Involvement of triplet state in the photodissociation of hydrogen peroxide: experimental evidence from time-resolved EPR study

The dissociation of photoexcited hydrogen peroxide to generate a pair of hydroxyl radicals is generally believed to take place in a repulsive electronic singlet state. The results presented here, based on time-resolved EPR experiments on the spin polarisation pattern of the acetone ketyl radical (CH₃)₂C^?OH, generated on photodissociation of H₂O₂ in 2-propanol with a 248?nm laser light, strongly indicate significant involvement of a repulsive triplet state of excited hydrogen peroxide.     

Understanding the mechanism of DNA deactivation in ion therapy of cancer cells: hydrogen peroxide action*

Changes in the medium of biological cells under ion beam irradiation has been considered as a possible cause of cell function disruption in the living body. The interaction of hydrogen peroxide, a long-lived molecular product of water radiolysis, with active sites of DNA macromolecule was studied, and the formation of stable DNA-peroxide complexes was considered. The phosphate groups of the macromolecule backbone were picked out among the atomic groups of DNA double helix as a probable target for interaction with hydrogen peroxide molecules. Complexes consisting of combinations including: the DNA phosphate group, H₂O₂ and H₂O molecules, and Na⁺ counterion, were considered. The counterions have been taken into consideration insofar as under the natural conditions they neutralise DNA sugar-phosphate backbone. The energy of the complexes have been determined by considering the electrostatic and the Van der Waals interactions within the framework of atom-atom potential functions. As a result, the stability of various configurations of molecular complexes was estimated. It was shown that DNA phosphate groups and counterions can form stable complexes with hydrogen peroxide molecules, which are as stable as the complexes with water molecules. It has been demonstrated that the formation of stable complexes of H₂O₂-Na⁺-PO₄ ^- may be detected experimentally by observing specific vibrations in the low-frequency Raman spectra. The interaction of H₂O₂ molecule with phosphate group of the double helix backbone can disrupt DNA biological function and induce the deactivation of the cell genetic apparatus. Thus, the production of hydrogen peroxide molecules in the nucleus of living cells can be considered as an additional mechanism by which high-energy ion beams destroy tumour cells during ion beam therapy.     

A novel imaging tool for hepatic portal system using phase contrast technique with hydrogen peroxide‐generated O2 gas

The objective of this study was to investigate the potential of hydrogen peroxide‐generated oxygen gas‐based phase contrast imaging (PCI) for visualizing mouse hepatic portal veins. The O₂ gas was made from the reaction between H₂O₂ and catalase. The gas production was imaged by PCI in real time. The H₂O₂ was injected into the enteric cavity of the lower sigmoid colon to produce O₂ in the submucosal venous plexus. The generated O₂ gas could be finally drained into hepatic portal veins. Absorption contrast imaging (ACI) and PCI of O₂‐filled portal veins were performed and compared. PCI offers high resolution and real‐time visualization of the O₂ gas production. Compared with O₂‐based ACI, O₂‐based PCI significantly enhanced the revealing of the portal vein in vivo. It is concluded that O₂‐based PCI is a novel and promising imaging modality for future studies of portal venous disorders in mice models.     

The role of hydrogen peroxide in the deposition of cerium-based conversion coatings

Cerium-based conversion coatings are progressing as an effective alternative to hazardous chromate-based systems used in the treatment of metal surfaces. However, there is still considerable debate over the mechanism by which these coatings are formed. Here, titrations of cerium-based conversion coating solutions were carried out in order to model the reactions that occur at the metal-solution interface during coating, with a particular emphasis on investigating the role of hydrogen peroxide (H₂O₂). The titration curves obtained support the proposed formation of Ce(III) peroxo complexes such as Ce(H₂O₂)³⁺ as an initial step, followed by deprotonation, oxidation and precipitation to form peroxo-containing Ce(IV) species such as Ce^(IV)(O₂)(OH)₂. The precipitates resulting from titrations were characterised by Raman spectroscopy, X-ray diffraction and thermogravimetric analysis, confirming the presence of peroxo bonds, and nano-sized CeO₂ crystallites that decreased in size with increasing H₂O₂ concentration. Characterisation of cerium conversion coatings on aluminium alloy surfaces confirmed the presence of peroxo species in the coatings, thereby supporting the titration model.     

Growth of SiO2 on InP substrate by liquid phase deposition

We have grown silicon dioxide (SiO₂) on indium phosphorous (InP) substrate by liquid phase deposition (LPD) method. With inserting InP wafer in the treatment solution composed of SiO₂ saturated hydrofluorosilicic acid (H₂SiF₆), 0.1 M boric acid (H₃BO₃) and 1.74 M diluted hydrochloric acid (HCl), the maximum deposition rate and refractive index for the as-grown LPD-SiO₂ film were about 187.5 Å/h and 1.495 under the constant growth temperature of 40 °C. The secondary ion mass spectroscope (SIMS) and energy dispersive X-ray (EDX) confirmed that the elements of silicon, oxygen, and chloride were found in the as-grown LPD-SiO₂ film. On the other hand, the effects of treatment solution incorporated with the hydrogen peroxide (H₂O₂) that can regulate the concentration of OH⁻ ion were also shown in this article. The experimental results represented that the deposition rate decreases with increasing the concentration of hydrogen peroxide due to the reduced concentration of SiO₂ saturated H₂SiF₆ in treatment solution.     

Raman‐induced Kerr effect spectroscopy of single‐wall carbon nanotubes aqueous suspensions in the range 0.1–10 and 100–250 cm−1

Here, we study a low (less than 0.1 µg/ml) concentration aqueous suspension of single‐wall carbon nanotubes (SWNTs) by Raman‐induced Kerr effect spectroscopy (RIKES) in the spectral bands 0.1–10 and 100–250 cm⁻¹. This method is capable of carrying out direct investigation of SWNT hydration layers. A comparison of RIKES spectra of SWNT aqueous suspension and that of milli‐Q water shows a considerable growth in the intensity of low wavenumber Raman modes. These modes in the 0.1–10 cm⁻¹ range are attributed to the rotational transitions of H₂O₂ and H₂O molecules. We explain the observed intensity increase as due to the production of hydrogen peroxide and the formation of a low‐density depletion layer on the water–nanotube interface. A few SWNT radial breathing modes (RBM)are observed (ω_RBM = 118.5, 164.7 and 233.5 cm⁻¹) in aqueous suspension, which allows us to estimate the SWNT diameters (∼2.0, 1.5, and 1 nm, respectively). Copyright © 2011 John Wiley & Sons, Ltd.     

Studies of New Peroxyoxalate-H<Subscript>2</Subscript>O<Subscript>2</Subscript> Chemiluminescence System Using Quinoxaline Derivatives as Green Fluorophores

Quinoxaline derivatives are a great interest as fluorescent emitters for peroxyoxalate chemiluminescence. Reaction of peroxyoxalates such as bis-(2,4,6-trichlorophenyl) oxalate with H₂O₂ can transfer energy to fluorophore via formation of dioxetanedione intermediate. Two quinoxaline derivatives used as a fluorophore in this study which produce a green light in the chemiluminescence systems. The relationship between the chemiluminescence intensity and concentrations of fluorophore, peroxyoxalate, sodium salicylate and hydrogen peroxide was investigated. Kinetic parameters for the peroxyoxalate-chemiluminescence were also calculated from the computer fitting of the corresponding chemiluminescence intensity/time profiles. It was found that the biphenylquinoxaline can be used as an efficient green fluorescent emitter.     

Mitochondrial respiratory chain is involved in insulin-stimulated hydrogen peroxide production and plays an integral role in insulin receptor autophosphorylation in neurons

Background  

Accumulated evidence suggests that hydrogen peroxide (H₂O₂) generated in cells during insulin stimulation plays an integral role in insulin receptor signal transduction. The role of insulin-induced H₂O₂ in neuronal insulin receptor activation and the origin of insulin-induced H₂O₂ in neurons remain unclear. The aim of the present study is to test the following hypotheses (1) whether insulin-induced H₂O₂ is required for insulin receptor autophosphorylation in neurons, and (2) whether mitochondrial respiratory chain is involved in insulin-stimulated H₂O₂ production, thus playing an integral role in insulin receptor autophosphorylation in neurons.     

Hydrogen peroxide treatment on ZnO substrates to investigate the characteristics of Pt and Pt oxide Schottky contacts

We utilize hydrogen peroxide (H₂O₂) treatment on (0 0 0 1) ZnO substrates to investigate the characteristics of Pt and Pt oxide Schottky contacts (SCs). X-ray rocking curves show the mosaicity structure becomes larger after H₂O₂ treatment. Photoluminescence (PL) spectra show the yellow-orange emission peaking at ∼576-580 nm with respect to deep level of oxygen interstitials introduced by H₂O₂ treatment. The threshold formation of ZnO₂ resistive layer on H₂O₂-treated ZnO for 45 min is observed from grazing-incidence X-ray diffraction. The better electrical characteristic is performed by Pt oxide SC with the larger barrier height (1.09 eV) and the lower leakage current (9.52 × 10⁻¹¹ A/cm² at −2 V) than Pt SC on the H₂O₂-treated ZnO for 60 min. X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometer (SIMS) examinations indicate the promoted interface oxide bonding and Zn outdiffusion for Pt oxide contact, different from Pt contact. Based on current-voltage, capacitance-voltage, X-ray diffraction, PL spectra, XPS, and SIMS results, the possible mechanism for effective rectifying characteristic and enhanced Schottky behavior is given.     

闭壳层金掺杂钛氧团簇阴离子解离氢分子研究

Dissociation of molecular hydrogen (H₂) is extensively studied to understand the mechanism of hydrogenation reactions. In this study, H₂ dissociation by Au₁-doped closed-shell titanium oxide cluster anions AuTi₃O₇^- and AuTi₃O₈^- has been identified by mass spectrometry and quantum chemistry calculations. The clusters were generated by laser ablation and massselected to react with H₂ in an ion trap reactor. In the reaction of AuTi₃O₈^- with H₂, the ion pair Au⁺-O₂^2- rather than Au⁺-O^2- is the active site to promote H₂ dissociation. This finding is in contrast with the previous result that the lattice oxygen is usually the reactive oxygen species in H₂ dissociation. The higher reactivity of the peroxide species is further supported by frontier molecular orbital analysis. This study provides new insights into gold catalysis involving H₂ activation and dissociation.     

A theoretical assignment on excited‐state intramolecular proton transfer mechanism for quercetin

In the present work, we investigate a new chromophore (ie, quercetin) (Simkovitch et al J Phys Chem B 119 [2015] 10244) about its complex excited‐state intramolecular proton transfer (ESIPT) process based on density functional theory and time‐dependent density functional theory methods. On the basis of the calculation of electron density ρ( r ) and Laplacian ?²ρ( r ) at the bond critical point using atoms‐in‐molecule theory, the intramolecular hydrogen bonds (O₁‐H₂?O₅ and O₃‐H₄?O₅) have been supported to be formed in the S₀ state. Comparing the prime structural variations of quercetin involved in its 2 intramolecular hydrogen bonds, we find that these 2 hydrogen bonds should be strengthened in the S₁ state, which is a fundamental precondition for facilitating the ESIPT process. Concomitantly, infrared vibrational spectra analysis further verifies this viewpoint. In good agreement with previous experimental spectra results, we find that quercetin reveals 2 kinds of excited‐state structures (quercetin* and quercetin‐PT1*) in the S₁ state. Frontier molecular orbitals depict the nature of electronically excited state and support the ESIPT reaction. Our scanned potential energy curves according to variational O₁‐H₂ and O₃‐H₄ coordinates demonstrate that the proton transfer process should be more likely to occur in the S₁ state via hydrogen bond wire O₁‐H₂?O₅ rather than O₃‐H₄?O₅ because of the lower potential energy barrier 2.3 kcal/mol. Our present work explains previous experimental result and makes up the deficiency of mechanism in previous experiment. In the end, we make a reasonable assignment for ESIPT process of quercetin.     

Synthesis and electrocatalytic activities of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanocubes

In this article, a hydrothermal method was developed to synthesize Co₃O₄ nanocubes using hydrogen peroxide (H₂O₂) as oxidant, Co(NO₃)₂·6H₂O as a cobalt source. The products are characterized in detail by multiform techniques including X-ray diffraction (XRD), energy dispersive X-ray analysis (EDS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results show that the obtained products are Co₃O₄ nanocubes with size ranging between 20 and 40 nm. The effects of the hydrogen peroxide concentration on the size of the products have been studied. The electrocatalytic activities of H₂O₂ reduction on Co₃O₄ nanocubes in phosphate buffer were also evaluated.     

Localisation of hydrogen peroxide accumulation during Solanum tuberosum cv. Rywal hypersensitive response to Potato virus Y

The reactive oxygen species hydrogen peroxide (H₂O₂) was detected cytochemically in Solanum tuberosum cv. Rywal tissues as a hypersensitive response (HR) 24 and 48 h after a Potato virus Y (PVY) infection.Hydrogen peroxide was detected in vivo by its reaction with 3.3-diaminobenzidine, producing a reddish-brown staining in contact with H₂O₂. Hydrogen peroxide was detected in the necrotic area of the epidermal and mesophyll cells 24 and 48 h after the PVY infection. Highly localised accumulations of H₂O₂ were found within xylem tracheary elements, and this was much more intensive than in non-infected leaves. Hydrogen peroxide was detected cytochemically in HR also by its reaction with cerium chloride, producing electron-dense deposits of cerium perhydroxides.Inoculation with PVY^NTN and also PVY^N Wi induced a rapid hypersensitive response during which highly localised accumulations of H₂O₂ was detected in plant cell walls. The most intensive accumulation was present in the bordering cell walls of necrotic mesophyll cells and the adjacent non-necrotic mesophyll cells. Intensive electron-dense deposits of cerium perhydroxide were found along ER cistrenae and chloroplast envelopes connected with PVY particles. The precipitates of hydrogen peroxide were detected in the nuclear envelope and along tracheary elements, especially when virus particles were present inside. The intensive accumulation of H₂O₂ at the early stages of potato–PVY interaction is consistent with its role as an antimicrobial agent and for this reason it has been regarded as a signalling molecule.     

Surface evolution of a gradient structured Ti in hydrogen peroxide solution

In this work, the interaction between hydrogen peroxide (H₂O₂) and a gradient structured Ti was investigated extensively. The gradient structured Ti (SMAT Ti) was produced by surface mechanical attrition treatment (SMAT), and then it was immersed in H₂O₂ solution for different time until 48 h at room temperature (25 °C). The structure and surface morphology evolution were examined by Raman spectra and scanning electron microscopy (SEM). The formation mechanism of nanoporous titania was discussed based on above results.     

H2O2–Ng dynamics predictions using an accurate potential energy surface

ABSTRACT

Based on ab initio calculations, our research group has built an analytical ground-state potential energy surface (PES) for hydrogen peroxide– noble gas (Ng) interactions, such as H₂O₂–He, H₂O₂–Ne, H₂O₂–Ar, H₂O₂–Kr, and H₂O₂–Xe complexes. From this PES, it was verified that the Ng presence does not affect the equilibrium values of the H₂O₂ dihedral angles. This happens because the H₂O₂ intramolecular barriers have much higher energies than the atom–bond interaction within these complexes. From this point of view, it is indeed reasonable to consider the H₂O₂ system as a rigid rotor, frozen at its equilibrium configuration. We present in this work the torsional motion for the H₂O₂ isolated system, the vibration–rotation energy levels and spectroscopic constants for hydrogen peroxide–noble gas by using the aforementioned PES. The predicted H₂O₂ torsional motions are in good agreement with both theoretical and experimental results available in the literature. Regarding H₂O₂–Ng ro-vibrational energies and spectroscopic constants, it is the first time that these calculations are presented in the literature. The current theoretical predictions are expected to be useful in the future experimental investigations.     

The effect of benzo‐annelation on intermolecular hydrogen bond and proton transfer of 2‐methyl‐3‐hydroxy‐4(1H)‐quinolone in methanol: A TD‐DFT study

Excited‐state intermolecular or intramolecular proton transfer (ESIPT) reaction has important potential applications in biological probes. In this paper, the effect of benzo‐annelation on intermolecular hydrogen bond and proton transfer reaction of the 2‐methyl‐3‐hydroxy‐4(1H)‐quinolone (MQ) dye in methanol solvent is investigated by the density functional theory and time‐dependent density functional theory approaches. Both the primary structure parameters and infrared vibrational spectra analysis of MQ and its benzo‐analogue 2‐methyl‐3‐hydroxy‐4(1H)‐benzo‐quinolone (MBQ) show that the intermolecular hydrogen bond O₁―H₂?O₃ significantly strengthens in the excited state, whereas another intermolecular hydrogen bond O₃―H₄?O₅ weakens slightly. Simulated electron absorption and fluorescence spectra are agreement with the experimental data. The noncovalent interaction analysis displays that the intermolecular hydrogen bonds of MQ are obviously stronger than that of MBQ. Additionally, the energy profile analysis via the proton transfer reaction pathway illustrates that the ESIPT reaction of MBQ is relatively harder than that of MQ. Therefore, the effect of benzo‐annelation of the MQ dye weakens the intermolecular hydrogen bond and relatively inhibits the proton transfer reaction.     

One‐Pot Synthesis of Algae‐Like MoS2/PPy Nanocomposite: A Synergistic Catalyst with Superior Peroxidase‐Like Catalytic Activity for H2O2 Detection

A facile one‐pot synthetic route is reported to prepare algae‐like molybdenum disulfide/polypyrrole (MoS₂/PPy) nanocomposite through a redox reaction between ammonium tetrathiomolybdate and pyrrole monomer under a hydrothermal condition without any other templates. The as‐prepared unique algae‐like MoS₂/PPy nanocomposites are composed of few layer MoS₂ nanosheets, which are covered with PPy. Structural and morphological characterizations of this unique nanocomposite are investigated by Fourier‐transform infrared spectra, Raman spectra, X‐ray diffraction pattern, X‐ray photoelectron spectra, energy‐dispersive X‐ray spectroscopy, and transmission electron microscopy. The as‐prepared MoS₂/PPy nanocomposites exhibit an excellent peroxidase‐like catalytic activity toward the oxidation of 3,3,5,5‐tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H₂O₂) in acetate buffer solution (pH 4.0), which provides a facile strategy for the colorimetric detection of H₂O₂ with a high sensitivity.     

Effect of additives for higher removal rate in lithium niobate chemical mechanical planarization

High roughness and a greater number of defects were created by lithium niobate (LN; LiNbO₃) processes such as traditional grinding and mechanical polishing (MP), should be decreased for manufacturing LN device. Therefore, an alternative process for gaining defect-free and smooth surface is needed. Chemical mechanical planarization (CMP) is suitable method in the LN process because it uses a combination approach consisting of chemical and mechanical effects. First of all, we investigated the LN CMP process using commercial slurry by changing various process conditions such as down pressure and relative velocity. However, the LN CMP process time using commercial slurry was long to gain a smooth surface because of lower material removal rate (MRR). So, to improve the material removal rate (MRR), the effects of additives such as oxidizer (hydrogen peroxide; H₂O₂) and complexing agent (citric acid; C₆H₈O₇) in a potassium hydroxide (KOH) based slurry, were investigated. The manufactured slurry consisting of H₂O₂-citric acid in the KOH based slurry shows that the MRR of the H₂O₂ at 2 wt% and the citric acid at 0.06 M was higher than the MRR for other conditions.     

Chemical and photochemical reactivity of 6‐hydroxymethyl‐7,8‐dihydropterin in aqueous solutions

6‐Hydroxymethyl‐7,8‐dihydropterin (H₂Hmp) is an intermediate in the biosynthesis of folate, a precursor of coenzymes involved in the metabolism of nucleotides and amino acids. In this work, we have investigated the reactions undergone by H₂Hmp in aqueous solutions at physiological pH, in the absence and in the presence of UV‐A radiation (320–400 nm). In air‐equilibrated solutions, H₂Hmp undergoes slow thermal oxidation (half‐life 37 h) to yield 7,8‐dihydroxanthopterin (H₂Xap) as the main product. The reaction of H₂Hmp with hydrogen peroxide also yields H₂Xap as a main product. In contrast, UV‐A excitation of H₂Hmp leads to the formation of a dimer identified by electrospray ionization mass spectrometry. The corresponding quantum yield of H₂Hmp consumption (Φ_?R) was independent of O₂ and reactant concentration and has a value of 0.10 (±0.02), more than twice higher than that measured for other 6‐subtituted 7,8‐dihydropterins. Copyright © 2012 John Wiley & Sons, Ltd.     

Mechanism and optimization of non-thermal plasma-activated water for bacterial inactivation by underwater plasma jet and delivery of reactive species underwater by cylindrical DBD plasma

Plasma-activated water (PAW) has been in use for the past decade in sanitization against bacteria and other microorganisms. This research study compared PAW generated by a DC positive flyback transformer (FBT) underwater plasma jet with delivery of reactive species underwater by cylindrical dielectric barrier discharge (C-DBD) with a neon transformer. A Box–Behnken design was adopted as a response surface methodology (RSM) to design the experimental plan and optimize operating parameters including time, gas flow, and gas ratio. The physical responses comprise optical emission spectroscopy (OES), pH, oxidation-reduction potential (ORP), and electrical conductivity (EC). The chemical responses consist of hydrogen peroxide (H₂O₂) and hydroxyl radicals (OH·). The biological responses include Escherichia coli reduction and Staphylococcus aureus reduction. The optimal condition for underwater plasma jet was found to be Ar gas with a flow rate of 3 slm for 6.5 min of treatment time, which can reduce E. coli and S. aureus to 7.14 ± 0.14 and 3.10 ± 0.26 in log, respectively. Also, the optimal condition for delivery of reactive species underwater by C-DBD plasma was found to be Ar (99%): O₂ (1%) gas mixture with an Ar gas flow rate of 4 slm for a treatment time of 11.5 min, which could reduce E. coli and S. aureus to 0.45 ± 0.07 and 2.45 ± 0.23 in log, respectively.