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Mechanistic Insight into the Chemiluminescent Decomposition of Cypridina Dioxetanone and the Chemiluminescent, Fluorescent Properties of the Light Emitter of Cypridina Bioluminescence
journal contribution
posted on 2019-10-16, 18:36 authored by Chun-Gang Min, Qing-Bo Liu, Yan Leng, Carla M. Magalhães, Shao-Jun Huang, Chun-Xia Liu, Xi-Kun Yang, Luís Pinto da SilvaCypridina bioluminescence has been increasingly
used in bioimaging, bioanalysis, and biomedicine, due to high quantum
yield and high signal-to-noise ratio. However, there is still no consensus
regarding different aspects of the chemiluminescent mechanism of this
system, which impairs the development of new applications. Herein,
we have used a theoretical DFT and TD-DFT approach to (i) determine
the identity of the dioxetanone species responsible for efficient
chemiexcitation and (ii) identify the bioluminescent emitter and determine
if light-emission occurs from the fluorescent or chemiluminescent
state. Our results demonstrate that upon oxygenation of the imidazopyrazinone
scaffold, a dioxetanone with a neutral amide group and a cationic
guanidinopropyl group is formed. This species is efficiently chemiexcited
(with no obvious charge transfer step) to the corresponding oxyluciferin
with a neutral amide and cationic guanidinopropyl groups. After the
“dark” chemiluminescent state, this oxyluciferin species
is converted into a bright blue-emitting fluorescent state.
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chemiluminescent mechanismLight Emitteroxyluciferin speciesdioxetanone speciesCypridina Bioluminescence Cypridina bioluminescenceCypridina Dioxetanonecationic guanidinopropyl groupFluorescent PropertiesTD-DFT approachcationic guanidinopropyl groupscharge transfer stepamide groupimidazopyrazinone scaffoldChemiluminescent DecompositionMechanistic Insightbioluminescent emitterchemiluminescent state
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