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Electronic chemiexcitation in biological systems: bioluminescence and photochemistry in the dark

Grant number: 17/22501-2
Support type:Research Projects - Thematic Grants
Duration: October 01, 2018 - September 30, 2023
Field of knowledge:Biological Sciences - Biophysics - Radiology and Photobiology
Principal researcher:Etelvino José Henriques Bechara
Grantee:Etelvino José Henriques Bechara
Home Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
Principal researchers:Cassius Vinicius Stevani
Assoc. researchers:Anderson Garbuglio de Oliveira
Associated scholarship(s):20/04082-5 - Quenching of triplet acetone by alkylated sorbates, esterified or peptide derivatives, BP.IC
20/16000-3 - Functional characterization of candidate genes for the biological clock of Neonothopanus gardneri and its relationship with bioluminescence, BP.DD
19/26503-5 - Equisetumpyrone detection and characterization of H3H-like enzymes in plants, BP.IC
+ associated scholarships 19/26510-1 - Influence of light on growth and bioluminescence of the fungus Neonothopanus gardneri, BP.TT
19/24515-6 - Sources, targets and biological responses of triplet species and singlet oxygen: pathogenicity and quenching, BP.PD
19/21782-3 - Caffeic Acid Cycle (CAC) in fungal bioluminescence: luciferin antioxidant effect, oxyluciferin recycling and oxidative stress, BP.DD
19/12605-0 - Bioluminescence of Fungi, Millipede and Marine Organisms: Chemical and Biological Aspects, BP.PD
19/11458-4 - Generation of singlet oxygen by the oxidation of formylhydrazines found in fungi, BP.IC
19/01029-9 - Bioluminescent fungal cultures & ecological studies of the fungus-animal interaction, BP.TT
18/25842-8 - Sources, Targets and Biological Responses of Triplet Species and Singlet Oxygen: Pathogenicity and Quenching., BP.PD - associated scholarships

Abstract

Light, molecular oxygen, and free radicals are the essence of life... for the good and the evil. They provide energy and matter for living beings, but charge a high price - diseases, ageing, death -, via electron-transfer reactions and electronic photo- and chemiexcitation of molecules. Our project concerns these processes through the study of the molecular nature of living lights (bioluminescence, BL) and typical photochemical reactions that proceed in the absence of light when driven by electronically excited products ('photo'chemistry in the dark). Chemical mechanisms, biological functions and technological uses of BL fungi and marine animals will be investigated. In the BL field, we plan to elucidate the luciferin/luciferase systems, biological functions, ecological role, phylogeny, and details of mechanisms of light emission. Preliminary data point to complex coadjuvant enzymes and co-factors like hydroxylase and NAD(P)H in fungi, photoprotein and Fe(II) in the worm-like species. Phylogenetic connections among North-American, Asian, and Brazilian fungus species will be identified. Interestingly, all fungi use the polyphenol hispidin as the luciferin (3-hydroxyhispidin) precursor, which also occurs in ferns like horsetail (Equisetum sp.). BL inhibitors and activators can be harnessed to develop analytical tools for biological samples and imaging modified organisms. The puzzling occurrence of typical photoproducts in vegetal and animal tissues not exposed to light, and the detection of weakly emissive excited products (e.g., triplet carbonyls and singlet oxygen) in peroxidase-catalyzed reactions and lipoperoxidations, prompted Cilento and White to advance the "photo(bio)chemistry in the dark" theory. Triplet carbonyls are long-lived and display diradical behavior, thereby can travel across cell sites, hit diverse targets, cause chemical damage, and trigger biological responses. Among our interests are chemical damage to hemeproteins like horseradish peroxidase (HRP), cytochrome c, myoglobin, and hemoglobin when acting as peroxidases on substrates capable of generating triplet carbonyls. Methylated and long chain linear sorbate esters and peptide-derivatives (cell-penetrating peptides) will be tested as triplet quenchers in vitro and in cell cultures. Accordingly, ethyl sorbate blocks the formation of DNA pyrimidine dimers to a significant extent long after UV irradiation of melanin-rich melanocyte cultures as we have previously reported. On the other hand, we predict production of singlet oxygen and toxic aldehydes initiated by peroxynitrite Michael addition to acrolein, an air and fried food contaminant implicated in ageing-related diseases. Another probable source of singlet oxygen to be studied are formylhydrazine derivatives - potentially lethal toxins found in the mushroom genus Gyromitra - under oxidation by peroxynitrite or HRP/H2O2. The rationale underlying the latter two proposals is the intermediacy of geminal hydrogen atom-bearing vinylperoxyl and formylperoxyl radicals, the necessary condition for the singlet oxygen-generating Russell reaction. Singlet oxygen oxidizes fatty acids, proteins and DNA leading to adverse and, paradoxically, beneficial cell signaling responses. Our project will accumulate knowledge underlying the chemiexcitation field and analytical tools, and will foster international collaborations. (AU)

Articles published in Agência FAPESP Newsletter about the research grant:
Descoberto o primeiro inseto sul-americano que emite luz azul 
Descubierto el primer insecto sudamericano que emite luz azul 
First South American insect that emits blue light is discovered 
Articles published in other media outlets (69 total):
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Correio Popular (Campinas, SP): Descoberto inseto que emite luz azul (29/Sep/2019)
Estadão.com: Descoberto o primeiro inseto sul-americano que emite luz azul (18/Sep/2019)
Folha de Pernambuco online: Descoberto o primeiro inseto sul-americano que emite luz azul (18/Sep/2019)
Portal Exame: Pesquisadores descobrem 1º inseto que emite luz azul na América Latina (18/Sep/2019)
UFSCar -Universidade Federal de São Carlos: Estudo identifica sistema bioluminescente em mosquito que emite luz azul (07/Aug/2020)
Vivimetaliun: Inseto descoberto no Brasil é o primeiro encontrado na América do Sul que emite luz azul (24/Jan/2020)
Espaço Ecológico no Ar: Descoberto o primeiro inseto sul-americano que emite luz azul (29/Dec/2019)
NCYT Amazings (Espanha): Descubierto el primer insecto sudamericano que emite luz azul (07/Nov/2019)
Catalunya Vanguardista (Espanha): Primer insecto sudamericano que emite luz azul (07/Nov/2019)
El Espectador (Uruguai): Descubierto el primer insecto sudamericano que emite luz azul (06/Nov/2019)
Mundo Agropecuario (Venezuela): Se descubre el primer insecto sudamericano que emite luz azul (04/Nov/2019)
Blog Conhecimentos Gerais e Cultura: Pesquisadores brasileiros descobrem nova espécie de inseto (04/Nov/2019)
Saran Noticias e Variedades: Descoberto em São Paulo primeiro inseto sul-americano que emite luz azul (03/Nov/2019)
HypeScience: Inseto descoberto no Brasil é o primeiro encontrado na América do Sul que emite luz azul (03/Nov/2019)
FayerWayer: Descubren por primera vez un insecto que emite luz azul en Brasil (02/Nov/2019)
Phys.Org (Reino Unido): First South American insect that emits blue light is discovered (31/Oct/2019)
News Medical (Austrália): Discovery of first blue light emitting South American insect (31/Oct/2019)
Notizie Scientifiche (Itália): Scoperto nuovo moscerino le cui larve emettono luci blu in Brasile (31/Oct/2019)
Inside Ecology (Reino Unido): Discovery of first blue light emitting South American insect (31/Oct/2019)
Biotech News (Austrália): Discovery of first blue light emitting South American insect (31/Oct/2019)
Novinite.com (Bulgária): Discovery of first blue light emitting South American insect (31/Oct/2019)
Innovations Report (Alemanha): First South American insect that emits blue light is discovered (31/Oct/2019)
Bioengineer (Reino Unido): First South American insect that emits blue light is discovered (30/Oct/2019)
Science Codex: First South American insect that emits blue light is discovered (30/Oct/2019)
Scienmag Science Magazine (Reino Unido): First South American Insect That Emits Blue Light Is Discovered (30/Oct/2019)
Brightsurf: First South American insect that emits blue light is discovered (30/Oct/2019)
Career Biotech: First South American insect that emits blue light is discovered (30/Oct/2019)
Devdiscourse (Índia): Brazilian researchers discover insect in South America emitting blue light (30/Oct/2019)
7thSpace: First South American insect that emits blue light is discovered (30/Oct/2019)
Scienstack: First South American insect that emits blue light is discovered (30/Oct/2019)
Health Europa (Reino Unido): First South American insect that emits blue light is discovered (08/Oct/2019)
O Chefão da Notícia: Brasileiros descobrem inseto que emite luz azul (03/Oct/2019)
Renova Mídia: Brasileiros descobrem inseto que emite luz azul (03/Oct/2019)
Galileu online: Inseto sul-americano que emite luz azul é descoberto por brasileiros (30/Sep/2019)
ON Jornal: Descoberto o primeiro inseto sul-americano que emite luz azul (30/Sep/2019)
Central das Notícias: Cientistas descobrem inseto que emite luz azul (29/Sep/2019)
Correio Popular (Campinas, SP) online: Cientistas descobrem inseto que emite luz azul (28/Sep/2019)
Agência USP de Inovação: Descoberto o primeiro inseto sul-americano que emite luz azul (27/Sep/2019)
Jornal da USP online: Descoberto o primeiro inseto sul-americano que emite luz azul (26/Sep/2019)
Revista Ecológico online: Descoberto o primeiro inseto sul-americano que emite luz azul (25/Sep/2019)
Sou Ecológico: Descoberto o primeiro inseto sul-americano que emite luz azul (25/Sep/2019)
Noroeste Online: Descoberto o primeiro inseto sul-americano que emite luz azul (21/Sep/2019)
O Sul: Descoberto o primeiro inseto sul-americano que emite luz azul (21/Sep/2019)
O Dia (Rio de Janeiro, RJ) online: Cientistas descobrem primeiro inseto sul-americano que emite luz azul (21/Sep/2019)
O Sul online: Descoberto o primeiro inseto sul-americano que emite luz azul (20/Sep/2019)
Brasil CT&I: Descoberto o primeiro inseto sul-americano que emite luz azul (20/Sep/2019)
Espaço Ecológico no Ar: Pesquisadores descobrem 1º inseto que emite luz azul na América Latina (19/Sep/2019)
Portal Gazeta de São Carlos: Descoberto o primeiro inseto sul-americano que emite luz azul - Portal Gazeta São Carlos (19/Sep/2019)
Aventuras no Conhecimento: Descoberto o primeiro inseto sul-americano que emite luz azul (19/Sep/2019)
Gazeta do Cerrado: Pesquisadores descobrem 1º inseto que emite luz azul na América Latina | Gazeta do Cerrado | (19/Sep/2019)
Clube dos Animais: Pesquisadores descobrem 1º inseto que emite luz azul na América Latina (19/Sep/2019)
O Tempo online: Descoberto o primeiro inseto sul-americano que emite luz azul (18/Sep/2019)
Terra: Descoberto o primeiro inseto sul-americano que emite luz azul (18/Sep/2019)
Zero Hora online: Primeiro inseto sul-americano que emite luz azul é descoberto em São Paulo (18/Sep/2019)
Planeta Universitário: Descoberto o primeiro inseto sul-americano que emite luz azul (18/Sep/2019)
Esteta : Descoberto o primeiro inseto sul-americano que emite luz azul (18/Sep/2019)
Planeta online: Cientistas descobrem primeiro inseto sul-americano que emite luz azul (18/Sep/2019)
Pampulha online: Descoberto o primeiro inseto sul-americano que emite luz azul (18/Sep/2019)
O Estado (MS) online: Primeiro inseto que emite luz azul é descoberto no Brasil (18/Sep/2019)
JC Notícias (São Paulo, SP): Descoberto o primeiro inseto sul-americano que emite luz azul (18/Sep/2019)
Super Notícia 91,7 FM: Descoberto o primeiro inseto sul-americano que emite luz azul (18/Sep/2019)
Planet Earth Water Air Green Brazil: Descoberto o primeiro inseto sul-americano que emite luz azul (18/Sep/2019)
Fbi Controle Cia: Cientistas descobrem primeiro inseto sul-americano que emite luz azul (18/Sep/2019)
Farol de Notícias: Descoberto primeiro inseto que emite luz azul (18/Sep/2019)
Jornal Joseense News: Descoberto o primeiro inseto sul-americano que emite luz azul (18/Sep/2019)
Jornal Integração: Descoberto o primeiro inseto sul-americano que emite luz azul (18/Sep/2019)
O Tempo (Contagem, MG) online: Descoberto o primeiro inseto sul-americano que emite luz azul (18/Sep/2019)
Pantanal Notícias MS: Pesquisadores descobrem 1º inseto que emite luz azul na América Latina (18/Sep/2019)
Long Room (EUA): First South American insect that emits blue light is discovered (11/Feb/2019)

Scientific publications (9)
(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)
RAMOS, LUIZ D.; MANTOVANI, MARIANA C.; SARTORI, ADRIANO; DUTRA, FERNANDO; STEVANI, CASSIUS V.; BECHARA, ETELVINO J. H. Aerobic co-oxidation of hemoglobin and aminoacetone, a putative source of methylglyoxal. Free Radical Biology and Medicine, v. 166, p. 178-186, APR 2021. Web of Science Citations: 0.
MORAES, V, GABRIELA; HANNON, MARY COLLEEN; SOARES, DOUGLAS M. M.; STEVANI, V, CASSIUS; SCHULZE, ANJA; OLIVEIRA, ANDERSON G. Bioluminescence in Polynoid Scale Worms (Annelida: Polynoidae). FRONTIERS IN MARINE SCIENCE, v. 8, FEB 18 2021. Web of Science Citations: 1.
RAMOS, LUIZ D.; PRADO, FERNANDA M.; STEVANI, V, CASSIUS; DI MASCIO, PAOLO; BECHARA, ETELVINO J. H. l-Tryptophan Interactions with the Horseradish Peroxidase-Catalyzed Generation of Triplet Acetone. Photochemistry and Photobiology, v. 97, n. 2 FEB 2021. Web of Science Citations: 1.
MIRZA, JEREMY D.; MIGOTTO, ALVARO E.; YAMPOLSKY, ILIA V.; DE MORAES, GABRIELA V.; TSARKOVA, ALEKSANDRA S.; OLIVEIRA, ANDERSON G. Chaetopterus variopedatusBioluminescence: A Review of Light Emission within a Species Complex. Photochemistry and Photobiology, v. 96, n. 4, p. 768-778, JUL 2020. Web of Science Citations: 0.
VENTURA, FERNANDA F.; MENDES, LUIZ F.; OLIVEIRA, ANDERSON G.; BAZITO, REINALDO C.; BECHARA, ETELVINO J. H.; FREIRE, RENATO S.; STEVANI, V, CASSIUS. Evaluation of Phenolic Compound Toxicity Using a Bioluminescent Assay with the Fungus Gerronema viridilucens. Environmental Toxicology and Chemistry, v. 39, n. 8 JUN 2020. Web of Science Citations: 0.
GONCALVES, LETICIA C. P.; MASSARI, JULIO; LICCIARDI, SAYMON; PRADO, FERNANDA M.; LINARES, EDLAINE; KLASSEN, ALINE; TAVARES, MARINA F. M.; AUGUSTO, OHARA; DI MASCIO, PAOLO; BECHARA, ETELVINO J. H. Singlet oxygen generation by the reaction of acrolein with peroxynitrite via a 2-hydroxyvinyl radical intermediate. Free Radical Biology and Medicine, v. 152, p. 83-90, MAY 20 2020. Web of Science Citations: 0.
GALEAZZO, GABRIELA A.; MIRZA, JEREMY D.; DORR, FELIPE A.; PINTO, ERNANI; STEVANI, V, CASSIUS; LOHRMANN, KARIN B.; OLIVEIRA, ANDERSON G. Characterizing the Bioluminescence of the Humboldt Squid, Dosidicus gigas (d'Orbigny, 1835): One of the Largest Luminescent Animals in the World. Photochemistry and Photobiology, v. 95, n. 5, p. 1179-1185, SEP 2019. Web of Science Citations: 0.
FALASCHI, RAFAELA L.; AMARAL, DANILO T.; SANTOS, ISAIAS; DOMINGOS, ADAO H. R.; JOHNSON, GRANT A.; MARTINS, ANA G. S.; VIROOMAL, IMRAN B.; POMPEIA, SERGIO L.; MIRZA, JEREMY D.; OLIVEIRA, ANDERSON G.; BECHARA, ETELVINO J. H.; VIVIANI, VADIM R.; STEVANI, V, CASSIUS. Neoceroplatus betaryiensis nov. sp. (Diptera: Keroplatidae) is the first record of a bioluminescent fungus-gnat in South America. SCIENTIFIC REPORTS, v. 9, AUG 5 2019. Web of Science Citations: 0.
RAFAELA LOPES FALASCHI; GRANT A. JOHNSON; CASSIUS VINICIUS STEVANI. The new species Neoceroplatus betaryiensis nov. sp. (Diptera: Keroplatidae) from Neotropical Region. Papéis Avulsos de Zoologia (São Paulo), v. 59, p. -, 2019.

Please report errors in scientific publications list by writing to: cdi@fapesp.br.