Electrospray ionization mass spectrometry of platinum anticancer agents

Abstract

Quantification and identification of platinum drugs and their metabolites in biological samples has always been difficult because these compounds are thermally unstable, non-volatile and insoluble. We have demonstrated that electrospray ionization mass spectrometry can be a valuable technique for direct mass spectral analysis of platinum anticancer agents and for obtaining structural information as a result of fragmentation. Full-scan spectra were obtained with approximately 10 pmol samples. These results show the potential of applying this technique in pharmacokinetic studies of platinum anticancer drugs.

ESIMS Studies and Calculations on Alkali‐Metal Adduct Ions of Ruthenium Olefin Metathesis Catalysts and Their Catalytic Activity in Metathesis Reactions

“…General Remarks: CH 2 Cl 2 , anhydrous CH 3 OH, Ru catalysts 1 and 2, alkali metal chloride salts LiCl, NaCl, KCl, and CsCl, 1,6-heptadiene (5), 1,7-octadiene (6), 1,8-nonadiene (7), 1,9-decadiene (14), cyclooctene (18), and 1,5-hexadiene (22) were purchased from Aldrich (Steinheim, Germany) and used as received. All reactions were performed at room temperature.…”

“…Presumably, in these compounds, adduction occurs through the halogen atom. [14] We have observed that this simple cationization with alkali-metal cations is also possible with 1 and enables the detection and the study of this important catalyst.…”

“…[13][14][15] The addition of Na + has been used to characterize a range of neutral rhenium-bipyridine complexes [14] and Henderson et al observed alkali-metal (Li + , Na + , and K + ) adduct ions with Ru carbonyl compounds and suggested that such electron-rich compounds have sufficient charge residing on the CO lig-A C H T U N G T R E N N U N G ands to enable attachment to the cation. [15] Grubbs et al used alkali-metal ions as templates to direct the RCM reaction to the formation of unsaturated crown ether analogues, [16] which demonstrates that the introduction of alkalimetal ions would not block the metathesis activity of cataScheme 1.…”

“…Ring-closing metathesis (RCM) reactions of 1,6-heptadiene (5), 1,7-octadiene (6) and 1,8-nonadiene (7) were studied in the presence of KCl and the ruthenium alkylidene intermediates 8, 9, and 10, respectively, were detected as cationized monophosphine and bisphosphine ruthenium complexes. Acyclic diene metathesis (ADMET) polymerization of 1,9-decadiene (14) and ring-opening metathesis polymerization (ROMP) of cyclooctene (18) were studied ana-A C H T U N G T R E N N U N G logously, and the expected ruthenium alkylidene intermediates were directly intercepted from reaction solution and characterized unambiguously by their isotopic patterns and ESIMS/MS. ADMET polymerization was not observed for 1,5-hexadiene (22), but the formation of the intramolecularly stabilized monophosphine ruthenium complex 23 a was seen.…”

The behaviour of [Pt(η3-allyl)XP(C6H5)3] complexes in electrospray ionization conditions compared with those achieved by other ionization methods

“…The filament emitter was heated by a current of 26-28 mA. 10 The three spectra (Table 1) The only ions which can be directly related to the original structures are those at m/z 497, present in all the spectra. These ions could originate either by primary losses of X .…”