The Molecular Basis of Organic Chemiluminescence

Abstract

Bioluminescence (BL) and chemiluminescence (CL) are interesting and intriguing phenomena that involve the emission of visible light as a consequence of chemical reactions. The mechanistic basis of BL and CL has been investigated in detail since the 1960s, when the synthesis of several models of cyclic peroxides enabled mechanistic studies on the CL transformations, which led to the formulation of general chemiexcitation mechanisms operating in BL and CL. This review describes these general chemiexcitation mechanisms—the unimolecular decomposition of cyclic peroxides and peroxide decomposition catalyzed by electron/charge transfer from an external (intermolecular) or an internal (intramolecular) electron donor—and discusses recent insights from experimental and theoretical investigation. Additionally, some recent representative examples of chemiluminescence assays are given.

Spirostrain-Accelerated Chemiexcitation of Dioxetanes Yields Unprecedented Detection Sensitivity in Chemiluminescence Bioassays

“…There have been several previous computational studies of “charge-transfer-induced luminescence” (CTIL) and variations in timing of charge transfer, O–O, and C–C cleavage. − The extensive and elegant results by Yue and Liu for the adamantyl compound, studied by us as shown in Figure B, showed that the mechanism of dioxetane ring opening involves charge transfer by state crossing during the O–O cleavage transition state . Our activation barrier is very similar to their results with the CAM-B3LYP/6-31G­(d) method.…”

A mitochondria-targeted chemiluminescent probe for detection of hydrogen sulfide in cancer cells, human serum and in vivo

“…78–80 Additionally, they bear a modular scaffold, which can be simply modified toward the development of activity-based probes. Accordingly, new generation 1,2-dioxetane derivatives have been developed to monitor numerous analytes ranging from enzymes to ROS and biothiols including H 2 S. 81–86 Very recently, we have introduced the first ever example of a mitochondria-targeted chemiluminescence agent by modifying the phenoxy 1,2-dioxetane core, which was responsive to the leucine aminopeptidase (LAP) enzyme, with a well-established mitochondrion targeting triphenylphosphonium (TPP) group. 87 Cationic nature of TPP is critical to ensure the attraction between the probe and the negatively charged membrane of mitochondria as previously shown in the literature.…”

Chemiluminescence of a Firefly Luciferin Analogue Reveals that Formation of the Key Intermediate Responsible for Excited State Generation Occurs on a Fully Concerted Step

“…Since obtaining and elucidating the structure, as well as achieving the synthesis of the luciferin substrate (LUC, Scheme ) by Bitler et al and White et al in the late 1950s, , extensive experimental and theoretical research has been conducted to understand the mechanism involved in the efficient bioluminescence (BL) of Photinus pyralis. , The study of BL in general benefits from computational simulations of entire systems, − as well as from working with chemiluminescence (CL) reactions that serve as comprehensive models and analogues of BL processes. , …”

“…3,4 The study of BL in general benefits from computational simulations of entire systems, 5−8 as well as from working with chemiluminescence (CL) reactions that serve as comprehensive models and analogues of BL processes. 3,9 The widely accepted mechanism for BL emission involves a complex sequence of reactions (Scheme 1) at the active site of the luciferase enzyme. 3 First, the luciferase catalyzes the conversion of LUC into the dianionic luciferyl adenylate (LUC-AMP) intermediate in the presence of Mg 2+ and ATP.…”