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On-Line Raman Measurement of the Radiation-Enhanced Reaction of Cellobiose with Hydrogen Peroxide
Not Available
Dissolved Oxygen Redox as the Source of Hydrogen Peroxide and Hydroxyl Radical in Sonicated Emulsive Water Microdroplets
Sonicated emulsive water microdroplets (SEWMs) accelerate and enable a variety of catalyst-free chemical transformations. However, significant unanswered questions remain regarding the chemical intermediates they form and their possible redox origin. In this study, we identified dissolved O 2 as the primary originator of reactive oxygen species (ROS) such as OH• and H 2 O 2. We uncovered the role of dissolved O 2 redox by using a combination of microelectrochemical methods to detect H 2 O 2 , isotopic methods to identify the source of H 2 O 2 , and a combination of electron spin resonance and the DMPO spin trap to detect radicals such as OH•. Notably, we found that H 2 O 2 production is correlated with O 2 content via a reduction pathway enabled by a sufficiently large reducing power that can additionally generate H 2 and even perform Pb electroless deposition on Au and Cu metal substrates. Building on our findings, continuous O 2 bubbling of SEWMs showed accumulation of H 2 O 2 up to ∼88 mM in the aqueous phase within 1 h of sonication, demonstrating the scale-up promise of this method. Distinct to sonochemistry of a single phase, this study advances our understanding of the confluence of redox and chemical reaction mechanisms within SEWMs as a biphasic system. This insight paves the way for improving their reaction kinetics, yield, and selectivity, positioning these attractive redox microreactors as alternatives to traditional electrolyzers.
Hydrogen peroxide sensor HPCA1 is an LRR receptor kinase in Arabidopsis
Not provided.
Production of hydrogen peroxide in an intra-meander hyporheic zone at East River, Colorado.
The traditionally held assumption that photo-dependent processes are the predominant source of H 2 O 2 in natural waters has been recently questioned by an increasing body of evidence showing the ubiquitiousness of H 2 O 2 in dark water bodies and in groundwater. In this study, we conducted field measurement of H 2 O 2 in an intra-meander hyporheic zone and in surface water at East River, CO. On-site detection using a sensitive chemiluminescence method suggests H 2 O 2 concentrations in groundwater ranging from 6 nM (at the most reduced region) to ~ 80 nM (in a locally oxygen-rich area) along the intra-meander transect with a maxima of 186 nM detected in the surface water in an early afternoon, lagging the maximum solar irradiance by ~1.5 h. Our results suggest that the dark profile of H 2 O 2 in the hyporheic zone is closely correlated to local redox gradients, indicating that interactions between various redox sensitive elements could play an essential role. Due to its transient nature, the widespread presence of H 2 O 2 in the hyporheic zone indicates the existence of a sustained balance between H 2 O 2 production and consumption, which potentially involves a relatively rapid succession of various biogeochemically important processes (such as organic matter turnover, metal cycling and contaminant mobilization). More importantly, this study confirmed the occurrence of reactive oxygen species at a subsurface redox transition zone and further support our understanding of redox boundaries on reactive oxygen species generation and as key locations of biogeochemical activity.
Effect of surface modification on silica supported Ti catalysts for cyclohexene oxidation with vapor-phase hydrogen peroxide
Surface modification via grafting of organic moieties on a Lewis acid catalyst (silica supported Ti catalyst, Ti-SiO 2 ) alters the activation of H 2 O 2 in vapor-phase cyclohexene epoxidation. Grafting a fluorous group (1H,1H-perfluoro-octyl) suppresses activity of Ti-SiO 2 . Conversely, grafting either a nonpolar group (octyl) or a polar aprotic group (triethylene glycol monomethyl ether) enhances rates and shifts selectivity toward trans-1,2-cyclohexanediol.
Experimental and computational studies of the kinetics of the reaction of hydrogen peroxide with the amidogen radical
In this work, the pulsed-laser photolysis/laser-induced fluorescence method is used to study the kinetics of the reaction of NH 2 with H 2 O 2 to yield a second-order rate constant of (2.42 ± 0.55) × 10 –14 cm 3 molecule –1 s –1 at 412 K in 10–22 mbar of Ar bath gas. There are no prior measurements for comparison. To check this value and enable reliable extrapolation to other temperatures, we also compute thermal rate constants for this process over the temperature range 298–3000 K via multi-structural canonical variational transition-state theory with small-curvature multidimensional tunneling (MS-CVT/SCT). The CVT/SCT rate constants are derived using a dual-level direct dynamics approach utilizing single-point CCSD(T)-F12b/cc-pVQZ-F12 energies—corrected for core-valence and scalar relativistic effects—and M06-2X/MG3S geometries, gradients, and Hessians—for all stationary and non-stationary points along the reaction path. The multistructural method with torsional anharmonicity, based on a coupled torsional potential, is then employed to calculate correction factors for the rate constants, accounting for the comprehensive effects of torsional anharmonicity on the kinetics of this reaction system. The final MS-CVT/SCT rate constants are found to be in good agreement with our measurements and can be expressed in modified Arrhenius form as 2.13 × 10 –15 (T/298 K) 4.02 exp(–513 K/T) cm 3 molecule –1 s –1 over the temperature range of 298–3000 K.
2,4–dinitroanisole transformation during advanced oxidation with ultraviolet light emitting diodes and hydrogen peroxide
This study investigated the kinetics and reaction mechanisms associated with advanced oxidation of 2,4-dinitroanisole (DNAN) with light emitting diodes (LEDs) in the UV/H2O2 process. The pseudo first-order reaction rate constants for DNAN oxidation depended on the H 2 O 2 /DNAN molar ratio and were between 0.017 and 0.026 min –1 . Hydroxyl radical scavenging was strongly implicated by the experimental results. High mass spectrophotometric chromatograms showed the presence of several by-products, including three with ecotoxicity that is greater than that of DNAN. Transformation pathways were analysed using Density Functional Theory (DFT), which helped to predict the presence of experimentally detected DNAN by-products by considering Mulliken charges. Furthermore, this study is the first to elucidate DNAN transformation mechanisms using both experimental studies and computational chemistry.
Imaging of Hydrogen Peroxide and Methyl in Nanosecond Pulsed Plasmas by Photofragmentation Laser-Induced Fluorescence.
Abstract not provided.
Absolute rate constant for the reaction of atomic chlorine with hydrogen peroxide vapor over the temperature range 265-400 K
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Intensity of the hydrogen peroxide v6/b/ band around 1266 cm
Laboratory spectra of the V6(b) band of H2O2 at 1266/cm have been obtained at a resolution of 0.06/cm and at temperatures ranging from 278 to 294 K. A total band intensity of 375 + or - 17 per sq cm per amagat is determined from the spectra. Special techniques to handle the H2O2 samples in a way that minimizes abundance determination errors are discussed.
Concerning the electrosynthesis of hydrogen peroxide and peroxodisulfates. Section 2: Optimization of electrolysis cells using an electrolyzer for peroxodisulfuric acid as an example
The model is presented of an electrolyzer for peroxodisulfuric acid, and it is analyzed mathematically. Its application for engineering and economic optimization is investigated in detail. The mathematical analysis leads to conclusions concerning the change in position of the optimum with respect to the various target functions due to changes of the individual design-caused and economic parameters.
An observed upper limit on stratospheric hydrogen peroxide
Observations collected by a ground-based heterodyne receiver of an emission from the 7(0.7)-6(1.5) rotational torsional transition of H2O2 at 270.610 GHz are studied. An integrated spectrometer output of the data obtained at Mauna Kea, Hawaii in late May and early June of 1983 is presented. The removal of the ozone line background profile from the data is described. With no signal detected in the output of a 256-channel filter spectrometer the calculation of an upper limit on stratospheric H2O2 is possible. The utilization of the mixing ratio profile of Sze and Ko (1984) to compute the limit of H2O2 is examined. An upper limit for H2O2 of approximately 1 x 10 to the 14th/cu cm between 30-50 km is established.
Evidence for stratospheric hydrogen peroxide
A statistically significant measurement of H2O2 in the stratosphere has been obtained. The results were obtained from the 112.19/cm RQ5 branch of the torsional-rotational spectrum with a remote-sensing far-infrared Fourier transform spectrometer during the Balloon Intercomparison Campaign (BIC-2), on June 20, 1983. The concentration above the balloon gondola is unexpectedly large, corresponding to 0.68 + or - 0.21 parts per billion by volume (ppbv) at an effective altitude of 38.3 km. Below the gondola altitude the concentration of H2O2 is slightly less than expected from the model predictions at 33.2 km (0.19 + or - 0.05 ppbv) and significantly less than expected at 29.3 km (0.08 + or - 0.03 ppbv).
Hydrogen peroxide and the evolution of oxygenic photosynthesis
Possible pathways for the evolution of oxygenic photosynthesis in the early reducing atmosphere of the earth are discussed. It is suggested that the abiotic production of atmospheric oxidants could have provided a mechanism by which locally oxidizing conditions were sustained within spatially confined habitats thus removing the available reductants and forcing photosynthetic organisms to utilize water (rather than ferrous or sulfide ions) as the electron donor. It is argued that atmospheric H2O2 played the key role in inducing oxygenic photosynthesis, because, as peroxide concentrations local environments increased, primitive organisms would not only be faced with a loss of a reductant, but would be also forced to develop a biochemical apparatus (such as catalase) that would protect them against the products of oxygenic photosynthesis. This scenario allows for the early evolution of oxygenic photosynthesis at the time when global conditions were still anaerobic.
Investigation of the Diborane - Hydrogen Peroxide Propellant Combination
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