Measuring the polarization and lifetime
of fluorophores in different
microenvironments. (a) TEM image of a catalyst particle consisting
of a solid SiO2 core decorated with Pt nanoparticles and
then coated with a mesoporous SiO2 shell. (b) Schematic
showing the preferred orientation of Amplex red (blue platelets) and
resorufin (red platelet) within the tunnel-like pores of the mesoporous
SiO2 shell. The white arrow indicates the dipole moment
of a resorufin molecule. (c, d) Schematics showing the excitation
of resorufin molecules (red squares) generated from the oxidation
of Amplex red (black triangles) by Pt nanoparticles (gold spheres)
on a SiO2 core (dark gray sphere) within the pores (light
gray cylinders) of the mesoporous SiO2 shell. (c) Linearly
polarized light will selectively excite resorufin molecules whose
dipole moments align with the polarization direction (green arrows)
of the incident laser excitation during SMF imaging. (d) Circularly
polarized light (green spiral) will not lead to selective excitation.
(e) Under linearly polarized light, an elliptical distribution of
localizations was observed for resorufin molecules, indicating they
are aligned within the tunnels of the mesoporous SiO2 shell.
(f) Under circularly polarized light, a circular distribution of localizations
was observed. Panels (a) through (f) are adapted from ref (71) under a Creative Commons
license.223 (g) Schematic for the incorporation
of a fluorescent BODIPY tag into either polynorbornene (R = H) or
polydicyclopentadiene (R = polymer branches, cross-links, or the other
half of the dicyclopentadiene monomer) through ring-opening metathesis
polymerization using a third-generation ruthenium Grubbs catalyst.
Approximately 1 in 107 monomer units incorporate the fluorescent
label. (h) Fluorescence lifetime images during growth of polydicyclopentadiene
particles before the Ru catalyst was added (left panel) and at different
times after addition of the catalyst. The time after catalyst addition
is given above each image. The molecular weight of the polymer determined
by fluorescence lifetime imaging microscopy (MW FLIM), and the intensity-averaged fluorescence lifetime (τ) are
given below each image. The fluorescence lifetime increases as the
polymer particles grow. Panels (g) and (h) are adapted with permission
from ref (203). Copyright
2022 American Chemical Society.