Synthesis and photophysical properties of thioglycosylated chlorins, isobacteriochlorins, and bacteriochlorins for bioimaging and diagnostics.
The facile synthesis and photophysical properties of three nonhydrolyzable thioglycosylated porphyrinoids are reported. Starting from meso-perfluorophenylporphyrin, the nonhydrolyzable thioglycosylated porphyrin (PGlc₄), chlorin (CGlc₄), isobacteriochlorin (IGlc₄), and bacteriochlorin (BGlc₄) can be made in 2-3 steps. The ability to append a wide range of targeting agents onto the perfluorophenyl moieties, the chemical stability, and the ability to fine-tune the photophysical properties of the chromophores make this a suitable platform for development of biochemical tags, diagnostics, or as photodynamic therapeutic agents. Compared to the porphyrin in phosphate buffered saline, CGlc₄ has a markedly greater absorbance of red light near 650 nm and a 6-fold increase in fluorescence quantum yield, whereas IGlc₄ has broad Q-bands and a 12-fold increase in fluorescence quantum yield. BGlc₄ has a similar fluorescence quantum yield to PGlc₄ (<10%), but the lowest-energy absorption/emission peaks of BGlc₄ are considerably red-shifted to near 730 nm with a nearly 50-fold greater absorbance, which may allow this conjugate to be an effective PDT agent. The uptake of CGlc₄, IGlc₄, and BGlc₄ derivatives into cells such as human breast cancer cells MDA-MB-231 and K:Molv NIH 3T3 mouse fibroblast cells can be observed at nanomolar concentrations. Photobleaching under these conditions is minimal.
Singh
Sunaina
S
Department of Chemistry & Biochemistry, Hunter College of the City University of New York, New York 10065, United States.
Aggarwal
Amit
A
Thompson
Sebastian
S
Tomé
João P C
JP
Zhu
Xianchun
X
Samaroo
Diana
D
Vinodu
Mikki
M
Gao
Ruomei
R
Drain
Charles Michael
CM
D000818:Animals; D045744:Cell Line, Tumor; D005453:Fluorescence; D006801:Humans; D051379:Mice; D057054:Molecular Imaging / Q000379:methods*; D015394:Molecular Structure; D041681:NIH 3T3 Cells; D010777:Photochemistry; D011166:Porphyrins / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000138:chemical synthesis / Q000737:chemistry*
D011166:Porphyrins; D013438:Sulfhydryl Compounds; C452433:bacteriochlorin; C452434:isobacteriochlorin; C006969:chlorin