Dual Chemiexcitation by a Unique Dioxetane Scaffold Gated by an OR Logic Set of Triggers

Abstract

Chemiexcitation of phenoxy‐1,2‐dioxetane chemiluminescent luminophores is initiated by electron transfer from a meta‐positioned phenolate ion to the peroxide‐dioxetane bond. Here we report the development of a unique 1,2‐dioxetane chemiluminescent scaffold with chemiexcitation gated by an OR logic dual‐set of triggering events. This scaffold is composed of meta‐dihydroxyphenyl‐1,2‐dioxetane‐adamantyl molecules, equipped with acrylic acid and chlorine substituents, that chemiexcitation under physiological conditions. A dual‐mode chemiluminescent probe, armed with two different triggering substrates designed for activation by the enzymes β‐galactosidase and alkaline phosphatase, was synthesized. The probe emitted intense light signals in the response to each enzyme, demonstrating its ability to serve as a single‐component chemiluminescent sensor for dual‐analyte detection. We also demonstrated the ability of the probe to detect β‐galactosidase and phosphatase activities in bacteria. This is the first 1,2‐dioxetane scaffold capable of responding to two different chemiexcitation events from two different positions on the same dioxetane molecule. We anticipate that the OR‐gated mode of chemiexcitation, described herein, will find utility in the preparation of chemiluminescent probes with a dual‐analyte detection/imaging mode.