title: Computational prediction and experimental evaluation of a photoinduced electron-transfer sensor.
abstract: An approach is presented for the design of photoinduced electron-transfer-based sensors. The approach relies on the computational and theoretical prediction of electron-transfer kinetics based on Rehm-Weller and Marcus theories. The approach allows evaluation of the photophysical behavior of a prototype fluorescent probe/sensor prior to the synthesis of the molecule. As a proof of concept, a prototype sensor for divalent metal ions is evaluated computationally, synthesized, and then analyzed spectroscopically for its fluorescence response to zinc. Calculations predicted that the system would show a competition between electron transfer and fluorescence in the free state. In the zinc-bound state, the compound was predicted to be more highly fluorescent, due to the inhibition of electron transfer. Both predictions were confirmed experimentally. A nonzero fluorescence signal was observed in the absence of zinc and an enhancement was observed in the presence of zinc. Specifically, a 56-fold enhancement was observed over a 10-fold increase in zinc concentration.
authors.forename: Matthew E
authors.initials: ME
authors.lastname: McCarroll
authors.forename: Yu
authors.initials: Y
authors.lastname: Shi
authors.forename: Samantha
authors.initials: S
authors.lastname: Harris
authors.forename: Surendra
authors.initials: S
authors.lastname: Puli
authors.forename: Irene
authors.initials: I
authors.lastname: Kimaru
authors.forename: Ruisong
authors.initials: R
authors.lastname: Xu
authors.forename: Lichang
authors.initials: L
authors.lastname: Wang
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Dyer