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Singlet molecular oxygen and peroxides in chemical biology


Aerobic metabolism and various toxicological and pharmacological reactions can generate "reactive" oxygen species capable of damaging biological molecules and triggering deleterious side effects. To counteract these effects, the cell is equipped with a set of enzymatic and chemical antioxidant defense lines. A balance between pro-oxidants and antioxidants constitutes the normal condition of aerobic life; an imbalance in favor of the pro-oxidants is termed "oxidative stress".Singlet molecular oxygen (1O2) has been shown to be generated in biological systems and have been implicated in cell defense mechanisms against viruses and bacteria. In addition to these effects, 1O2 can be responsible for ultraviolet A-induced activation of gene expression. Biological targets for 1O2 include unsaturated fatty acids, proteins, and DNA. However, unraveling the role of 1O2 in biological systems has been hampered by the difficulties to obtain 1O2 free from further reactive species. Our studies focus on providing the mechanism by which 1O2 and other reactive oxygen species play their physiological and pathological roles. We have been devoted to develop suitable 1O2 generators based on the thermolysis of endoperoxides. These compounds are chemically inert and have been employed as versatile sources of 1O2. Evidence has been accumulated during the last three decades on the strong implication of "reactive" oxygen species and one-electron oxidants in the generation of peroxides from several nucleobases, amino acids and unsaturated lipid components. Singlet oxygen is also a major source of peroxidation of several key cellular components. The breakdown products of the rather unstable peroxide (ROOH) as hydroperoxide precursors thus produced from exposure to endogenous or exogenous oxidizing agents may be implicated in deleterious biological effects such as cellular lethality, aging, mutagenesis and carcinogenesis. It may be added that oxidative processes to biomolecules are also involved in the etiology of other diseases including arteriosclerosis, arthritis, cataract and diabetes. The purpose of the present project is to extend our understanding of the reactions between reactive oxygen species, specifically 1O2 and ROOH with biomolecules in vitro and in vivo emphasizing the following aspects. Description of the main peroxidation reactions initiated by 1O2 and ROOH within key cellular targets including pyrimidine and purine nucleobases, several lipid components and amino acids. Studies on the molecular effects of the initial formation of the above peroxides within cellular components. Search of stable degradation products of biomolecules (ex. nucleobase) hydroperoxides that may be considered as the chemical signature of the formation of the latter unstable compounds that can be measured within cellular structure (ex. DNA, lipids, proteins). Major efforts have been devoted to the elucidation of the mechanisms of peroxidation of major cellular biomolecules including nucleic acids, lipids and proteins. Relevant peroxidation pathways are now available at least for the main components of the key cellular biomolecules although there is still a need of further studies, particularly for isolating and characterizing putative peroxides. Attempts should also be made to validate in the whole biomolecules the mechanisms of formation of peroxides that were inferred from model studies. Another relevant major topic deals with the search of molecular signature of the peroxide/1O2 formation in targeted biomolecules within cells upon exposure to oxidative conditions. It may be anticipated that gentle and sensitive mass spectrometric methods such as tandem mass spectrometry (MS/MS) in association with HPLC and the use of 18O-labeled peroxide/1O2 should constitute powerful tools for this purpose. (AU)

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Scientific publications (31)
(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)
MANO, CAMILA M.; PRADO, FERNANDA M.; MASSARI, JULIO; RONSEIN, GRAZIELLA E.; MARTINEZ, GLAUCIA R.; MIYAMOTO, SAYURI; CADET, JEAN; SIES, HELMUT; MEDEIROS, MARISA H. G.; BECHARA, ETELVINO J. H.; et al. Excited singlet molecular O-2 ((1)Delta g) is generated enzymatically from excited carbonyls in the dark. SCIENTIFIC REPORTS, v. 4, . (12/12663-1, 06/56530-4, 13/07937-8)
PERES, PATRICIA S.; VALERIO, ANDRESSA; CADENA, SILVIA M. S. C.; WINNISCHOFER, SHEILA M. B.; SCALFO, ALEXSANDRA C.; DI MASCIO, PAOLO; MARTINEZ, GLAUCIA R.. Glutathione modifies the oxidation products of 2 `-deoxyguanosine by singlet molecular oxygen. Archives of Biochemistry and Biophysics, v. 586, p. 33-44, . (12/12663-1, 13/07937-8)
RONSEIN, GRAZIELLA E.; WINTERBOURN, CHRISTINE C.; DI MASCIO, PAOLO; KETTLE, ANTHONY J.. Cross-linking methionine and amine residues with reactive halogen species. Free Radical Biology and Medicine, v. 70, p. 278-287, . (12/12663-1, 13/07937-8)
DI MASCIO, PAOLO; MARTINEZ, GLAUCIA R.; MIYAMOTO, SAYURI; RONSEIN, GRAZIELLA E.; MEDEIROS, MARISA H. G.; CADET, JEAN. Singlet molecular oxygen: Dusseldorf - Sao Paulo, the Brazilian connection. Archives of Biochemistry and Biophysics, v. 595, n. SI, p. 161-175, . (11/10048-5, 12/12663-1, 13/07937-8)
PRADO, FERNANDA M.; SCALFO, ALEXSANDRA C.; MIYAMOTO, SAYURI; MEDEIROS, MARISA H. G.; DI MASCIO, PAOLO. Generation of Singlet Molecular Oxygen by Lipid Hydroperoxides and Nitronium Ion(dagger). Photochemistry and Photobiology, v. 96, n. 3, SI, . (12/12663-1, 13/07937-8)
VALERIO, HELLEN PAULA; RAVAGNANI, FELIPE GUSTAVO; RONSEIN, GRAZIELLA ELIZA; DI MASCIO, PAOLO. A single dose of Ultraviolet-A induces proteome remodeling and senescence in primary human keratinocytes. SCIENTIFIC REPORTS, v. 11, n. 1, . (15/07768-7, 13/07937-8, 12/12663-1, 16/11430-4, 16/00696-3)
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, . (18/25842-8, 12/12663-1, 13/07937-8, 17/27059-6, 17/22501-2)
DI MASCIO, PAOLO; MARTINEZ, GLAUCIA R.; MIYAMOTO, SAYURI; RONSEIN, GRAZIELLA E.; MEDEIROS, MARISA H. G.; CADET, JEAN. Singlet Molecular Oxygen Reactions with Nucleic Acids, Lipids, and Proteins. CHEMICAL REVIEWS, v. 119, n. 3, p. 2043-2086, . (13/07937-8, 16/00696-3, 12/12663-1)
STANLEY, CHRISTOPHER P.; MAGHZAL, GHASSAN J.; AYER, ANITA; TALIB, JIHAN; GILTRAP, ANDREW M.; SHENGULE, SUDHIR; WOLHUTER, KATHRYN; WANG, YUTANG; CHADHA, PREET; SUARNA, CACANG; et al. Singlet molecular oxygen regulates vascular tone and blood pressure in inflammation. Nature, v. 566, n. 7745, p. 548+, . (12/12663-1, 13/07937-8)
GHOGARE, ASHWINI A.; DEBAZ, CIRO J.; OLIVEIRA, MARILENE SILVA; ABRAMOVA, INNA; MOHAPATRA, PRABHU P.; KWON, KITAE; GREER, EDYTA M.; PRADO, FERNANDA MANSO; VALERIO, HELLEN PAULA; DI MASCIO, PAOLO; et al. Experimental and DFT Computational Insight into Nitrosamine Photochemistry-Oxygen Matters. Journal of Physical Chemistry A, v. 121, n. 32, p. 5954-5966, . (13/07937-8, 11/10048-5, 12/12663-1)
OLIVEIRA, MARILENE SILVA; CHOROCIEJUS, GABRIEL; ANGELI, JOSE PEDRO F.; VILA VERDE, GIULIANA; AQUINO, GILBERTO L. B.; RONSEIN, GRAZIELLA E.; OLIVEIRA, MAURICIO CESAR BOF DE; BARBOSA, LIVEA F.; MEDEIROS, MARISA H. G.; GREER, ALEXANDER; et al. Heck reaction synthesis of anthracene and naphthalene derivatives as traps and clean chemical sources of singlet molecular oxygen in biological systems. PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES, v. 19, n. 11, p. 1590-1602, . (12/12663-1, 13/07937-8)
MARQUES, EMERSON FINCO; MEDEIROS, MARISA H. G.; DI MASCIO, PAOLO. Singlet oxygen-induced protein aggregation: Lysozyme crosslink formation and nLC-MS/MS characterization. Journal of Mass Spectrometry, v. 54, n. 11, p. 894-905, . (12/12663-1, 13/07937-8)
LIMA, ALEX S.; PRIETO, KATIA R.; SANTOS, CARLA S.; VALERIO, HELLEN PAULA; GARCIA-OCHOA, EVELYN Y.; HUERTA-ROBLES, AURORA; BELTRAN-GARCIA, MIGUEL J.; DI MASCIO, PAOLO; BERTOTTI, MAURO. In-vivo electrochemical monitoring of H2O2 production induced by root-inoculated endophytic bacteria in Agave tequilana leaves. BIOSENSORS & BIOELECTRONICS, v. 99, p. 108-114, . (15/02095-4, 12/12663-1, 14/22396-6, 13/07937-8)
MENONI, HERVE; DI MASCIO, PAOLO; CADET, JEAN; DIMITROV, STEFAN; ANGELOV, DIMITAR. Chromatin associated mechanisms in base excision repair - nucleosome remodeling and DNA transcription, two key players. Free Radical Biology and Medicine, v. 107, p. 159-169, . (12/12663-1, 13/07937-8)
YAGURA, TEITI; SCHUCH, ANDRE PASSAGLIA; MACHADO GARCIA, CAMILA CARRIAO; REILY ROCHA, CLARISSA RIBEIRO; MORENO, NATALIA CESTARI; FRIEDMANN ANGELI, JOSE PEDRO; MENDES, DAVI; SEVERINO, DIVINOMAR; SANCHEZ, ANGELICA BIANCHINI; DI MASCIO, PAOLO; et al. Direct participation of DNA in the formation of singlet oxygen and base damage under UVA irradiation. Free Radical Biology and Medicine, v. 108, p. 86-93, . (13/08028-1, 14/15982-6, 12/12663-1, 13/07937-8)
BELTRAN-GARCIA, MIGUEL J.; WHITE, JR., JAMES F.; PRADO, FERNANDA M.; PRIETO, KATIA R.; YAMAGUCHI, LYDIA F.; TORRES, MONICA S.; KATO, MASSUO J.; MEDEIROS, MARISA H. G.; DI MASCIO, PAOLO. Nitrogen acquisition in Agave tequilana from degradation of endophytic bacteria. SCIENTIFIC REPORTS, v. 4, . (11/10048-5, 12/12663-1, 13/07937-8)
MIYAMOTO, SAYURI; MARTINEZ, GLAUCIA R.; MEDEIROS, MARISA H. G.; DI MASCIO, PAOLO. Singlet molecular oxygen generated by biological hydroperoxides. JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY B-BIOLOGY, v. 139, n. SI, p. 24-33, . (13/07937-8, 12/12663-1)
BISPO, VANDERSON S.; DE ARRUDA CAMPOS, IVAN P.; DI MASCIO, PAOLO; MEDEIROS, MARISA H. G.. Structural Elucidation of a Carnosine-Acrolein Adduct and its Quantification in Human Urine Samples. SCIENTIFIC REPORTS, v. 6, . (11/10048-5, 12/12663-1, 13/07937-8)
SILVA, VANIA APARECIDA; PRADO, FERNANDA MANSO; ANTUNES, WERNER CAMARGOS; CARDOSO PAIVA, RITA MARCIA; GAVA FERRAO, MARIA AMELIA; ANDRADE, ALAN CARVALHO; DI MASCIO, PAOLO; LOUREIRO, MARCELO EHLERS; DAMATTA, FABIO MURILO; MIYASAKA ALMEIDA, ANDREA. Reciprocal grafting between clones with contrasting drought tolerance suggests a key role of abscisic acid in coffee acclimation to drought stress. Plant Growth Regulation, v. 85, n. 2, p. 221-229, . (12/12663-1, 13/07937-8)
CADET, JEAN; DAVIES, KELVIN J. A.; MEDEIROS, MARISA H. G.; DI MASCIOD, PAOLO; RICHARD WAGNER, J.. Formation and repair of oxidatively generated damage in cellular DNA. Free Radical Biology and Medicine, v. 107, p. 13-34, . (12/12663-1, 13/07937-8)
KASKOVA, ZINAIDA M.; DORR, FELIPE A.; PETUSHKOV, VALENTIN N.; PURTOV, KONSTANTIN V.; TSARKOVA, ALEKSANDRA S.; RODIONOVA, NATALJA S.; MINEEV, KONSTANTIN S.; GUGLYA, ELENA B.; KOTLOBAY, ALEXEY; BALEEVA, NADEZHDA S.; et al. Mechanism and color modulation of fungal bioluminescence. SCIENCE ADVANCES, v. 3, n. 4, . (13/07914-8, 10/11578-5, 13/16885-1, 13/07937-8, 14/14866-2, 12/12663-1)
MACEDO-RAYGOZA, GLORIA M.; VALDEZ-SALAS, BENJAMIN; PRADO, FERNANDA M.; PRIETO, KATIA R.; YAMAGUCHI, LYDIA F.; KATO, MASSUO J.; CANTO-CANCHE, BLONDY B.; CARRILLO-BELTRAN, MONICA; DI MASCIO, PAOLO; WHITE, JAMES F.; et al. Enterobacter cloacae, an Endophyte That Establishes a Nutrient-Transfer Symbiosis With Banana Plants and Protects Against the Black Sigatoka Pathogen. FRONTIERS IN MICROBIOLOGY, v. 10, . (12/12663-1, 13/07937-8, 14/50316-7)
MARQUES, EMERSON FINCO; MEDEIROS, MARISA H. G.; DI MASCIO, PAOLO. Lysozyme oxidation by singlet molecular oxygen: Peptide characterization using [O-18]-labeling oxygen and nLC-MS/MS. Journal of Mass Spectrometry, v. 52, n. 11, p. 739-751, . (12/12663-1, 13/07937-8)
GENARO-MATTOS, THIAGO C.; QUEIROZ, RAPHAEL F.; CUNHA, DANIELA; APPOLINARIO, PATRICIA P.; DI MASCIO, PAOLO; NANTES, ISELI L.; AUGUSTO, OHARA; MIYAMOTO, SAYURI. Cytochrome c Reacts with Cholesterol Hydroperoxides To Produce Lipid- and Protein-Derived Radicals. BIOCHEMISTRY, v. 54, n. 18, p. 2841-2850, . (08/57721-3, 12/12663-1, 13/07937-8)
KAWAI, CINTIA; FERREIRA, JULIANA C.; BAPTISTA, MAURICIO S.; NANTES, ISELI L.. Not Only Oxidation of Cardiolipin Affects the Affinity of Cytochrome c for Lipid Bilayers. Journal of Physical Chemistry B, v. 118, n. 41, p. 11863-11872, . (12/12663-1, 12/07456-7, 12/50680-5, 13/07937-8)
MARTINEZ, GLAUCIA REGINA; BRUM, HULYANA; SASSAKI, GUILHERME LANZI; DE SOUZA, LAURO MERA; DE MELO LOUREIRO, ANA PAULA; GENNARI DE MEDEIROS, MARISA HELENA; DI MASCIO, PAOLO. Oxidation of 1-N-2-etheno-2'-deoxyguanosine by singlet molecular oxygen results in 2'-deoxyguanosine: a pathway to remove exocyclic DNA damage?. Biological Chemistry, v. 399, n. 8, p. 859-867, . (12/12663-1, 13/07937-8)
BELTRAN-GARCIA, MIGUEL J.; PRADO, FERNANDA M.; OLIVEIRA, MARILENE S.; ORTIZ-MENDOZA, DAVID; SCALFO, ALEXSANDRA C.; PESSOA, JR., ADALBERTO; MEDEIROS, MARISA H. G.; WHITE, JAMES F.; DI MASCIO, PAOLO. Singlet Molecular Oxygen Generation by Light-Activated DHN-Melanin of the Fungal Pathogen Mycosphaerella fijiensis in Black Sigatoka Disease of Bananas. PLoS One, v. 9, n. 3, . (12/12663-1, 06/56530-4, 13/07937-8)
PUEYO, MANUEL T.; MUTAFCI, BRUNA A.; SOTO-ARRIAZA, MARCO A.; DI MASCIO, PAOLO; CARMONA-RIBEIRO, ANA M.. The Self-Assembly of a Cyclic Lipopeptides Mixture Secreted by a B. megaterium Strain and Its Implications on Activity against a Sensitive Bacillus Species. PLoS One, v. 9, n. 5, . (11/00046-5, 12/12663-1, 06/56530-4, 13/07937-8)
OLIVEIRA, MARLENE SILVA; GHOGARE, ASH-WINI A.; ABRAMOVA, INNA; GREER, EDYTA M.; PRADO, FERNANDA MANSO; DI MASCIO, PAOLO; GREER, ALEXANDER. Mechanism of Photochemical O-Atom Exchange in Nitrosamines with Molecular Oxygen. Journal of Organic Chemistry, v. 80, n. 12, p. 6119-6127, . (12/12663-1, 13/07937-8)
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, . (19/24515-6, 17/22501-2, 12/12663-1, 13/07937-8)
COSTA, ROGERIO F.; OLIVEIRA, MARILENE S.; AGUIAR, ANTONIO S. N.; CUSTODIO, JEAN M. F.; DI MASCIO, PAOLO; SABINO, JOSE R.; VERDE, GIULIANA V.; PERBONE DE SOUZA, JOAO CARLOS; SANTIN, LAURIANE G.; CAMARGO, ADEMIR J.; et al. Synthesis and Structural Studies of Two New Anthracene Derivatives. CRYSTALS, v. 11, n. 8, . (13/07937-8, 12/12663-1)

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