title: Examination of chlorin-bacteriochlorin energy-transfer dyads as prototypes for near-infrared molecular imaging probes.
abstract: New classes of synthetic chlorin and bacteriochlorin macrocycles are characterized by narrow spectral widths, tunable absorption and fluorescence features across the red and near-infrared (NIR) regions, tunable excited-state lifetimes (<1 to >10 ns) and chemical stability. Such properties make dyad constructs based on synthetic chlorin and bacteriochlorin units intriguing candidates for the development of NIR molecular imaging probes. In this study, two such dyads (FbC-FbB and ZnC-FbB) were investigated. The dyads 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. In both constructs, energy transfer from the chlorin to bacteriochlorin occurs with a rate constant of approximately (5 ps)(-1) and a yield of >99%. Thus, each dyad effectively behaves as a single chromophore with an exceptionally large Stokes shift (85 nm for FbC-FbB and 110 nm for ZnC-FbB) between the red-region absorption of the chlorin and the NIR fluorescence of the bacteriochlorin (lambda(f) = 760 nm, Phi(f) = 0.19, tau approximately 5.5 ns in toluene). The long-wavelength transitions (absorption, emission) of each constituent of each dyad exhibit narrow (<or=20 nm) spectral widths. The narrow spectral widths enabled excellent selectivity in excitation and detection of one chlorin-bacteriochlorin energy-transfer dyad in the presence of the other upon diffuse optical tomography of solution-phase phantoms.
authors.affiliation: Department of Chemistry, Washington University, St. Louis, MO, USA.
authors.forename: Hooi Ling
authors.initials: HL
authors.lastname: Kee
authors.forename: Ralph
authors.initials: R
authors.lastname: Nothdurft
authors.forename: Chinnasamy
authors.initials: C
authors.lastname: Muthiah
authors.forename: James R
authors.initials: JR
authors.lastname: Diers
authors.forename: Dazhong
authors.initials: D
authors.lastname: Fan
authors.forename: Marcin
authors.initials: M
authors.lastname: Ptaszek
authors.forename: David F
authors.initials: DF
authors.lastname: Bocian
authors.forename: Jonathan S
authors.initials: JS
authors.lastname: Lindsey
authors.forename: Joseph P
authors.initials: JP
authors.lastname: Culver
authors.forename: Dewey
authors.initials: D
authors.lastname: Holten
mesh_terms: D004121:Dimethyl Sulfoxide / Q000737:chemistry; D004735:Energy Transfer; D005456:Fluorescent Dyes / Q000737:chemistry; D008665:Metalloporphyrins / Q000138:chemical synthesis / Q000737:chemistry; D015335:Molecular Probes / Q000032:analysis / Q000737:chemistry*; D015394:Molecular Structure; D010777:Photochemistry; D011166:Porphyrins / Q000737:chemistry*; D019265:Spectroscopy, Near-Infrared; D013237:Stereoisomerism; D014050:Toluene / Q000737:chemistry
chemical_list: D005456:Fluorescent Dyes; D008665:Metalloporphyrins; D015335:Molecular Probes; D011166:Porphyrins; C452433:bacteriochlorin; C006969:chlorin; D014050:Toluene; D004121:Dimethyl Sulfoxide