Glycosylated zinc(II) phthalocyanines as efficient photosensitisers for photodynamic therapy. Synthesis, photophysical properties and in vitro photodynamic activity

Org Biomol Chem. 2008 Jun 21;6(12):2173-81. doi: 10.1039/b802212g. Epub 2008 Apr 18.

Abstract

Treatment of 3- or 4-nitrophthalonitrile with 1,2:5,6-di-O-isopropylidene-alpha-d-glucofuranose or 1,2:3,4-di-O-isopropylidene-alpha-d-galactopyranose in the presence of K(2)CO(3) gave the corresponding glycosubstituted phthalonitriles. These precursors underwent self-cyclisation, or mixed-cyclisation with the unsubstituted phthalonitrile, to afford the tetra- or mono-glycosylated zinc(ii) phthalocyanines, respectively. As shown by absorption spectroscopy, these compounds were not significantly aggregated in organic solvents, giving a weak to moderate fluorescence emission. Upon irradiation these compounds could sensitise the formation of singlet oxygen in DMF, with quantum yields in the range of 0.40-0.66. The in vitro photodynamic activities of these compounds against HepG2 human hepatocarcinoma and HT29 human colon adenocarcinoma cells were also studied. The mono-glycosylated phthalocyanines exhibited significantly higher photocytotoxicity compared with the tetra-alpha-glycosylated analogues, having IC(50) values down to 0.9 muM. The tetra-beta-glycosylated counterparts were essentially inactive. The lower photocytotoxicities of the tetra-glycosylated phthalocyanines are in line with their lower cellular uptake and/or higher aggregation tendency as reflected by weaker intracellular fluorescence, and lower efficiency at generating intracellular reactive oxygen species. For the mono-glycosylated phthalocyanines, the higher uptake can be attributed to their hydrophilic saccharide units, which increase the amphiphilicity of the macrocycles.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Cell Line, Tumor
  • Glycosylation
  • Humans
  • Indoles / chemistry
  • Indoles / pharmacology*
  • Isoindoles
  • Magnetic Resonance Spectroscopy
  • Organometallic Compounds / chemistry
  • Organometallic Compounds / pharmacology*
  • Photochemotherapy*
  • Photosensitizing Agents / chemistry
  • Photosensitizing Agents / pharmacology*
  • Spectrometry, Fluorescence
  • Spectrometry, Mass, Electrospray Ionization
  • Spectrophotometry, Ultraviolet
  • Zinc Compounds

Substances

  • Indoles
  • Isoindoles
  • Organometallic Compounds
  • Photosensitizing Agents
  • Zinc Compounds
  • Zn(II)-phthalocyanine