Advanced chemistry of dioxetane-based chemiluminescent substrates originating from bioluminescence

Unprecedented hydroxyl radical-dependent two-step chemiluminescence production by polyhalogenated quinoid carcinogens and H 2 O 2

“…Compared with the previously reported classic CL-producing systems (21)(22)(23)(24)(25)(26), the TCBQ∕H 2 O 2 CL-producing system in this study showed the following unique characteristics: The two-step CL produced by TCBQ∕H 2 O 2 was directly and specifically dependent on the two-step intrinsic production of • OH, but not on other reactive oxygen species such as superoxide anion radical and singlet oxygen. It should also be noted that the CL produced by TCBQ∕H 2 O 2 could be observed under normal physiological pH, or even under weak acidic conditions, whereas alkaline or strong alkaline conditions are required for the classic luminol and lucigen systems.…”

“…Chemiluminescence is a phenomenon in which chemically generated molecules in excited states liberate energy with light emission, which is generally accompanied by decomposition of organic peroxides (21)(22)(23)(24)(25)(26). Based on the luminescent properties of electronically excited product, CL could be divided as direct CL, in which excited product directly exhibits CL, and indirect CL, such as chemically initiated electron-exchange luminescence (CIEEL), in which excited product first transfers the excitation energy to suitable luminescer, and then the electronically excited luminescer emits CL (21)(22)(23). If the CL production by TCBQ∕H 2 O 2 were through the CIEEL mechanism, the addition of fluorescent agents such as riboflavin or 9,10-diphenylanthracene (DPA) should have marked impact on CL production (21-23).…”

Detection of hydrogen peroxide with chemiluminescent micelles

“…Peroxalate chemiluminescence is a three component reaction between hydrogen peroxide, a peroxalate ester, and a fl uorescent dye and has great potential for hydrogen peroxide imaging because of its high sensitivity and excellent specifi city (Stevani et al 2000;Arnous et al 2002;Matsumoto 2004). However, the application of peroxalate chemiluminescence for in vivo imaging of hydrogen peroxide is challenging because it requires sequestering fl uorescent dyes and peroxalate esters within close proximity in vivo.…”

“…Hydrogen peroxide diffuses into the micelles and reacts with its peroxalate esters, generating a high energy dioxetanedione intermediate which then chemically excites encapsulated dyes (5), leading to photon emission and the detection of hydrogen peroxide (6). (Matsumoto 2004;Koike et al 2006). One of unique features of the peroxalate micelles is their specifi city to hydrogen peroxide.…”

Estudo dos mecanismos de quimi-excitação na decomposição induzida de peróxidos: uma comparação entre sistemas inter e intramoleculares

“…Um dioxetano tricíclico (Esquema 7), segundo relatado recentemente [74], possui um dos mais altos rendimentos quânticos de emissão (φ S = 0,9 em TBAF/DMSO) para esse tipo de composto.…”