Highly selective fluorescent OFF-ON thiol probes based on dyads of BODIPY and potent intramolecular electron sink 2,4-dinitrobenzenesulfonyl subunits

Org Biomol Chem. 2011 May 21;9(10):3844-53. doi: 10.1039/c0ob00910e. Epub 2011 Apr 12.

Abstract

Two highly selective OFF-ON green emitting fluorescent thiol probes (1 and 2) with intense absorption in the visible spectrum (molar extinction coefficient ε is up to 73 800 M(-1) cm(-1) at 509 nm) based on dyads of BODIPY (as electron donor of the photo-induced electron transfer, i.e.PET) and 2,4-dinitrobenzenesulfonyl (DNBS) (as electron acceptor of the PET process) were devised. The single crystal structures of the two probes were determined. The distance between the electron donor (BODIPY fluorophore) and the electron acceptor (DNBS) of probe 2 is larger than that of probe 1, as a result the contrast ratio (or the PET efficiency) of probe 2 is smaller than that of probe 1. However, fluorescence OFF-ON switching effects were observed for both probe 1 and probe 2 in the presence of cysteine (the emission enhancement is 300-fold for probe 1 and 54-fold for probe 2). The fluorescence OFF-ON sensing mechanism is rationalized by DFT/TDDFT calculations. We demonstrated with DFT calculations that DNBS is ca. 0.76 eV more potent to accept electrons than the maleimide moiety. The probes were used for fluorescent imaging of cellular thiols.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Boron Compounds / chemistry*
  • Cell Line
  • Crystallography, X-Ray
  • Darkness
  • Dinitrofluorobenzene / analogs & derivatives
  • Dinitrofluorobenzene / chemistry
  • Electron Transport / radiation effects
  • Fluorescent Dyes / chemical synthesis
  • Fluorescent Dyes / chemistry*
  • Models, Molecular
  • Molecular Conformation
  • Quantum Theory
  • Spectrometry, Fluorescence
  • Sulfhydryl Compounds / analysis*
  • Sulfhydryl Compounds / chemistry
  • Sulfonamides / chemistry*

Substances

  • 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene
  • Boron Compounds
  • Fluorescent Dyes
  • Sulfhydryl Compounds
  • Sulfonamides
  • 2,4-dinitrofluorobenzene sulfonic acid
  • Dinitrofluorobenzene