Campus Units

Chemistry, Ames Laboratory

Document Type

Article

Publication Version

Submitted Manuscript

Publication Date

5-18-2018

Journal or Book Title

Journal of the American Chemical Society

Volume

140

Issue

23

First Page

7343

Last Page

7346

DOI

10.1021/jacs.8b04040

Abstract

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.

Comments

This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in the Journal of the American Chemical Society, copyright © American Chemical Society after peer review. To access the final edited and published work see DOI: 10.1021/jacs.8b04040. Posted with permission.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Published Version

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