH 7.2. Compared to bare glassy carbon electrode (GCE), the modified electrode displays a shift of the oxidation potential in the negative direction with significant increase in the peak current for both the analytes. At modified electrode well‐defined anodic peaks at potential of 1248 mV and 994 mV are observed for 2′‐dAdo and adenine respectively. Linear calibration curves were obtained within the concentration range 10 nM to 100 μM for both the compounds in 0.1 M phosphate buffer solution (PBS) with the limit of detection 0.8×10^?8 M and 0.95×10^?8 M for 2′‐dAdo and adenine respectively. The analytical utility of the present method is demonstrated by quantitative detection of 2′‐dAdo and adenine in human urine of normal subjects as well as in patients with hepatocellular carcinoma. Interfering effect of some coexisting metabolites has also been reported.     

A NADH Sensor Based on 1,2‐Naphththoquinone Electropolymerized on Multi‐walled Carbon Nanotubes Modified Glassy Carbon Electrode

A new carbon nanotubes modified electrode (poly‐Nq‐MWCNTs/GCE) was fabricated by electropolymerization of 1,2‐naphththoquinone to the surface of multi‐walled carbon nanotubes modified electrode by casting method. The morphology of the nanocomposite was characterized by scanning electron microscopy. Cyclic voltammetry and chronoamperometry were applied to investigate the electrochemical properties of the poly‐Nq‐MWCNTs nanocomposite modified electrode. The result of electrochemical experiments showed that such modified electrode had a favorable catalytic ability to oxidation of β‐nicotinamide adenine dinucleotide (NADH). The resulted sensor was sensitiveness to NADH and achieved 95β of the steady‐state current within 5s. Furthermore, the anodic peak current was linear to the concentration of NADH for the range from 1.0 μM to 0.14 mM. The linear equation was: I(μA) = 0.3987 + 0.1035c (μmol/L), the correlation coefficient r = 0.9962, the detect limit is down to 1 × 10^?7 M (S/N = 3) and the sensitivity is 0.1035 μA/mmol. The well catalytic activity of the sensor was ascribed to the synergistic effect role played by MWCNTs and poly‐Nq. Moreover, the based sensor possesses good stability and reproducibility.     

Electrochemical Determination of 2‐Nitrophenol in Water Samples Using Mg‐Al‐SDS Hydrotalcite‐Like Clay Modified Glassy Carbon Electrode

A glassy carbon electrode (GCE) modified with Mg‐Al‐SDS hydrotalcite‐like clay (SDS‐HTLC) was used for the sensitive voltammetric determination of 2‐nitrophenol (2‐NP) utilizing the oxidation process. The results indicate the prepared modified electrode has an excellent electrocatalytic activity toward 2‐NP oxidation, lowering the oxidation overpotential and increasing the oxidation current. Under optimal conditions, the oxidation current was proportional to 2‐NP concentration in the range from 1.0×10^?6 to 6.0×10^?4 M with the detection limit of 5.0×10^?7 M by DPV (S/N=3). The fabricated electrode was applied for 2‐NP determination in water samples and the recovery for these samples was from 95.6 to 103.5%.     

NADH Oxidation Catalyzed by Electropolymerized Azines on Carbon Nanotube Modified Electrodes

Electropolymerizing azines on a carbon nanotube (CNT) modified electrode yields a high‐surface area interface with excellent electrocatalytic activity towards NADH oxidation. Electrodeposition of poly(methylene green) (PMG) and poly(toluidine blue) (PTBO) on the carboxylated CNT‐modified electrodes was achieved by cyclic voltammetry. The PMG‐CNT interface demonstrates 5.0 mA cm^?2 current density for NADH oxidation at 50 mV vs. Ag|AgCl in 20 mM NADH solution. The kinetics of NADH electrocatalysis were analyzed using a quantitative mass‐transport‐corrected model with NADH bulk concentration and applied potential as independent variables. This high‐rate poly(azine)‐CNT interface is potentially applicable to high‐performance bioconversion, bioenergy and biosensors involving NADH‐dependent dehydrogenases.     

Graphene Functionalized Graphite Electrode with Diphenylacetylene for Sensitive Electrochemical Determination of Adenosine‐5′‐triphosphate

In this paper a molecular wire modified carbon paste electrode (MW‐CPE) was firstly prepared by mixing graphite powder with diphenylacetylene (DPA). Then a graphene (GR) and chitosan (CTS) composite film was further modified on the surface of MW‐CPE to receive the graphene functionalized electrode (CTS‐GR/MW‐CPE), which was used for the sensitive electrochemical detection of adenosine‐5′‐triphosphate (ATP). The CTS‐GR/MW‐CPE exhibited excellent electrochemical performance and the electrochemical behavior of ATP on the CTS‐GR/MW‐CPE was carefully studied by cyclic voltammetry with an irreversible oxidation peak appearing at 1.369 V (vs. SCE). The electrochemical parameters such as charge transfer coefficient (α) and electrode reaction standard rate constant (k_s) were calculated with the results of 0.53 and 5.28×10^?6 s^?1, respectively. By using differential pulse voltammetry (DPV) as detection technique, the oxidation peak current showed good linear relationship with ATP concentration in the range from 1.0 nM to 700.0 µM with a detection limit of 0.342 nM (3σ). The common coexisting substances, such as uric acid, ascorbic acid and guanosine‐5′‐triphosphate (GTP), showed no interferences and the modified electrode was successfully applied to injection sample detection.     

Detection of NADH and Ethanol at Titanium Containing MCM‐41 with Low Overpotential

Titanium‐containing MCM‐41 (Ti‐MCM‐41) modified glassy carbon electrode (GCE) can exhibit an excellent electrocatalytic activity towards the oxidation of β‐Nicotinamide adenine dinucleotide (NADH). A dramatic decrease in the overvoltage of NADH oxidation reaction is observed at 0.28 V vs. SCE. The application in the amperometric biosensing of ethanol using alcohol dehydrogenase enzyme (ADH) also has been demonstrated with this material. The proposed sensor shows a highly sensitivity, an acceptable reproducibility and a good stability. The linear range of ethanol is 25–1000 μM and the detection limit is 8.0 μM. Ti‐MCM‐41 modified electrode not only can be used to detect the concentration of NADH in biochemical reaction, but also as the potential matrix for the construction of dehydrogenases sensor.     

Au‐TiO2/Graphene Nanocomposite Film for Electrochemical Sensing of Hydrogen Peroxide and NADH

We describe a simple method for preparing Au‐TiO₂/graphene (GR) nanocomposite by deposition of Au nanoparticles (NPs) on TiO₂/GR substrates. The as‐prepared Au‐TiO₂/GR was characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The presence of Au NPs on TiO₂/GR surface remarkably improves the electrocatalytic activity towards the oxidation of hydrogen peroxide (H₂O₂) and β‐nicotinamide adenine dinucleotide (NADH). The Au‐TiO₂/GR modified glassy carbon (GC) electrode exhibits good amperometric response to H₂O₂ and NADH, with linear range from 10 to 200 µM and 10 to 240 µM, and detection limit of 0.7 and 0.2 µM, respectively.     

Electrocatalytic Oxidation and Voltammetric Determination of L‐Cysteic Acid at the Surface of p‐Bromanil Modified Carbon Paste Electrode

The electrochemical properties of L ‐cysteic acid studied at the surface of p‐bromanil (tetrabromo‐p‐benzoquinone) modified carbon paste electrode (BMCPE) in aqueous media by cyclic voltammetry (CV) and double step potential chronoamperometry. It has been found that under optimum condition (pH 7.00) in cyclic voltammetry, the oxidation of L ‐cysteic acid at the surface of BMCPE occurs at a half‐wave potential of p‐bromanil redox system (e.g., 100 mV vs. Ag|AgCl|KCl_sat), whereas, L ‐cysteic acid was electroinactive in the testing potential ranges at the surface of bare carbon paste electrode. The apparent diffusion coefficient of spiked p‐bromanil in paraffin oil was also determined by using the Cottrell equation. The electrocatalytic oxidation peak current of L ‐cysteic acid exhibits a linear dependency to its concentration in the ranges of 8.00×10^?6 M–6.00×10^?3 M and 5.2×10^?7 M–1.0×10^?5 M using CV and differential pulse voltammetry (DPV) methods, respectively. The detection limits (2σ) were determined as 5.00×10^?6 M and 4.00×10^?7 M by CV and DPV methods. This method was used as a new, selective, rapid, simple, precise and suitable voltammetric method for determination of L ‐cysteic acid in serum of patient's blood with migraine disease.     

Electrochemical Sensor for the Determination of Dopamine in Presence of High Concentration of Ascorbic Acid Using a Fullerene‐C60 Coated Gold Electrode

A fullerene‐C₆₀‐modified gold electrode is employed for the determination of dopamine in the excess of ascorbic acid using square‐wave voltammetry. Based on its strong catalytic function towards the oxidation of dopamine and ascorbic acid, the overlapping voltammetric response of both the biomolecules at the bare electrode is resolved into two well‐defined voltammetric peaks with lowered oxidation potential and enhanced oxidation currents. Linear calibration curves for dopamine are obtained using square‐wave voltammetry over the concentration range 1 nM–5.0 μM in 0.1 M phosphate buffer solution at pH 7.2 with a correlation coefficient of 0.9931 and the detection limit (3σ) is estimated to be 0.26×10^?9 M. The interference studies showed that the presence of physiologically common interferents (i.e. uric acid, citric acid, tartaric acid, glucose and sodium chloride) negligibly affects the response of dopamine. The practical analytical utility of the method is illustrated by quantitative determination of dopamine in commercially available pharmaceutical formulation and human body fluids, viz. urine and blood plasma, without any preliminary treatment.     

Synthesis and Characterization of Novel Quinone‐Amine Polymer/Carbon Nanotubes Composite for Sensitive Electrocatalytic Detection of NADH

A novel nanocomposite of quinone‐amine polymer and multiwalled carbon nanotubes was synthesized from iodate‐oxidation/Michael addition reaction of 1,2‐dihydroxybenzene with o‐phenylenediamine, which was characterized by TEM, FTIR and UV‐vis spectra. The nanocomposite modified Au electrode with well‐defined quinone redox peaks effectively mediated the oxidation of NADH in pH 7.0 phosphate buffer, with an overpotential decrease by ca. 470 mV (vs. bare Au), a limit of detection of 6.4 nmol L^?1 and good antiinterferent ability.     

η1‐Allypalladium Complexes with Tridentate PNP’ Ligand for the Assembly of Modified Screen Printed Electrodes: an Electrochemical Study

Specific Pd‐based organometallic complex, in particular the [Pd(η¹‐CH₂? CH=CH₂)(P? N? P’)]BF₄ was used for the assembly of chemically modified Screen Printed Electrodes (SPEs) and their electrochemical reactivity was also investigated. For this purpose potassium ferricyanide, hexaammineruthenium(III) chloride, sodium hexachloroiridate‐(III) hydrate, ascorbic acid (AA), uric acid (UA), acetaminophen (Ac), guanine (G) and adenine (A) were used to study the electron‐transfer processes, which occurred at modified SPEs, fabricated by using the [Pd(η¹‐CH₂? CH=CH₂)(P? N? P’)]BF₄, applying the drop casting procedure. Interesting results were obtained in the case of the guanine (G) quantitative detection, especially in terms of a wide range of concentration (2.5–40 nM), an high sensitivity (of 49.0 A M^?1 cm^?2), a low detection limit (LOD=1.0 nM) and a fast response time (of t=2 s). The intra‐electrode reproducibility (RSD%) was <1 % for the same SPE used for each point of the calibration plot. The inter‐electrode reproducibility (RSD%), estimated by using different SPEs for each single point of the quantitative calibration graph, ranging from 5 to 10 %, better than that exhibited by other different chemical sensors, described in literature, and reported in this work for comparison. In addition, the high selectivity of the chemically modified sensors toward the oxidation of guanine, exhibited in presence of a mixture of G+A, in the same electrochemical bath solution, could be related to the different electro‐catalytic mechanisms, as demonstrated by the XPS study. This chemical sensor prototype could be very promising for bio‐medicine applications.     

Selective Electrochemical Epinephrine Sensor Using Self‐Assembled Monomolecular Film of 1,8,15,22‐Tetraaminophthalocyanatonickel(II) on Gold Electrode

This article describes the highly sensitive and selective determination of epinephrine (EP) using self‐assembled monomolecular film (SAMF) of 1,8,15,22‐tetraamino‐phthalocyanatonickel(II) (4α‐Ni^IITAPc) on Au electrode. The 4α‐Ni^IITAPc SAMF modified electrode was prepared by spontaneous adsorption of 4α‐Ni^IITAPc from dimethylformamide solution. The modified electrode oxidizes EP at less over potential with enhanced current response in contrast to the bare Au electrode. The standard heterogeneous rate constant (k°) for the oxidation of EP at 4α‐Ni^IITAPc SAMF modified electrode was found to be 1.94×10^?2 cm s^?1 which was much higher than that at the bare Au electrode. Further, it was found that 4α‐Ni^IITAPc SAMF modified electrode separates the voltammetric signals of ascorbic acid (AA) and EP with a peak separation of 250 mV. Using amperometric method the lowest detection limit of 50 nM of EP was achieved at SAMF modified electrode. Simultaneous amperometric determination of AA and EP was also achieved at the SAMF modified electrode. Common physiological interferents such as uric acid, glucose, urea and NaCl do not interfere within the potential window of EP oxidation. The present 4α‐Ni^IITAPc SAMF modified electrode was also successfully applied to determine the concentration of EP in commercially available injection.     

Electrochemical Sensing of NADH and Glutamate Based on Meldola Blue in 1,2‐Diaminobenzene and 3,4‐Ethylenedioxythiophene Polymer Films

The redox mediator Meldola blue (MB) was entrapped into two polymers, poly‐1,2‐diaminobenzene (p‐DAB) and poly‐3,4‐ethylenedioxythiophene (p‐EDOT) by potential cycling and films were applied to NADH oxidation with subsequent glutamate detection using immobilized glutamate dehydrogenase. Both polymer films were tested for electrocatalysis of NADH using amperometry at E_app=0.1 V vs. Ag/AgCl and similar response characteristics were obtained with sensitivity values of 6.1 nA μM^?1, linear range up to 0.5 mM (R²=0.9972) and LOD of 50 μM. Subsequent amperometric determination of glutamate resulted in sensitivity 0.7 nA μM^?1, linearity 0–100 μM and detection limit of 2 μM glutamate.     

Electrochemical Fabrication of Prussian Blue Nanocube‐decorated Electroreduced Graphene Oxide for Amperometric Sensing of NADH

In this study, Prussian blue (PB) film on the electroreduced graphene oxide (ERGO)‐modified Au electrode surface (ERGO/PB) is easily prepared by means of cyclic voltammetric technique in the mixture of K₃Fe(CN)₆ and FeCl₃. Its electrochemical behaviors for NADH biosensor are studied. The structural and morphological characters of modified electrode material are analyzed with using of XPS, XRD, Raman, EDS, and SEM techniques. ERGO/PB hybrid nanocomposite for NADH biosensor is exhibited to the higher catalytic effect (linear range from 1.0 to 100 μM, detection limit of 0.23 μM at S/N=3) compared to naked Au, ERGO‐modified Au, and PB‐modified Au electrodes. In addition to, ERGO/PB electrode was used to voltammetric and amperometric detection of H₂O₂. ERGO/PB electrodes also showed the same behavior as the NADH sensor. This ERGO/PB‐modified electrode supplied a simple, new, and low‐cost route for amperometric sensing of both NADH and H₂O₂.