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Generation of localized highly concentrated hydrogen peroxide clusters in water by X-rays.
Free Radical Research ( IF 3.3 ) Pub Date : 2020-06-19 , DOI: 10.1080/10715762.2020.1774574
Megumi Ueno 1 , Ikuo Nakanishi 1 , Ken-Ichiro Matsumoto 1
Affiliation  

The formation of highly concentrated hydrogen peroxide (H2O2) clusters (localized circumstance) in an aqueous solution during X-ray irradiation was demonstrated. The relationship between H2O2 concentration and hydrogen donor-independent reduction of nitroxyl radicals was examined. The method to measure the distance between the clusters (localized circumstance) was assessed by comparing the simulation and the experimental results. Reaction mixtures containing a nitroxyl redox probe, 4-hydroxyl-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPOL) and 3-carbamoyl-2,2,5,5-tetramethylpyrrolidine-N-oxyl (CmP) at 0.1 mM were prepared containing several different concentrations (1.0 mM‒9.8 M) of H2O2. The reaction mixture was irradiated by 12000 μW/cm2 UVB for 2 min, and reduction of the electron paramagnetic resonance (EPR) signal of the nitroxyl radicals was measured. An aliquot (2 µL) of 200 mM K3[Fe(CN)6] or FeCl3 solution was added to 200 µL of the reaction mixture, and the time course of the EPR signal of the nitroxyl radicals was measured. To estimate the distance between the H2O2 clusters, a series of nitroxyl radical solutions with several different concentrations (0.06 μM‒2.28 mM) was irradiated with X-rays, and the degree of reduction of nitroxyl radicals in each sample was measured. UVB, K3[Fe(CN)6], or FeCl3-induced EPR signal loss of the nitroxyl radicals was observed with H2O2 concentrations greater than 10 mM or 100 mM, respectively. The EPR signal loss of nitroxyl radicals, TEMPOL or CmP, may occur in highly concentrated H2O2 circumstances after oxidative stimulation. Plotting the X-ray-induced reduction of nitroxyl radicals versus their density revealed the high-concentration H2O2 clusters to be separated by 40‒47 nm. Ionizing irradiation of an aqueous solution creates a localized highly concentrated H2O2 environment.



中文翻译:

X射线在水中生成局部高浓度过氧化氢簇。

证实了在X射线照射期间在水溶液中形成高浓度过氧化氢(H 2 O 2)团簇(局部环境)。研究了H 2 O 2浓度与不依赖氢供体的硝基氧基自由基还原之间的关系。通过比较仿真结果和实验结果,评估了测量簇之间距离的方法(局部情况)。包含硝氧基氧化还原探针,4-羟基-2,2,6,6-四甲基哌啶-N-氧基(TEMPOL)和3-氨基甲酰基-2,2,5,5-四甲基吡咯烷-N-氧基(CmP)的反应混合物制备了0.1 mM的氢气,其中包含几种不同浓度(1.0 mM‒9.8 M)的H2 O 2。用12000μW/ cm 2的UVB照射反应混合物2分钟,并测量了硝酰基自由基的电子顺磁共振(EPR)信号的降低。将200 mM K 3 [Fe(CN)6 ]或FeCl 3溶液的等分试样(2 µL)添加到200 µL反应混合物中,并测量硝酰基自由基的EPR信号的时间过程。为了估计H 2 O 2簇之间的距离,用X射线照射一系列具有几种不同浓度(0.06 μM‒2.28 mM)的硝酰自由基溶液,并测量每个样品中硝酰自由基的还原程度。UVB,K 3 [Fe(CN)参见图6 ],或在H 2 O 2浓度分别大于10 mM或100 mM时观察到FeCl 3诱导的硝基氧基自由基的EPR信号损失。氧化刺激后,在高浓度H 2 O 2的情况下,可能会发生硝基氧基TEMPOL或CmP的EPR信号丢失。绘制X射线诱导的硝基氧基自由基还原与其密度的关系图,结果表明高浓度的H 2 O 2簇被隔开40‒47 nm。水溶液的电离辐射产生局部高浓度的H 2 O 2环境。

更新日期:2020-06-30
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