Unexpected Coelenterazine Degradation Products of <i>Beroe abyssicola</i> Photoprotein Photoinactivation

Burakova, Ludmila P.; Lyakhovich, M. S.; Mineev, Konstantin S.; Petushkov, Valentin N.; Zagitova, Renata I; Tsarkova, Aleksandra S.; Kovalchuk, Sergey I.; Yampolsky, Ilia V.; Vysotski, Eugene S.; Kaskova, Zinaida M.

doi:10.1021/acs.orglett.1c02410

Cited by 8 publications

(22 citation statements)

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“…28 The employed theoretical protocol was already used with success in the study of this type of system. [9][10][11][12]22,23,25,26,29,30 ■ RESULTS AND DISCUSSION In this study, we intend to elucidate the chemical details behind the thermolysis and potential chemiexcitation of the two Coelenterazine dioxetane species proposed by both Teranishi et al 21 and Burakova et al, 17 as found in Scheme 1. From now on, these dioxetane species will be termed Clz- Dxt-1 and Clz-Dxt-2, respectively.…”

Section: ■ Computational Detailsmentioning

confidence: 95%

“…Furthermore, while dioxetanes are capable of efficient singlet chemiexcitation, 18,19 the study of Burakova et al did not report the thermolysis of Coelenterazine dioxetane as a luminescent pathway. 17 It should be noted that while rare, the study of Burakova et al was not the first to mention a Coelenterazine dioxetane species and its respective thermolysis. 17 In 1996, Teranishi et al studied the chemiluminescent properties of a hydroperoxide derivative of Coelenterazine (Scheme 1) and found that it decomposed via the formation of a dioxetane intermediate (a "mirror" species of that proposed by Burakova et al) but without relevant luminescence.…”

Section: ■ Introductionmentioning

confidence: 99%

“…17 It should be noted that while rare, the study of Burakova et al was not the first to mention a Coelenterazine dioxetane species and its respective thermolysis. 17 In 1996, Teranishi et al studied the chemiluminescent properties of a hydroperoxide derivative of Coelenterazine (Scheme 1) and found that it decomposed via the formation of a dioxetane intermediate (a "mirror" species of that proposed by Burakova et al) but without relevant luminescence. 21 Thus, these reports indicate that besides Coelenterazine dioxetanone, its dioxetane counterpart can also play a role in the bioluminescent and chemiluminescent reactions of Coelenterazine.…”

Section: ■ Introductionmentioning

confidence: 99%

“…For example, Inouye et al studied the degradation process of ( S )-2-peroxycoelenterazine in aequorin under conditions of protein denaturation and found that by acid treatment the major product was Coelenteramine and not Coelenteramide (with no significant luminescence) . Burakova et al also found recently some unexpected Coelenterazine degradation products of Beroe abyssicola photoprotein photoinactivation . One of these degradation products was identified as a substituted hydantoin compound, termed 4 Z / E (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

“…This report is of note as while dioxetanes are similar to dioxetanones, in which both high-energy intermediates are capable of chemiexcitation, − the former ones have not been associated with the bioluminescent reactions of Coelenterazine. Furthermore, while dioxetanes are capable of efficient singlet chemiexcitation, , the study of Burakova et al did not report the thermolysis of Coelenterazine dioxetane as a luminescent pathway …”

Section: Introductionmentioning

confidence: 99%

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Theoretical Study of the Thermolysis Reaction and Chemiexcitation of Coelenterazine Dioxetanes

Magalhães

Silva

2022

J. Phys. Chem. A

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Coelenterazine and other imidazopyrazinones are important bioluminescent substrates widespread in marine species and can be found in eight phyla of luminescent organisms. Light emission from these systems is caused by the formation and subsequent thermolysis of a dioxetanone intermediate, whose decomposition allows for efficient chemiexcitation to singlet excited states. Interestingly, some studies have also reported the involvement of unexpected dioxetane intermediates in the chemiand bioluminescent reactions of Coelenterazine, albeit with little information on the underlying mechanisms of these new species. Herein, we have employed a theoretical approach based on density functional theory to study for the first time the thermolysis reaction and chemiexcitation profile of two Coelenterazine dioxetanes. We have found that the thermolysis reactions of these species are feasible but with relevant energetic differences. More importantly, we found that the singlet chemiexcitation profiles of these dioxetanes are significantly less efficient than the corresponding dioxetanones. Furthermore, we identified triplet chemiexcitation pathways for the Coelenterazine dioxetanes. Given this, the chemiexcitation of these dioxetanes should lead only to minimal luminescence. Thus, our theoretical investigation of these systems indicates that the thermolysis of these dioxetanes should only provide "dark" pathways for the formation of nonluminescent degradation products of the chemi-and bioluminescent reactions of Coelenterazine and other imidazopyrazinones.

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