Four‐membered cyclic peroxides: Carriers of chemical energy

Abstract

Four-membered cyclic peroxides are high-energy compounds often associated to cold light emission, but whose chemical and biological roles are still matters of debate. The often-dangerous synthesis of 1,2-dioxetanes, achieved around 50 years ago, has been mastered over the years to a point where some derivatives are commercially available. This fact does not imply that 1,2-dioxetanes can be conveniently prepared in the gram scale or that the synthesis of analogous 1,2-dioxetanones and the elusive 1,2-dioxetanedione are simple. Important questions on the mechanism of chemiluminescence and bioluminescence reactions are under experimental and theoretical scrutiny. The available data have contributed to relate structural and medium effects to the quantum efficiency of these compounds to produce excited states. Consequently, such peroxides have been suggested to produce biologically relevant electronically excited species in vivo in the absence of light. The connection of this hypothesis with melanin-mediated photodamage in the dark has renewed the interest in such cyclic peroxides. This review gives some insight on the synthesis, chemiluminescence mechanism, and biological relevance of 1,2-dioxetanes, 1,2-dioxetanones, and 1,2-dioxetanedione and provides practical protocols for those interested in engaging this field.

Upconversion of Reductants

“…Peroxides are attractive precursors for reductive upconversion because they combine the kinetic instability of weak (and easily reducible) O−O bonds with the potential of forming very strong C=O bonds . Below, we will provide several examples of how energy associated with reductive upconversion can be used to produce photons in the visible energy range for applications in chemo‐ and bioluminescence.…”

Hochkonversion von Reduktionsmitteln

“…Peroxide sind vielversprechende Vorstufen fürd ie reduktive Hochkonversion, da sie die kinetische Instabilität schwacher (und leicht reduzierbarer) O-O-Bindungen [20] mit dem Potenzial zur Bildung sehr starker C=O-Bindungen kombinieren. [21] In der Folge stellen wir einige Beispiele vor, die zeigen, wie die mit der reduktiven Hochkonversion verbundene Energie zur Erzeugung von Photonen im sichtbaren Energiebereich, fürA nwendungen in der Chemo-und Biolumineszenz, genutzt werden kann.…”

Brazilian Bioluminescent Beetles: Reflections on Catching Glimpses of Light in the Atlantic Forest and Cerrado

“…3, 2). This intermediate then undergoes cyclization with release of AMP to a putative four-membered ring peroxide (Fig.3, 3), named α-peroxylactone or dioxetanone (Bartoloni et al 2015, Bastos et al 2017, whose cleavage (Fig. 3, 7) yields CO 2 and the oxyluciferin in the excited singlet, fluorescent state (Fig.…”