期刊信息

  • 刊名： 河北师范大学学报（自然科学版）Journal of Hebei Normal University (Natural Science)
  • 主办： 河北师范大学
  • ISSN： 1000-5854
  • CN： 13-1061/N
  • 中国科技核心期刊
  • 中国期刊方阵入选期刊
  • 中国高校优秀科技期刊
  • 华北优秀期刊
  • 河北省优秀科技期刊

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基于密度泛函理论的全氟辛烷磺酸质谱裂解规律研究

  • (1.河北师范大学 化学与材料科学学院，河北 石家庄050024； 2.中国农业科学院 农业质量标准与检测技术研究所，北京100081)
  • DOI： 10.13763/j.cnki.jhebnu.nse.202203002

Research of Perfluorooctanesulfonate Mass Fragmentation Based on Density Functional Theory

摘要/Abstract

摘要：

基于密度泛函理论的第一性原理，在B3LYP/6-31G(d,p)基组下，优化了全氟辛烷磺酸(PFOS)分子、准分子离子和各质谱裂解碎片离子的结构，获得稳定的几何构型，计算了PFOS分子电离前后的自然布局分析（NPA）电荷、电子密度差、键长、Mayer键级、键裂解能，并对重排离子的过渡态进行搜寻，进而推导出碎片离子在质谱裂解过程中的形成途径.计算结果表明，PFOS分子形成准分子离子后，分子结构中的SO3-最易失去，从而形成m/z 80的基峰，C2F5-(m/z 119),CF2SO3-(m/z 130),C3F7-(m/z 169),C2F4SO3-(m/z 180)和C3F6SO3-(m/z 230)均是由PFOS直接裂解形成，其质谱信号响应与断裂化学键的键裂解能存在相关关系.同时验证了FSO3-是由氟原子重排形成的结论，并在质谱上形成m/z 99的峰.该研究通过分析多种量子化学参数，丰富了PFOS的电喷雾质谱的裂解规律，有助于PFOS分子的准确鉴定，也可为研究其他全氟化合物质谱裂解规律提供理论和方法参考.

Abstract：

The first-principle calculation method of density functional theory at the level of B3LYP/6-31G(d, p) was adopted to optimize the accurate structure of molecular ion, quasi-molecular ion and other fragments ion of perfluorooctanesulfonate (PFOS) from electrospray ionization mass spectrometry.The stable geometry configuration was obtained.The formation pathway of fragment ions was deduced by calculating NPA charge, electron density difference, bond length, Mayer bond level and bond dissociation energy.The transition state of rearrangement ions was searched.The results showed that the most easily lost group in structure is SO3-, thus the base peaks of m/z 80 was formed.The ions of C2F5-(m/z 119), CF2SO3-(m/z 130), C3F7-(m/z 169), C2F4SO3-(m/z 180) and C3F6SO3- (m/z 230) were all formed by direct dissociation of PFOS, and their mass spectrum signal response showed correlation to bond dissociation energy of chemical bonds.In addition, it was also verified that FSO3- was formed by rearrangement of fluorine atoms.Therefore, a peak of m/z 99 was formed in the mass spectrum.This study expounds the fragmentation pathway of ESI-MS of PFOS by analyzing a variety of quantum chemical parameters, which is benefit to the accurate identification of PFOS molecules，and can also provides theoretical and methodological references for the study of the fragmentation pathway of mass spectrometry for other perfluorochemicals.

关键词

关键词： 质谱； 全氟辛烷磺酸； 密度泛函理论； 量子计算化学
Key words： mass spectrometry ; PFOS ; density functional theory ; quantum chemistry

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