Phosphorescent oxygen sensor with dendritic protection and two-photon absorbing antenna

J Am Chem Soc. 2005 Aug 24;127(33):11851-62. doi: 10.1021/ja052947c.

Abstract

Imaging oxygen in 3D with submicron spatial resolution can be made possible by combining phosphorescence quenching technique with multiphoton laser scanning microscopy. Because Pt and Pd porphyrin-based phosphorescent dyes, traditionally used as phosphors in biological oxygen measurements, exhibit extremely low two-photon absorption (2PA) cross-sections, we designed a nanosensor for oxygen, in which a 2P absorbing antenna is coupled to a metalloporphyrin core via intramolecular energy transfer (ET) with the purpose of amplifying the 2PA induced phosphorescence of the metalloporphyrin. The central component of the device is a polyfunctionalized Pt porphyrin, whose triplet state emission at ambient temperatures is strong, occurs in the near infrared and is sensitive to O2. The 2PA chromophores are chosen in such a way that their absorption is maximal in the near infrared (NIR) window of tissue (e.g., 700-900 nm), while their fluorescence is overlapped with the absorption band(s) of the core metalloporphyrin, ensuring an efficient antenna-core resonance ET. The metalloporphyrin-antenna construct is embedded inside the protecting dendritic jacket, which isolates the core from interactions with biological macromolecules, controls diffusion of oxygen and makes the entire sensor water-soluble. Several Pt porphyrin-coumarin based sensors were synthesized and their photophyics studied to evaluate the proposed design.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Absorption
  • Biosensing Techniques*
  • Lasers
  • Luminescent Measurements*
  • Metalloporphyrins / chemical synthesis
  • Metalloporphyrins / chemistry*
  • Microscopy, Fluorescence, Multiphoton
  • Nanotechnology / methods
  • Oxygen / analysis*
  • Photons*
  • Platinum / chemistry*
  • Sensitivity and Specificity

Substances

  • Metalloporphyrins
  • Platinum
  • Oxygen