Amperometric determination of hydrogen peroxide with a manganese dioxide film-modified screen printed carbon electrode

A carbon thick film electrode modified with an MnO₂-film is investigated as an amperometric detector for hydrogen peroxide in flow-injection analysis (FIA). At an operating potential of +0.48 V vs. Ag/AgCl catalytic oxidation of the analyte is exploited for amperometric monitoring. Experimental parameters, such as pH of the carrier, working potential, flow rate and injection volume, are optimized. The amperometric signals are linearly proportional to the concentration of H₂O₂ in the range from 0.005 to 10 mg/L, showing a detection limit (3σ) of 2.3 μg/L. The method is applied to the determination of H₂O₂ in rain water and to a simple assay to quantify glucose in human plasma. Received: 29 January 1998 / Revised: 4 May 1998 / Accepted: 13 May 1998     

Flow Injection Amperometric Analysis of H2O2 at Platinum Nanoparticles Modified Pencil Graphite Electrode

A Pt nanoparticle modified Pencil Graphite Electrode (PGE) was proposed for the electrocatalytic oxidation and non‐enzymatic determination of H₂O₂ in Flow Injection Analysis (FIA) system. Platinum nanoparticles (PtNPs) electrochemically deposited on pretreated PGE (p.PGE) surface by recording cyclic voltammograms of 1.0 mM of H₂PtCl₆ solution in 0.10 M KCl at scan rate of 50 mV s⁻¹ for 30 cycles. Cyclic voltammograms show that the oxidation peak potential of H₂O₂ shifts from about +700 mV at bare PGE to +50 mV at PtNPs/p.PGE vs. Ag/AgCl /KCl (sat.). It can be concluded that PtNPs/p.PGE exhibits a good electrocatalytic activity towards oxidation of H₂O₂. Then, FI amperometric analysis of H₂O₂ was performed under optimized conditions using a new homemade electrochemical flow cell which was constructed for PGE. Linear range was found as 2.5 μM to 750.0 μM H₂O₂ with a detection limit of 0.73 μM (based on S_b/m of 3). As a result, this study shows the first study on the FI amperometric determination of H₂O₂ at PtNPs/p.PGE which exhibits a simple, low cost, commercially available, disposable sensor for H₂O₂ detection. The proposed electrode was successfully applied to determination of H₂O₂ in real sample.     

Room temperature ionic liquid doped DNA network immobilized horseradish peroxidase biosensor for amperometric determination of hydrogen peroxide

A novel electrochemical H₂O₂ biosensor was constructed by embedding horseradish peroxide (HRP) in a 1-butyl-3-methylimidazolium tetrafluoroborate doped DNA network casting on a gold electrode. The HRP entrapped in the composite system displayed good electrocatalytic response to the reduction of H₂O₂. The composite system could provide both a biocompatible microenvironment for enzymes to keep their good bioactivity and an effective pathway of electron transfer between the redox center of enzymes, H₂O₂ and the electrode surface. Voltammetric and time-based amperometric techniques were applied to characterize the properties of the biosensor. The effects of pH and potential on the amperometric response to H₂O₂ were studied. The biosensor can achieve 95% of the steady-state current within 2 s response to H₂O₂. The detection limit of the biosensor was 3.5 μM, and linear range was from 0.01 to 7.4 mM. Moreover, the biosensor exhibited good sensitivity and stability. The film can also be readily used as an immobilization matrix to entrap other enzymes to prepare other similar biosensors. Figure Horseradish peroxidase (HRP) embedded in a 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM·BF ₄ ) doped DNA network can be used to fabricate a HRP sensor for the determination of H₂O₂     

Electrodeposition of TiO2 Nanoparticles on Multiwalled Carbon Nanotube Arrays for Hydrogen Peroxide Sensing

In this work, an amperometric H₂O₂ sensor based on TiO₂/MWCNTs electrode is reported. TiO₂ nanoparticles were synthesized on vertically aligned multiwalled carbon nanotube (MWCNT) arrays by electrodeposition. The morphology of the TiO₂/MWCNTs was characterized by scanning electron microscopy (SEM). The electrochemical performance of the TiO₂/MWCNTs electrode for detection of H₂O₂ was investigated by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and chronoamperometry. The TiO₂/MWCNTs electrode displays high electrocatalytic activity towards oxidation of H₂O₂ in 0.1 M phosphate buffer solution (PBS, pH 7.4). At an applied potential of +0.40 V, the TiO₂/MWCNTs electrode exhibits a linear dependence (R=0.998) in the H₂O₂ concentration up to 15.0×10^?3 M with a sensitivity of 13.4 μA mM^?1 and detection limit of 4.0×10^?7 M with signal/noise=3. The optimal response time is less than 5 s with addition of 1 mM H₂O₂. The TiO₂/MWCNTs electrode presents stable, high sensitivity and also exhibits fast amperometric response to the detection of H₂O₂, which is promising for the development of H₂O₂ sensor.     

Amperometric Biosensor for Hydrogen Peroxide Based on Electrodeposited Sub-micrometer Gold Modified Glassy Carbon Electrode

IntroductionAmperometricbiosensorofhydrogenperoxideisofpracticalimportancebecauseofitswideapplicationsinchemical,biological,clinical,environmentalandmanyotherfields.Forimprovementofsensor抯quality,vari-ouskindsofchemicalmodificationmethodshavebeendevelopedforreducingredoxoverpotentialsofH2O2atelectrodesurfaces,increasingthedetectionsensitivity,linearrange,stabilityandlivetime.Ithasbeenshownthattheuseofsub-micrometersizedmetalparticlessuchasPt-blackcansignificantlyimprovethequalityofthebiosens…     

Sensitive Amperometric Sensing of Hydrogen Peroxide Using Ag Nanowire Array Electrode

The amperometric sensor based on a silver nanowire (80 nm in diameter Ag NW) array electrode was fabricated and characterized with scanning electron microscope (SEM). The electrode showed good electrocatalytic activity for reduction of hydrogen peroxide. The effects of the applied polarization potential, pH, time interval between successive injections of analyte, injection volume and H₂O₂ concentration in a single injection on the electrochemical performance of the sensor were studied. It was found that the optimized operating conditions for the proposed sensor are: the potential of ?200 mV, pH between 7.4 and 9.0, 60 s time interval, 10 µL injection volume, and 500 µM H₂O₂ in single injection. The proposed Ag NW array sensor is free of interference from ascorbic acid, uric acid and glucose.     

TNT determination based on its degradation by immobilized HRP with electrochemical sensor

Based on the mechanism of 2,4,6-Trinitrotoluene (TNT) degradation, an amperometric hydrogen peroxide biosensor was constructed for the determination of trace amounts of TNT by immobilization of MWCNTs, HRP and Nafion onto the surface of glassy carbon electrode (GCE). The Nafion/MWCNTs/HRP biosensor was capable of degrading TNT with the consumption of H₂O₂ and HRP in 0.2 mol/L PBS (pH 7.0). Trace TNT was quantitative analyzed by the current decrease of H₂O₂ at the reductive potential of −0.35 V using cyclic voltammetry (CV). Effect of the ratio of MWCNTs/HRP, initial concentration of H₂O₂ and electrolyte’s pH were also optimized by CV. Under the optimal conditions, the current decrease of H₂O₂ that was consumed by TNT degradation was proportional to TNT ranging from 8.8 × 10⁻⁹ mol/L to 2.64 × 10⁻⁷ mol/L with a detection limit of 3.0 × 10⁻⁹ mol/L (S/N = 3). It developed a new way for simple, rapid and sensitive measurement of trace TNT.     

Flow Injection Determination of Hydrogen Peroxide Using a Carbon Paste Electrode Modified with a Manganese Dioxide Film

Abstract

A manganese dioxide film modified carbon paste electrode was developed for use as an amperometric sensor for the determination of hydrogen peroxide (H₂O₂) in ammoniacal aqueous solutions. The electrode showed a stable response towards H₂O₂ after electrochemical activation. Effects of flow rate, operating potential, concentration, injection volume and interferences were investigated. A linear response towards H₂O₂ from 5 μg.l^?1 to 450 mg.l^?1 and a detection limit (3 signal-to-noise ratio) of 4.7 μg.l^?1 was found. The method was employed for the determination of H₂O₂ in rain water samples.     

Determination of hydrogen peroxide based on calcined layered double hydroxide-modified glassy carbon electrode in flavored beverages

In this paper, we developed an amperometric hydrogen peroxide (H₂O₂) sensor based on cobalt-containing calcined layered double hydroxide (Co CLDH). The electrocatalytic activity of the Co CLDH towards the determination of H₂O₂ showed a fast response and high sensitivity. Moreover, the sensor exhibited good reproducibility and long-term stability. The superior electrocatalytic response to H₂O₂ is mainly attributed to the large surface area, minimized diffusion resistance, and enhanced electron transfer of the synthesized Co CLDH. This method with good analytical performance, low cost, and straightforward preparation made this novel electrode material promising for the determination of trace H₂O₂ in beverages with high accuracy, demonstrating its potential for practical application.     

Hydrogen Peroxide Sensor Based on Hemoglobin Immobilized on Glassy Carbon Electrode with SiO2 Nanoparticles/Chitosan Film as Immobilization Matrix

Abstract

A novel amperometric sensor of hydrogen peroxide was constructed. Hemoglobin (Hb) was successfully immobilized on nanometer‐sized SiO₂, which was supported by chitosan. Chitosan was acted as dispersant. The determination of hydrogen peroxide was performed in the presence of an electron mediator hydroquinone. Hb immobilized on the SiO₂/chitosan composite film displayed excellent electrocatalytical activity to the reduction of H₂O₂. The linear range of detection towards H₂O₂ was from 6.25×10^?7 to 1.63×10^?4mol/L with a detection limit of 1.8×10^?7mol/L (S/N=3). The apparent Michaelis‐Menten constant (K ^app _M) was found to be 0.75mmol/L.     

Vertically Aligned CuO Nanowires Based Electrode for Amperometric Detection of Hydrogen Peroxide

Vertically aligned copper oxide (CuO) nanowires were synthesized by directly heating copper foil on a hotplate under ambient conditions. The as‐grown CuO nanowires film is mechanically stable and was facilely attached to a glassy carbon (GC) electrode, offering an excellent electrochemical sensing platform. The CuO nanowires electrode shows excellent electrocatalytic response to H₂O₂ with significantly lower overpotentials for its oxidation and reduction and also exhibits a fast response and high sensitivity for the amperometric detection of H₂O₂. The novel vertically aligned CuO nanowires electrode is readily applicable to other analytes and has great potential applications in the electrochemical detection.     

A hydrogen peroxide biosensor based on multiwalled carbon nanotubes-polyvinyl butyral film modified electrode

A novel approach to construct a amperometric biosensor for determination of H₂O₂ is described. Horseradish peroxidase (HRP) as a base enzyme was immobilized into the mixture of multiwalled carbon nanotubes (MWNTs) and polyvinyl butyral (PVB). Taking the classical hydroquinone as mediator, cyclic voltammetry and amperometric measurements were used to study and optimize the performance of the resulting H₂O₂ biosensor. The effect of the concentration of MWNTs, HRP, hydroquinone, solution pH, and the working potential of amperometry on the electrochemical biosensor was systematically studied. The results showed that the fabricated biosensor demonstrated significant electrocatalytic activity for the reduction of hydrogen peroxide with wide linear range from 0.000832 to 0.6 mM, and low detection limit 0.000167 mM (S/N = 3) with fast response time less than 8 s. The apparent Michaelis–Menten constant was determined to be 0.049 mM. Additionally, the biosensor exhibited high sensitivity, rapid response and good long-term stability.     

Separation-free amperometric enzyme immunoassay

A new technique for conducting a separation-free amperometric enzyme immunoassay is described using DNP-aminocaproic acid as the analyte. The technique is based on the combined use of a recently described separation-free enzyme immunoassay (19) and an electrode system that senses H₂O₂. Oxidation of glucose to gluconate and H₂O₂ by the enzyme reconstituted from DNP-conjugate apoglucose oxidase (DPN-CAGO) and FAD was continuously measured amperometrically. The reconstitution was inhibited by preincubation with anti-DNP antibody before adding FAD. This antibody-induced inhibition of the reconstituting of the holoenzyme was reversed by adding DNP-amino caproic acid to DNP-CAGO before adding the antibody to DNP-CAGO. Based on (a) the antibody-induced inhibition of holoenzyme reconstitution, (b) a specific ligand-induced reversal of the inhibition, and (c) an electrochemical system that measures H₂O₂, we developed a separation-free (homogeneous) amperometric enzyme immunoassay.     

Simultaneous Detection of Peracetic Acid and Hydrogen Peroxide by Amperometry at Pt and Au Electrodes

Based on preliminary voltammetric investigations at both Pt and Au electrodes in aqueous solutions buffered at different pH values in the range 0–10, two possible profitable triple‐pulse amperometric approaches were developed for determining simultaneously peroxyacetic acid (PAA) and hydrogen peroxide present in the same samples. At both surfaces a pulsed waveform applied at rotating‐disc electrodes was adopted to take advantage on one hand of the optimized signal reproducibility achieved by this potential multistep antifouling approach and on the other hand of the constant thickness of the diffusion layer, which is necessary when the recording of time‐independent currents is desired. At a rotating‐disc Pt electrode an anodic selective signal was indeed recorded for H₂O₂ alone, while PAA contents could be inferred only from the difference of convenient signals, since at all pHs explored its sole cathodic reaction could be observed at potentials coincident with those proper for the reduction of H₂O₂ too. The same pulse approach at Au electrodes instead provided totally independent signals for the two analytes considered, thus proving to be suitable for their independent detection. In fact, H₂O₂ alone undergoes anodic oxidation also at this surface, while the reduction of PAA occurs at potentials less cathodic than those required for H₂O₂. At both electrodes, the best results turned out to be achieved at pH 0 in terms of both precision (±2–4%) and detection limits (0.2–0.3 mM), as well as of linear range which extended for about three orders of magnitude. The kinetics of the equilibrium involving the generation of H₂O₂ from the reaction of PAA with water was also evaluated, since it was suspected of making unreliable the proposed amperometric approaches.     

Picomolar Detection of Hydrogen Peroxide at Glassy Carbon Electrode Modified with NAD+ and Single Walled Carbon Nanotubes

Potential cycling was used for oxidation of NAD⁺ and producing an electroactive redox couple which strongly adsorbed on the electrode surface modified with single walled carbon nanotubes (SWCNTs). Modified electrode shows a pair of well defined and nearly reversible redox peaks at pH range 1–13 and the response showed a surface‐controlled electrode process. The surface coverage and heterogeneous electron transfer rate constant (k_s) of adsorbed redox couple onto CNTs films were about 6.32×10^?10 mol cm^?2 and 2.0 (±0.20) s^?1, respectively, indicating the high loading ability of CNTs toward the oxidation product of NAD⁺ (2,8‐dihydroxy adenine dinucleotide) and great facilitation of the electron transfer between redox couple and CNTs immobilized onto electrode surface. The modified electrode exhibited excellent electrocatalytic activity for H₂O₂ reduction at reduced overpotential. The catalytic rate constant for H₂O₂ reduction was found to be 2.22(±0.20)×10⁴ M^?1 s^?1. The catalytic reduction current allows the amperometric detection of H₂O₂ at an applied potential of ?0.25 V vs. Ag/AgCl with a detection limit of 10 pM and linear response up to 100 nM and resulting analytical sensitivity 747.6 nA/pM. The remarkably low detection limit (10 pM) is the lowest value ever reported for direct H₂O₂ determination on the electrodes at pH 7. The modified electrode can be used for monitoring H₂O₂ without the need for an enzyme or enzyme mimic. The proposed method for rapid amperometric detection of H₂O₂ is low cost and high throughput. Furthermore, the sensor can be used to any detection scheme that uses enzymatically generated H₂O₂ as a reactive product in biological systems.     

Catalysis‐Electrochemical Detection of Horseradish Peroxidase at Zeptomole Level in Capillary Zone Electrophoresis

Capillary zone electrophoresis with catalysis‐electrochemical detection has been developed and applied to determining horseradish peroxidase (HRP) at zeptomole levels. In this method, an on‐line enzyme catalysis reactor with a reaction capillary was designed. Isoenzymes of HRP were separated by capillary zone electrophoresis, and then they catalyzed the enzyme substrate 3,3′,5,5′‐tetramethylbenzide (TMB(Red)) and H₂O₂ in the reaction capillary. The reaction product, TMB(Ox), could be determined using amperometric detection on a carbon fiber microdisk bundle electrode at the outlet of the reaction capillary. Because of enzyme amplification, a significant amount of TMB(Ox) could be produced for detection. Therefore, the limit of detection (LOD) of HRP is very low. The optimum conditions of the method are 1.5×10^?2 mol/L borate (pH 7.4) for the run buffer, 2×10^?3 mol/L for the concentration of H₂O₂, 2×10^?4 mol/L TMB(Red)+2.0×10^?2 mol/L citrate‐phosphate (pH 5.0) for the substrate solution, 40 cm for the liquid pressure height, 20 kV for the separation voltage, 100 mV for the detection potential. HRP could be measured with a detection limit of 4.8×10^?12 mol/L or 47.5 zmol (S/N=3). The linear range is from 2.40×10^?11 to 2.40×10^?8 mol/L. Using this method, commercial HRP was measured at zeptomole within ten minutes.     

Direct electrochemistry of hemoglobin on graphene/Fe3O4 nanocomposite-modified glass carbon electrode and its sensitive detection for hydrogen peroxide

Graphene/Fe₃O₄ nanocomposite was prepared for the immobilization of hemoglobin (Hb) to improve the electron transfer between Hb and glass carbon electrode (GCE). The characterization of nanocomposites was described by transmission electron microscopy, Fourier transform infrared, Raman spectroscopy, and X-ray photoelectron spectroscopy, respectively. The electrochemistry of Hb on the graphene/Fe₃O₄-based GCE was investigated by cyclic voltammetry and amperometric measurement. The modified electrode showed a wide linear range from 0.25 μmol/L to 1.7 mmol/L with a correlation coefficient of 0.9967. The detection limit of the H₂O₂ biosensor was estimated at 6.0?×?10^?6?mol/L at a signal-to-noise ratio of 3.     

A Facile Preparation of H2O2 Sensors Using Layer‐by‐Layer Deposited Thin Films Composed of Poly(ethyleneimine) and Carboxymethyl Cellulose as Matrices for Immobilizing Hemin

A layer‐by‐layer (LbL) thin film composed of poly(ethyleneimine) (PEI) and carboxymethyl cellulose (CMC) was prepared on the surface of a gold (Au) disk electrode and the LbL layer was impregnated with hemin to fabricate amperometric hydrogen peroxide (H₂O₂) sensors. Hemin can be easily immobilized in the LbL layer by immersing the LbL film‐coated electrode in the hemin solution. The hemin‐modified electrode thus prepared exhibited an amperometric response to H₂O₂ on the basis of the electrochemical reduction catalyzed by hemin. The output current of the hemin‐modified electrode depended on the concentration of H₂O₂ over the range of 0.005–1.0 mM. Thus, the LbL film composed of PEI and CMC was found to be an excellent material for the facile preparation of hemin‐based H₂O₂ sensors.     

A hydrogen peroxide biosensor based on horseradish peroxidase/poly(L-leucine)/polydopamine modified glassy carbon electrode

A simple and practical sensor of hydrogen peroxide (H₂O₂) was designed successfully. The mixture of horseradish peroxidase (HRP) and chitosan (Chit) are effectively immobilized on the surface of poly-L-leucine/polydopamine modified glassy carbon electrode (PL-LEU/PDA/GCE). Under the optimum conditions, the biosensor based on HRP exhibits a fast amperometric response (within 3 s) to H₂O₂. The linear response range of the sensor is 0.5–952.0 μmol L^–1, with the detection limit of 0.1 μmol L^–1 (S/N = 3) and the sensitivity of 0.23 A L moL^–1 cm^–2. The apparent Michaelis–Menten constant (k _M ^app) of the biosensor is evaluated to be 0.12 mmol L^–1, which suggests that the HRP-Chit/PL-LEU/PDA/GCE shows a higher affinity for H₂O₂. The sensor exhibits good sensitivity, selectivity, stability and reproducibility. The proposed method has been successfully applied to the determination of H₂O₂ in practical samples.     

Stability Improvement of Prussian Blue by a Protective Cellulose Acetate Membrane for Hydrogen Peroxide Sensing in Neutral Media

The cellulose acetate covered Prussian blue modified glassy carbon electrode (GCE/PB/CA) was fabricated as a novel hydrogen peroxide sensor. It was shown by scanning electron microscope (SEM) and atomic force microscope (AFM) that Prussian blue was covered and protected by cellulose acetate perfectly. The modified electrode showed a good electrocatalytic activity for H₂O₂ reduction in neutral aqueous solution. H₂O₂ was detected amperometrically in 0.05 mol/L phosphate buffer solutions (pH 7.0, containing 0.1 mol/L KCl as supporting electrolyte) at an applied potential of ?0.2 V (vs. SCE). The response current was proportional to the concentration of H₂O₂ in the range of 1.0×10^?5 mol/L to 2.5×10^?4 mol/L with the detection limit of 2.2×10^?6 mol/L at a signal to noise ratio 3.