Fast atom bombardment mass spectrometry of cisplatin analogs.
Fast atom bombardment mass spectrometry of cisplatin analogs.
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顺铂类似物的快原子轰击质谱法。
DOI：
10.1002/bms.1200130106
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发表时间：
1986
期刊：
影响因子：
--
通讯作者：
Ted T. Chang
中科院分区：
文献类型：
--
作者：
Marshall M. Siegel;P. Bitha;Ralph Grassing Child;J. Hlavka;Yang;Ted T. Chang
PtLACl2和PtLALB类型的顺铂类似物热不稳定，不挥发，高度不溶性。对于这些铂配位配合物，LA是双齿胺配体，LB是双齿羧酸配体。这些化合物的结构解析的质谱数据在文献中是缺失的，因为它们很难电离。然而，常规的快速原子轰击质谱方法已经开发出来，利用二甲基亚砜：硫甘油酯的混合溶剂体系，其比例约为1:3 v/v。利用正离子和负离子电离模式，从两类化合物的代表性分子中观察到具有结构意义的离子。[M-H]-离子存在于两类化合物中，而[M + H]+离子只存在于PtLALB类化合物中。当暴露在快原子束下时，观察到的其他离子在顺铂类似物和混合溶剂系统的凝聚相溶液化学方面被合理化。导致顺铂类似物在缩合相中电离的两种机制似乎是：用二甲亚砜取代配体和在顺铂类似物上加入氯和电离溶剂[二甲基亚砜+ H]+和[硫甘油酯- H]-。假设电离溶剂的加成反应是由于溶剂的碱度和它们在形成铂(II)-硫键时的反应性不同而发生的。
Cisplatin analogs of the type PtLACl2 and PtLALB are thermally unstable, non-volatile and highly insoluble. For these platinum coordination complexes, LA is a bidentate amine ligand and LB is a bidentate carboxylate ligand. Mass spectral data for structural elucidation of these compounds are absent in the literature because they are difficult to ionize. Nevertheless, a routine fast atom bombardment mass spectroscopic method has been developed utilizing the mixed solvent system of dimethyl sulfoxide:thioglycerol in a ratio of about 1:3 v/v. Using both positive and negative ionization modes, structurally significant ions were observed from representative molecules of the two named classes of compounds. [M-H]- ions were observed in both structural classes while [M + H]+ ions were observed only in the PtLALB class of compounds. Additional ions observed are rationalized in terms of the condensed-phase solution chemistry of the cisplatin analogs and the mixed solvent system when exposed to the fast atom beam. The two mechanisms causing ionization of the cisplatin analogs in the condensed phase appear to be: displacement of the ligands with dimethyl-sulfoxide and addition of chloride and the ionized solvents [dimentyl sulfoxide + H]+ and [thioglycerol - H]- to the cisplatin analogs. It is hypothesized that the addition reactions of the ionized solvents occur because of the differences in the basicity of the solvents and their reactivity in forming platinum(II)-sulfur bonds.