Computational Prediction and Experimental Evaluation of a Photoinduced Electron-Transfer Sensor

Document Type

Article

Publication Date

11-1-2006

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.

DOI

https://doi.org/10.1021/jp065876s

Additional Files

Share

COinS