Fluorescence lifetime properties of near-infrared cyanine dyes in relation to their structures.

Structurally diverse near-infrared (NIR) absorbing polymethine dyes were prepared and their fluorescence lifetimes (FLT) were evaluated in relation to their structural features. Comparative FLT analysis based on the modification of methine chain length and heterocyclic system showed that indolium or benz[e]indolium heptamethine dyes exhibited longer FLT than the benz[c,d]indolium trimethine dye. Modification of heterocyclic system alone with an intact chain length showed that indolium-based heptamethine dyes showed approximately 30% longer FLT than the benz[e]indolium-based dyes. In general, the FLT of polymethine dyes increased from polar to non-polar solvents. In addition, correlation study between the theoretical and the experimental FLT for indocyanine green (ICG) suggests that the lack of structural rigidity for these cyanine dyes is primarily responsible for the loss of the excited state energy via non-radiative pathway.

[1]  S. J. Strickler,et al.  Relationship between Absorption Intensity and Fluorescence Lifetime of Molecules , 1962 .

[2]  Quincy L. Mattingly,et al.  Steady-state and picosecond laser fluorescence studies of nonradiative pathways in tricarbocyanine dyes Implications to the design of near-IR fluorochromes with high fluorescence efficiencies , 1994 .

[3]  W. Mcgimpsey,et al.  Excited State Relaxation in Cyanine Dyes: A Remarkably Efficient Reverse Intersystem Crossing from Upper Triplet Levels , 1997 .

[4]  J. S. Reynolds,et al.  Imaging of Spontaneous Canine Mammary Tumors Using Fluorescent Contrast Agents , 1999, Photochemistry and photobiology.

[5]  Samuel Achilefu,et al.  Heptamethine cyanine dyes with a robust C-C bond at the central position of the chromophore. , 2006, The Journal of organic chemistry.

[6]  R. Weissleder,et al.  Monofunctional near-infrared fluorochromes for imaging applications. , 2005, Bioconjugate chemistry.

[7]  Eva M. Sevick-Muraca,et al.  Pharmacokinetics of ICG and HPPH-car for the Detection of Normal and Tumor Tissue Using Fluorescence, Near-infrared Reflectance Imaging: A Case Study¶ , 2000, Photochemistry and photobiology.

[8]  Yunpeng Ye,et al.  Synthesis and characterization of a macrocyclic near-infrared optical scaffold. , 2003, Journal of the American Chemical Society.

[9]  F. Lesage,et al.  Whole-body fluorescence lifetime imaging of a tumor-targeted near-infrared molecular probe in mice. , 2005, Journal of biomedical optics.

[10]  S. Soper,et al.  Near-infrared heavy-atom-modified fluorescent dyes for base-calling in DNA-sequencing applications using temporal discrimination. , 1998, Analytical chemistry.

[11]  M. Cava,et al.  Thioanhydrides. 3. Synthesis, properties and Diels-Alder reactions of sulfur analogs of 1,8-naphthalic anhydride , 1989 .

[12]  E. Akkaya,et al.  Infrared fluorescence sensing of submicromolar calcium: pushing the limits of photoinduced electron transfer , 2000 .

[13]  G. Schuster,et al.  ELECTRONIC RELAXATION IN A SERIES OF CYANINE DYES : EVIDENCE FOR ELECTRONIC AND STERIC CONTROL OF THE ROTATIONAL RATE , 1995 .

[14]  M. Reddington.  NEW GLYCOCONJUGATED CYANINE DYES AS FLUORESCENT LABELING REAGENTS , 1998 .

[15]  F. A. Mikhailenko,et al.  2-Methylbenz[c,d]indole and its derivatives , 1981 .

[16]  A. Ebner,et al.  Cy3B™: Improving the Performance of Cyanine Dyes , 2004, Journal of Fluorescence.

[17]  V. Ntziachristos,et al.  Concurrent MRI and diffuse optical tomography of breast after indocyanine green enhancement. , 2000, Proceedings of the National Academy of Sciences of the United States of America.

[18]  S. Techert,et al.  Photophysical properties of 3,3 '-diethylthiacarbocyanine iodide in binary mixtures , 2003 .

[19]  N. Tamai,et al.  Fluorescence lifetime standards for time and frequency domain fluorescence spectroscopy. , 2007, Analytical chemistry.

[20]  S. Achilefu,et al.  Synthesis and spectral properties of near-infrared aminophenyl-, hydroxyphenyl-, and phenyl-substituted heptamethine cyanines. , 2008, The Journal of organic chemistry.

[21]  Hiroyasu Sato,et al.  Viscosity-Dependent Decay Dynamics of the S2 State of Cyanine Dyes with 3, 5, and 7 Methine Units by Picosecond Fluorescence Lifetime Measurements , 1996 .

[22]  R. Davidson,et al.  Intramolecular quenching of the excited singlet state of a naphthyl group by halogeno substituents , 1980 .

[23]  S. Achilefu,et al.  Novel receptor-targeted fluorescent contrast agents for in vivo tumor imaging. , 2000, Investigative radiology.

[24]  S. McGlynn,et al.  Molecular Spectroscopy of the Triplet State. , 1969 .