Citation: SUN Yun, YANG Ru, SUN Chuan-Qiang, LIU Hai-Pei, WANG Yan, JIANG Xue-Hui. Study on Fragmentation of Linear Alkanes in Proton-Transfer-Reaction Mass Spectrometry[J]. Chinese Journal of Analytical Chemistry, ;2019, 47(9): 1359-1365. doi: 10.19756/j.issn.0253-3820.191221 shu

Study on Fragmentation of Linear Alkanes in Proton-Transfer-Reaction Mass Spectrometry

1.
School of Precision Instrument and Opto-Electronics Engineering, Tianjin University, Tianjin 300072, China;
2.
Tianjin Boomscience Co. Ltd, Tianjin 300400, China

Received Date: 22 April 2019
Revised Date: 24 June 2019

Fund Project: This work was supported by the Tianjin Science and Technology Plan Project (No.16YFXTSF00020) and the National Major Scientific Instruments and Equipment Development Project of China (No.2013YQ090875).

The pure standards of 10 linear alkanes (C₆-C₁₅) were detected by proton-transfer-reaction mass spectrometry (PTR-MS) through a self-made liquid sampling device. The experimental results showed that the fragmentation of linear alkanes in PTR-MS underwent similar patterns in the electron impact ionization source (EI). It could be seen from the mass spectrum that the main products were a series of[C_iH_2i+1]⁺,[C_iH_2i-1]⁺ and[C_iH_2i-3]⁺ (i ≥ 3) ions. In the experiment, protonated molecular ions[M+H]⁺ were not detected, and the appearance of[M-H]⁺ ions and other fragment ions indicated that once the protonated product of the alkane was formed, dehydrogenation or direct cleavage occurred. Furthermore, it was found that the relative abundance of fragment ions was affected greatly by E/N (the ratio of electric field strength, E, and number density of particles in the drift tube, N). In the range of 80-170 Td, as the E/N value increased, the relative abundances of the fragment ions with high m/z would decrease first, until the signal was below the detection limit of the instrument and could not be detected. The relative abundance of the fragment ions with low m/z (such as[C₄H₉]⁺ (m/z 57),[C₃H₇]⁺ (m/z 43), etc.) first increased and then decreased, while the relative abundances of the fragment ions[C₃H₅]⁺ (m/z 41) always showed an upward trend. This indicated that the fragment ions with high m/z would undergo secondary cracking under high E/N conditions, and the fragment ions with low m/z were generated step by step.
- Proton transfer,
- Proton-transfer-reaction mass spectrometry,
- Linear alkane,
- Fragment ion
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