Selective binding of a bioactive porphyrin-based photosensitizer to the G-quadruplex from the KRAS oncogene promoter

Int J Biol Macromol. 2020 Feb 15:145:244-251. doi: 10.1016/j.ijbiomac.2019.12.152. Epub 2019 Dec 20.

Abstract

Background: The G-quadruplex-forming sequence within the KRAS proto-oncogene P1 promoter is a promising target for anticancer therapy. Porphyrin derivatives are among the most rewarding G-quadruplex binders. They can also behave as photosensitizers.

Methods: Three water-soluble, positively charged porphyrin-like compounds were synthesized and tested for their interaction with the KRAS G-quadruplex by circular dichroism, fluorescence, and molecular docking calculations. For a comparison of ligands binding affinity and selectivity, TMPyP4 was taken as a reference.

Results: One out of the three tested compounds proved biological activity and selectivity for G-quadruplex over duplex DNA. It also showed to discriminate between different G-quadruplex topologies, with a preference for the parallel over antiparallel conformation. Molecular docking studies suggested a preferential binding to the 3'-end of the KRAS G-quadruplex driven through π-π stacking interactions. Biological assays also revealed a good photodynamic-induced cytotoxicity on HeLa cells.

Conclusions: The reported results show that these porphyrin-like compounds could actually give the basis for the development of G-quadruplex ligands with effective photodynamic-induced cytotoxicity on cancer cells.

General significance: The possibility of obtaining photosensitizers with improved physico-chemical features and able to selectively target G-quadruplexes is a very interesting perspective to develop new therapeutic agents.

Keywords: Biophysics; Chlorins; G-quadruplex; Ligands; Photodynamic activity; Singlet oxygen generation.

MeSH terms

  • G-Quadruplexes / drug effects*
  • G-Quadruplexes / radiation effects
  • HeLa Cells
  • Humans
  • Inverted Repeat Sequences
  • Ligands
  • Light
  • Molecular Docking Simulation
  • Oligonucleotides / chemical synthesis
  • Photochemotherapy / methods
  • Photosensitizing Agents / chemical synthesis
  • Photosensitizing Agents / pharmacology*
  • Porphyrins / chemical synthesis
  • Porphyrins / pharmacology*
  • Promoter Regions, Genetic*
  • Proto-Oncogene Mas
  • Proto-Oncogene Proteins p21(ras) / genetics*
  • Proto-Oncogene Proteins p21(ras) / metabolism
  • Solubility
  • Water

Substances

  • KRAS protein, human
  • Ligands
  • MAS1 protein, human
  • Oligonucleotides
  • Photosensitizing Agents
  • Porphyrins
  • Proto-Oncogene Mas
  • Water
  • Proto-Oncogene Proteins p21(ras)