Investigation of the cyclopentadienyl loss of titanocene-DNA adducts in negative ESI-MS/MS

Bruni, Pia Simona; Eberle, Rahel; Schürch, Stefan (25 October 2018). Investigation of the cyclopentadienyl loss of titanocene-DNA adducts in negative ESI-MS/MS (Unpublished). In: Annual Meeting of the Swiss Group for Mass Spectrometry (SGMS). Beatenberg, Switzerland. October 25-26, 2018.

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Metallocenes and their derivatives have been found to be a promising alternative to the widely used platinum-based anticancer drugs. Same as platinum-based agents, metallocenes, such as Titanocene dichloride (Cp2TiCl2, Cp = cyclopentadienyl), bind to nuclear DNA, inhibiting the cell replication and, therefore, reducing the growth of the cancer cells.
Current investigations with positive ESI-MS/MS on the binding mechanism of titanocene have revealed the phosphate group adjacent to a thymine nucleobase as favored binding site. In contrast to the backbone fragmentation occurring after CID of cationic adducts ([M+Cp2Ti]n+), CID of cationic titanocene-DNA adducts ([M+Cp2Ti]n-) lead to the loss of the cyclopentadienyl ligands and only minor backbone scission. On closer consideration, the resulting ion was identified as the odd-electron titanium-DNA adduct [M+Ti]n-•. This implies that one cyclopentadienyl is lost as C5H5•, whereas the other is released as C5H6. High-resolution tandem Mass Spectrometry has been used to further investigate this unusual electron transfer during the ligand loss as well as the localization of the remaining unpaired electron.

Item Type:

Conference or Workshop Item (Poster)


08 Faculty of Science > Department of Chemistry, Biochemistry and Pharmaceutical Sciences (DCBP)

UniBE Contributor:

Bruni, Pia Simona, Eberle, Rahel, Schürch, Stefan


500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry
500 Science




Stefan Schürch

Date Deposited:

19 Sep 2019 13:53

Last Modified:

05 Dec 2022 15:29


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