Timothy J. Jensen

The synthesis of new benzo[a]- and [b]xanthene dye frameworks is described. A unique benzo[a]xanthene, seminaphtho[a]fluorone (SNAFR-1), is studied in a variety of media. The optimization of solution parameters and excitation wavelengths allows SNAFR-1 to display red, green, and blue emission bands of approximately equal intensities and also to produce white light. Ratiometric red (anion) and green (neutral) emissions are observed upon varying solution pH. A pH-independent violet-blue emission band is due to the addition of nucleophiles to the benzylic carbon of SNAFR-1.

A series of symmetrical cationic phthalocyanines (Pcs) with either Zn(II) or Si(IV) metal ions and two bulky axial ligands on the silicon complexes was synthesized in high yields. The photophysical (absorption, emission, fluorescence, and singlet oxygen quantum yields) and cellular (uptake, toxicity, and subcellular localization) properties of this series of Pcs were investigated. The Si(IV)-Pcs exist mainly as monomers in aqueous media and have higher fluorescent quantum yields in protic solvents (methanol and water) than the Zn(II)-Pcs. The presence of eight short PEG groups at the periphery of a Zn(II)-Pc significantly increases its solubility in protic solvents, but a centrally chelated silicon ion and associated bulky axial ligands were more efficient in preventing aggregation of the Pc macrocycles. The singlet oxygen quantum yields for this series of Pcs in DMSO are in the range 0.09-0.15. All Pcs were readily taken up by human HEp2 cells, and the extent of their accumulation within cells depends on their hydrophobic character. Intracellularly, all Pcs localized preferentially within the cell lysosomes. The Zn(II)-Pc 11 and Si(IV)-Pcs 12 and 14 were found to be the most phototoxic (IC50 = 2.2 microM at a 1 J cm(-2) light dose) of this series of compounds.