Showing papers on "Hydrogen peroxide published in 2004"

Radical generation by the interaction of transition metals with common oxidants.

Abstract: Nine transition metals were tested for the activation of three oxidants and the generation of inorganic radical species such as sulfate, peroxymonosulfate, and hydroxyl radicals. From the 27 combinations, 14 M/Ox couples demonstrated significant reactivity toward transforming a model organic substrate such as 2,4-dichlorophenol and are further discussed here. It was found that Co(II) and Ru(III) are the best metal catalysts for the activation of peroxymonosulfate. As expected on the basis of the Fenton reagent, Fe(III) and Fe(II) were the most efficient transition metals for the activation of hydrogen peroxide. Finally, Ag(I) showed the best results toward activating persulfate. Quenching studies with specific alcohols (tert-butyl alcohol and ethanol) were also performed to identify the primary radical species formed from the reactive M/Ox interactions. The determination of these transient species allowed us to postulate the rate-determining step of the redox reactions taking place when a metal is coupled with an oxidant in aqueous solution. It was found that when Co(II), Ru(III), and Fe(II) interact with peroxymonosulfate, freely diffusible sulfate radicals are the primary species formed. The same was proven for the interaction of Ag(I) with persulfate, but in this case caged or bound to the metal sulfate radicals might be formed as well. The conjunction of Ce(III), Mn(II), and Ni(II) with peroxymonosulfate showed also to generate caged or bound to the metal sulfate radicals. A combination of sulfate and hydroxyl radicals was formed from the conjunction of V(III) with peroxymonosulfate and from Fe(II) with persulfate. Finally, the conjunction of Fe(III), Fe(II), and Ru(III) with hydrogen peroxide led primarily to the generation of hydroxyl radicals. It is also suggested here that the redox behavior of a particular metal in solution cannot be predicted based exclusively on its size and charge. Additional phenomena such as metal hydrolysis as well as complexation with other counterions present in solution might affect the thermodynamics of the overall process and are further discussed here.

Photocatalytic degradation of azo dye acid red 14 in water on ZnO as an alternative catalyst to TiO2

Abstract: The degradation of acid red 14 (AR14), commonly used as a textile dye, can be photocatalysed by ZnO. Using advanced oxidation processes (AOPs), zinc oxide appears to be a suitable alternative to TiO2 for water treatment. In this study, a detailed investigation of photocatalytic degradation of acid red 14 is presented. Photodegradation efficiency was small when the photolysis was carried out in the absence of ZnO and it was also negligible in the absence of UV light. The semi-log plot of dye concentration versus time was linear, suggesting first order reaction (K=0.0548 min−1). The effects of some parameters such as pH, amount of photocatalyst, hydrogen peroxide and ethanol concentration were also examined. The addition of proper amount of hydrogen peroxide improved the decolorization, while the excess hydrogen peroxide could quenched the formation of hydroxyl radicals ( OH). As our results indicated that ethanol inhibited the photodegradation of dye, we concluded from the inhibitive effect of ethanol that hydroxyl radicals played a significant role in the photodegradation of dye. This should not undermine direct oxidation caused by positive holes.

Visible light-induced photocatalytic degradation of Acid Orange 7 in aqueous TiO2 suspensions

Abstract: The photocatalytic degradation of a model azo-dye (Acid Orange, AO7) in aerated aqueous TiO2 dispersion has been studied under visible light (λ>400 nm) irradiation. The presence and role of oxidative species, such as singlet oxygen ( 1 O 2 ), superoxide (O2− ) and hydroperoxy (HO2 ) radicals was examined with the use of appropriate quenchers of these species. The reaction pathway of dye degradation was also investigated by monitoring the temporal evolution of intermediates and final products on both the photocatalyst surface and in solution, with the use of a variety of techniques, including GC–MS, FTIR and UV-Vis spectroscopies. It has been found that complete decolorization of the solution may be achieved, accompanied by a substantial decrease of the chemical oxygen demand (COD) of the solution. Evidence is presented that the main oxidative species is O2− (or HO2 ), while singlet oxygen, when formed, is also active. The adsorbed dye molecule is initially cleaved in the vicinity of the azo-bond and the resulting fragments are oxidized toward compounds of progressively lower molecular weight and, eventually, to CO2 and inorganic ions. However, when the solution is bleached, formation of active oxidative species does not take place, oxidation reactions cease and the concentrations of the dye intermediates remain practically stable upon further exposure to visible light irradiation. Formation of photoinduced hydrogen peroxide, which is also generated under the present conditions, also stops when the dye concentration in solution drops to very low levels. This behavior has been explained evoking the photosensitization mechanism of wide band-gap semiconductors, according to which the reaction is triggered by excitation of the dye molecule by visible light photons, followed by charge injection to the conduction band of the semiconductor and subsequent production of active oxygen radicals. Formation of the latter oxidizing species is possible only in the presence of visible light-absorbing compounds and cannot take place after fragmentation of the parent AO7 molecule in the vicinity of the azo-bond and decolorization.

A selective, cell-permeable optical probe for hydrogen peroxide in living cells.

Abstract: We present the synthesis, properties, and biological applications of Peroxyfluor-1 (PF1), a new type of optical probe for intracellular imaging of hydrogen peroxide in living biological samples. PF1 utilizes a boronate deprotection mechanism to provide unprecedented selectivity and optical dynamic range for detecting H2O2 in aqueous solution over similar reactive oxygen species including superoxide, nitric oxide, tert-butyl hydroperoxide, and hydroxyl radical. We further demonstrate the value of this reagent for biological applications by imaging changes in [H2O2] in living mammalian cells.

Down-Regulation of Metallothionein, a Reactive Oxygen Scavenger, by the Small GTPase OsRac1 in Rice

Abstract: Metallothioneins are small, ubiquitous Cys-rich proteins known to be involved in reactive oxygen species (ROS) scavenging and metal homeostasis We found that the expression of a metallothionein gene (OsMT2b) was synergically down-regulated by OsRac1 and rice (Oryza sativa) blast-derived elicitors Transgenic plants overexpressing OsMT2b showed increased susceptibility to bacterial blight and blast fungus OsMT2b-overexpressing cells showed reduced elicitor-induced hydrogen peroxide production In contrast, homozygous OsMT2b::Tos17-inserted mutant and OsMT2b-RNAi-silenced transgenic cells showed significantly higher elicitor-induced hydrogen peroxide production than the wild-type cells In vitro assay showed that recombinant OsMT2b protein possessed superoxide- and hydroxyl radical-scavenging activities Taken together, these results showed that OsMT2b is an ROS scavenger and its expression is down-regulated by OsRac1, thus potentiating ROS, which function as signals in resistance response The results suggest that OsRac1 plays a dual role as an inducer of ROS production and a suppressor of ROS scavenging

Hydrogen Peroxide Poisoning

Abstract: Hydrogen peroxide is an oxidising agent that is used in a number of household products, including general-purpose disinfectants, chlorine-free bleaches, fabric stain removers, contact lens disinfectants and hair dyes, and it is a component of some tooth whitening products. In industry, the principal use of hydrogen peroxide is as a bleaching agent in the manufacture of paper and pulp. Hydrogen peroxide has been employed medicinally for wound irrigation and for the sterilisation of ophthalmic and endoscopic instruments. Hydrogen peroxide causes toxicity via three main mechanisms: corrosive damage, oxygen gas formation and lipid peroxidation. Concentrated hydrogen peroxide is caustic and exposure may result in local tissue damage. Ingestion of concentrated (>35%) hydrogen peroxide can also result in the generation of substantial volumes of oxygen. Where the amount of oxygen evolved exceeds its maximum solubility in blood, venous or arterial gas embolism may occur. The mechanism of CNS damage is thought to be arterial gas embolisation with subsequent brain infarction. Rapid generation of oxygen in closed body cavities can also cause mechanical distension and there is potential for the rupture of the hollow viscus secondary to oxygen liberation. In addition, intravascular foaming following absorption can seriously impede right ventricular output and produce complete loss of cardiac output. Hydrogen peroxide can also exert a direct cytotoxic effect via lipid peroxidation. Ingestion of hydrogen peroxide may cause irritation of the gastrointestinal tract with nausea, vomiting, haematemesis and foaming at the mouth; the foam may obstruct the respiratory tract or result in pulmonary aspiration. Painful gastric distension and belching may be caused by the liberation of large volumes of oxygen in the stomach. Blistering of the mucosae and oropharyngeal burns are common following ingestion of concentrated solutions, and laryngospasm and haemorrhagic gastritis have been reported. Sinus tachycardia, lethargy, confusion, coma, convulsions, stridor, sub-epiglottic narrowing, apnoea, cyanosis and cardiorespiratory arrest may ensue within minutes of ingestion. Oxygen gas embolism may produce multiple cerebral infarctions. Although most inhalational exposures cause little more than coughing and transient dyspnoea, inhalation of highly concentrated solutions of hydrogen peroxide can cause severe irritation and inflammation of mucous membranes, with coughing and dyspnoea. Shock, coma and convulsions may ensue and pulmonary oedema may occur up to 24-72 hours post exposure. Severe toxicity has resulted from the use of hydrogen peroxide solutions to irrigate wounds within closed body cavities or under pressure as oxygen gas embolism has resulted. Inflammation, blistering and severe skin damage may follow dermal contact. Ocular exposure to 3% solutions may cause immediate stinging, irritation, lacrimation and blurred vision, but severe injury is unlikely. Exposure to more concentrated hydrogen peroxide solutions (>10%) may result in ulceration or perforation of the cornea. Gut decontamination is not indicated following ingestion, due to the rapid decomposition of hydrogen peroxide by catalase to oxygen and water. If gastric distension is painful, a gastric tube should be passed to release gas. Early aggressive airway management is critical in patients who have ingested concentrated hydrogen peroxide, as respiratory failure and arrest appear to be the proximate cause of death. Endoscopy should be considered if there is persistent vomiting, haematemesis, significant oral burns, severe abdominal pain, dysphagia or stridor. Corticosteroids in high dosage have been recommended if laryngeal and pulmonary oedema supervene, but their value is unproven. Endotracheal intubation, or rarely, tracheostomy may be required for life-threatening laryngeal oedema. Contaminated skin should be washed with copious amounts of water. Skin lesions should be treated as thermal burns; surgery may be required for deep burns. In the case of eye exposure, the affected eye(s) shod eye(s) should be irrigated immediately and thoroughly with water or 0.9% saline for at least 10-15 minutes. Instillation of a local anaesthetic may reduce discomfort and assist more thorough decontamination.

TEMPO-Mediated Oxidation of Polysaccharides: Survey of Methods and Applications

Abstract: This review deals with TEMPO as a catalyst in oxidation of alcohol functions in polysaccharides. Synthesis of TEMPO and derivatives and the mechanism of the oxidative cycle in which TEMPO is involved in oxidation of alcohols are discussed. Results of oxidation of various polysaccharides with respect to yield, and introduction of the functional groups (aldehyde and/or carboxylate) are presented. Most of the primary oxidants are not ideal, as they produce large amounts of salts, e.g., sodium chloride from sodium hypochlorite. Results and perspectives are given to change the salt-based oxidative systems for much cleaner oxygen or hydrogen peroxide/enzyme-based TEMPO systems. Moreover, several immobilized TEMPO systems have been developed.

Widespread sulfenic acid formation in tissues in response to hydrogen peroxide

Abstract: A principal product of the reaction between a protein cysteinyl thiol and hydrogen peroxide is a protein sulfenic acid. Because protein sulfenic acid formation is reversible, it provides a mechanism whereby changes in cellular hydrogen peroxide concentration may directly control protein function. We have developed methods for the detection and purification of proteins oxidized in this way. The methodology is based on the arsenite-specific reduction of protein sulfenic acid under denaturing conditions and their subsequent labeling with biotin–maleimide. Arsenite-dependent signal generation was fully blocked by pretreatment with dimedone, consistent with its reactivity with sulfenic acids to form a covalent adduct that is nonreducible by thiols. The biotin tag facilitates the detection of protein sulfenic acids on Western blots probed with streptavidin–horseradish peroxidase and also their purification by streptavidin–agarose. We have characterized protein sulfenic acid formation in isolated hearts subjected to hydrogen peroxide treatment. We have also purified and identified a number of the proteins that are oxidized in this way by using a proteomic approach. Using Western immunoblotting we demonstrated that a highly significant proportion of some individual proteins (68% of total in one case) form the sulfenic derivative. We conclude that protein sulfenic acids are widespread physiologically relevant posttranslational oxidative modifications that can be detected at basal levels in healthy tissue, and are elevated in response to hydrogen peroxide. These approaches may find widespread utility in the study of oxidative stress, particularly because hydrogen peroxide is used extensively in models of disease or redox signaling.

Direct preparation of carbon nanofiber electrodes via pyrolysis of iron(II) phthalocyanine: Electrocatalytic aspects for oxygen reduction

Abstract: A facile method for the direct preparation of carbon nanofiber (CNF) electrodes by pyrolysis of iron(II) phthalocyanine on nickel substrates is reported. Uniform, large area coverage is observed with aligned bundles of CNFs exhibiting bamboo-like, hollow fibril morphology possessing diameters of 40−60 nm and lengths of ∼10 μm. The electrochemical behavior and stability of CNF electrodes as oxygen reduction catalysts were investigated by electrochemical methods. Without necessitation for extensive electrode pretreatment or surface activation, these electrodes demonstrate significant electrocatalytic activity in aqueous KNO3 solutions at neutral to basic pH for the reduction of dioxygen to hydrogen peroxide, O2 + H2O + 2e- ⇌ H + OH-. As determined from chronocoulometry, slopes of Anson plots indicate that the overall electrochemical reaction proceeds by the peroxide pathway via two successive two-electron reductions. pH-dependent cyclic voltammetry studies indicate that the CNF electrodes are very active to...

Redox regulation of OxyR requires specific disulfide bond formation involving a rapid kinetic reaction path.

Abstract: The Escherichia coli OxyR transcription factor is activated by cellular hydrogen peroxide through the oxidation of reactive cysteines. Although there is substantial evidence for specific disulfide bond formation in the oxidative activation of OxyR, the presence of the disulfide bond has remained controversial. By mass spectrometry analyses and in vivo labeling assays we found that oxidation of OxyR in the formation of a specific disulfide bond between Cys199 and Cys208 in the wild-type protein. In addition, using time-resolved kinetic analyses, we determined that OxyR activation occurs at a rate of 9.7 s(-1). The disulfide bond-mediated conformation switch results in a metastable form that is locally strained by approximately 3 kcal mol(-1). On the basis of these observations we conclude that OxyR activation requires specific disulfide bond formation and that the rapid kinetic reaction path and conformation strain, respectively, drive the oxidation and reduction of OxyR.

Role of hydrogen peroxide in bactericidal action of catechin.

Abstract: Catechin (epicatechin (EC), epicatechin gallate (ECg), epigallocatechin (EGC) and epigallocatechin gallate (EGCg)), which occur in green tea and black tea, possess strong bactericidal action. We observed a reactive oxygen species that was generated from the catechins as the active mechanism: and this reactive oxygen was identified. EGCg reacted with the dissolved oxygen in aqueous solution, resulting in the generation of hydrogen peroxide. Hydrogen peroxide production derived from EGCg rose with increasing pH. EGCg (0.22 mmol/l) in neutral solution (0.1 mol/l phosphate buffer pH 7.0: PBS) quantitatively generated 0.2 mmol/l hydrogen peroxide after 60 min incubation. The bactericidal effect of EGCg is dependent on hydrogen peroxide levels produced by EGCg; moreover, EGCg action was inhibited by treatment with catalase. Both bactericidal effects correlated closely when the effects of EGCg and hydrogen peroxide for the bacterium (9 of 10 kinds of bacterial strains) were examined. Therefore, hydrogen peroxide, which is generated by EGCg, appears to be involved in the bactericidal action of EGCg.

Photo-irradiated titanium dioxide catalyzes site specific DNA damage via generation of hydrogen peroxide.

Abstract: Titanium dioxide (TiO2) is a potential photosensitizer for photodynamic therapy. In this study, the mechanism of DNA damage catalyzed by photo-irradiated TiO2 was examined using [32P]-5'-end-labeled DNA fragments obtained from human genes. Photo-irradiated TiO2 (anatase and rutile) caused DNA cleavage frequently at the guanine residue in the presence of Cu(II) after E. coli formamidopyrimidine-DNA glycosylase treatment, and the thymine residue was also cleaved after piperidine treatment. Catalase, SOD and bathocuproine, a chelator of Cu(I), inhibited the DNA damage, suggesting the involvement of hydrogen peroxide, superoxide and Cu(I). The photocatalytic generation of Cu(I) from Cu(II) was decreased by the addition of SOD. These findings suggest that the inhibitory effect of SOD on DNA damage is due to the inhibition of the reduction of Cu(II) by superoxide. We also measured the formation of 8-oxo-7,8-dihydro-2'-deoxyguanosine, an indicator of oxidative DNA damage, and showed that anatase is more active than rutile. On the other hand, high concentration of anatase caused DNA damage in the absence of Cu(II). Typical free hydroxyl radical scavengers, such as ethanol, mannnitol, sodium formate and DMSO, inhibited the copper-independent DNA photodamage by anatase. In conclusion, photo-irradiated TiO2 particles catalyze the copper-mediated site-specific DNA damage via the formation of hydrogen peroxide rather than that of a free hydroxyl radical. This DNA-damaging mechanism may participate in the phototoxicity of TiO2.

New Heterogeneous Polyoxometalate Based Mesoporous Catalysts for Hydrogen Peroxide Mediated Oxidation Reactions

Abstract: Inorganic−organic hybrid mesoporous materials were prepared by cocrystallization of a “sandwich” type polyoxometalate, [ZnWZn2(H2O)2(ZnW9O34)2]12-, and branched tripodal organic polyammonium salts, tris[2-(trimethylammonium)ethyl]-1,3,5-benzenetricarboxylate or 1,3,5-tris[4-(N,N,N-trimethylammoniumethylcarboxyl)phenyl]benzene trications. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed formation of three-dimensional perforated coral-shaped amorphous materials with the organic cations surrounding polyoxometalate anions. N2 sorption analysis showed that the hybrid materials have a BET surface area of ∼30−50 m2 g-1 and an average pore diameter of 36 A leading to the classification of these materials as mesoporous materials with moderate surface areas. These hybrid materials behaved as very effective and selective heterogeneous catalysts for the epoxidation of allylic alcohols and oxidation of secondary alcohols to ketones with hydrogen peroxide as oxidant. The activity and...

Hydrogen peroxide and ozone formation in hybrid gas-liquid electrical discharge Reactors

Abstract: Ozone in the gas phase and hydrogen peroxide in the liquid phase were simultaneously formed in hybrid electrical discharge reactors, known as the hybrid-series and hybrid-parallel reactors, which utilize both gas phase nonthermal plasma formed above the water surface and direct liquid phase corona-like discharge in the water. In the series configuration the high voltage needle-point electrode is submerged and the ground electrode is placed in the gas phase above the water surface. The parallel configuration employs a high voltage electrode in the gas phase and a high voltage needle-point electrode in the liquid phase with the ground electrode placed at the gas-liquid interface. In both hybrid reactors the gas phase concentration of ozone reached a power-dependent steady state, whereas the hybrid-parallel reactor produced a substantially larger amount of ozone than the hybrid series. Hydrogen peroxide was produced in both hybrid reactors at a similar rate to that of a single-phase liquid electrical discharge reactor. The resulting concentration of H/sub 2/O/sub 2/ in the hybrid reactors, however, depended on the pH of the solution and the gas phase ozone concentration since H/sub 2/O/sub 2/ was decomposed by dissolved ozone at high pH.

Effect of Agglomeration of Pt/C Catalyst on Hydrogen Peroxide Formation

Abstract: Various amounts of 20 wt % Pt/C catalysts (56.7-5.7 μg c a r b o n cm - 2 ) were loaded on glassy carbon (GC) disk electrode, and the effect of agglomeration on hydrogen peroxide formation in oxygen reduction was investigated by the rotating ring-disk electrode technique. The formation of H 2 O 2 was enhanced with a decrease in agglomeration of Pt/C. Even in the operating potential range of polymer electrolyte fuel cell cathodes (0.6-0.8 V), 10% hydrogen peroxide was formed at 5.7 μg c a r b o n cm - 2 Pt/C loaded on GC. These results revealed that series two-electron reduction pathway, which is negligible on clean bulk Pt surface, does exist on Pt particles supported on carbon.

Biotechnological applications of peroxidases

Abstract: Peroxidases are widely distributed in nature. Reduction of peroxides at the expense of electron donating substrates, make peroxidases useful in a number of biotechnological applications. Enzymes such as lignin peroxidase and manganese peroxidase, both associated with lignin degradation, may be successfully used for biopulping and biobleaching in the paper industry, and can produce oxidative breakdown of synthetic azo dyes. Oxidative polymerization of phenols and aromatic amines conducted by horseradish peroxidase (HRP) in water and water-miscible organic solvents, may lead to new types of aromatic polymers. Site directed mutagenesis of HRP has been used to improve the enantioselectivity of arylmethylsulfide oxidations. Peroxidase has a potential for soil detoxification, while HRP as well as soybean and turnip peroxidases have been applied for the bioremediation of wastewater contaminated with phenols, cresols, and chlorinated phenols. Peroxidase based biosensors have found use in analytical systems for determination of hydrogen peroxide and organic hydroperoxides, while co-immobilized with a hydrogen peroxide producing enzyme, they can be used for determination of glucose, alcohols, glutamate and choline. Peroxidase has also been used for practical analytical applications in diagnostic kits, such as quantitation of uric acid, glucose, cholesterol, lactose, and so on. Enzyme linked immunorbent assay (ELISA) tests on which peroxidase is probably the most common enzyme used for labeling an antibody, are a simple and reliable way of detecting toxins, pathogens, cancer risk in bladder and prostate, and many other analytes. Directed evolution methods, appear to be a valuable alternative to engineer new catalyst forms of plant peroxidases from different sources to overcome problems of stability and to increase thermal resistance.