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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
Principal Investigator:Etelvino José Henriques Bechara
Grantee:Etelvino José Henriques Bechara
Home Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
Co-Principal Investigators:Cassius Vinicius Stevani
Assoc. researchers:Anderson Garbuglio de Oliveira
Associated scholarship(s):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

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
First South American insect that emits blue light is discovered 
Articles published in other media outlets (48 total):
More itemsLess items
Descubierto el primer insecto sudamericano que emite luz azul 
Descubierto el primer insecto sudamericano que emite luz azul 
Pesquisadores brasileiros descobrem nova espécie de inseto 
Descoberto em São Paulo primeiro inseto sul-americano que emite luz azul 
Descubren por primera vez un insecto que emite luz azul en Brasil 
First South American insect that emits blue light is discovered 
First South American insect that emits blue light is discovered 
First South American insect that emits blue light is discovered 
First South American insect that emits blue light is discovered 
First South American insect that emits blue light is discovered 
First South American insect that emits blue light is discovered 
First South American insect that emits blue light is discovered 
Brazilian researchers discover insect in South America emitting blue light 
First South American insect that emits blue light is discovered 
First South American insect that emits blue light is discovered 
Brasileiros descobrem inseto que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Inseto sul-americano que emite luz azul é descoberto por brasileiros 
Descoberto inseto que emite luz azul 
Cientistas descobrem inseto que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Pesquisadores descobrem 1º inseto que emite luz azul na América Latina 
Pesquisadores descobrem 1º inseto que emite luz azul na América Latina 
Primeiro inseto que emite luz azul é descoberto no Brasil 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Cientistas descobrem primeiro inseto sul-americano que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Pesquisadores descobrem 1º inseto que emite luz azul na América Latina 
Primeiro inseto sul-americano que emite luz azul é descoberto em São Paulo 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Descoberto primeiro inseto que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Cientistas descobrem primeiro inseto sul-americano que emite luz azul 
Descoberto o primeiro inseto sul-americano que emite luz azul 
Descoberto o primeiro inseto sul 
Pesquisadores descobrem 1º inseto que emite luz azul na América Latina 

Scientific publications
(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)
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.