Photoactivatable Red Chemiluminescent AIEgen Probe for In Vitro/Vivo Imaging Assay of Hydrazine

Abstract

Here, we have developed a novel photoactivatable red chemiluminescent AIEgen probe (ACL), based on the combination of the red-emission AIEgen fluorophore (TPEDC) that shows excellent singlet oxygen ( 1 O 2 )-generation ability and the precursor of Schaap's dioxetane (the linker connected to adamantane is the CC bond) that can be modified to target various analytes, for in vitro and in vivo measurement of hydrazine. Prior to applying for sensing detection, the CC bond connected to adamantane in ACL was first converted into dioxetane by irradiation to form the activated chemiluminescent AIEgen probe (ACLD). Then, the self-immolative reaction was triggered upon the deprotection of the acylated phenolic hydroxyl group in ACLD in the presence of hydrazine, resulting in the release of the high energy held in the 1,2-dioxetanes, and then, the chemiexcitation was triggered, thereby producing red chemiluminescence through the intramolecular chemiluminescence resonance energy transfer from Schaap's dioxetane to TPEDC. This chemiluminescent AIEgen probe was evaluated in a clean buffer environment as well as using living cells and mouse models.

Oxygen‐Sensing Chemiluminescent Iridium(III) 1,2‐Dioxetanes: Unusual Coordination and Activity

“…These unusual responses could be explained by taking into consideration the photosensitizing ability of Ir(III) complexes, [31] yielding either visible‐light induced decomposition of the dioxetane ring (Scheme S5A), or photo‐assisted conversion of 5 and 6 into their respective dioxetanes ( IrCL‐4 and IrCL‐5 ), which then decompose quickly or partially transform into another species in solution (Scheme S5B). A similar type of fluorophore‐assisted photodecomposition [32] or in‐situ dioxetane formation of Schaap dioxetanes [33] has been previously suggested. A more detailed discussion is provided in the supporting information.…”

Recent Applications and Future Perspectives of Chemiluminescent and Bioluminescent Imaging Technologies

“…Moreover, Li and colleagues developed an innovative photoactivatable red CL AIEgen platform (ACL) for the exogenous (in a clean buffer environment) and endogenous (in living cells and mouse models) visualization of hydrazine. 68 The developed CL probe relied on a combination of the redemission AIEgen fluorophore (TPEDC), which has a superior 1 O 2 production capability, and the dioxetane precursor unit for the estimation of hydrazine in vitro and in vivo. By applying white light irradiation, the C�C bond attached to adamantine unit in ACL was first transformed to dioxetane to form the activated ACL probe.…”

State-of-the-art self-luminescence: a win–win situation

“…As another example, Li and co-workers developed a hydrazine-recognized photoactivatable unimolecular NIR CL probe by nonconjugated linking AIEgen fluorophore and the precursor of Schaap's dioxetane. 47 Upon administration of hydrazine and light irradiation simultaneously, the dual-activated intramolecular CRET occurred and NIR CL emission was observed. The unimolecular approach extends the application of AIE-powered CL probes in biological assays to other chemical species.…”