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Chlorin-bacteriochlorin energy-transfer dyads as prototypes for near-infrared molecular imaging probes: controlling charge-transfer and fluorescence properties in polar media.

Abstract：

:The photophysical properties of two energy-transfer dyads that are potential candidates for near-infrared (NIR) imaging probes are investigated as a function of solvent polarity. The dyads (FbC-FbB and ZnC-FbB) contain either a free base (Fb) or zinc (Zn) chlorin (C) as the energy donor and a free base bacteriochlorin (B) as the energy acceptor. The dyads were studied in toluene, chlorobenzene, 1,2-dichlorobenzene, acetone, acetonitrile and dimethylsulfoxide (DMSO). In both dyads, energy transfer from the chlorin to bacteriochlorin occurs with a rate constant of approximately (5-10 ps)(-1) and a yield of >99% in nonpolar and polar media. In toluene, the fluorescence yields (Phif=0.19) and singlet excited-state lifetimes (tau approximately 5.5 ns) are comparable to those of the benchmark bacteriochlorin. The fluorescence yield and excited-state lifetime decrease as the solvent polarity increases, with quenching by intramolecular electron (or hole) transfer being greater for FbC-FbB than for ZnC-FbB in a given solvent. For example, the Phif and tau values for FbC-FbB in acetone are 0.055 and 1.5 ns and in DMSO are 0.019 and 0.28 ns, whereas those for ZnC-FbB in acetone are 0.12 and 4.5 ns and in DMSO are 0.072 and 2.4 ns. The difference in fluorescence properties of the two dyads in a given polar solvent is due to the relative energies of the lowest energy charge-transfer states, as assessed by ground-state redox potentials and supported by molecular-orbital energies derived from density functional theory calculations. Controlling the extent of excited-state quenching in polar media will allow the favorable photophysical properties of the chlorin-bacteriochlorin dyads to be exploited in vivo. These properties include very large Stokes shifts (85 nm for FbC-FbB, 110 nm for ZnC-FbB) between the red-region absorption of the chlorin and the NIR fluorescence of the bacteriochlorin (lambdaf=760 nm), long bacteriochlorin excited-state lifetime (approximately 5.5 ns), and narrow (

journal_name

Photochem Photobiol

journal_title

Photochemistry and photobiology

authors

Kee HL,Diers JR,Ptaszek M,Muthiah C,Fan D,Lindsey JS,Bocian DF,Holten D

doi

10.1111/j.1751-1097.2008.00532.x

subject

Has Abstract

pub_date

2009-07-01 00:00:00

pages

909-20

issue

eissn

0031-8655

issn

1751-1097

pii

PHP532

journal_volume

pub_type

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Chlorin-bacteriochlorin energy-transfer dyads as prototypes for near-infrared molecular imaging probes: controlling charge-transfer and fluorescence properties in polar media.