Theoretical modulation of singlet/triplet chemiexcitation of chemiluminescent imidazopyrazinone dioxetanone via C-8-substitution

• Type: Article in International Scientific Journal
• Date: 2017

Authors

Pinto da Silva, LP (Author) FCUP; Magalhaes, CM (Author) FCUP; Crista, DMA (Author) Other; Joaquim C G E Esteves da Silva (Author) FCUP

Journal

Title: Photochemical & Photobiological Sciences

Vol. 16

Pages: 897-907

ISSN: 1474-905X

Publisher: Springer Nature

Indexing

ISI Web of Knowledge - 20 Citations

Scopus - 21 Citations

Other information

Authenticus ID: P-00N-19D

DOI: 10.1039/c7pp00012j

Abstract (EN): Coelenterazine, a member of the imidazopyrazinone class of chemiluminescent substrates, presents significant potential as a dynamic probe of reactive oxygen species in a biological environment, such as a superoxide anion, in which these species are important in cellular biology and pathology. The objective of the current study was to understand in what way the efficiency of singlet and triplet chemiexcitation could be modulated, towards a more efficient use of imidazopyrazinone-based compounds as dynamic chemiluminescent probes. To this end the thermolysis of imidazopyrazinone dioxetanone, substituted at the C-8-position with electron-donating or electron-withdrawing groups, was characterized with a theoretical approach based on density functional theory. Substituents with different electron-donating/withdrawing characters have only a limited effect on the singlet chemiexcitation of anionic dioxetanone. For neutral dioxetanone, both electron-withdrawing and weak electron-donating substituents increase singlet chemiexcitation, to the contrary of strong electron-donating groups. During their thermolysis reaction, all molecules presented regions of degeneracy with triplet states, thereby indicating the possibility of triplet chemiexcitation.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 11