Substituent effects on the sensitivity of a quinoline photoremovable protecting group to one- And two-photon excitation

M. Jarrett Davis, Christopher H. Kragor, Khalilah G. Reddie, Hunter C. Wilson, Yue Zhu, Timothy M. Dore

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Photoremovable protecting groups that can reveal biologically important functional groups through one- and two-photon excitation (1PE and 2PE, respectively) have promise in regulating physiological function in a temporally and spatially restricted manner. Only a few chromophores have sufficient sensitivity to 2PE suitable for use as "caging groups" in physiology experiments. It would be useful to develop structure-property relationships of chromophores, so that chromophores with high two-photon uncaging action cross-sections (δ u) can be designed. The 8-bromo-7- hydroxyquinolinyl chromophore (BHQ) releases a variety of functional groups through 1PE and 2PE. Swapping the bromine substituent for a nitro (NHQ), cyano (CyHQ), or chloro (CHQ) or exchanging the hydroxy for dimethylamino (DMAQ and DMAQ- Cl) or sulfhydryl (TQ) significantly alters the photochemical and photophysical properties of the quinoline chromophOrg. CyHQ-OAc demonstrated a 3-fold increase in sensitivity for acetate release, whereas NHQ- OAc was photochemically insensitive. The quantum efficiencies (Q u) of the amino and sulfhydryl derivatives were about an order of magnitude lower than that of BHQ-OAc. All of the chromophores showed diminished sensitivity to 2PE compared to BHQ-OAc, but the CyHQ, DMAQ, and DMAQ-Cl chromophores are sufficiently sensitive for physiological use. The high sensitivity of CyHQ to 1PE will be useful in biological applications requiring short exposure with low light intensity.

Original languageEnglish (US)
Pages (from-to)1721-1729
Number of pages9
JournalJournal of Organic Chemistry
Issue number4
StatePublished - Feb 20 2009

ASJC Scopus subject areas

  • Organic Chemistry


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