Synthesis and cell phototoxicity of a triply bridged fused diporphyrin appended with six thioglucose units

Abstract

A triply bridged fused diporphyrin appended with six thioglucose units is reported. This new, chemically and photochemically stable amphiphilic compound is taken up by breast cancer cells and causes cell death upon light exposure. Photophysical studies reveal absorption bands in the near IR region, and photosensitized formation of singlet oxygen in high quantum yields.

Heterocyclic Nanographenes and Other Polycyclic Heteroaromatic Compounds: Synthetic Routes, Properties, and Applications

“…With PIFA, a regioselectivity dependent on meso -substituents was achieved in the synthesis of 244.5 , in which the ODRC reaction occurred only between porphyrin subunits bearing electron-rich 3,5-di- tert -butylphenyl groups . PIFA oxidation was instrumental in the synthesis of 244.7 , a derivative containing six thioglucose units appended to perfluoroaryl substituents, which could not be obtained with the DDQ/Sc­(OTf) 3 oxidant . The amphiphilic compound 244.7 , which is chemically and photochemically stable, was taken up by breast cancer cells and caused cell death upon exposure to light.…”

“…1350 PIFA oxidation was instrumental in the synthesis of 244.7, a derivative containing six thioglucose units appended to perfluoroaryl substituents, which could not be obtained with the DDQ/Sc(OTf) 3 oxidant. 1354 The amphiphilic compound 244.7, which is chemically and photochemically stable, was taken up by breast cancer cells and caused cell death upon exposure to light. Further photophysical studies of 244.7 revealed absorption bands in the near IR region (the lowest energy at 1090 nm in DMSO), and photosensitized formation of singlet oxygen with high quantum yield (0.78 ± 0.03 in DMSO).…”

Glycosylated Porphyrins, Phthalocyanines, and Other Porphyrinoids for Diagnostics and Therapeutics

“…Singh et al 169 recently reported the synthesis and phototoxicity of NIR dye hexathioglucose triply bridged fused porphyrin (Figure 37). The singlet oxygen quantum yield of this compound in DMSO was found to be 0.78 ± 0.03.…”

“…The core 5,10,15,20-tetrakis­(2,3,4,5,6-pentafluorophenyl)­porphyrin (TPPF 20 , Figure ) chromophore has proven to be a remarkably versatile platform on which a wide variety of biotargeting, biocompatibility, and functional motifs can be rapidly appended in excellent yields; therefore, it has been adopted by many laboratories for evaluation of different molecular design concepts with diverse functionalities. ,− The facile nucleophilic aromatic substitution of the 4-fluorine group by primary S, N, and O groups enables rapid synthesis of dyes appended with diverse substituents including small polylysine peptides, boron clusters, PEGs, and polyamines. ,− This approach can also afford combinatorial libraries of porphyrins wherein the statistical mixture is obtained when the substituents all have the same nucleophile. , Increasing temperatures are needed as the nucleophile becomes harder. This is an improvement over the synthesis of combinatorial libraries from a mixture of aldehydes and pyrroles because of the variable reactivity of the aldehydes, the low yield of the porphyrin, and the purification …”

Fluorinated porphyrinoids as efficient platforms for new photonic materials, sensors, and therapeutics

“…41,43–47 There are few examples where more than one biomolecular motif ( e.g . cell targeting, hydrophilic, or chemotherapeutic) can be appended to a dye but the molecular topology of the porphyrinoids allows a range of substitutions.…”