Application of flavonoids - quercetin and rutin - as new matrices for matrix-assisted laser desorption/ionization time-of-flight mass spectrometric analysis of Pt(II) and Pd(II) complexes

Attempts are being made to overcome the resistance of tumour cells to platinum (Pt) drugs by the synthesis of new generations of Pt complexes, and it is important to find appropriate and simple methods for the characterization of those novel complexes. The additional applicability of such a method for the analysis of the interactions of metal complexes with biomolecules would be advantageous. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) seems to possess the capability to become this method of choice, since it could be applied to low-mass complexes as well as for the analysis of large biomolecules. In this work the applicability of flavonoids - quercetin and rutin - as matrices for MALDI-TOFMS analysis of dichlorido(ethylendiamine)platinum(II) ([PtCl2(en)]), dichlorido(diaminocyclohexane)platinum(II) ([PtCl2(dach)]) and chloride (diethylenetriamine) palladium(II) chloride ([PdCl(dien)]Cl) complexes is demonstrated. Spectra of Pt(II) and Pd(II) complexes recorded in the presence of quercetin and rutin are rather simple: Pt(II) complexes generate [M+Na](+) or [M+K](+)ions, whereas the investigated Pd(II) complex gives ions generated by the loss of one Cl- or HCl. Flavonoids give a relatively small number of well-defined ions in the low-mass region (at m/z 303.3 for quercetin and m/z 633.5 for rutin). Quercetin and rutin can be applied in much lower concentrations than other common MALDI matrices and require rather low laser intensity. We speculate that flavonoids stabilize the structures of the metal complexes and that they may be useful for the analysis of other biologically active metal complexes, thus implying their broader applicability. Copyright (C) 2009 John Wiley & Sons, Ltd.