Novel Oximato-Bridged Platinum(II) Di- and Trimer(s): Synthetic, Structural, and in Vitro Anticancer Activity Studies

Author(s)
Yulia Scaffidi-Domianello, Anton Legin, Michael Jakupec, Alexander Roller, Vadim Yu Kukushkin, Mathea Sophia Galanski, Bernhard Keppler
Abstract

Novel platinum complexes of trans geometry [PtCl2{(Z)-R(H)C=NOH}(2)] [R = Me (1), Et (3)] and [PtCl2{(E)-R(H)C=NOH}{(Z)-R(H)C=NOH}] [R = Me (2), Et (4)] as well as the classic traris-[PtCl2(R2C=NOH)(2)] [R = Me, Et] were reacted with an equivalent amount of silver acetate in acetone solution at ambient temperature, resulting in formation of unprecedented head-to-tail-oriented oximato-bridged dimers [PtCl{mu-(Z)-R(H)C=NO}{(Z)-R(H)C= NOH}](2) [R = Me (5), Et (7)], [PtCl{mu-(Z)-R(H)C=NO}{(E)-R(H)C=NOH)](2) [R = Me (6), Et (8)], and [PtCl(pR(2)C=NO)(R2C=NOH)](2) [R = Me (9), Et (10)], correspondingly. The dimeric species feature a unique six-membered diplatinacycle and represent the first example of oxime ligands coordinated to platinum via the oxygen atom. All complexes were characterized by elemental analyses, electrospray ionization mass spectrometry, IR and multinuclear (H-1, C-13, and Pt-195) NMR spectroscopy, as well as X-ray diffraction in the cases of dimers 6 and 9. Furthermore, the crystal and molecular structures of a trimeric wdmato-bridged complex 11 comprising three platinum units connected in a chain way were established. The cytotoxicity of both dimers and the respective monomers was comparatively evaluated in three human cancer cell lines: cisplatin-sensitive CH1 cells as well as cisplatin-resistant SW480 and A549 cells, whereupon structure activity relationships were drawn. Thus, it was found that dimerization results in a substantial (up to 7-fold) improvement of IC50 values of (aldoxime)Pt-II compounds, whereas for the analogous complexes featuring ketoxime ligands the reverse trend was observed. Remarkably, the novel dimers yielded no cross-resistance with cisplatin in SW480 cells, exhibiting up to 2-fold enhanced cytotoxicity in comparison with. the CH1 cell line and thereby possessing a promising potential to overcome resistance toward platinum anticancer drugs. The latter point was also confirmed by investigating the potency of apoptosis induction in the case of one monomer as well as one dimer; the investigated complexes proved to be strong apoptotic agents which could induce cell death even in the cisplatin-resistant SW480 cell line.

Organisation(s)
Department of Inorganic Chemistry
External organisation(s)
Saint Petersburg State University
Journal
Inorganic Chemistry
Volume
51
Pages
7153-7163
No. of pages
11
ISSN
0020-1669
DOI
https://doi.org/10.1021/ic300148e
Publication date
2012
Peer reviewed
Yes
Austrian Fields of Science 2012
104003 Inorganic chemistry
Sustainable Development Goals
SDG 3 - Good Health and Well-being
Portal url
https://ucrisportal.univie.ac.at/en/publications/20176785-2ec6-4e56-9205-e165b1c83e80