{1460} revision 8 modified: 05-29-2019 19:41 gmt

A friend postulated using the triplet state phosphorescence as a magnetically-modulatable dye. E.g. magnetically slice a scattering biological sample, rather than slicing optically (light sheet, 2p) or mechanically. After a little digging:

I'd imagine that it should be possible to design a molecule -- a protein cage, perhaps a (fully unsaturated) terpine -- which isolates the excited state from oxygen quenching.

Adam Cohen at Harvard has been working a bit on this very idea, albeit with fluorescence not phosphorescence --

  • Optical imaging through scattering media via magnetically modulated fluorescence (2010)
    • The two species, pyrene and dimethylaniline are in solution.
    • Dimethylaniline absorbs photons and transfers an electron to pyrene to produce a singlet radical pair.
    • The magnetic field represses conversion of this singlet into a triplet; when two singlet electrons combine, they produce exciplex fluorescence.
  • Addition of an aliphatic-ether 12-O-2 linker improves things significantly --
  • Mapping Nanomagnetic Fields Using a Radical Pair Reaction (2011)
  • Which can be used with a 2p microscope:
  • Two-photon imaging of a magneto-fluorescent indicator for 3D optical magnetometry (2015)
    • Notably, use decay kinetics of the excited state to yield measurements that are insensitive to photobleaching, indicator concentration, or local variations in optical excitation or collection efficiency. (As opposed to ΔF/F\Delta F / F )
    • Used phenanthrene (3 aromatic rings, not 4 in pyrene) as the excited electron acceptor, dimethylaniline again as the photo-electron generator.
    • Clear description:
      • A molecule with a singlet ground state absorbs a photon.
      • The photon drives electron transfer from a donor moiety to an acceptor moiety (either inter or intra molecular).
      • The electrons [ground state and excited state, donor] become sufficiently separated so that their spins do not interact, yet initially they preserve the spin coherence arising from their starting singlet state.
      • Each electron experiences a distinct set of hyperfine couplings to it's surrounding protons (?) leading to a gradual loss of coherence and intersystem crossing (ISC) into a triplet state.
      • An external magnetic field can lock the precession of both electrons to the field axis, partially preserving coherence and supressing ISC.
      • In some chemical systems, the triplet state is non-fluorescence, whereas the singlet pair can recombine and emit a photon.
      • Magnetochemical effects are remarkable because they arise at a magnetic field strengths comparable to hyperfine energy (typically 1-10mT).
        • Compare this to the Zeeman effect, where overt splitting is at 0.1T.
    • phenylanthrene-dimethylaniline was dissolved in dimethylformamide (DMF). The solution was carefully degassed in nitrogen to prevent molecular oxygen quenching.

Yet! Magnetic field effects do exist in solution: