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Comparison of the binding stoichiometries of positively charged DNA-binding drugs using positive and negative ion electrospray ionization mass spectrometry

Gupta, Rajesh, Beck, Jennifer L., Ralph, Stephen F., Sheil, Margaret M., & Aldrich-Wright, Janice R. (2004) Comparison of the binding stoichiometries of positively charged DNA-binding drugs using positive and negative ion electrospray ionization mass spectrometry. Journal of the American Society for Mass Spectrometry, 15(10), pp. 1382-1391.

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Abstract

Positive and negative ion electrospray ionization (ESI) mass spectra of complexes of positively charged small molecules (distamycin, Hoechst 33258, [Ru(phen)2dpq]Cl2 and [Ru(phen)2dpqC]Cl2) have been compared. [Ru(phen)2dpq]Cl2 and [Ru(phen)2dpqC]Cl2 bind to DNA by intercalation. Negative ion ESI mass spectra of mixtures of [Ru(phen)2dpq]Cl2 or [Ru(phen)2dpqC]Cl2 with DNA showed ions from DNA-ligand complexes consistent with solution studies.

In contrast, only ions from freeDNAwere present in positive ion ESI mass spectra of mixtures of [Ru(phen)2dpq]Cl2 or [Ru(phen)2dpqC]Cl2 with DNA, highlighting the need for obtaining ESI mass spectra of non-covalent complexes under a range of experimental conditions.

Negative ion spectra of mixtures of the minor groove binder Hoechst 33258 with DNA containing a known minor groove binding sequence were dominated by ions from a 1:1 complex.

In contrast, in positive ion spectra there were also ions present from a 2:1 (Hoechst 33258: DNA) complex, suggesting an alternative binding mode was possible either in solution or in the gas phase. When Hoechst 33258 was mixed with a DNA sequence lacking a high affinity minor groove binding site, the negative ion ESI mass spectra showed that 1:1 and 2:1 complexes were formed, consistent with existence of binding modes other than minor groove binding. The data presented suggest that comparison of positive and negative ion ESI-MS spectra might provide an insight into various binding modes in both solution and the gas phase.

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ID Code: 51627
Item Type: Journal Article
Keywords: DNA binding drugs, mass spectrometry, ESI-MS, intercalation, minor groove binders
DOI: 10.1016/j.jasms.2004.07.005
ISSN: 1879-1123
Subjects: Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > ANALYTICAL CHEMISTRY (030100)
Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > INORGANIC CHEMISTRY (030200)
Australian and New Zealand Standard Research Classification > BIOLOGICAL SCIENCES (060000) > BIOCHEMISTRY AND CELL BIOLOGY (060100) > Analytical Biochemistry (060101)
Divisions: Current > QUT Faculties and Divisions > Faculty of Health
Current > Institutes > Institute of Health and Biomedical Innovation
Deposited On: 17 Jul 2012 08:28
Last Modified: 26 Jul 2012 13:37

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