Cholate-interspersed porphyrin-anthraquinone conjugates: photonuclease activity of large sized, 'tweezer-like' molecules

Abstract

In a new approach towards the development of a 'dual-wavelength dual-mechanism' type of photosensitizer for use in photodynamic therapy (PDT), covalently linked bichromophoric systems comprising of porphyrin (P) and anthraquinone (AnQ) subunits have been synthesized and fully characterized by FAB-MS, IR, UV-Visible and ¹H NMR methods. The porphyrin donor and the anthraquinone acceptor subunits of these mono- or bis-intercalating hybrid molecules are interspersed with either cholate or polymethylene spacers. There exists minimal ground- and singlet-state interaction between the porphyrin and anthraquinone subunits in the giant-sized, cholate-interspersed P-AnQ systems as revealed by a comparison of their spectroscopic and electrochemical properties with those of the corresponding individual reference compounds. On the other hand, quenching of fluorescence observed for the P-AnQ systems endowed with polymethylene spacers has been interpreted in terms of a possible intramolecular electron transfer between the singlet porphyrin and the anthraquinone acceptor. When excited into their porphyrin absorption band maxima, each new P-AnQ system could generate singlet molecular oxygen in good-to-moderate yield. Wavelength-dependent photonuclease activity of these new bis-intercalating species has been examined.