Cheng C, Pittenauer E, Gross M L
Department of Chemistry, Washington University, St. Louis, Missouri, USA.
J Am Soc Mass Spectrom. 1998 Aug;9(8):840-4. doi: 10.1016/S1044-0305(98)00053-1.
Fast atom bombardment-produced [M + Na]+ ions of tristearoylglycerol and [M - H]- ions of stearic or nervonic acid undergo charge-remote fragmentations (CRFs) to produce one series of product ions reflecting CnH2n + 2, losses, whereas electrospray ionization-produced ions fragment to give two series of product ions reflecting CnH2n + 2 and CnH2n + 1 losses. These results and those from previous studies show that the mechanisms and energetics of CRFs are complex and unsettled. We demonstrate that several pathways are simultaneously involved in CRFs, and the preference for certain pathways (by CnH2n + 1 and CnH2n + 2 losses) is determined by the internal energy of the compound itself and the ionization and activation energies that are applied to it.
甘油三硬脂酸酯经快速原子轰击产生的[M + Na]+离子以及硬脂酸或神经酸经快速原子轰击产生的[M - H]-离子会发生电荷远程裂解（CRF），生成一系列反映CnH2n + 2损失的产物离子，而电喷雾电离产生的离子裂解后会生成反映CnH2n + 2和CnH2n + 1损失的两个系列的产物离子。这些结果以及先前研究的结果表明，电荷远程裂解的机制和能量学很复杂且尚无定论。我们证明，电荷远程裂解同时涉及多种途径，而对某些途径（通过CnH2n + 1和CnH2n + 2损失）的偏好由化合物本身的内能以及施加于其上的电离能和活化能决定。
