Exploring the Structure-Activity Relationships of Albumin-Targeted Picoplatin-Based Platinum(IV) Prodrugs

Author(s)
Martijn Dijkstra, Hemma Schueffl, Barbora Adamova, Oliver Baumfried, Alexander Kastner, Walter Berger, Bernhard K. Keppler, Petra Heffeter, Christian R. Kowol
Abstract

Platinum(II) complexes prevail as first-line treatment for many cancers but are associated with serious side effects and resistance development. Picoplatin emerged as a promising alternative to circumvent GSH-induced tumor resistance by introducing a bulky 2-picoline ligand. Although clinical studies were encouraging, picoplatin did not receive approval. Interestingly, the anticancer potential of prodrugs based on picoplatin is widely underexplored, and even less so the respective tumor-targeting approaches. We synthesized two new “hybrid” picoplatin(II) derivatives with an oxalate or cyclobutane dicarboxylate leaving group and their corresponding platinum(IV) prodrugs with an albumin-targeting maleimide moiety or a succinimide as reference. Picoplatin(II) and its derivatives indeed reacted much slower with GSH compared to the respective analogs cisplatin, carboplatin, or oxaliplatin. While PicoCarbo(IV) and PicoOxali(IV) were reduced slowly in the presence of ascorbic acid, picoplatin(IV) was extremely unstable. All three prodrugs were widely inactive in the MTT assays. The platinum(IV)-maleimide complexes rapidly bound to albumin with stable conjugates for >25 h. Albumin-binding resulted in elevated platinum plasma levels, prolonged blood circulation, and enhanced tumor accumulation of the prodrugs in mice bearing CT26 tumors. However, only maleimide-functionalized PicoCarbo(IV) and picoplatin(II) significantly inhibited tumor growth. One possible explanation is that for albumin-binding platinum(IV) prodrugs, the bulky 2-picoline moiety prevents sufficient activation/reduction to unlock their full anticancer potential.

Organisation(s)
Department of Inorganic Chemistry
External organisation(s)
Vienna Doctoral School in Chemistry (DoSChem), Medizinische Universität Wien, Research Cluster Translational Cancer Therapy Research
Journal
Inorganic Chemistry
Volume
64
Pages
2554-2566
No. of pages
13
ISSN
0020-1669
DOI
https://doi.org/10.1021/acs.inorgchem.4c05269
Publication date
01-2025
Peer reviewed
Yes
Austrian Fields of Science 2012
104003 Inorganic chemistry, 301904 Cancer research
ASJC Scopus subject areas
Physical and Theoretical Chemistry, Inorganic Chemistry
Sustainable Development Goals
SDG 3 - Good Health and Well-being
Portal url
https://ucrisportal.univie.ac.at/en/publications/5c333303-3d32-4035-a25e-fcc907b4bca3