Orderly Arranged Fluorescence Dyes as a Highly Efficient Chemiluminescence Resonance Energy Transfer Probe for Peroxynitrite

Chemiluminescence (CL) probes for reactive oxygen species (ROS) are commonly based on a redox reaction between a CL reagent and ROS, leading to poor selectivity toward a specific ROS. The energy-matching rules in the chemiluminescence resonance energy transfer (CRET) process between a specific ROS donor and a suitable fluorescence dye acceptor is a promising method for the selective detection of ROS. Nevertheless, higher concentrations of fluorescence dyes can lead to the intractable aggregation-caused quenching effect, decreasing the CRET efficiency. In this report, we fabricated an orderly arranged structure of calcein-sodium dodecyl sulfate (SDS) molecules to improve the CRET efficiency between ONOOH* donor and calcein acceptor. Such orderly arranged calcein-SDS composites can distinguish peroxynitrite (ONOO-) from a variety of other ROS owing to the energy matching in the CRET process between ONOOH* donor and calcein acceptor. Under the optimal experimental conditions, ONOO- could be assayed in the range of 1.0-20.0 mu M, and the detection limit for ONOO- [signal-to-noise ratio (S/N) = 3] was 0.3 mu M. The proposed strategy has been successfully applied in both detecting ONOO(-) in cancer mouse plasma samples and monitoring the generation of ONOO- from 3-morpholinosydnonimine (SIN-1). Recoveries from cancer mouse plasma samples were in the range of 96-105%. The success of this work provides a unique opportunity to develop a CL tool to monitor ONOO- with high selectivity in a specific manner. Improvement of selectivity and sensitivity of CL probes holds great promise as a strategy for developing a wide range of probes for various ROS by tuning the types of fluorescence dyes.