Tuning the Intramolecular Chemiexcitation of Neutral Dioxetanones by Interaction with Ionic Species

• Type: Article in International Scientific Journal
• Date: 2022-06-16

Authors

Luís Pinto da Silva (Author) FCUP; Carla M. Magalhães (Author) FCUP; Joaquim C G E Esteves da Silva (Author) FCUP

Journal

Title: Molecules

Serial No. 3 Vol. 27 No. 969

Pages: 3861-3861

ISSN: 1420-3049

Publisher: MDPI

Indexing

ISI Web of Knowledge - 4 Citations

Scopus

Associated Projects

ChemiTumorTher - Quimioluminescência Marinha como uma Terapia Anticancro de Amplo Espectro com uma Selectividade e Actividade Tumoral Melhorada

Other information

Authenticus ID: P-00W-RHC

DOI: 10.3390/molecules27123861

Abstract (EN): The intramolecular chemiexcitation of high-energy peroxide intermediates, such as dioxetanones, is an essential step in different chemi- and bioluminescent reactions. Here, we employed the Time-Dependent Density Functional Theory (TD-DFT) methodology to evaluate if and how external stimuli tune the intramolecular chemiexcitation of model dioxetanones. More specifically, we evaluated whether the strategic placement of ionic species near a neutral dioxetanone model could tune its thermolysis and chemiexcitation profile. We found that these ionic species allow for the dark catalysis of the thermolysis reaction by reducing the activation barrier to values low enough to be compatible with efficient chemi- and bioluminescent reactions. Furthermore, while the inclusion of these species negatively affected the chemiexcitation profile compared with neutral dioxetanones, these profiles appear to be at least as efficient as anionic dioxetanones. Thus, our results demonstrated that the intramolecular chemiexcitation of neutral dioxetanones can be tuned by external stimuli in such a way that their activation barriers are decreased. Thus, these results could help to reconcile findings that neutral dioxetanones could be responsible for efficient chemi-/bioluminescence, while being typically associated with high activation parameters.

Language: English

Type (Professor's evaluation): Scientific

No. of pages: 13