Potentiometric flow-injection determination of trace hydrogen peroxide based on its induced reaction in iron(III)-iron(II) potential buffer containing bromide and molybdenum(VI)

A rapid and highly sensitive potentiometric flow-injection method for the determination of trace hydrogen peroxide was developed by use of an Fe(III)-Fe(II) potential buffer solution containing bromide and Mo(VI). The analytical method was based on a linear relationship between a concentration of hydrogen peroxide and a largely transient potential change of an oxidation-reduction potential electrode due to bromine generated by the reaction of hydrogen peroxide with the potential buffer solution. The oxidation of bromide to bromine by hydrogen peroxide occurred very rapidly with the assistance of Mo(VI) when Fe(II) existed in the potential buffer solution. It was estimated by batchwise experiments that hydroxyl radical, OH., was generated by the reaction of hydrogen peroxide with Fe(II) as an intermediate, and subsequently oxidized bromide to bromine. In a flow system, analytical sensitivities to hydrogen peroxide obtained by the detection of the transient change of potential were enhanced about 75 fold compared with those obtained by using the potential change caused by the reaction of hydrogen peroxide with the potential buffer solution without bromide and Mo(VI). Sensitivities increased with decreasing concentration of the Fe(III)-Fe(II) buffer in the reagent solution. The detection limit (S/N = 3) of 4 x 10(-7) M (13.6 ppb) was achieved by using the 1 x 10(-4) M Fe(III)-Fe(II) buffer containing 0.4 M NaBr, 1.0 M H(2)SO(4) and 0.5% (NH(4))(6)Mo(7)O(24). Analytical throughput was approximately 40 h(-1) and the RSD (n = 6) was 0.6% for measurement of 4 x 10(-6) M hydrogen peroxide. The proposed method was applied to the determination of hydrogen peroxide in real rainwater samples, and was found to provide a good recovery for H(2)O(2) added to rainwater samples.     

Potentiometric determination of bromate using an Fe(III)-Fe(II) potential buffer by circulatory flow-injection analysis.

A method for the potentiometric determination of bromate by circulatory flow injection analysis (CFIA) is described. The procedure involves the use of an Fe(III)-Fe(II) potential buffer solution, which is recycled via a reservoir. The analytical method is based on a linear relationship between the concentration of bromate and a very transient potential change in the electrode potential due to the generation of intermediate bromine during the reaction of bromate with the Fe(III)-Fe(II) potential buffer solution, which also contains NaBr, (NH4)6Mo7O24 and H2SO4. An aliquot (5 microl) of a bromate sample solution was injected into the stream of the potential buffer solution, 100 ml of which was circulated at a flow rate of 1 ml/min; the potential buffer solution stream was then returned to the reservoir after passing through a flow-through redox electrode detector. A potential change due to the reaction of the injected sample with the potential buffer in a reaction coil was measured with the detector in the form of a peak signal. The effects of the bromide, sulfuric acid and Fe(III)-Fe(II) concentrations in the potential buffer, and length of the reaction coil on the peak heights were examined in order to optimize the proposed CFIA method. The analytical sensitivities to bromate were 5.6 mV/microM for 1 x 10(-2) M and 30.9 mV/microM for 1 x 10(-3) M in the concentration of Fe(III)-Fe(II) in a potential buffer solution containing 0.35 M NaBr, 0.2% (NH4)6Mo7O24 and 1 M H2SO4. The detection limit of bromate obtained by a 1 x 10(-3) M Fe(III)-Fe(II) potential buffer solution was 0.02 microM (2.5 ppb). The numbers of repetitive determinations in which the relative sensitivities within 5% were regarded as being tolerated were ca. 4000 and 2000 for the use of only 100 ml of 1 x 10(-2) M and 1 x 10(-3) M Fe(III)-Fe(II) potential buffer solution, respectively.     

Electrochemical and photosensitized redox reactions of a prussian blue film layered on a WO3/[Ru(bpy)3]2+/polymer hybrid film.

A hybrid film of WO(3)/tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)(3)](2+))/poly(sodium 4-styrenesulfonate) (PSS) (denoted as a WRP hybrid film) was prepared as a base layer on an indium tin oxide electrode substrate by cathodic electrodeposition from a colloidal ternary solution containing peroxotungstic acid, [Ru(bpy)(3)](2+), and PSS. Prussian blue, Fe(III) (4)[Fe(II)(CN)(6)](3) (Fe(II)-Fe(III)) was cathodically electrodeposited on the WRP hybrid film from a Berlin brown (Fe(III)-Fe(III)) colloidal solution to give a WRP/Fe(II)-Fe(III) bilayer film. Spectrocyclic voltammetry measurement of the WRP/Fe(II)-Fe(III) bilayer film reveals that Prussian white (Fe(II)-Fe(II)) is oxidized to Fe(II)-Fe(III) by electrogenerated Ru(III), and Fe(II)-Fe(III) is re-reduced to Fe(II)-Fe(II) by electrogenerated H(x)WO(3). Visible-light irradiation of the WRP hybrid film generates a small photocurrent (approximately 8 nA cm(-2)) at 0.4 V of an applied potential, whereas irradiation of the WRP/Fe(II)-Fe(II) bilayer film (Fe(II)-Fe(III) is electrochemically reduced to the Fe(II)-Fe(II) state) significantly generates a steady photoanodic current of 2.0-1.1 microA cm(-2) under the same conditions, thus demonstrating that the photoanodic current is produced by the layered Fe(II)-Fe(II) film. The photoaction spectrum of the bilayer film reveals that the photoanodic current is based on the photoexcitation of [Ru(bpy)(3)](2+). The photogeneration of Fe(II)-Fe(III) from Fe(II)-Fe(II) is shown by the absorption spectral change of the bilayer film on irradiation. These results corroborate the notion that Fe(II)-Fe(II) is oxidized by photogenerated Ru(III) to generate Fe(II)-Fe(III). However, the rate of photogeneration of Fe(II)-Fe(III) is slow, which could be ascribed to the fast back electron transfer (ET) from WO(3) to Ru(III), comparable with the forward ET from Fe(II)-Fe(II) to Ru(III). The fast back ET could be a crucial problem for the [Ru(bpy)(3)](2+)-sensitized reaction in the hybrid film.     

Hydrogen peroxide formation upon oxidation of oxalic acid in presence and absence of oxygen and of manganese(II)--III. Iron(III) and copper(II) as retarders

The formation of considerable amounts of hydrogen peroxide upon the slow addition of various oxidizing agents to oxalic acid in dilute sulphuric acid in the presence of oxygen and Mn(II) is greatly retarded in the presence of Fe(III) or Cu(II). With hydrogen peroxide as oxidizing agent and a trace of Fe(II) there is considerable decomposition of peroxide, under a nitrogen atmosphere, after a few hours at 25 degrees in light (from a tungsten lamp), and less decomposition in the dark. This decomposition is decreased by Mn(II) and also when the original mixture contains Fe(III). With oxygen as the oxidizing agent Fe(II) is about 100 times as effective an inhibitor of peroxide formation as Fe(III). With all oxidizing agents used, Cu(II) is some 6-10 times more effective as a retarder than Fe(III). The inhibition is accounted for by the reaction Fe(III) [or Cu(II)] + CO(-)(2) --> Fe(II) [or Cu(I)] + CO(2).     

Diiron amido-imido complex [(CpFe)2(mu2-NHPh)(mu2-NPh)]: synthesis and a net hydrogen atom abstraction reaction to form a bis(imido) complex

A reaction between [CpFeCl]x and LiNHPh (1 equiv to Fe) produces a new paramagnetic Fe(II)-Fe(III) mu2-amido-mu2-imido complex [(CpFe)2(mu2-NHPh)(mu2-NPh)] (1), which, upon interaction with 2,2'-azobis(2,4-dimethylvaleronitrile), undergoes a net N-H hydrogen atom abstraction reaction to give a diamagnetic Fe(III)-Fe(III) mu2-imido dimer [CpFe(mu2-NPh)]2 (2). The molecular structures of 1 and 2 have been determined by single-crystal X-ray diffraction.     

Novel iron(III) porphyrazine complex. Complex speciation and reactions with NO and H2O2

The complex [iron(III) (octaphenylsulfonato)porphyrazine] (5-), Fe (III)(Pz), was synthesized. The p K a values of the axially coordinated water molecules were determined spectrophotometrically and found to be p K a 1 = 7.50 +/- 0.02 and p K a 2 = 11.16 +/- 0.06. The water exchange reaction studied by (17)O NMR as a function of the pH was fast at pH = 1, k ex = (9.8 +/- 0.6) x 10 (6) s (-1) at 25 degrees C, and too fast to be measured at pH = 10, whereas at pH = 13, no water exchange reaction occurred. The equilibrium between mono- and diaqua Fe (III)(Pz) complexes was studied at acidic pH as a function of the temperature and pressure. Complex-formation equilibria with different nucleophiles (Br (-) and pyrazole) were studied in order to distinguish between a five- (in the case of Br (-)) or six-coordinate (in the case of pyrazole) iron(III) center. The kinetics of the reaction of Fe (III)(Pz) with NO was studied as a model ligand substitution reaction at various pH values. The mechanism observed is analogous to the one observed for iron(III) porphyrins and follows an I d mechanism. The product is (Pz)Fe (II)NO (+), and subsequent reductive nitrosylation usually takes place when other nucleophiles like OH (-) or buffer ions are present in solution. Fe (III)(Pz) also activates hydrogen peroxide. Kinetic data for the direct reaction of hydrogen peroxide with the complex clearly indicate the occurrence of more than one reaction step. Kinetic data for the catalytic decomposition of the dye Orange II by H 2O 2 in the presence of Fe (III)(Pz) imply that a catalytic oxidation cycle is initiated. The peroxide molecule first coordinates to the iron(III) center to produce the active catalytic species, which immediately oxidizes the substrate. The influence of the catalyst, oxidant, and substrate concentrations on the reaction rate was studied in detail as a function of the pH. The rate increases with increasing catalyst and peroxide concentrations but decreases with increasing substrate concentration. At low pH, the oxidation of the substrate is not complete because of catalyst decomposition. The observed kinetic traces at pH = 10 and 12 for the catalytic cycle could be simulated on the basis of the obtained kinetic data and the proposed reaction cycle. The experimental results are in good agreement with the simulated ones.     

Studies on catalytic fluorescence formation with peroxidase-like metallotetrakis(N-methylpyridiniumyl) porphyrins

The relative ability of peroxidase-like metallotetrakis(N-methylpyridiniumyl)porphyrins [Me-TMPyP, Me = Mn(III), Fe(III), Co(III), Ni(II), Cu(II), and Zn(II)] to catalyse the hydrogen peroxide oxidation of homovanillic acid to a fluorescent dimer has been studied. The complexes of Mn, Fe and Co are effective catalysts in the reaction, but the complexes of Ni, Cu and Zn are not. The catalytic behaviour of Mn-TMPyP, Fe-TMPyP and Co-TMPyP has been compared with that of HRP in both enzymatic and kinetic analysis. The sequence of peroxidase-like catalytic activity is Mn-TMPyP> Co-TMPyP> Fe-TMPyP. The catalytic activity of Mn-TMPyP is 84% of that of HRP. These Me-TMPyP (Me = Mn, Fe, and Co) compounds are good substitutes for HRP in enzymatic analysis. Traces of hydrogen peroxide and glucose can be determined with the Me-TMPyP systems.     

Fe(II)-EDTA chelate-induced aromatic hydroxylation of terephthalate as a new method for the evaluation of hydroxyl radical-scavenging ability.

The investigation of Fe(II)-EDTA chelate-induced aromatic hydroxylation of terephthalate in pH 7.4 phosphate buffer solution and a new method for the evaluation of hydroxyl radical-scavenging ability are reported. The method is based on attack of the hydroxyl radical on the terephthalate to produce highly fluorescent 2-hydroxyterephthalate, which is detected fluorimetrically. The formation of hydroxyl radical is believed to be the result of the reduction of molecular oxygen by Fe(II)-EDTA to form superoxide radical, which in turn dismutates to hydrogen peroxide, and then Fe(II)-EDTA catalyzes the decomposition of hydrogen peroxide to produce hydroxyl radical. The mechanism of the generation of hydroxyl radical in the proposed system was confirmed. This study established a simple and inexpensive method for the evaluation of the scavenging ability of some compounds on hydroxyl radicals.     

CATALASE MIMIC WITH Fe (II) METALLOMICELLE

The effect of Fe (II) metallomicelle as a model of catalase, which was formed by adding surfactants (CTAB, SDS, LSS, Brij35) in Fe (II) -trien complex of molar ratios 1: 500 on the decomposition of hydrogen peroxide was investigated at 20°C and 30°C in pH 10 using KI-color and UV Spectrophotometry. A kinetic model for metallomicellar catalysis was proposed. The association constant of the ternary complex K and the rate constant of the decomposition of hydrogen peroxide k3 were obtained. The results indicate that the metallomicelles making up of Fe (II) metal complex and cationic or nonionic surfactants have obvious catalysis on the decomposition of hydrogen peroxide, but the metallomicelles making up of Fe (II) metal complex and anionic or zwitterionic surfactants have inhibition on this reaction.     

On-line precipitation/dissolution system for the preconcentration and determination of manganese traces by atomic absorption spectrometry

Flame atomic absorption spectrometry was used for the determination of Mn in biological material following preconcentration by precipitation. The proposed preconcentration method is based on the continuous precipitation of Mn(II) as hydrated Mn(IV) oxide in ammonia buffer and dissolution of the precipitate with hydrogen oxalate or dilute nitric acid. The sensitivity of the Mn determination is increased by the presence of hydrogen peroxide, which raises the rate of oxidation of Mn(II) to Mn(IV). By using a time-based technique (at a sample loading rate of 4 ml min⁻¹) a concentration factor of up to 55 was obtained using 24 ml of sample. The effect of concurrent cations was investigated; the most adverse effect was exerted by Fe(III), which interfered at concentrations 50 times higher than that of Mn(II).     

Further mechanistic information on the reaction between FeIII(edta) and hydrogen peroxide: observation of a second reaction step and importance of pH

A detailed study of the effect of buffer, temperature, and pressure on the reaction of hydrogen peroxide with [Fe(III)(edta)H(2)O](-) was performed using stopped-flow techniques. The reaction was found to consist of two steps and resulted in the formation of the already characterized high-spin Fe(III) side-on bound peroxo complex. The second step of the reaction was found to be independent of the hydrogen peroxide concentration. Formation of the purple peroxo complex is only observable above pH 7.5. Both reaction steps are affected by specific and general acid-catalysis. Five different buffer systems were used to clarify the role of general acid-catalysis in these reactions. Both reaction steps reveal an element of reversibility, which disappears on decreasing the acid concentration. The positive volumes of activation for both the forward and reverse reactions of the first step suggest a dissociative interchange substitution process for the reversible end-on binding of hydrogen peroxide to [Fe(III)(edta)H(2)O](-). The small negative volume of activation for the second reaction step suggests an associative interchange mechanism for the formation of the side-on bound peroxo complex that is accompanied by dissociation of one of the four carboxylates of edta. A detailed mechanism in agreement with all the reported kinetic data is presented.     

Heterometallic Co(III)(4)Fe(III)(2) Schiff Base Complex: Structure, Electron Paramagnetic Resonance, and Alkane Oxidation Catalytic Activity

The heterometallic complex [Co(4)Fe(2)OSae(8)]·4DMF·H(2)O (1) was synthesized by one-pot reaction of cobalt powder with iron chloride in a dimethylformamide solution of salicylidene-2-ethanolamine (H(2)Sae) and characterized by single crystal X-ray diffraction analysis, magnetic measurements, high frequency electron paramagnetic resonance (HF-EPR), and M?ssbauer spectroscopies. The exchange coupling in the Fe(III)-Fe(III) pair is of antiferromagnetic behavior with J/hc = -190 cm(-1). The HF-EPR spectra reveal an unusual pattern with a hardly detectable triplet signal of the Fe(III) dimer. The magnitude of D (ca. 13.9 cm(-1)) was found to be much larger than in related dimers. The catalytic investigations disclosed an outstanding activity of 1 toward oxidation of cycloalkanes with hydrogen peroxide, under mild conditions. The most efficient system showed a turnover number (TON) of 3.57 × 10(3) with the concomitant overall yield of 26% for cyclohexane, and 2.28 × 10(3)/46%, respectively, for cyclooctane. A remarkable turnover frequency (TOF) of 1.12 × 10(4) h(-1) (the highest initial rate W(0) = 3.5 × 10(-4) M s(-1)) was achieved in oxidation of cyclohexane. Kinetic experiments and selectivity parameters led to the conclusion that hydroxyl radicals are active (attacking C-H bonds) species. Kinetic and electrospray ionization mass spectrometry (ESI-MS) data allowed us to assume that the trinuclear heterometallic particle [Co(2)Fe(Sae)(4)](+), originated from 1 in solution, could be responsible for efficient generation of hydroxyl radicals from hydrogen peroxide.     

Reaction of hydrogen peroxide with tetraazamacrocyclic complex of iron(II) in the presence of nitrogeneous bases

The kinetics of hydrogen peroxide oxidation of Fe(II) to Fe(III) complexed with tetraazamacrocyclic ligand was studied, and a decrease in the reaction rate was observed in the presence of nitrogeneous bases, capable of forming hexacoordinated complexes with tetraazamacrocyclic compound of iron(II). The rate of reaction is proprotional to the concentration of the iron complex and hydrogen peroxide and inversely proportional to the concentration of the nitrogeneous base. A mechanism for the course of the reaction has been proposed, and the rate constants of the oxidation of the pentacoordinated iron(II) complexes have been calculated. It was shown that the addition of the fifth donor particle (in particular imidazole) activates the iron(II) atom with respect to the oxidation reaction. It was found that a tetraazamacrocyclic complex of iron(II) is capable of displaying a peroxidase type activity.Translated from Teoreticheskaya Eksperimental'naya Khimiya, Vol. 22, No. 3, pp. 309–316, May–June, 1986.     

A dihydroxo-bridged Fe(II)-Fe(III) complex: a new member of the diiron diamond core family

The first structurally characterized Fe(II)-Fe(III) complex containing a M2(mu-OH)2 diamond core is a Robin and Day class II mixed-valence complex.     

Determination of hydrogen peroxide by iron(III) complex of thiacalix[4]arenetetrasulfonate on a modified ion-exchanger with peroxidase-like catalytic activity.

An iron(III) complex of thiacalix[4]arenetetrasulfonate on a modified anion-exchanger (Fe3+-TCAS(A-500)) has shown high peroxidase-like activity at pH 5 - 6 for the reaction of quinoid-dye formation between 3-methyl-2-benzothiazolinone hydrazone and N-(3-sulfopropyl)aniline in the presence of hydrogen peroxide. Utilizing the peroxidase-like activity of Fe3+-TCAS(A-500) for this reaction, a method using Fe3+-TCAS(A-500) was applied for the spectrophotometric determination of hydrogen peroxide. The calibration curve by the method using Fe3+-TCAS(A-500) was linear over the range from 1 to 10 microg of hydrogen peroxide in a 1 ml sample solution. The apparent molar absorptivity for hydrogen peroxide was 2.4 x 10(4) l mol(-1) cm(-1). which was about 80% of that by peroxidase under the same conditions. This determination method of hydrogen peroxide using Fe3+-TCAS(A-500) was applied for the determination of glucose in diluted normal and abnormal control serum I and II.     

Ru(III), Cr(III), Fe(III) complexes of Schiff base ligands bearing phenoxy Groups: Application as catalysts in the synthesis of vitamin K3

Two polydentade Schiff base ligands and their Ru(III), Cr(III) and Fe(III) complexes were synthesized and characterized by elemental analysis (C, H, N), UV/Vis, FT IR, ¹H and ¹³C NMR, LC–MS/MS, molar conductivity and magnetic susceptibility techniques. The absorption bands in the electronic spectra and magnetic moment measurements verified an octahedral environment around the metal ions in the complexes. The thermal stabilities were investigated using TGA. The synthesized complexes were used in the catalytic oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1,4-naphthoquinone; vitamin K₃, menadione, 2MNQ; using hydrogen peroxide, acetic acid and sulfuric acid. L₁-Fe(III) complex showed very efficient catalytic activity with 58.54% selectivity in the conversions of 79.11%.     

Direct electrochemistry and electrocatalytic characteristic of heme proteins immobilized in a new sol-gel polymer film

Heme proteins were immobilized on glass carbon electrodes by poly (N-isopropylac-yamide-co-3-methacryloxy-propyl-trimethoxysilane) (PNM) and exhibited a pair of well-defined, quasi-reversible cyclic voltammetric peaks at about -0.35 V versus a saturated calomel electrode in pH 7.0 buffer solution, corresponding to hemeFe(III)+e-->hemeFe(II). Some electrochemical parameters were calculated by performing nonlinear regression analysis of square wave voltammetry (SWV) experimental data. The formal potential was linearly dependent on pH, indicating the electron transfer of Fe(III)/Fe(II) redox couple accompanied by the transfer of proton. Ultraviolet visible and Fourier transform infrared spectra suggested that the conformation of proteins in the PNM films retained the essential feature of its native secondary structure. Atomic force microscopy images demonstrated the existence of interaction between heme proteins and PNM. N,N-dimethylformamide (DMF) played an important role in immobilizing proteins and enhancing electron transfer between proteins and electrodes. Electrochemical catalytic reductions of hydrogen peroxide and trichloroacetic acid by proteins entrapped in PNM film were also discussed, showing the potential applicability of the film modified electrodes as a biosensor.     

Extraction of Mn(II), Co(II), Cr(III) and Fe(III) from succinic acid medium by high molecular weight amines

The extraction behavior of Mn(II), Co(II), Cr(III) and Fe(III) has been studied in high molecular weight amines from succinic acid medium. The effect of different variables, like, type of amine, effect of pretreatment of amine with various acids, type of diluent and concentration of metal, succinate, hydrogen ions and amine, has been investigated. Extraction of Cr(III) and Fe(III) species is proposed and some binary separations achieved.     

Catalytic wave of hydrogen in systems based on iron(II) nitrosyl complexes

The electroreduction of Fe(III) at a dropping mercury electrode in an acetate buffer solution containing NO ₂ ^- and NH ₄ ⁺ ions and some hydroxy acids was studied. Based on the fact that the current depends on a number of factors, it was concluded that the wave observed was catalytic wave of hydrogen. The proposed mechanism of the process includes the electroreduction of the Fe(III) complex, the formation of a mixed-ligandFe(II) complex, and its protonation and reduction at a dropping mercury electrode with the liberation of hydrogen. Presented at the V All-Russian Conference with the Participation of CIS Countries on Electrochemical Methods of Analysis (EMA-99), Moscow, December 6–8, 1999.     

Zeolite-encapsulated Cr(III), Fe(III), Ni(II), Zn(II) and Bi(III) salpn complexes as catalysts for the decomposition of H2O2 and oxidation of phenol

Cr(III), Fe(III), Bi(III), Ni(II) and Zn(II) complexes of N,N′-bis(salicylidene)propane-1,3-diamine (H₂salpn) encapsulated in Y-zeolite were prepared by flexible ligand method. These complexes were characterized by chemical and thermal analyses, FT-IR and electronic spectral studies and their XRD pattern. The encapsulated materials are active catalysts for the decomposition of hydrogen peroxide and for the oxidation of phenol using H₂O₂ as oxidant with good selectivity.