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Excited state absorption study in hematoporphyrin IX.

Leonardo De Boni1, Carlos Toro, Florencio E Hernandez

  • 1Department of Chemistry, University of Central Florida, P.O. Box 162366, Orlando, FL 32816, USA.

Journal of Fluorescence
|September 17, 2009
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Summary

Hematoporphyrin IX in DMSO exhibits reverse saturable absorption due to transitions to high singlet excited states. Picosecond pump-probe and Z-scan methods reveal excited state dynamics and vibronic progression.

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Area of Science:

  • Photophysics
  • Nonlinear Optics
  • Molecular Spectroscopy

Background:

  • Hematoporphyrin IX is a photosensitizer with potential applications in photodynamic therapy.
  • Understanding its excited-state properties is crucial for optimizing its efficacy and minimizing side effects.
  • Dimethyl sulfoxide (DMSO) is a common solvent that can influence porphyrin photophysics.

Purpose of the Study:

  • To investigate the excited-state absorption (ESA) of Hematoporphyrin IX in DMSO.
  • To elucidate the nonlinear optical properties and excited-state dynamics.
  • To identify the origin of nonlinear effects using a three-level model.

Main Methods:

  • Open aperture Z-scan technique with picosecond pulses.
  • White-light continuum pump-probe spectroscopy with picosecond pulses.
  • Fluorescence lifetime and fluorescence quantum yield measurements.

Main Results:

  • Evidence of transitions to high singlet excited states, not triplet states.
  • Observation of vibronic progression in the Q-band due to ground-state photobleaching.
  • Demonstration of reverse saturable absorption (RSA) across most of the studied spectral range.
  • Detection of a long relaxation component for the first singlet excited state.

Conclusions:

  • The excited-state absorption of Hematoporphyrin IX in DMSO is dominated by singlet-singlet transitions.
  • Reverse saturable absorption is a significant nonlinear optical property of this system.
  • The observed dynamics are consistent with fluorescence measurements, supporting a three-level model for the nonlinear effects.