Mechanistic Insight into the Chemiluminescent Decomposition of Cypridina Dioxetanone and the Chemiluminescent, Fluorescent Properties of the Light Emitter of Cypridina Bioluminescence

• Type: Article in International Scientific Journal
• Date: 2019

Authors

Min, CG (Author) Other; Liu, QB (Author) Other; Leng, Y (Author) Other; Magalhaes, CM (Author) Other; Huang, SJ (Author) Other; Liu, CX (Author) Other; Yang, XK (Author) Other; da Silva, LP (Author) FCUP

Journal

Title: Journal of Chemical Information and Modeling

Vol. 59

Pages: 4393-4401

ISSN: 1549-9596

Publisher: American Chemical Society

Indexing

ISI Web of Knowledge - 14 Citations

Scopus - 13 Citations

Other information

Authenticus ID: P-00R-78Q

DOI: 10.1021/acs.jcim.9b00614

Abstract (EN): Cypridina 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.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 9