Characterization of sulfonated phthalocyanines by mass spectrometry and capillary electrophoresis

Abstract

We report the characterization of sulfonated phthalocyanines using capillary electrophoresis and mass spectrometry. Derivatives investigated included the copper, cobalt, zinc and metal-free sulfonated phthalocyanines. In general, sulfonated phthalocyanines were found as aggregates in capillary electrophoresis separations, even at low concentration. Separations were much better at pH 9.0 than at pH 2.5. The addition of β-cyclodextrin did not alter the electropherograms significantly. The electropherograms of commercially available copper phthalocyanine-3,4',4″,4‴-tetrasulfonic acid and 4,4',4″,4‴-tetrasulfonic acid were very different, consistent with the latter compound having a structure that is not fully sulfonated. Matrix-assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI) were used to characterize the sulfonated phthalocyanines. In general, MALDI gave better results than ESI. Mass spectral evidence was obtained for a pentasulfonated species of both the metal-free phthalocyanine and zinc phthalocyanine when these species were made by sulfonation of the metal-free phthalocyanine (followed by zinc insertion in the latter case). Sulfonated tetraphenylporphyrin derivatives were used as standards for mass spectrometry and to estimate the effect of net charge on the capillary electrophoresis migration time for sulfonated tetrapyrroles. Clean separation of the sulfonated tetraphenylporphyrin derivatives [5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS4), 5,10,15-tris(4-sulfonatophenyl)-20-phenylporphyrin (TPPS3) and 5,10-bis(4-sulfonatophenyl)-15,20-diphenylporphyrin (TPPS2a)] was observed by capillary electrophoresis.