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首页> 外文期刊>Rapid Communications in Mass Spectrometry: RCM >Product ion distributions for the reactions of NO~+ with some physiologically significant volatile organosulfur and organoselenium compounds obtained using a selective reagent ionization time-of-flight mass spectrometer
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Product ion distributions for the reactions of NO~+ with some physiologically significant volatile organosulfur and organoselenium compounds obtained using a selective reagent ionization time-of-flight mass spectrometer

机译：使用选择性试剂电离飞行时间质谱仪获得的NO〜+与某些生理上重要的挥发性有机硫和有机硒化合物反应的产物离子分布

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摘要

The reactions of NO~+ with volatile organic compounds (VOCs) in Selective Reagent Ionization Time-of-Flight Mass Spectrometry (SRI-TOF-MS) reactors are relatively poorly known, inhibiting their use for trace gas analysis. The rationale for this product ion distribution study was to identify the major product ions of the reactions of NO~+ ions with 13 organosulfur compounds and 2 organoselenium compounds in an SRI-TOF-MS instrument and thus to prepare the way for their analysis in exhaled breath, in skin emanations and in the headspace of urine, blood and cell and bacterial cultures. METHODS: Product ion distributions have been investigated by a SRI-TOF-MS instrument at an E/N in the drift tube reactor of 130 Td for both dry air and humid air (4.9% absolute humidity) used as the matrix gas. The investigated species were five monosulfides (dimethyl sulfide, ethyl methyl sulfide, methyl propyl sulfide, allyl methyl sulfide and methyl 5-methyl-2-furyl sulfide), dimethyl disulfide, dimethyl trisulfide, thiophene, 2-methylthiophene, 3-methylthiophene, methanethiol, allyl isothiocyanate, dimethyl sulfoxide, and two selenium compounds - dimethyl selenide and dimethyl diselenide. RESULTS: Charge transfer was seen to be the dominant reaction mechanism in all reactions under study forming the M+ cations. For methanethiol and allyl isothiocyanate significant fractions were also observed of the stable adduct ions NO+M, formed by ion-molecule association, and [M-H]~+ ions, formed by hydride ion transfer. Several other minor product channels are seen for most reactions indicating that the nascent excited intermediate (NOM)~(+*) adduct ions partially fragment along other channels, most commonly by the elimination of neutral CH_3, CH_4 and/or C_2H_4 species that are probably bound to an NO molecule. Humidity had little effect on the product ion distributions. CONCLUSIONS: The findings of this study are of particular importance for data interpretation in studies of volatile organosulfur and volatile organoselenium compounds employing SRI-TOF-MS in the NO+ mode.
机译：在选择性试剂电离飞行时间质谱（SRI-TOF-MS）反应器中，NO〜+与挥发性有机化合物（VOC）的反应相对较不为人所知，这限制了它们在痕量气体分析中的应用。该产物离子分布研究的基本原理是在SRI-TOF-MS仪器中确定NO〜+离子与13种有机硫化合物和2种有机硒化合物反应的主要产物离子，从而为呼出气体的分析准备方法。呼吸，皮肤散发以及尿液，血液，细胞和细菌培养物的顶部空间。方法：已通过SRI-TOF-MS仪器在E / N为130 Td的漂移管反应器中研究了用作基质气体的干燥空气和潮湿空气（绝对湿度为4.9％）的产物离子分布。所研究的物种是五种一硫化物（二甲基硫醚，乙基甲基硫醚，甲基丙基硫醚，烯丙基甲基硫醚和甲基5-甲基-2-呋喃硫醚），二甲基二硫醚，二甲基三硫醚，噻吩，2-甲基噻吩，3-甲基噻吩，甲硫醇，异硫氰酸烯丙酯，二甲基亚砜和两种硒化合物-二甲基硒化物和二甲基二硒化物。结果：在研究的所有形成M +阳离子的反应中，电荷转移是主要的反应机理。对于甲烷硫醇和烯丙基异硫氰酸酯，还观察到了显着比例的离子-分子缔合形成的稳定加合物离子NO + M和氢离子转移形成的[M-H]〜+离子。对于大多数反应，还可以看到其他几个次要产物通道，这表明新生的受激发中间体（NOM）〜（+ *）加合物离子会沿着其他通道部分碎裂，最常见的是消除了中性CH_3，CH_4和/或C_2H_4与NO分子结合。湿度对产物离子分布影响很小。结论：本研究的发现对于使用SRI-TOF-MS在NO +模式下研究挥发性有机硫和挥发性有机硒化合物的数据解释特别重要。

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