Determination of Hydrogen Peroxide Concentrations By Flow Injection Analysis Based On the Enhanced Chemiluminescent Reaction Using Peroxidase

Abstract

The technique of flow injection analysis was employed in the determination of hydrogen peroxide. the method was based on the chemiluminescence reaction of luminol with H₂O₂ which is catalyzed by horseradish peroxidase and enhanced by p-iodophenol. Hydrogen peroxide was linearly detected in the range 10^?6M-10^?4M by measuring the maximum intensity of light emitted. the detection limit is about 1 · 10^?6M hydrogen peroxide. Transition metal cations at millimolar concentrations do not have any interference on the determination of hydrogen peroxide by FIA based on the enhanced chemiluminescent reaction. This technique is relatively rapid and simple, and permits measurement of up to 80 samples/hr using generally available equipment.     

Screening of chemiluminescent systems for the determination of some biologically important organic compounds

Screening tests are described for the development of chemiluminescence systems (oxidizing systems) capable of detecting biological organic compounds. The light emission depends strongly on the oxidizing systems employed. Acidic permanganate system gives rise to light emission for many compounds, including catechols, catecholamines, triphenols and indoles. The following oxidizing systems led specifically to chemiluminescence for hydroquinone, adrenaline or phenylpyruvic acid: 10^?1 M thiosulphate with 10^?1 M sodium hydroxide and 10^?4 M Ag (I), 0.3 % hydrogen peroxide with 10^?3 M sodium hydroxide/50% acetonitrile and 10^?4 M Fe (II), and 0.3% hydrogen peroxide with 10^?2 M sodium hydroxide/10^?2 M didodecyldimethylammonium bromide and 10^?4 M Co(II), respectively.     

Flow Injection Amperometric Determination of Hydrogen Peroxide at Low Level in Aqueous Solution

Abstract

A method is proposed for the flow-injection amperometric determination of hydrogen peroxide. Iodine is generated, by injecting hydrogen peroxide solution into an eluent 0.2 M in potassium iodide and 1 Min sulphuric acid and 5×10^?3M in Mo(VI) and is monitored at a platinum electrode that is being held at 0.1 V versus SCE. the rectilinearity range is from 10^?3?10^?6 M and the method is simple, accurate and compared favourably with the titrimetric method involving starch as indicator.     

Flow-injection determination of sulphite and assay of sulphite oxidase

Sulphite (1–80 × 10^?5 M) in formaldehyde-stabilized solutions is determined by injection into a flowing stream of pH 8.5 phosphate buffer, passing through a mini-column of sulphite oxidase immobilized on controlled-pore glass, with amperometric detection of the hydrogen peroxide produced. Sulphite oxidase (5–100 U l^?) is determined by injection into a flowing stream of formaldehyde-stabilized 2 × 10^?3 M sodium sulphite in pH 8.0 phosphate buffer; hydrogen peroxide is again monitored.     

Determination of Hydrogen Peroxide by Electrochemiluminescence Using a Chitosan–graphene Composite Film Doped Cadmium-Tellurium Quantum Dot Modified Glassy Carbon Electrode

Here is reported the novel determination of hydrogen peroxide by electrochemiluminescence using a chitosan–graphene composite film doped cadmium-tellurium quantum dot modified glassy carbon electrode. The cadmium-tellurium quantum dots were studied by absorption and fluorescence spectroscopy. Scanning electron microscopy and electrochemical impedance spectroscopy were used to characterize the structure morphology of the composite matrix. The electrochemiluminescence emission was linear with the concentration of hydrogen peroxide in the range of 3.5?×?10^?7 to 1.1?×?10^?5?M with a determination limit of 2.1?×?10^?7?M. Furthermore, the modified electrode showed excellent reproducibility and stability.     

Flow-injection amperometric determination of oxalate with immobilized oxalate oxidase

Oxalate is immobilized on controlled-pore glass and is used on-line in a glass minicolumn (2.5×25 mm). The hydrogen peroxide formed is detected amperometrically. Oxalate (6×10^?6?9×10^?4 M) is determined in a flowing stream of pH 3.5 citrate (or succinate) buffer. As little as 20 ng (in 40 μl; 5.7×10^?6 M) of oxalate can be detected. Copper inhibition can be removed either by adding EDTA to the carrier stream or incorporating a chelating-resin minicolumn into the flow system prior to the enzyme column.     

Flow injection determination of hydrogen peroxide by means of a solid-state-peroxyoxalate chemiluminescence reactor

A solid-state reactor for detection of hydrogen peroxide in aqueous samples by peroxyoxalate chemiluminescence is described. Bis(2,4,6-trichlorophenyl)oxalate in solid form is packed into a bed reactor, which eliminates mixing problems and facilitates the instrumental development. Perylene is added as a sensitizer to a water/acetonitrile (20:80) carrier stream into which the samples (200–600 μl) are injected. Detection limits of 6 × 10^?9 M H₂O₂ (0.2 μg l^?1) are obtained with both a commercial and a home-made luminescence detector. Calibration graphs are linear up to 10^?5 M. The r.s.d. for 2 × 10^?7 M (6.7 μg^?1) hydrogen peroxide (n = 10) is 2.8%. Sample throughput is ca. 120 h^?1.     

Nickel hexacyanoferrate nanoparticles/nano silver coated multiwalled carbon nanotubes nanocomposite for the detection of hydrogen peroxide

A new nanocomposite was developed by combination of nickel hexacyanoferrate nanoparticles (NiNP) and nano silver coated multiwalled carbon nanotubes (nano Ag-MWNTs). The NiNP/nano Ag-MWNTs nanocomposite was charactered by scanning electron microscopy (SEM). The NiNP/nano Ag-MWNTs nanocomposite modified glassy carbon (GC) electrode was used to investigate the electrochemical reduction of hydrogen peroxide. The results showed that NiNP and nano Ag-MWNTs provided the synergistic effect toward this process. The obtained NiNP/nano Ag-MWNTs/GC electrode showed a wide linear response range of 1 × 10^?6 to 1 × 10^?4 and 5 × 10^?4 to 0.01 M hydrogen peroxide with correlation coefficients of 0.998 and 0.997, fast response time (2 s), and good selectivity toward the electrocatalytic reduction of hydrogen peroxide. The detection limit (S/N = 3) of hydrogen peroxide was 5 × 10^?7 M.     

Development of an Amperometric Enzymatic Biosensor Based on Gold Modified Magnetic Nanoporous Microparticles

Gold modified nanoporous silica based magnetic microparticles have been prepared as support for the immobilization of the enzyme horseradish peroxidase (HRP). The enzyme modified gold microparticles were retained onto the surface of a solid carbon paste electrode with the help of a permanent magnet. The analytical performances of the resulting biosensor were characterized by studying hydroquinone (HQ) and hydrogen peroxide. The former was monitored by the direct electroreduction of the biocatalytically generated quinone. Several experimental parameters influencing the biosensor response were investigated. A linear response to HQ was obtained in the concentration range comprised between 5×10^?7 and 4.5×10^?6 M with a detection limit of 4×10^?7 M. The enzyme electrode provided a linear response to hydrogen peroxide over a concentration range comprised between 5×10^?7?1.3×10^?4 M with a detection limit of 4×10^?7 M. The inhibition of the biosensor response in the presence of thiols e.g. cysteine, captopril, glutathione and Nacystelyn (NAL) has been pointed out.     

A solid-state chemiluminescence detector for hydrogen peroxide based on an immobilized luminophore : Application to Rain Water

The construction and functioning of a chemiluminescence detector for hydrogen peroxide is described. It is based on peroxyoxalate chemiluminescence and consists of a two-bed reactor packed with solid trichlorophenyloxalate (TCPO) and 3-aminofluoranthene immobilized on controlled pore glass beads. Optimal conditions (pH, solvent, TCPO purity) for flow-independent operation are discussed. Samples can be injected into a moving stream or directly into the monitor with a syringe so as to provide a manually operated field monitor. The detection limit is 1.5 × 10^?8 M, and calibration graphs are linear over six orders of magnitude. The r.s.d. for the manual monitoring mode is ±3% for 17 μg l^?1 hydrogen peroxide. A sample throughput of 100 h^?1 is possible in the flow injection mode, and 40 samples h^?1 for manual injection.     

Grape tissue-based electrochemical sensor for the determination of hydrogen peroxide

The use of grape tissue as a source of catalase for the determination of hydrogen peroxide is reported. A slice of grape tissue attached to the membrane of a Clark-type oxgen sensor was used to monitor the oxidation of hydrogen peroxide by catalase. At the steady state, the sensor responds linearly to hydrogen peroxide in the concentration range 1 × 10^?5–5 × 10^?4 M. The response time (T₉₀) was of the order of 1 min for this sensor. No interference was observed from ethanol, amino acids, glucose and lactic acid. The long-term stability of the grape tissue sensor was much better than previously reported immobilized enzyme and liver tissue-based hydrogen peroxide sensors.     

Feasibility of low-voltage cathodic electroluminescence at oxide-covered aluminum electrodes for trace metal determinations in aqueous solutions

Metal-catalyzed electroluminescence is generated at an oxide-covered aluminum electrode during the reduction of oxygen, potassium peroxodisulfate, and especially hydrogen peroxide in aqueous solutions. The feasibility of this electroluminescence for the determination of copper (5 × 10^?9 M) and thallium (> 10^?10 M) is demonstrated.     

Study of the mimetic peroxidase-catalysed chemiluminescence reaction

The chemiluminescence behaviour of the reaction in which the Mn-TPPS₄ complex the mimetic enzyme of peroxidase [manganese tetrakis(sulphophenyl)porphine] acts as a catalyst for the oxidation of luminol by hydrogen peroxide was studied. The reaction product luminesces at 427 nm. Trace amounts of hydrogen peroxide and glucose can be determined with detection limits of 5.5 × 10^?9 and 2.7 × 10^?9 M, respectively. The characteristics of Mn-TPPS₄ were compared with those of horseradish peroxidase.     

Amperometric determination of hydrogen peroxide in pickling baths for copper and copper alloys by flow injection analysis

The hydrogen peroxide is oxidized at + 1.5 V vs. SCE at a glassy carbon electrode of the wall-jet type. The samples are diluted about 100 times in a dispersion coil before entering the amperometric detector. The calibration curve is linear from 10^?4 to 1 M H₂O₂, when 5-μl samples are used. With 50-μl samples the detection limit decreases to 10^?6 M H₂O₂. Neither metal ions (Cu²⁺, Zn²⁺, Ni²⁺, Al³⁺) up to 0.5 M nor changes in the sulfuric acid concentration of the samples between 0.1 and 1 M interfere with the hydrogen peroxide determination. About 75 samples can be analyzed per hour.     

Sensitive Flow-Injection Electrochemical Determination of Hydrogen Peroxide at a Palladium Nanoparticle-Modified Pencil Graphite Electrode

A novel flow-injection amperometric method was proposed for the sensitive and enzymeless determination of hydrogen peroxide based on its electrocatalytic reduction at a palladium nanoparticle-modified pretreated pencil graphite electrode in a laboratory-constructed electrochemical flow cell. Cyclic voltammograms of the unmodified and modified electrodes were recorded in pH 7.0 phosphate buffer containing 0.10 M KCl at a scan rate of 50?mV s^?1 for the investigation of electrocatalytic reduction of hydrogen peroxide at the palladium nanoparticle-modified pretreated pencil graphite electrode. Cyclic voltammograms of the pretreated pencil graphite electrode revealed an irreversible oxidation peak and a weak reduction peak of hydrogen peroxide at +1100?mV and –450?mV vs. an Ag/AgCl/KCl saturated reference electrode. However, the reduction of hydrogen peroxide was observed at –100?mV with an increase in current in the cyclic voltammograms of the palladium nanoparticle-modified pretreated pencil graphite electrode compared to the unmodified electrode. These results indicate that the palladium nanoparticle-modified pretreated pencil graphite electrode exhibits efficient electrocatalytic activity for the reduction of hydrogen peroxide. A linear concentration range was obtained between .01 and 10.0?mM hydrogen peroxide with a detection limit of 3.0 µM from flow injection amperometric current–time curves recorded in pH 7.0 phosphate buffer at –100?mV and a 2.0?mL min^?1 flow rate. The novelty of this work relies on its use of a laboratory-constructed flow cell constructed for the pencil graphite electrode using these inexpensive, disposable, and electrochemically reactive modified electrodes for the amperometric determination of hydrogen peroxide in a flow injection analysis system.     

Semiconductor laser fluorimetry for enzyme and enzymatic assays

Near-infrared semiconductor laser fluorimetry is applied to assays of xanthine and xanthine oxidase. The fluorescence of indocyanine green in the near-infrared region is quenched by hydrogen peroxide. Xanthine is converted to uric acid by xanthine oxidase, in a reaction which also produces hydrogen peroxide; xanthine can be determined by measuring the decrease in fluorescence intensity of the dye added to the sample solution. The calibration graph for xanthine is linear from 5 × 10^?5 M to 5 × 10^?7 M. The enzyme activity can also be determined.     

Electrocatalysis via Direct Electrochemistry of Myoglobin Immobilized on Colloidal Gold Nanoparticles

The direct electron transfer between immobilized myoglobin (Mb) and colloidal gold modified carbon paste electrode was studied. The Mb immobilized on the colloidal gold nanoparticles displayed a pair of redox peaks in 0.1 M pH 7.0 PBS with a formal potential of –(0.108 ± 0.002) V (vs. NHE). The response showed a surface‐controlled electrode process with an electron transfer rate constant of (26.7 ± 3.7) s ^?1 at scan rates from 10 to 100 mV s^?1 and a diffusion‐controlled process involving the diffusion of proton at scan rates more than 100 mV s^?1. The immobilized Mb maintained its activity and could electrocatalyze the reduction of both hydrogen peroxide and nitrite. Thus, the novel renewable reagentless sensors for hydrogen peroxide and nitrite were developed, respectively. The activity of Mb with respect to the pseudo peroxidase with a K_M^app value of 0.65 mM could respond linearly to hydrogen peroxide concentration from 4.6 to 28 μM. The sensor exhibited a fast amperometric response to NO₂^? reduction and reached 93% of steady‐state current within 5 s. The linear range for NO₂^? determination was from 8.0 to 112 μM with a detection limit of 0.7 μM at 3σ.     

Amperometric Biosensors Based on Platinum Nanowires

Abstract

Platinum nanowires (PtNW) were prepared by an electrodeposition strategy using nanopore alumina template. The nanowires prepared were dispersed in chitosan (CHIT) solution and stably immobilized onto the surface of glassy carbon electrode (GCE). The electrochemical behavior of PtNW‐modified electrode and its application to the electrocatalytic reduction of hydrogen peroxide (H₂O₂) are investigated. The modified electrode allows low potential detection of hydrogen peroxide with high sensitivity and fast response time. As an application example, the glucose oxidase was immobilized onto the surface of PtNW‐modified electrode through cross‐linking by glutaric dialdehyde. The detection of glucose was performed in phosphate buffer at –0.2 V. The resulting glucose biosensor exhibited a short response time (<8 s), with a linear range of 10^?5?10^?2 M and detection limit of 5×10^?6 M.     

The kinetics of complex formation between Ti(IV) and hydrogen peroxide

The kinetics of the formation of the titanium‐peroxide [TiO²⁺₂] complex from the reaction of Ti(IV)OSO₄ with hydrogen peroxide and the hydrolysis of hydroxymethyl hydroperoxide (HMHP) were examined to determine whether Ti(IV)OSO₄ could be used to distinguish between hydrogen peroxide and HMHP in mixed solutions. Stopped‐flow analysis coupled to UV‐vis spectroscopy was used to examine the reaction kinetics at various temperatures. The molar absorptivity (ε) of the [TiO²⁺₂] complex was found to be 679.5 ± 20.8 L mol^?1 cm^?1 at 405 nm. The reaction between hydrogen peroxide and Ti(IV)OSO₄ was first order with respect to both Ti(IV)OSO₄ and H₂O₂ with a rate constant of 5.70 ± 0.18 × 10⁴ M^?1 s^?1 at 25°C, and an activation energy, E_a = 40.5 ± 1.9 kJ mol^?1. The rate constant for the hydrolysis of HMHP was 4.3 × 10^?3 s^?1 at pH 8.5. Since the rate of complex formation between Ti(IV)OSO₄ and hydrogen peroxide is much faster than the rate of hydrolysis of HMHP, the Ti(IV)OSO₄ reaction coupled to time‐dependent UV‐vis spectroscopic measurements can be used to distinguish between hydrogen peroxide and HMHP in solution. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 457–461, 2007     

A Multicommuted Flow‐based System for Hydrogen Peroxide Determination by Chemiluminescence Detection Using a Photodiode

Abstract

A simple, rapid, and automated assay for hydrogen peroxide in pharmaceutical samples was developed by combining the multicommutation system with a chemiluminescence (CL) detector. The detection was performed using a spiral flow‐cell reactor made from polyethylene tubing that was positioned in front of a photodiode. It allows the rapid mixing of CL reagent and analyte and simultaneous detection of the emitted light. The chemiluminescence was based on the reaction of luminol with hydrogen peroxide catalyzed by hexacyanoferrate(III).

The feasibility of the flow system was ascertained by analyzing a set of pharmaceutical samples. A linear response within the range of 2.2–210 µmol l^?1 H₂O₂ with a LD of 1.8 µmol l^?1 H₂O₂ and coefficient of variations smaller than 0.8% for 1.0×10^?5 mol l^?1 and 6.8×10^?5 mol l^?1 hydrogen peroxide solutions (n=10) were obtained. Reagents consumption of 90 µg of luminol and 0.7 mg of hexacyanoferrate(III) per determination and sampling rate of 200 samples per hour were also achieved.