高等学校化学学报

高等学校化学学报 ›› 2005, Vol. 26 ›› Issue (12): 2340.

• 研究论文 • 上一篇    下一篇

乌头碱类生物碱电喷雾串联质谱行为及碎片离子稳定性的量子化学计算

陈兰慧1,金莲姬1,苏忠民1,仇永清1,王勇2,刘淑莹2   

  1. 1.东北师范大学化学学院功能材料化学研究所,长春130024;2.中国科学院长春应用化学研究所,长春130022
  • 收稿日期:2005-06-02 出版日期:1905-03-14 发布日期:1905-03-14
  • 通讯作者: 苏忠民(1960年出生)，男，博士，教授，博士生导师，从事量子化学和功能材料化学研究.E-mail:zmsu@nenu.edu.cn；
  • 基金资助:

    国家自然科学基金(批准号：20373009)资助.

ESI-MSn Behavior and Quantum Chemistry Calculation of Stability of Fragment Ions of Diester-diterpenoid Alkaloids(DDA)

CHEN Lan-Hui1, JIN Lian-Ji1, SU Zhong-Min1*, QIU Yong-Qing1, WANG Yong2, LIU Shu-Ying2*   

  1. 1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China;
    2. Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
  • Received:2005-06-02 Online:1905-03-14 Published:1905-03-14
  • Contact: SU Zhong-Min;E-mail:zmsu@nenu.edu.cn；

被引次数

51

摘要：

乌头碱类生物碱电喷雾串联质谱数据对于分析该类化合物的生物活性及毒性提供了实验依据,结合量子化学计算分析乌头类生物碱电喷雾串联质谱碎片稳定性及其断裂规律,可以深入研究乌头碱类的构效关系.用abinitio HF/6-31G*方法优化六种乌头类生物碱结构,在此基础上计算相关活性部位母体与取代基之间的结合能,用以比较、判断化学键的稳定性.用此计算结果较好地解释了C8乙酰基、C14苯甲酰基和N-乙基/甲基等3种取代基失去的先后顺序,以及R3为OH·的吸电子效应对周围原子的影响;研究了缩环丢失中性CO分子的过程，从理论上预测了连在不同位置的4种甲氧基的失去规律.这表明电喷雾串联质谱中乌头碱类化合物经多次碰撞所产生的统计结果与量子化学计算结果符合得较好.

关键词: 乌头碱;电喷雾质谱；串联质谱;从头算;结合能, 乌头碱, 电喷雾质谱, 串联质谱, 从头算, 结合能

Abstract:

Quantum chemistry calculations were carried out to theoretically analyze the stability of fragments and the rules of elimination of substituents in electrospray ionization tandem mass spectra(ESI-MSn) for DDA. Geometries of the six DDA were optimized at ab initio HF/6-31G* level. The calculations provided the binding energies of the corresponding active bonds and the comparison of the data gave the criterion about the stability of chemical bonds. The order of eliminations of carboxyl, benzyl, ethyl or methyl as well as the influence on eliminations of ·OH at C3 on the atoms around also studied. The process of elimination of CO and the rules of elimination of four methoxy groups on different carbon atoms were predicted theoretically. The results of Quantum chemistry calculation were in pretty agreement with the experimental data of ESI-MSn.

Key words: Diester-diterpenoid alkaloids(DDA); Electrospray ionization mass spectrometry(ESI-MS); Tandem-mass spectrometry(MSn); Ab initio; Binding energy, Diester-diterpenoid alkaloids(DDA), Electrospray ionization mass spectrometry(ESI-MS), Tandem-mass spectrometry(MS~(n)), (Ab initio, ) Binding energy

中图分类号: 

TrendMD: