Hiraoka Kenzo, Rankin-Turner Stephanie, Ninomiya Satoshi, Shimada Haruo, Kinoshita Kazumasa, Yamabe Shinichi
Clean Energy Research Center, University of Yamanashi, 4-3-11 Takeda, Kofu, Yamanashi 400-8511, Japan.
W. Harry Feinstone Department of Molecular Microbiology & Immunology, Johns Hopkins Bloomberg School of Public Health, Johns Hopkins University, Baltimore, MD, 21205, USA.
Mass Spectrom (Tokyo). 2021;10(1):A0100. doi: 10.5702/massspectrometry.A0100. Epub 2021 Dec 25.
CO and O are known to be strong oxidizing reagents in biological systems. CO in particular can cause serious damage to DNA and proteins by H abstraction reactions. However, H abstraction of CO in the gas phase has not yet been reported. In this work we report on gas-phase ion/molecule reactions of CO and O with various molecules. CO was generated by the corona discharge of an O reagent gas using a cylindrical tube ion source. O was generated by the application of a 15 kHz high frequency voltage to a sharp needle in ambient air at the threshold voltage for the appearance of an ion signal. In the reactions of CO , a decrease in signal intensities of CO accompanied by the simultaneous increase of that of HCO was observed when organic compounds with H-C bond energies lower than ∼100 kcal mol such as -hexane, cyclohexane, methanol, ethanol, 1-propanol, 2-propanol, and toluene were introduced into the ion source. This clearly indicates the occurrence of H abstraction. O abstracts H from acid molecules such as formic, acetic, trifluoroacetic, nitric and amino acids. Gas-phase CO may play a role as a strong oxidizing reagent as it does in the condensed phase. The major discharge product CO in addition to O , O, and NO that are formed in ambient air may cause damage to biological systems.
已知一氧化碳(CO)和氧(O)在生物系统中是强氧化试剂。特别是CO可通过氢提取反应对DNA和蛋白质造成严重损害。然而,气相中CO的氢提取尚未见报道。在这项工作中,我们报道了CO和O与各种分子的气相离子/分子反应。使用圆柱形管离子源通过O反应气的电晕放电产生CO。通过在环境空气中以离子信号出现的阈值电压向尖针施加15kHz高频电压来产生O。在CO的反应中,当将具有低于约100千卡摩尔的H-C键能的有机化合物(如正己烷、环己烷、甲醇、乙醇、1-丙醇、2-丙醇和甲苯)引入离子源时,观察到CO信号强度降低,同时HCO信号强度增加。这清楚地表明发生了氢提取。O从甲酸、乙酸、三氟乙酸、硝酸和氨基酸等酸性分子中提取H。气相CO可能像在凝聚相中一样,作为强氧化试剂发挥作用。除了在环境空气中形成的O、O、NO之外,主要放电产物CO可能会对生物系统造成损害。