拟除虫菊酯类农药在NCI源和EI源中的质谱行为
Mass Spectrometry Behavior of Pyrethroid Pesticides in NCI and EI Sources
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摘要: 通过分析19种拟除虫菊酯类农药（pyrethroid pesticides, PyPs）在负化学离子源（NCI）和电子轰击离子源（EI）中的碎片离子信息，得出每种农药在不同离子源中的质谱行为差异。在NCI源中，PyPs获得1个热电子，形成负离子后不稳定而发生热裂解，与酯基相连的碳氧键断裂形成菊酯烷酸根离子，再脱去中性分子（如CO2、HF、HCl、HCF3等）形成各种碎片离子。一般情况下，含卤原子越多的PyPs，其在NCI源的响应越高。在EI源中，PyPs裂解规律为：1） 与羰基相连的碳氧键发生α-断裂脱去1分子CO，得到含环丙烷结构的特征碎片离子；2） 发生六元环的氢原子重排，当含有苄基苯基醚且甲基上有氰基取代基的PyPs，易形成m/z 181、208特征碎片离子，而不含氰基的PyPs易形成m/z 183特征碎片离子。
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关键词:
- 拟除虫菊酯类农药 /
- 负化学离子源（NCI） /
- 电子轰击离子源（EI） /
- 质谱 /
- 裂解规律
Abstract: The mass spectrometry behaviors of 19 kinds of pyrethroid pesticides (PyPs) in different ion sources were obtained by analyzing and comparing their ion fragment information in negative chemical ionization (NCI) and electron impact ionization (EI). In this work, the fragment information of precursor and product ions of PyPs in NCI and EI sources was obtained by different instrument acquisition modes. In NCI source, it was easy to lose one hydrogen halide molecule to form a secondary ion when PyPs with cyclopropane structure, such as bifenthrin and cypermethrin. And, the stronger electronegativity of functional group connected to the cyclopropane, the stronger its ionic strength. It was easy to lose one CO2 to form secondary ions for the others that without cyclopropane structure, such as flucythrinate and fluvalinate. PyPs obtained a hot electron in NCI source, which was unstable after forming an anion and thermal cracking occurs. After cleavage of carbon oxygen bond linked to ester group, a negative pyrethroid alkane radical was formed, and then neutral molecules (such as CO2, HF, HCl, HCF3, etc.) were lost to form various fragment ions. In EI source, the ester or benzyl positions of PyPs were prone to cleavage. When the ester group was broken, some PyPs would produce RCO+, the common fragment ion of carboxylic acid esters, such as benfluthrin and bifenthrin. However, most PyPs only showed fragment ion R+ on mass spectrum, the ion RCO+ was not been seen, such as cyfluthrin and flucythrinate. First, the C—O bond of PyPs connected to the carbonyl group underwent α breaking, and then a molecule of CO was lost resulting in a characteristic ion fragment containing a cyclopropane structure. The second was that a hydrogen atom rearrangement of six membered ring occurs after one electron was lost on benzene ring. The m/z 181 and m/z 208 were formed when it contained benzyl phenyl ether and the methyl group had a substituted cyano group, while the m/z 183 was formed when it didn't contain a substituted cyano group. -
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