Mechanistic aspects regarding the induced decomposition of hydroperoxides and silylperoxides derived from lophine

• Grant number: 16/10585-4
• Support type: Scholarships in Brazil - Doctorate
• Effective date (Start): August 01, 2016
• Effective date (End): December 31, 2021
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal researcher: Fernando Heering Bartoloni
• Grantee: Andréia Boaro
• Home Institution: Centro de Ciências Naturais e Humanas (CCNH). Universidade Federal do ABC (UFABC). Ministério da Educação (Brasil). Santo André , SP, Brazil
• Associated scholarship(s): 19/15871-3 - Light emitting arginine derivatives as tags for antimicrobial peptides, BE.EP.DR

Abstract

One of the first descriptions found in the literature about a chemiluminescent reaction is the autoxidation of lophine, reported by Radziszewski in 1877. It is postulated that the lophine reaction with oxygen in the presence of a strong base, leads to the formation of a hydroperoxide, which undergoes a base-induced cyclization generating a 1,2-dioxetane intermediate. The decomposition of this cyclic peroxide leads to the singlet excited state of an amidine, which decays to the ground state by fluorescence, emitting an intense yellow light. The oxidation reaction of lophine and its derivatives has been studied previously, but a deeper understanding about the mechanism operating in this interesting reaction is still yet to be acquired. This project proposes to carry out a detailed study of the mechanism that acts in the formation of emitting excited states for such transformation. As such, hydroperoxides with different substituents on the aromatic rings will be synthesized from the photooxygenation of their corresponding lophine derivatives. The hydroperoxides will be protected with a t-butyldimethylsilyl group, in order to obtain the silylperoxides derivatives. Also, hydroperoxides and silylperoxides containing a hydroxyl group as a substituent at the ortho, meta and para positions will be prepared. Kinetic studies of the chemiluminescence emission will be performed, inducing the decomposition of hydroperoxides with different bases and of silylperoxides with fluoride. Thus, it will be investigated the effect of substituents on the kinetics and singlet excited state formation quantum yields of the induced decomposition of these peroxides.

Scientific publications

(4)

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

BOARO, ANDREIA; REIS, ROBERTA ALBINO; SILVA, CAROLINA SANTANA; MELO, DIEGO ULYSSES; GONCALVES COSTA PINTO, ALEXANDER GARRETA; BARTOLONI, FERNANDO HEERING. Evidence for the Formation of 1,2-Dioxetane as a High-Energy Intermediate and Possible Chemiexcitation Pathways in the Chemiluminescence of Lophine Peroxides. Journal of Organic Chemistry, v. 86, n. 9, p. 6633-6647, MAY 7 2021. Web of Science Citations: 0.

BOARO, ANDREIA; AGEITOS, LUCIA; TORRES, MARCELO; BARTOLONI, FERNANDO HEERING; DE LA FUENTE-NUNEZ, CESAR. Light-Emitting Probes for Labeling Peptides. CELL REPORTS PHYSICAL SCIENCE, v. 1, n. 12 DEC 23 2020. Web of Science Citations: 1.

SOARES, ANDRESSA R.; REIS, ROBERTA A.; MELO, DIEGO U.; BOARO, ANDREIA; BARTOLONI, FERNANDO H. Better late than never! Transition state character involved in the neutral solvolysis of an oxalic ester determined by the ionizing power of ethanol/water and methanol/water mixtures. JOURNAL OF MOLECULAR LIQUIDS, v. 316, OCT 10 2020. Web of Science Citations: 0.

REIS, ROBERTA ALBINO; BOARO, ANDREIA; ORFAO, RONALDO BARROS; MELO, DIEGO ULYSSES; BARTOLONI, FERNANDO HEERING. The decomposition of triphenylimidazole-para-acetate follows specific base catalysis and can be conveniently followed by fluorescence. LUMINESCENCE, v. 34, n. 2, p. 234-242, MAR 2019. Web of Science Citations: 0.