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Issue 8, 2013
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Unravelling molecular mechanisms in the fluorescence spectra of doxorubicin in aqueous solution by femtosecond fluorescence spectroscopy

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Abstract

Doxorubicin (DOX) is a potent anti-tumoral agent widely used for cancer therapy. Despite numerous studies, the fluorescence properties of DOX, usually exploited for the characterization of the interaction with biological media, have until now led to controversial interpretations, mainly due to self-association of the drug in aqueous solution. We present here the first femtosecond study of DOX based on measurements with the fluorescence up-conversion technique in combination with time-correlated single photon counting using the same laser source. We provide evidence that fluorescence signals of DOX stem from monomers and dimers. DOX dimerization induces a dramatic decrease in the fluorescence quantum yield from 3.9 × 10−2 to 10−5 associated with the red shift of the fluorescence spectrum by ∼25 nm. While the fluorescence lifetime of the monomer is 1 ns, the dimer fluorescence is found to decay with a lifetime of about 2 ps. In contrast to monomers, the fluorescence anisotropy of dimers is found to be negative. These experimental observations are consistent with an ultrafast internal conversion (<200 fs) between two exciton states, possibly followed by a charge separation process.

Graphical abstract: Unravelling molecular mechanisms in the fluorescence spectra of doxorubicin in aqueous solution by femtosecond fluorescence spectroscopy

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Publication details

The article was received on 14 Nov 2012, accepted on 21 Dec 2012 and first published on 21 Dec 2012


Article type: Paper
DOI: 10.1039/C2CP44056C
Citation: Phys. Chem. Chem. Phys., 2013,15, 2937-2944
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    Unravelling molecular mechanisms in the fluorescence spectra of doxorubicin in aqueous solution by femtosecond fluorescence spectroscopy

    P. Changenet-Barret, T. Gustavsson, D. Markovitsi, I. Manet and S. Monti, Phys. Chem. Chem. Phys., 2013, 15, 2937
    DOI: 10.1039/C2CP44056C

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