Hydroxyl radicals

  • 文章类型: Journal Article
    稻田土壤中频繁的洪水和排水循环导致铁(Fe)矿物的还原溶解和Fe(II)物种的再氧化,同时产生强劲且一致的活性氧(ROS)输出。在这项研究中,我们对代表性稻田土壤在洪水排水过程中Fe物种和ROS的时空变化进行了全面评估。我们的实验室柱实验表明,溶解的O2浓度降低导致水-土壤界面以下的Fe快速还原,在延长的驱油时间内,水性Fe(II)转化为固体Fe(II)相。因此,•液相的OH生产能力降低,而固相的OH生产能力提高。•50天后,固相的OH生产能力从227-271μmolkg-1(在1-11cm深度内)增加到500-577至499-902μmolkg-1,3个月,和1年的孵化,分别。排水期间,动态·OH的产生是由O2消耗和Fe(II)氧化引发的。ROS捕获膜和原位捕获表明,土壤表面是强烈产生H2O2和•OH的活性区,而由于有限的氧气渗透,在较深的土壤层(>5cm)中观察到有限的ROS产生。这些发现为稻田氧化还原过渡带中动态Fe循环与ROS产生之间复杂的相互作用提供了更多见解。
    Frequent cycles of flooding and drainage in paddy soils lead to the reductive dissolution of iron (Fe) minerals and the reoxidation of Fe(II) species, all while generating a robust and consistent output of reactive oxygen species (ROS). In this study, we present a comprehensive assessment of the temporal and spatial variations in Fe species and ROS during the flooding-drainage process in a representative paddy soil. Our laboratory column experiments showed that a decrease in dissolved O2 concentration led to rapid Fe reduction below the water-soil interface, and aqueous Fe(II) was transformed into solid Fe(II) phases over an extended flooding time. As a result, the •OH production capacity of liquid phases was reduced while that of solid phases improved. The •OH production capacity of solid phases increased from 227-271 μmol kg-1 (within 1-11 cm depth) to 500-577 to 499-902 μmol kg-1 after 50 day, 3 month, and 1 year incubation, respectively. During drainage, dynamic •OH production was triggered by O2 consumption and Fe(II) oxidation. ROS-trapping film and in situ capture revealed that the soil surface was the active zone for intense H2O2 and •OH production, while limited ROS production was observed in the deeper soil layers (>5 cm) due to the limited oxygen penetration. These findings provide more insights into the complex interplay between dynamic Fe cycling and ROS production in the redox transition zones of paddy fields.
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  • 文章类型: Journal Article
    该研究考察了不同参数对通过湿法同时去除SO2和NOX的影响。已经比较了两种单独的工艺来去除烟气,即臭氧/UV和H2O2/UV。该研究旨在开展使用臭氧/H2O2和紫外光同时去除SO2和NOX的比较研究,并找到每个过程的能耗(也称为EEO)。UV与O3和H2O2的结合在产生羟基自由基中起着至关重要的作用。臭氧/H2O2、烟气、和紫外强度进行了研究,在不同的pH值和温度下的溶液,以实现最大程度的去除烟气。For,在臭氧化过程中,观察到烟气的去除率随紫外线强度的增加而增加,在较高的紫外线强度(250瓦)下,在最佳温度308K下,NOX的去除率为92%,SO2的去除率为95%。对于H2O2/UV工艺,(250W紫外线强度)在313K时,NOX的去除率为95%,SO2为100%,0.3LPM烟气流量。对于95%的NOx/SO2去除效率,两种方法获得的EEO值小于1。
    The study investigates the effect of different parameters for the removal of SO2 and NOx through a wet process concurrently. Two separate processes have been compared for the removal of flue gases, that is, Ozone/UV and H2O2/UV. The research aims to develop a comparative study for the removal of SO2 and NOx simultaneously using Ozone/H2O2 and UV light and find the energy consumption (also known as EEO) for each process. Combining UV with O3 and H2O2 play a crucial role in generating hydroxyl radicals. Different combinations of Ozone/H2O2, flue gas, and UV intensity were studied at different pH and temperatures of the solution to achieve maximum removal of the flue gases. For, the ozonation process it was observed that the removal% of flue gases increases with increasing UV intensity, and at higher UV intensity (250 W), the removal% for NOx is 92% and SO2 is 95% simultaneously at optimum temperature 308 K. For H2O2/UV process (250 W UV intensity), removal% for NOx is 95% and SO2 is 100% at 313 K, 0.3 LPM flow rate of flue gases. The EEO values obtained for both processes were less than 1 for 95% NOx/SO2 removal efficiency.
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  • 文章类型: Journal Article
    光解作为户外空气化学引发剂的重要性已得到广泛认可,但其在室内化学加工中的作用往往被忽视。本文利用最近的实验数据修改了一个详细的化学模型,用它来研究玻璃类型的影响,人工室内照明,浑浊,一年中的时间和纬度对室内光解速率以及室内空气化学的影响。从LED切换到未覆盖的荧光灯管,预计室内羟基自由基浓度增加了约13%。然而,从透射波长超过380nm的室外光的玻璃移动到透射波长超过315nm的太阳光的玻璃导致预测的羟基自由基增加超过400%。对于我们研究的物种来说,包括臭氧,氮氧化物,亚硝酸,甲醛,和羟基自由基,后者对室内光解速率的变化最敏感。二氧化氮和甲醛的浓度基本不变,与室外交换和内部沉积控制其室内浓度。现代灯,如LED,与低透射眼镜一起,可能会减少室内光解的影响和潜在有害物种的产生。需要对不同室内空气混合物的健康影响进行研究以证实这一结论。
    The importance of photolysis as an initiator of air chemistry outdoors is widely recognized, but its role in chemical processing indoors is often ignored. This paper uses recent experimental data to modify a detailed chemical model, using it to investigate the impacts of glass type, artificial indoor lighting, cloudiness, time of year and latitude on indoor photolysis rates and hence indoor air chemistry. Switching from an LED to an uncovered fluorescent tube light increased predicted indoor hydroxyl radical concentrations by ~13%. However, moving from glass that transmitted outdoor light at wavelengths above 380 nm to one that transmitted sunlight above 315 nm led to an increase in predicted hydroxyl radicals of more than 400%. For our studied species, including ozone, nitrogen oxides, nitrous acid, formaldehyde, and hydroxyl radicals, the latter were most sensitive to changes in indoor photolysis rates. Concentrations of nitrogen dioxide and formaldehyde were largely invariant, with exchange with outdoors and internal deposition controlling their indoor concentrations. Modern lights such as LEDs, together with low transmission glasses, will likely reduce the effects of photolysis indoors and the production of potentially harmful species. Research is needed on the health effects of different indoor air mixtures to confirm this conclusion.
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  • 文章类型: Journal Article
    过氧化氢作为中间体和产物在铜酶和单核铜络合物还原双氧中起着重要作用。铜(II)三(2-吡啶基甲基)胺络合物(Cu-tmpa)已显示在O2的电化学4电子还原过程中产生H2O2作为中间体。我们研究了Cu-tmpa在中性水溶液中的电化学过氧化氢还原反应(HPRR)。反应的催化速率常数比双氧还原低一个数量级。确定H2O2还原的显着溶剂动力学同位素效应(KIE)为1.4至1.7,表明类Fenton反应途径是可能的催化机理,涉及单个铜位点,该位点在该过程中产生中间的铜(II)羟基物种和游离的羟基阴离子。
    Hydrogen peroxide plays an important role as an intermediate and product in the reduction of dioxygen by copper enzymes and mononuclear copper complexes. The copper(II) tris(2-pyridylmethyl)amine complex (Cu-tmpa) has been shown to produce H2O2 as an intermediate during the electrochemical 4-electron reduction of O2. We investigated the electrochemical hydrogen peroxide reduction reaction (HPRR) by Cu-tmpa in a neutral aqueous solution. The catalytic rate constant of the reaction was shown to be one order of magnitude lower than the reduction of dioxygen. A significant solvent kinetic isotope effect (KIE) of 1.4 to 1.7 was determined for the reduction of H2O2, pointing to a Fenton-like reaction pathway as the likely catalytic mechanism, involving a single copper site that produces an intermediate copper(II) hydroxo species and a free hydroxyl radical anion in the process.
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  • 文章类型: Journal Article
    废水中难降解抗抑郁药的有效去除具有挑战性。在这项研究中,将半胱氨酸辅助的Fe2+/过硫酸盐系统(Fe2+/Cys/PS)的新策略应用于文拉法辛(Ven,作为典型的抗抑郁药)降解。结果表明,Fe2+/Cys/PS过程中Ven的去除明显加速和增强,并在最佳剂量下在5分钟内实现完全降解。进一步分析表明,Ven降解效率与化学浓度(即Fe2+,Cys和PS)和操作条件(即pH和温度)。此外,所述反应不受可能存在于实际废水基质中的共存有机物(即富里酸)和无机离子(即Cl-)的影响。机理探索表明Cys的存在促进了Fe3+/Fe2+的氧化还原循环,从而提高了活性氧的产量(ROS)。通过自由基清除剂验证,OH被认为是Fe2/Cys/PS过程中Ven降解的主要ROS。此外,确定了Ven降解的主要中间体,并提出了可能的转化途径,其中OH攻击的羟基化是主要反应。此外,用密度泛函理论(DFT)计算了Ven中的活性反应位点,这与观察到的代谢途径一致。
    The effective removal of refractory antidepressant in wastewater is challenging. In this study, a novel strategy of cysteine-assisted Fe2+/persulfate system (Fe2+/Cys/PS) was applied for the venlafaxine (Ven, as a typical antidepressant) degradation. The obtained results revealed that the Ven removal was evidently accelerated and enhanced in Fe2+/Cys/PS process, and achieved complete degradation in 5 min with optimal dosage. Further analysis indicated that the Ven degradation efficiency was associated with the chemical concentrations (i.e. Fe2+, Cys and PS) and operational conditions (i.e. pH and temperature). Moreover, the reactions were not impacted by the co-occurring organic matters (i.e. fulvic acid) and inorganic ions (i.e. Cl-) potentially existing in real wastewater matrices. Mechanistic explorations demonstrated that the presence of Cys promoted the Fe3+/Fe2+ redox cycle, and thus enhanced the reactive oxygen species yields (ROS). The OH was considered as the primary ROS in Fe2+/Cys/PS process for Ven degradation via the radical scavenger verification. Also, the main intermediates of Ven degradation were identified, and the possible transformation pathway was proposed, in which the hydroxylation attacked by the OH was the main reaction. Moreover, the active reaction sites in Ven were calculated with the density function theory (DFT), which was consistent with the observed metabolic routes.
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  • 文章类型: Comparative Study
    Sonodynamic therapy (SDT) is a new manner of killing cancer cells based on the cytotoxic interactions of ultrasound with sonosensitizing agents. It is shown that gold nanoparticles (GNPs) increase the efficiency of cavitation activity of ultrasound. In this study the influence of a single and/or two frequencies of ultrasound waves to generate hydroxyl radicals (·OH) was assessed in the presence of protoporphyrin IX (PpIX) and/or GNPs. Ultrasound cavitation activity was determined by recording fluorescence signals from chemical terephthalic acid (TA) dosimeters with or without PpIX and/or GNPs at the frequencies of 0.8 and 2.4 MHz individually and aggregately. To study hydroxyl radicals, experiments were performed with and without hydroxyl radical scavengers mannitol, histidine, and sodium azide. Cavitation activity was amplified by increasing ultrasound intensity and exposure time. The cavitation activity induced by dual ultrasound frequency was remarkably higher than the summation of effects produced by individual frequencies. All three scavengers reduced the fluorescence signal level. The effect of GNPs on intensifying cavitation activity at higher frequency was greater than that of lower frequency. PpIX showed a more effective sonosensitizing property at the lower frequency. Also, estimated synergism at dual frequency irradiation was improved in the presence of GNPs. We found that GNPs increased hydroxyl radical production at 2.4 MHz and that PpIX increased hydroxyl radical production at 0.8 MHz. Dual frequency exposure was more effective than single frequency exposure. PpIX at low frequency and gold nanoparticles at high frequency both enhance sonodynamic treatment efficacy.
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  • 文章类型: Journal Article
    In this study, Fe2+-modified goethite with low defects (α-Fe(Fe2+)OOH) was synthesized and characterized. Results revealed that α-Fe(Fe2+)OOH is a nano magnetic material with goethite (α-FeOOH) -type structures and has fewer Lewis acid of Fe3+ on its surface. Moreover, α-Fe(Fe2+)OOH was effective in catalytic ozonation of 4-chloronitrobenzene (4-CNB), which is a probe contaminant that cannot be efficiently removed through sole ozonation. The removal of 4-CNB increased with ozone concentration and α-Fe(Fe2+)OOH dosage, but decreased with the presence of carbonate, sulfate and phosphate. The catalytic activity of α-Fe(Fe2+)OOH also showed a dependence on solution pH. The presence of humic acid accelerated 4-CNB removal at low concentration but inhibited the removal at high concentration. In comparison with α-FeOOH, α-Fe(Fe2+)OOH significantly enhanced hydroxyl radicals generation and reduced Fe ions release in this process. The hydroxyl groups of Fe3+ on α-FeOOH and α-Fe(Fe2+)OOH surface was active site for ozone decomposition into hydroxyl radicals. Introducing Fe2+ significantly increased the density of surface hydroxyl groups relative to α-FeOOH. This enhancement significantly promoted hydroxyl radicals generation and 4-CNB degradation in the solution.
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  • 文章类型: Journal Article
    We conducted an oral mucosal irritation study in hamsters to evaluate a therapeutic apparatus using hydrogen peroxide (H2O2) photolysis for periodontitis treatment (ISO 10993-Part 10, Annex B.3). The cheek pouches in 15 male hamsters were allocated to one of six groups. Group 1 received pure water treatment (control group). Group 2 received laser irradiation at 80 mW. Group 3 received 3% H2O2. Groups 4-6 received laser irradiation of 3% H2O2 at 80, 40, and 20 mW, respectively. The total treatment time was set at 7 min and treatment was repeated three times at approximately 1-h intervals. Macroscopic and microscopic histologic observations of the treated sites were performed immediately after each treatment and/or 24 h after the last treatment. The mean scores in macroscopic and histologic examinations in all six groups were 0. Accordingly, irritation indices calculated by subtracting the mean score in each experimental group from that in the control group (Group 1) were 0. Our results suggest that treatment with the apparatus has no mucosal irritation potential in hamster cheek pouches under test conditions simulating clinical conditions.
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  • 文章类型: Journal Article
    含有抗生素阿莫西林(AMX)的水溶液的电化学降解已在使用亚化学计量氧化钛(Ti4O7)阳极的未分割电解池中进行了广泛研究,通过等离子体沉积来阐述。羟基自由基对AMX的氧化降解被评估为施加电流的函数,并被发现遵循伪一级动力学。由于H2O2的产生,碳毡阴极的使用提高了工艺的氧化能力。与Ti4O7阳极相比,使用尺寸稳定阳极(DSA)和Pt阳极在低电流强度下的比较研究导致较低的矿化效率:DSA和Pt的TOC去除率分别为36%和41%,而Ti4O7阳极的TOC去除率为69%。此外,在类似的操作条件下使用掺硼金刚石(BDD)阳极可以达到更高的矿化效率(94%)。尽管与BDD相比,Ti4O7阳极的矿化速率较低,与经典阳极Pt和DSA相比,它表现出更好的性能,并且可以代替BDD阳极进行成本有效的电氧化过程。此外,还鉴定了几种芳香族和脂肪族氧化反应中间体和无机终产物,并提出了涉及这些中间体的AMX的合理矿化途径。
    Electrochemical degradation of aqueous solutions containing antibiotic amoxicillin (AMX) has been extensively studied in an undivided electrolytic cell using a sub-stoichiometric titanium oxide (Ti4O7) anode, elaborated by plasma deposition. Oxidative degradation of AMX by hydroxyl radicals was assessed as a function of applied current and was found to follow pseudo-first order kinetics. The use of carbon-felt cathode enhanced oxidation capacity of the process due to the generation of H2O2. Comparative studies at low current intensity using dimensional stable anode (DSA) and Pt anodes led to the lower mineralization efficiencies compared to Ti4O7 anode: 36 and 41% TOC removal for DSA and Pt respectively compared to 69% for Ti4O7 anode. Besides, the use of boron doped diamond (BDD) anode under similar operating conditions allowed reaching higher mineralization (94%) efficiency. Although Ti4O7 anode provides a lesser mineralization rate compared to BDD, it exhibits better performance compared to the classical anodes Pt and DSA and can constitutes an alternative to BDD anode for a cost effective electro-oxidation process. Moreover several aromatic and aliphatic oxidation reaction intermediates and inorganic end-products were identified and a plausible mineralization pathway of AMX involving these intermediates was proposed.
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  • 文章类型: Journal Article
    Sea cucumber Stichopus japonicus (S. japonicus) shows a strong ability of autolysis, which leads to severe deterioration in sea cucumber quality during processing and storage. In this study, to further characterize the mechanism of sea cucumber autolysis, hydroxyl radical production induced by ultraviolet A (UVA) irradiation was investigated. Homogenate from the body wall of S. japonicas was prepared and subjected to UVA irradiation at room temperature. Electron Spin Resonance (ESR) spectra of the treated samples were subsequently recorded. The results showed that hydroxyl radicals (OH) became more abundant while the time of UVA treatment and the homogenate concentration were increased. Addition of superoxide dismutase (SOD), catalase, EDTA, desferal, NaN3 and D2O to the homogenate samples led to different degrees of inhibition on OH production. Metal cations and pH also showed different effects on OH production. These results indicated that OH was produced in the homogenate with a possible pathway as follows: O2(-) → H2O2 → OH, suggesting that OH might be a critical factor in UVA-induced S. japonicus autolysis.
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