Kinetics of the iodate reduction by hydrogen peroxide and relation with the Briggs-Rauscher and Bray-Liebhafsky oscillating reactions

The iodate reduction by hydrogen peroxide in acidic solutions is part of the Bray-Liebhafsky and Briggs-Rauscher oscillating reactions. At low hydrogen peroxide concentrations, typical of the Bray-Liebhafsky reaction, its rate law is -d[IO(-)(3)]/dt = (k'(R) + k"(R)[H(+)])[IO(-)(3)][H(2)O(2)] with k'(R) = 1.3 × 10(-7)(20°), 7.8 × 10(-7) (39°), 1.4 × 10(-5) M(-1) s(-1) (60°) and k"(R) = 1.5 × 10(-5) (25°), 6.2 × 10(-5) (39°), 6.3 × 10(-4) M(-2) s(-1) (60°). It is explained by a non-radical mechanism. At high hydrogen peroxide concentrations, typical of the Briggs-Rauscher reaction, a new reaction pathway appears with a rate more than proportional to [H(2)O(2)](2) and nearly independent of [IO(3)(-)] > 0.01 M. This pathway is inhibited by scavengers of free radicals. We suggest that it has a radical mechanism starting with IOH + H(2)O(2)? IOOH + H(2)O and IOOH+H(2)O(2)→ IO˙ + H(2)O+HOO˙.     

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.     

The effective peroxidase-like activity of chitosan-functionalized CoFe2O4 nanoparticles for chemiluminescence sensing of hydrogen peroxide and glucose

Here, we report a highly simple and general protocol for functionalization of the CoFe(2)O(4) NPs with chitosan polymers in order to make CoFe(2)O(4) NPs disperse and stable in solution. The functionalized CoFe(2)O(4) NPs (denoted as CF-CoFe(2)O(4) NPs) were characterized by scanning electron microscope (SEM), thermogravimetric (TG), X-ray diffraction (XRD) and FT-IR spectra. It was found that the CoFe(2)O(4) NPs were successfully decorated and uniformly dispersed on the surface of chitosan without agglomeration. The CF-CoFe(2)O(4) NPs were found to increase greatly the radiation emitted during the CL oxidation of luminol by hydrogen peroxide. Results of ESR spin-trapping experiments demonstrated that the CF-CoFe(2)O(4) NPs showed catalytic ability to H(2)O(2) decomposition into ˙OH radicals. On this basis, a highly sensitive and rapid chemiluminescent method was developed for hydrogen peroxide in water samples and glucose in blood samples. Under optimum conditions, the proposed method allowed the detection of H(2)O(2) in the range of 1.0 × 10(-9) to 4.0 × 10(-6) M and glucose in the range of 5.0 × 10(-8) to 1.0 × 10(-5) M with detectable H(2)O(2) as low as 500 pM and glucose as low as 10 nM, respectively. This proposed method has been successfully applied to detect H(2)O(2) in environmental water samples and glucose in serum samples with good accuracy and precision.     

On-line screening methods for antioxidants scavenging superoxide anion radical and hydrogen peroxide by liquid chromatography with indirect chemiluminescence detection

The identification of radical species is possible by the electron spin resonance technique. However, the antioxidants in complex matrices such as biological and food samples are difficult to determine. Hence, we developed novel screening systems for antioxidants, which are mainly eliminating superoxide anion radical (O(2)(-)) and hydrogen peroxide (H(2)O(2)), by HPLC with luminol-based chemiluminescence (CL) detection. When the sample contains antioxidants, inhibited peaks corresponding to each antioxidant are observed on the chromatogram. The antioxidant activities of catechins and flavones were determined with flow injection analysis by the proposed indirect CL. The scavenging activity for H(2)O(2) and O(2)(-) were different from each catechin and flavone. Furthermore, the potential was dependent upon the number and the position of OH functional group in the structure. Some applications such as the screening of antioxidants in tea products were also investigated. In spite of many peaks appeared on the chromatogram at UV detection, only the peaks corresponding to the compounds having elimination effect to O(2)(-) and/or H(2)O(2) were detected as inhibited peaks. Consequently, the proposed HPLC-CL seems to provide new screening systems for antioxidants possessing inhibition activity of O(2)(-) and H(2)O(2).     

The mechanism of carbon dioxide catalysis in the hydrogen peroxide N-oxidation of amines

The reactivity of the peroxymonocarbonate ion, HCO4- (an active oxidant derived from the equilibrium reaction of hydrogen peroxide and bicarbonate), has been investigated in the oxidation of aliphatic amines. Tertiary aliphatic amines are oxidized to the corresponding N-oxides in high yields, while secondary amines give corresponding nitrones. A closely related mechanism for the H2O2 oxidation of tertiary amines catalyzed by CO2 (under 1 atm) and H2O2 at 25 degrees C is proposed. The rate laws for the oxidation of N-methylmorpholine (1) to N-methylmorpholine N-oxide and N,N-dimethylbenzylamine (2) to N,N-dimethylbenzylamine N-oxide have been obtained. The second-order rate constants for the oxidation by HCO4- are k1 .016 M(-1) s(-1) for 1 in water and k1=0.042 M(-1) s(-1) for 2 in water/acetone (5:1). The second-order rate constants for tertiary amine oxidations by HCO4- are over 400-fold greater than those for H2O2 alone. Activation parameters for oxidation of 1 by HCO4- in water are reported (DeltaH=36+/-2 kJ mol(-1) and DeltaS=-154+/-7 J mol(-1) K(-1)). The BAP (NH4HCO3-activated peroxide) or CO2/H2O2 oxidation reagents are simple and economical methods for the preparation of tertiary amine N-oxides. The reactions proceed to completion, do not require extraction, and afford the pure N-oxides in excellent yields in aqueous media.     

Evaluation of luminol-H(2)O(2)-KIO(4) chemiluminescence system and its application to hydrogen peroxide, glucose and ascorbic acid assays

A novel chemiluminescence (CL) system was evaluated for the determination of hydrogen peroxide, glucose and ascorbic acid based on hydrogen peroxide, which has a catalytic-cooxidative effect on the oxidation of luminol by KIO(4). Hydrogen peroxide can be directly determined by luminol-KIO(4)-H(2)O(2) CL system. The detection limit was 3.0x10(-8) mol l(-1) and the calibration graph was linear over the range of 2.0x10(-7)-6.0x10(-4) mol l(-1). The relative standard deviation of H(2)O(2) was 1.1% for 2.0x10(-6) mol l(-1) (N=11). Glucose was indirectly determined through measuring the H(2)O(2) generated by the oxidation of glucose in the presence of glucose oxidase at pH 7.6. The present method provides a source for H(2)O(2), which, in turn, coupled with the luminol-KIO(4)-H(2)O(2) CL reaction system. The CL was linearly correlated with glucose concentration of 0.6-110 mug ml(-1). The relative standard deviation was 2.1% for 10 mug ml(-1) (N=11). Detection limit of glucose was 0.08 mug ml(-1). Ascorbic acid was also indirectly determined by the suppression of luminol-KIO(4)-H(2)O(2) CL system. The calibration curve was linear over the range of 1.0x10(-7)-1.0x10(-5) mol l(-1) of ascorbic acid. The relative standard deviation was 1.0% for 8.0x10(-7) mol l(-1) (N=11). Detection limit of ascorbic acid was 6.0x10(-8) mol l(-1). These proposed methods have been applied to determine glucose, ascorbic acid in tablets and injection.     

Enhancing effect of alcoholic solvent on hydrosulfite-hydrogen peroxide chemiluminescence system

In this work, a chemiluminescence (CL) reaction between hydrogen peroxide (H(2)O(2)) and sodium hydrosulfite (NaHSO(3)) was developed. Hydroxyl radical ((?)OH) and sulfite radical ((?)SO(3)(-)) were the main intermediates generated in the NaHSO(3)-H(2)O(2) CL system. Inhibition effects of radical scavengers such as thiourea, chloride ion, nitro blue tetrazolium chloride (NBT), and 5,5-dimethyl-1-pyrroline N-oxide (DMPO) indicated the existence of these two radicals. Singlet oxygen ((1)O(2)) and excited sulfur dioxide (SO(2)*) were emitting species involved in NaHSO(3)-H(2)O(2) CL system. (1)O(2) were confirmed by 1,4-diazobicyclo[2,2,2]octane (DABCO) and sodium azide (NaN(3)), which were specific (1)O(2) scavengers. In addition, electron spin resonance (ESR) spectra clearly show the existence of (1)O(2) and (?)OH. Alcoholic solvent, especially n-butanol, enhanced the ultraweak CL emission more than 40 times. The enhancing effect of alcoholic solvent on NaHSO(3)-H(2)O(2) CL system was ascribed to the formation of solvent cage, which can accelerate the reaction rate and protect the emitting species from quenching by water. The CL emission of the NaHSO(3)-n-butanol-H(2)O(2) system was measured by cutoff filters. The maximum wavelength was located around 490 nm, which belongs to (1)O(2). The wide peak from 400 to 600 nm is the characteristic peak of SO(2)*.     

Experimental studies on the chemiluminescence reaction mechanism of carbonate/bicarbonate and hydrogen peroxide in the presence of cobalt(II)

Chemiluminescence (CL) phenomena of carbonates or bicarbonates of potassium, sodium, or ammonium with hydrogen peroxide in the presence of cobalt sulfate were reported. After cobalt(II) solution was injected into the mixture of carbonate/bicarbonate and hydrogen peroxide, a CL signal was given out briefly. The CL conditions of these systems were optimized. The CL reaction mechanisms were studied experimentally by examining the spectrum emitted by the CL system and the effect of various free radical scavengers on CL emission intensity. The results showed that the maximal emission wavelengths of the CO32--H2O2-Co2+ and HCO3--H2O2-Co2+ systems were 440 and 490 nm, respectively. As a result, a radical scavenger of ascorbic acid, thiourea, and superoxide dismutase exhibited different effects on these CL systems. The different CL mechanisms involving the carbon dioxide dimer and the oxygen dimer were revealed, respectively.     

Cavity-enhanced measurements of hydrogen peroxide absorption cross sections from 353 to 410 nm

We report near-ultraviolet and visible absorption cross sections of hydrogen peroxide (H(2)O(2)) using incoherent broad-band cavity-enhanced absorption spectroscopy (IBBCEAS), a recently developed, high-sensitivity technique. The measurements reported here span the range of 353-410 nm and extend published electronic absorption cross sections by 60 nm to absorption cross sections below 1 × 10(-23) cm(2) molecule(-1). We have calculated photolysis rate constants for H(2)O(2) in the lower troposphere at a range of solar zenith angles by combining the new measurements with previously reported data at wavelengths shorter than 350 nm. We predict that photolysis at wavelengths longer than those included in the current JPL recommendation may account for up to 28% of the total hydroxyl radical (OH) production from H(2)O(2) photolysis under some conditions. Loss of H(2)O(2) via photolysis may be of the same order of magnitude as reaction with OH and dry deposition in the lower atmosphere; these processes have very different impacts on HO(x) loss and regeneration.     

Synthesis of a novel chemiluminescent reagent for the determination of hydrogen peroxide in snow waters

7-(4,6-Dichloro-1,3,5-triazinylamino)-4-methylcoumarin (DTMC) was synthesized as a completely new chemiluminescent reagent, and with it a novel chemiluminescence method was developed for the determination of hydrogen peroxide in the absence of any added catalyst or co-oxidant. The chemiluminescence intensity of the DTMC-H(2)O(2) system could be enhanced by the addition of cation surfactants. The chemiluminescence intensity was directly proportional to the concentration of H(2)O(2) in the range 1.0 x 10(-7)-4.0x10(-4) mol l(-1), and the detection limit was 4.0 x 10(-8) mol l(-1). The relative S.D. was 4.9% for 1.0 x 10(-6) mol l(-1) of H(2)O(2) (n=10). The selectivity of this method was high, and most of the transition metal ions have no effect on the determination. The proposed method has been applied to the determination of trace amounts of hydrogen peroxide in snow water. A possible mechanism of the chemiluminescence reaction is also discussed.     

Hydrogen and oxygen isotope values in hydrogen peroxide

Hydrogen peroxide (H(2)O(2)) is a widely used oxidizer with many commercial applications; unfortunately, it also has terrorist-related uses. We analyzed 97 hydrogen peroxide solutions representing four grades purchased across the United States and in Mexico. As expected, the range of hydrogen (δ(2)H, 230‰) and oxygen (δ(18)O, 24‰) isotope values of the H(2)O(2) solutions was large, reflecting the broad isotopic range of dilution waters. This resulted in predictable linear relationships of δ(2)H and δ(18)O values of H(2)O(2) solutions that were near parallel to the Meteoric Water Line (MWL), offset by the concentration of H(2)O(2) in the solution. By grade, dilute (3 to 35%) H(2)O(2) solutions were not statistically different in slope. Although the δ(2)H values of manufactured H(2)O(2) could be different from those of water, rapid H(2)O(2)-H(2)O exchange of H atoms eliminated any distinct isotope signal. We developed a method to measure the δ(18)O value of H(2)O(2) independent of dilution water by directly measuring O(2) gas generated from a catalase-induced disproportionation reaction. We predicted that the δ(18)O values of H(2)O(2) would be similar to that of atmospheric oxygen (+23.5‰), the predominant source of oxygen in the most common H(2)O(2) manufacturing process (median disproportionated δ(18)O=23.8‰). The predictable H-O relationships in H(2)O(2) solutions make it possible to distinguish commercial dilutions from clandestine concentration practices. Future applications of this work include synthesis studies that investigate the chemical link between H(2)O(2) reagents and peroxide-based explosive products, which may assist law enforcement in criminal investigations.     

Singlet oxygen generated from the decomposition of peroxymonocarbonate and its observation with chemiluminescence method

The decomposition of peroxymonocarbonate (HCO(4)(-)) has been investigated by flow-injection chemiluminescence (CL) method. An ultraweak CL was observed during mixing the bicarbonate and hydrogen peroxide solution in organic cosolvent. An appropriate amount of fluorescent organic compounds, such as dichlorofluorescein (DCF), was added to the HCO(4)(-) solution, a strong CL was recorded. Based on studies of the spectrum of fluorescence, CL and UV-vis spectra, electron spin trapping (ESR) technique, mass spectra (MS) and comparison with H(2)O(2)/hypochlorite (ClO(-)) and H(2)O(2)/molybdate (MoO(4)(-)) systems, the CL mechanism was proposed. The reaction is initiated by unimolecular homolysis of the peroxo O-O bond in HO-OCOO(-) molecule. It was suggested that the bond rearrangement within radicals yield superoxide ion (O(2)(*-)). The interaction of superoxide ion with perhydroxyl radical produces singlet oxygen ((1)O(2)). The energy transfers from singlet oxygen to DCF forming an excited energy acceptor (DCF*). Luminescence (lambda(max)=509 nm) was emitted during the relaxation of the energy acceptor to the ground state.     

Ultrasound-enhanced flow injection chemiluminescence for determination of hydrogen peroxide

A novel ultrasonic flow injection chemiluminescence (FI-CL) manifold for determining hydrogen peroxide (H2O2) has been designed and evaluated. Chemiluminescence obtained from the luminol-H2O2-cobalt(II) reaction was enhanced by applying 120 W of ultrasound for a period of 4 s to the reaction coil in the FI-CL system and this enhancement was verified by comparison with an identical manifold without ultrasound. The system was developed for determining ultra-trace levels of H2O2 and a calibration curve was obtained with a linear portion over the range of 10-200 nmol L(-1) H2O2 (correlation coefficient 0.9945). The detection limit (3sigma) and the quantification limit (LOQ) were found to be 1 x 10(-9) and 3.3 x 10(-9) mol L(-1) respectively and the relative standard deviation was 1.37% for 2 x 10(-7) mol L(-1) H2O2 (n = 10). The method was applied to the determination of trace amounts of H2O2 in purified water and natural water samples without any special pre-treatments.     

Stopped-flow spectrophotometric determination of hydrogen peroxide with hemoglobin as catalyst

A rapid and sensitive method was proposed for the determination of hydrogen peroxide based on the catalytic effect of hemoglobin using o-phenylenediamine as the substrate. Stopped-flow spectrophotometric method was used to study the kinetic behavior of the oxidation reaction. The catalytic effectiveness of hemoglobin was compared with other four kinds of catalysts. The initial rate of the formation of the reaction product 2,3-diaminophenazine at the wavelength of 425 nm was monitored, permitting a detection limit of 9.2x10(-9) mol/l H(2)O(2). A linear calibration graph was obtained over the H(2)O(2) concentration range 5.0x10(-8)-3.5x10(-6) mol/l, and the relative standard deviation at a H(2)O(2) concentration of 5.0x10(-7) mol/l was 2.08%. Satisfied results were obtained in the determination of H(2)O(2) in real samples by this method.     

基于石墨烯-壳聚糖-辣根过氧化物酶的H2O2生物传感器的研制

制备了石墨烯-壳聚糖(GR-CS)纳米复合材料,并将之与辣根过氧化物酶(HRP)混合,构建了基于石墨烯-壳聚糖-辣根过氧化物酶的生物传感器(GR-CS-HRP/GC)。探针及循环伏安研究表明,该界面具有优异的电子传导能力、较大的比表面积和良好的生物相容性,对H2O2的还原显示出较好的电催化活性,在工作电位为-0.2 V,0.05 mol/L的磷酸盐缓冲盐溶液(PBS,pH 6.8)中,该酶传感器对过氧化氢响应灵敏度高,检测范围宽,测定H2O2的线性范围为5.0×10-7～2×10-3mol/L(相关系数为0.998)。检出限为2.0×10-7mol/L(S/N=3)。并且表现出良好的稳定性和高选择性。该电极用于实际样品中H2O2的测定,结果令人满意。     

Detection of hydrogen peroxide in rainwater based on Mg-Al-carbonate layered double hydroxides-catalyzed luminol chemiluminescence

Using a green catalyst of luminol chemiluminescence (CL), Mg-Al-carbonate layered double hydroxides (denoted as Mg-Al-CO(3) LDHs), a novel, sensitive and rapid CL method was developed for the determination of hydrogen peroxide (H(2)O(2)). The corresponding linear regression equation was established in the range of 0.05-10 μM for H(2)O(2). The detection limit (S/N = 3) is 0.02 μM and the relative standard deviation (RSD) for nine repeated measurements of 1.0 μM H(2)O(2) was 2.9%. This proposed method has been successfully applied to detect H(2)O(2) in rainwater samples with good accuracy and precision. The novel methodology is expected to provide a general protocol for the determination of H(2)O(2) as well as for numerous other oxidase-based reactions giving H(2)O(2) as a product (e.g., glucose).     

Cobalt oxide/tetraruthenated cobalt-porphyrin composite for hydrogen peroxide amperometric sensors

A new composite material constituted by mu-{5,10,15,20-tetra(4-pyridyl)porphyrinato cobalt(iii)}-tetrakis-{chloro-bis-(2,2'-bipyridine)ruthenium(ii)} complex (or CoTRP) and cobalt oxide, exhibiting high stability and sensitivity for the quantification of hydrogen peroxide, was obtained by the electrochemical polymerization of the tetraruthenated cobalt porphyrin in alkaline medium. The optimized experimental conditions for the preparation of the modified glassy carbon electrodes and for analysis of H2O2 were carefully determined. Fast sequential analysis (120 determinations h(-1)) in a wide linear dynamic range (5.0 x 10(-7) mol L(-1) to 2.0 x 10(-3) mol L(-1)), with high sensitivity and low detection limit (2.0 x 10(-7) mol L(-1)), was achieved by using these electrodes and the batch injection analysis (BIA) technique. Such characteristics allied to a good stability were explored for the specific determination of hydrogen peroxide in six commercial cosmetics and pharmaceutical product samples, giving results in excellent agreement with those obtained by the spectrophotometric method.     

Isothermal decomposition of hydrogen peroxide dihydrate

We present a new method of growing pure solid hydrogen peroxide in an ultra high vacuum environment and apply it to determine thermal stability of the dihydrate compound that forms when water and hydrogen peroxide are mixed at low temperatures. Using infrared spectroscopy and thermogravimetric analysis, we quantified the isothermal decomposition of the metastable dihydrate at 151.6 K. This decomposition occurs by fractional distillation through the preferential sublimation of water, which leads to the formation of pure hydrogen peroxide. The results imply that in an astronomical environment where condensed mixtures of H(2)O(2) and H(2)O are shielded from radiolytic decomposition and warmed to temperatures where sublimation is significant, highly concentrated or even pure hydrogen peroxide may form.     

流动注射化学发光法测定槐米中槲皮素

在碱性溶液中槲皮素对过氧化氢氧化鲁米诺而产生的化学发光(CL)具有很强的抑制作用,且其CL强度的减弱程度与槲皮素浓度之间在一定的范围内呈线性关系。据此,并结合应用流动注射(FI)技术,提出了FI-CL测定槐米中槲皮素含量的方法。反应体系中所用试剂的最佳浓度为:①cH2O2=0.2mol.L-1;②c鲁米诺=8.5×10-4mol.L-1;③cNaOH=0.01mol.L-1。对槲皮素测定的线性范围为2.65×10-6～5.31×10-4mol.L-1之间,其检出限(3s/k)为9.26×10-7mol.L-1。用4×10-4mol.L-1槲皮素标准溶液进行精密度试验,测得相对标准偏差(n=11)为3.0%。分析试样时,先从槐米在pH 8～9的碱性溶液中提取芦丁,然后在微酸性(pH 5)溶液中使芦丁水解得到槲皮素粗品。将此粗品经反复重结晶得到槲皮素纯品,溶于乙醇(40+60)溶液中制成溶液,用于FI-CL分析。     

O?O bond homolysis in hydrogen peroxide

O O bond homolysis in hydrogen peroxide (H₂O₂) has been studied using theoretical methods of four conceptually different types: hybrid DFT (B3LYP, M06‐2X), double‐hybrid DFT (B2‐PLYP), coupled‐cluster (CCSD(T)), and multiconfigurational (CASPT2). In addition, the effects of basis set size have also been analyzed. For all of these methods, the O O bond homolysis in hydrogen peroxide has been found to proceed through hydrogen bonded radical pair complexes. Reaction barriers for collapse of the radical pairs to hydrogen peroxide are minute, leading to an overall very flat potential energy surface. However, hydrogen bonding energies in the radical pair complex expressed as the energy difference to two separate hydroxyl radicals are sizeable and exceed 10 kJ/mol for all theoretical methods considered in this study. © 2017 Wiley Periodicals, Inc.