Mimesis of peroxidase by Mn-TMPyP in the catalytic fluorescence reaction of the homovanillic acid-hydrogen peroxide system

The fluorescence produced by the catalytic effect of the manganese (III)-tetrakis-(N-methylpyridinium)porphyrin complex (Mn-TMPyP) on the oxidation of homovanillic acid by hydrogen peroxide has been studied. The reaction product fluoresces at 424 nm (with excitation at 316 nm). Traces of hydrogen peroxide (1.3 × 10^–7–2.4 × 10^–6 M) and glucose (1.5–5.0 g/ml) can be determined with good accuracy and reproducibility. The characteristics of the mimetic enzyme Mn-TMPyP have been compared with those of horseradish peroxidase.     

Microdetermination of phosphorus in organic compounds by indirect spectrophotometric reactions

Summary Organo phosphorus compounds are decomposed by closed-flask combustion. The phosphate ions produced are then converted to phosphomolybdic acid and extracted withiso- butyl acetate. The 12molybdate ions associated with each original phosphate ion are spectrophotometrically determined by reactions with alkaline hydrogen peroxide, hydrogen peroxide and benzidine and gallic acid. The colours are measured at 450, 400 and 400nm respectively.

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Zusammenfassung Organische Phosphorverbindungen werden im Schöniger-Kolben mineralisiert. Das Phosphat wird zu Phosphormolybdänsäure umgesetzt, miti-Butylacetat extrahiert und dann spektrophotometrisch bestimmt. Dazu bedient man sich der Reaktionen mit alkalischem Wasserstoffperoxid, mit Wasserstoffperoxid und Benzidin oder mit Gallussäure. Die Messungen erfolgen bei 450 nm im ersten Fall, bei 400 nm im Fall der beiden letztgenannten Farbreaktionen.

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This paper is taken from the Master's Thesis of S. A. I. Thoria.     

Fluorescent quenching method for determination of trace hydrogen peroxide in rain water

A simple and sensitive fluorescent quenching method for the determination of trace hydrogen peroxide (H(2)O(2)) has been proposed to determine hydrogen peroxide in rain water sample. The method is based on the reaction of H(2)O(2) with 3,3'-diethyloxadicarbocyanine iodide (DI) to form a compound which has no fluorescence in acetate buffer solution (pH 3.09). The maximum emission wavelength of the system is located at 604 nm with excitation at 570 nm. Under the optimal conditions, the calibration graph was obtained between the quenched fluorescence intensity and hydrogen peroxide concentration in the range of 5.0 x 10(-7) to 9.0 x 10(-4) mol L(-1). The proposed method was applied to determine H(2)O(2) in rain water samples, and the result was satisfactory. The mechanism involved in the reaction was also studied.     

Oxidation of azo dye Orange II with hydrogen peroxide catalyzed by 5,10,15,20-tetrakis[4-(diethylmethylammonio)phenyl]porphyrinato-cobalt(II)tetraiodide in aqueous solution

The catalytic oxidation of the azo dye Orange II by hydrogen peroxide in aqueous solution has been investigated using 5,10,15,20-tetrakis-[4-(diethylmethylammonio)phenyl]porphyrinato-cobalt(II) tetra iodide 1as catalyst. The oxidation reaction was followed by recording the UV–vis spectra of the reaction mixture with time at λ_max = 485 nm. The factors that may influence the oxidation of Orange II, such as the effect of reaction temperature, concentration of catalyst, hydrogen peroxide and orange II have been studied. The results of total organic carbon analysis showed 52% of dye mineralization under mild reaction conditions. Residual organic compounds in the reaction mixture were identified by using Gas chromatography-mass spectrometry. The decolorization rate and mineralization of the dye has been found to increase with increase of catalyst concentration and reaction temperature. The rate of dye oxidation decreased with increasing the concentration of dye, H₂O₂ and at higher pH than 9. Radical scavenging measurement indicated that decolorization of Orange II by H₂O₂/cobalt (II) porphyrin complex 1 involved the formation of hydroxyl radicals as the active species.     

Verbesserung der Empfindlichkeit der katalytischen Chemiluminescenzreaktion auf Kupfer

Zusammenfassung Die Lage des Gleichgewichtes der Komponenten bei der katalytischen Wirkung von Kupfer auf die Chemiluminescenz, die bei der Reaktion von Luminol mit Wasserstoffperoxid auftritt, wurde auf photoelektrischem und photographischen Wege untersucht. Man stellte fest, daß das Erlöschen der Chemiluminescenz von der Zerstörung des Wasserstoffperoxids abhängt. Der Einfluß der Art des Zusatzes von Wasserstoffperoxid auf die Leuchtintensität, ihre Dauer und Ausbeute wurde studiert.Als Resultat der Untersuchung ist es gelungen, die Empfindlichkeit der Kupferbestimmung durch Luminescenz zu verbessern. Die Bestimmung kann bis herab zu 3 · 10^–9 g Cu/ml durchgeführt werden.

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Summary The equilibrium position of the components in the catalytic action of copper on the chemiluminescence appearing in the reaction of luminol with hydrogen peroxide has been investigated by photoelectric and photographic means. The quenching of this luminescence has been found to depend on the decomposition of hydrogen peroxide. The effect of the way of addition of hydrogen peroxide on the intensity, time, and output of light has been exaimed.As a result of this investigation the sensitivity of the determination of copper by luminescence has been improved. The determination can be performed with minimum concentrations of 3 · 10^–9 g Cu/ml.

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Aus dem Russischen übersetzt von H. Kurtenacker.     

Fluorimetric determination of hydrogen peroxide in water using acetaminophen

A fluorimetric procedure for the determination of hydrogen peroxide, based on the oxidation of acetaminophen with hydrogen peroxide in acidic medium, is described. The calibration graph was linear in the range 5.0 x 10(-8) - 2.4 x 10(-5) M hydrogen peroxide at an emission wavelength of 333 nm with excitation at 298 nm. The method has been applied to the determination of hydrogen peroxide in rain water, and the recoveries in milk samples were good.     

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.     

Kinetic Spectrophotometric Determination of Manganese by Use of the Salicylaldehyde-Hydrogen Peroxide System

Abstract

A kinetic method is described for determining trace amounts of manganese(II), based on its catalytic effect on the oxidation of salicylaldehyde by hydrogen peroxide. The reaction is followed spectrophotometrically by measuring the rate of change of absorbance at 500 nm. The calibration graph is linear in the range 5–100 ng/ml with a relative error of ± 1.2%. The method has been applied to the determination of manganese in natural water.     

Spectrophotometric nonenzymatic determination of hydrogen peroxide using silver nanoparticles

A nonenzymatic method was developed for the detection and quantification of hydrogen peroxide using metallic sols obtained by the reduction of silver compounds with sodium borohydride in the presence of a surface stabilizer. These sols changed color on exposure to aqueous solutions of hydrogen peroxide. The nature of the stabilizer used in sol preparation affects spectral characteristics of the final product formed in the reaction with hydrogen peroxide. In the case of polyvinyl pyrrolidone, the intensity of the surface plasmon resosnance absorption band at 405 nm decreased. In using cetyltrimethylammonium bromide, a signal at 519 nm appeared along with the similar decrease in the absorption band at 408 nm. The band intensity depends on the concentration of hydrogen peroxide. The described phenomena can form a basis for the development of procedures for the qualitative and quantitative determination of hydrogen peroxide in water bodies.     

Kinetic studies on the reaction of N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetate chromium(III) with hydrogen peroxide

The rate of reaction of Cr(III)L (L=N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetate) with hydrogen peroxide was studied in aqueous media and was found to yield Cr(VI) over the temperature range of 25–41 °C. The reaction was followed spectrophotometrically at 396 nm under pseudo-first order conditions with hydrogen peroxide in a large excess. The reaction follows first-order kinetics in Cr(III). The dependence of the rate constant on hydrogen peroxide concentration is attributed to the formation of an intermediate between the monohydroxy chromium(III) complex and hydrogen peroxide which decomposes in the rate determining step. At high hydrogen peroxide concentration, the order is changed from first to zero order.The values of the intramolecular electron transfer rate constant, the formation constant of the intermediate complex and the activation parameters were calculated.     

Fluorimetric determination of hydrogen peroxide by use of the fluorescence reaction between N-(4'-hydroxyphenyl)-N-(4-methylquinolinyl)amine and cobalt(II) in the presence of trimethylstearylammonium chloride

The fluorimetric determination of hydrogen peroxide by using the fluorescence reaction between N-(4'-hydroxyphenyl)-N-(4-methylquinolinyl)amine (HPMQ), cobalt(II) and hydrogen peroxide in the presence of trimethylstearylammonium chloride (STAC) as a cationic surfactant was proposed. The calibration graph was linear in the range 0-2500 ng of hydrogen peroxide per 10 ml of solution at an emission wavelength of 522 nm with excitation at 410 nm. The recovery tests in foods were good.     

Simultaneous spectrofluorimetric determination of iron and manganese by a differential kinetic catalytic method

A kinetic method is presented for the simultaneous determination of iron(III) and manganese(II) based on the different reaction rates resulting from the catalytic effect of both metal ions on the oxidation of 2-hydroxybenzaldehyde thiosemicarbazone by hydrogen peroxide in an ammoniacal medium. The reaction is monitored spectrofluorimetrically at 440 nm and with excitation at 365 nm. Two sets of reaction conditions are established to maximize the effect of manganese compared to iron, and vice versa, and the data are evaluated from simultaneous equations. Mixtures of these metal ions at ng ml^?1 levels for iron/manganese ratios from 8:1 to 1:2 can be determined with an accuracy and precition of about 3% and 1%, respectively. The methods has been applied successfully to the determination of both metals in aluminium and copper alloys, beer, cheeses and soils.     

Analytical use of modified catalytic reaction rate: Kinetic determination of traces of aminopolycarboxylic acids,nickel and zinc

Summary The inhibitory effect of EDTA (or EGTA) on the copper-catalysed oxidation of 4,4-dihydroxybenzophenone thiosemicarbazone by hydrogen peroxide has been studied. The reaction is followed spectrophotometrically at 415 nm. EDTA and EGTA at the 10^–6 M level can be determined kinetically by two methods. The accuracy and precision are about 1% and 1.5% respectively. The method can be applied to the indirect determination of nickel and zinc in the range 130–300 ng/ml with acceptable results, by an indirect kinetic method.

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Analytische Anwendung einer modifizierten katalytischen Geschwindigkeitskonstante: kinetische Bestimmung von Spuren von Aminopolycarbonsäuren, Nickel und Zink

Zusammenfassung Die hemmende Wirkung von EDTA (oder EGTA) gegenüber der kupferkatalysierten Oxydation von 4,4-Dihydroxybenzophenonthiosemicarbazon durch Wasserstoffperoxid wurde untersucht. Die Reaktion wurde bei 415 nm spektrophotometrisch verfolgt. EDTA und EGTA können in 10^–6 M Größenordnung mit zwei verschiedenen Methoden kinetisch bestimmt werden. Die Genauigkeit beträgt etwa 1% bzw. 1,5%. Das Verfahren kann zur indirekten Bestimmung von Nickel und Zink in der Größenordnung 130–300 ng/ml mit annehmbaren Ergebnissen herangezogen werden.

     

Ru(III)-EDTA catalyzed oxidation of ascorbic acid by hydrogen peroxide in aqueous solution

The kinetics of oxidation of ascorbic acid to dehydroascorbic acid by hydrogen peroxide catalyzed by ethylenediaminetetraacetatoruthenate(III) has been studied over the pH range 1.50 – 2.50, at 30°C and μ = 0.1 M KNO₃. The reaction has a first-order dependence on ascorbic acid and Ru(III)-EDTA concentrations, an inverse first-order dependence on hydrogen ion concentration, and is independent of hydrogen peroxide concentration in the pH range studied. A mechanism has been proposed in which ascorbate anion forms a kinetic intermediate with the catalyst in a pre-equilibrium step. Ruthenium(III) is reduced to ruthenium(II) in a rate-determining step and is reoxidized with hydrogen peroxide back to the Ru(III) complex in a fast step.     

Experimentelle Beiträge zur katalytischen Bestimmung von Metallspuren

Zusammenfassung Die zur Bestimmung von Kobaltspuren schon früher vorgeschlagene Alizarin-Perborat- bzw. Alizarin-Wasserstoffperoxyd-Methode und die sich dabei abspielenden Reaktionen wurden eingehend untersucht. Durch Zugabe von Alizarin wird die Zersetzung von Wasserstoffperoxyd wesentlich vermindert, Alizarin vermag also Wasserstoffperoxyd unter geeigneten Verhältnissen zu stabilisieren. Kobaltspuren heben diese stabilisierende Wirkung nicht nur auf, sondern beschleunigen die Zersetzung des Wasserstoffperoxyds wesentlich. Diese Tatsache kann an Hand der raschen Farbänderung bzw. der raschen Abnahme des Wasserstoffperoxydgehaltes im Reaktionsgemisch verfolgt werden. Das Produkt der Reaktion zwischen Alizarin und Wasserstoffperoxyd übt keine stabilisierende Wirkung mehr aus.

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Summary The alizarin-perborate or alizarin-hydrogen peroxide methods, and their accompanying reactions, which had previously been proposed for the determination of traces of cobalt, were studied intensively. The decomposition of hydrogen peroxide is substantially decreased by adding alizarin. Therefore under proper circumstances alizarin is able to stabilize hydrogen peroxide. Traces of cobalt not only annul this stabilizing action but hasten the decomposition of the hydrogen peroxide to a considerable degree. This fact can be followed through the rapid change in color or through the rapid fall in the hydrogen peroxide content in the reaction mixture. The product of the reaction between alizarin and hydrogen peroxide no longer has any stabilizing action.

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Résumé On a étudié en détail les méthodes à l'alizarine-perborate ou à l'alizarineeau oxygénée, déjà recommandées pour le dosage de traces de cobalt, ainsi que les réactions qui entrent en jeu. L'addition d'alizarine réduit considérablement la décomposition de l'eau oxygénée; par conséquent, utilisée dans des conditions convenables, l'alizarine peut stabiliser l'eau oxygénée. Des traces de cobalt non seulement suppriment cette action stabilisante, mais accélèrent énormément la décomposition de l'eau oxygénée. On peut suivre cet état de fait au moyen du changement rapide de couleur ou au moyen de la diminution rapide de la teneur en eau oxygénée dans le mélange réactionnel. Le produit de la réaction entre l'alizarine et l'eau oxygénée n'exerce plus d'action stabilisante.

     

Catalytic effect of iron(III) on the oxidation of 2-hydroxybenzaldehyde thiosemicarbazone by hydrogen peroxide : Kinetic Fluorimetric Determination of Iron

A kinetic method is described for the determination of nanogram amounts of iron(III) based on its catalysis of the oxidation of 2-hydroxybenzaldehyde thiosemicarbazone by hydrogen peroxide in an ammoniacal medium. In order to monitor the reaction, the appearance rate of fluorescence of the oxidation product (λ_ex=365 nm, λ_em=440 nm) is measured. The calibration graph is linear in the range 10–60 ng ml^?1 iron(III) with an r.s.d, of ± 1.3%. The proposed method has few interferences and has been applied satisfactorily to the determination of iron in several alloys and minerals. A mechanism for the catalyzed reaction is proposed.     

Amperometric Determination of Lactic Acid. Applications on Milk Samples

Abstract

A hydrogen peroxide electrochemical sensor, coupled with immobilized lactate oxidase and covered with a cellulose acetate dialysis membrane has been applied in flow analysis of lactate in milk samples. The hydrogen peroxide produced by the enzymatic reaction is measured with a platinum electrode polarized at +650 mV versus Ag/AgCl. Milk samples were analyzed and compared with a spectophotometric reference method. The developed procedure is very simple and the short response time allows its use in assaying milk samples on dairy farms.     

Oxidation of 2,3,5-trimethylphenol to 2,3,5-trimethylbenzoquinone with aqueous hydrogen peroxide in the presence of spinel CuCo2O4

The catalytic oxidation of 2,3,5-trimethylphenol was carried out with aqueous hydrogen peroxide over spinel CuCo₂O₄; under the mild conditions, this study realized 80% selectivity for 2,3,5-trimethylquinone at 100% conversion of 2,3,5-trimethylphenol. The catalyst was investigated by XRD, TEM, UV–vis and FT-IR; and the reaction has been studied by different parameters like performance of different catalysts, effect of aqueous hydrogen peroxide, reaction time, reaction temperature, solvents, catalyst concentration, catalyst separation, and recycling of catalyst. Compared to the conventional methods, this method could be more eco-friendly.