Fluorous Phototriggers: Efficacy, Variability, and Mechanism Dependency with Neurotransmitter Release. Kenneth F. Stensrud, and Richard S. Givens. Department of Chemistry, University of Kansas, 1251 Wescoe Hall Drive, 4049 Malott Hall, Lawrence, KS, 66045-7582, Fax: 785-864-3846, givensr@ku.edu
Photoremovable protecting groups (ppg) afford both temporal and spatial control over release of substrates. Photolysis severs a covalent linkage between the chromophore and substrate, thereby reinstating the free, active substrate. Demonstrated photochemical and photophysical properties of p-hydroxyphenacyl (pHP) include rapid, efficient, and clean photorelease of a variety of bioactive species. For example, the photolysis of p-hydroxyphenacyl-γ-aminobutyric acid (pHP-GABA) occurs with greater than 20% efficiency for release with a rate constant of 1.82 x 108 s-1. Further studies have revealed improvements in these properties when electron withdrawing groups are attached to the pHP-GABA. New fluorinated pHP-γ-aminobutyric acid and l-glutamate derivatives have been synthesized and examined for their efficiencies and rates. In addition to photochemical studies, novel synthetic routes to these fluorinated, acetophenone-based chromophores will be highlighted.
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