Chemistry, Ames Laboratory
Journal or Book Title
Journal of the American Chemical Society
Photocages are light-sensitive chemical protecting groups that provide external control over when, where, and how much of a biological substrate is activated in cells using targeted light irradiation. Regrettably, most popular photocages (e.g., o-nitrobenzyl groups) absorb cell-damaging ultraviolet wavelengths. A challenge with achieving longer wavelength bond-breaking photochemistry is that long-wavelength-absorbing chromophores have shorter excited-state lifetimes and diminished excited-state energies. However, here we report the synthesis of a family of BODIPY-derived photocages with tunable absorptions across the visible/near-infrared that release chemical cargo under irradiation. Derivatives with appended styryl groups feature absorptions above 700 nm, yielding photocages cleaved with the highest known wavelengths of light via a direct single-photon-release mechanism. Photorelease with red light is demonstrated in living HeLa cells, Drosophila S2 cells, and bovine GM07373 cells upon ∼5 min irradiation. No cytotoxicity is observed at 20 μM photocage concentration using the trypan blue exclusion assay. Improved B-alkylated derivatives feature improved quantum efficiencies of photorelease ∼20-fold larger, on par with the popular o-nitrobenzyl photocages (εΦ = 50–100 M–1 cm–1), but absorbing red/near-IR light in the biological window instead of UV light.
American Chemical Society
Peterson, Julie A.; Wijesooriya, Chamari; Gehrmann, Elizabeth J.; Mahoney, Kaitlyn M.; Goswami, Pratik P.; Albright, Toshia; Syed, Aleem; Dutton, Andrew S.; Smith, Emily A.; and Winter, Arthur, "Family of BODIPY Photocages Cleaved by Single Photons of Visible/Near-Infrared Light" (2018). Chemistry Publications. 1223.