Model systems for fluorescence and singlet oxygen quenching by metalloporphyrins.
Next-generation photodynamic therapy agents will minimize extraneous phototoxicity by being active only at the target site. To this end, we have developed a model system to systematically investigate the excited-state quenching ability of a number of metalloporphyrins. Central metal ions that prefer four-coordinate, square planar orientations (Ag(II), Cu(II), Ni(II), Pd(II), and Zn(II)) were used. Porphyrin dimers based on 5-(4-aminophenyl)-10,15,20-triphenylporphyrin and comprising both a free base porphyrin and a metalloporphyrin covalently linked through a five-carbon alkyl chain were synthesized. The fluorescence and singlet oxygen quantum yields for the dimers were probed at 630 and 650 nm, respectively, resulting in the excitation of only the free base porphyrin and allowing a comparison of the quenching efficacy of each central metal ion. These results demonstrate that metalloporphyrins can serve as efficient quenchers, and may be useful in the design of novel light-activated therapeutic agents.
McCarthy
Jason R
JR
Center for Molecular Imaging Research, Massachusetts General Hospital and Harvard Medical School, 149 13th St., Rm 5406, Charlestown, MA 02129, USA. jason_mccarthy@hms.harvard.edu
Weissleder
Ralph
R
D000465:Algorithms; D002412:Cations; D003300:Copper / Q000737:chemistry; D019281:Dimerization; D004735:Energy Transfer; D005453:Fluorescence; D008665:Metalloporphyrins / Q000737:chemistry*; D008670:Metals / Q000737:chemistry*; D009532:Nickel / Q000737:chemistry; D010165:Palladium / Q000737:chemistry; D010778:Photochemotherapy / Q000379:methods*; D012834:Silver / Q000737:chemistry; D026082:Singlet Oxygen / Q000737:chemistry*; D013050:Spectrometry, Fluorescence / Q000379:methods; D013056:Spectrophotometry, Ultraviolet / Q000379:methods; D015032:Zinc / Q000737:chemistry
D002412:Cations; D008665:Metalloporphyrins; D008670:Metals; D026082:Singlet Oxygen; D012834:Silver; D010165:Palladium; D003300:Copper; D009532:Nickel; D015032:Zinc