Red-Light Activation of a Microtubule Polymerization Inhibitor via Amide Functionalization of the Ruthenium Photocage

Angew Chem Int Ed Engl. 2024 Jan 25;63(5):e202316425. doi: 10.1002/anie.202316425. Epub 2023 Dec 20.

Abstract

Photoactivated chemotherapy (PACT) is a promising cancer treatment modality that kills cancer cells via photochemical uncaging of a cytotoxic drug. Most ruthenium-based photocages used for PACT are activated with blue or green light, which penetrates sub-optimally into tumor tissues. Here, we report amide functionalization as a tool to fine-tune the toxicity and excited states of a terpyridine-based ruthenium photocage. Due to conjugation of the amide group with the terpyridine π system in the excited state, the absorption of red light (630 nm) increased 8-fold, and the photosubstitution rate rose 5-fold. In vitro, red light activation triggered inhibition of tubulin polymerization, which led to apoptotic cell death both in normoxic (21 % O2 ) and hypoxic (1 % O2 ) cancer cells. In vivo, red light irradiation of tumor-bearing mice demonstrated significant tumor volume reduction (45 %) with improved biosafety, thereby demonstrating the clinical potential of this compound.

Keywords: Hypoxia; Microtubule; Photocaging; Photopharmacology; Ruthenium.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Animals
  • Antineoplastic Agents* / chemistry
  • Antineoplastic Agents* / pharmacology
  • Mice
  • Microtubules
  • Neoplasms*
  • Polymerization
  • Ruthenium* / chemistry
  • Ruthenium* / pharmacology
  • Tubulin Modulators / pharmacology
  • Tubulin Modulators / therapeutic use

Substances

  • Ruthenium
  • Antineoplastic Agents
  • Tubulin Modulators