Molecular Basis of the Chemiluminescence Mechanism of Luminol.

CASPT2 cancer chemiluminescence density functional calculations electron transfer reaction mechanisms

Journal

Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783

Informations de publication

Date de publication:
05 Apr 2019
Historique:
received: 27 11 2018
revised: 22 01 2019
pubmed: 6 2 2019
medline: 6 2 2019
entrez: 6 2 2019
Statut: ppublish

Résumé

Light emission from luminol is probably one of the most popular chemiluminescence reactions due to its use in forensic science, and has recently displayed promising applications for the treatment of cancer in deep tissues. The mechanism is, however, very complex and distinct possibilities have been proposed. By efficiently combining DFT and CASPT2 methodologies, the chemiluminescence mechanism has been studied in three steps: 1) luminol oxygenation to generate the chemiluminophore, 2) a chemiexcitation step, and 3) generation of the light emitter. The findings demonstrate that the luminol double-deprotonated dianion activates molecular oxygen, diazaquinone is not formed, and the chemiluminophore is formed through the concerted addition of oxygen and concerted elimination of nitrogen. The peroxide bond, in comparison to other isoelectronic chemical functionalities (-NH-NH-, -N

Identifiants

pubmed: 30720222
doi: 10.1002/chem.201805918
doi:

Types de publication

Journal Article

Langues

eng

Pagination

5202-5213

Subventions

Organisme : Ministerio de Economía, Industria y Competitividad, Gobierno de España
ID : CTQ2017-87054-C2-2-P
Organisme : Ministerio de Economía, Industria y Competitividad, Gobierno de España
ID : RYC-2015-19234
Organisme : Ministerio de Economía, Industria y Competitividad, Gobierno de España
ID : MDM-2015-0538
Organisme : Conselleria d'Educació, Investigació, Cultura i Esport
ID : PROMETEO/2016/135
Organisme : Vetenskapsrådet
ID : 2016-033989

Informations de copyright

© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Auteurs

Angelo Giussani (A)

Institut de Ciència Molecular, Universitat de València, P.O. Box 22085, València, Spain.

Pooria Farahani (P)

Department of Theoretical Chemistry & Biology, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), KTH Royal Institute of Technology, 10691, Stockholm, Sweden.

Daniel Martínez-Muñoz (D)

Department of Chemistry-Ångström Laboratory, Uppsala University, P.O. Box 538, 75121, Uppsala, Sweden.

Marcus Lundberg (M)

Department of Chemistry-Ångström Laboratory, Uppsala University, P.O. Box 538, 75121, Uppsala, Sweden.

Roland Lindh (R)

Department of Chemistry-Ångström Laboratory, Uppsala University, P.O. Box 538, 75121, Uppsala, Sweden.

Daniel Roca-Sanjuán (D)

Institut de Ciència Molecular, Universitat de València, P.O. Box 22085, València, Spain.

Classifications MeSH