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Cyclic organic peroxides: synthesis and mechanism of reduction

Abstract

The fenton-like reductive cleavage of organic peroxides by FeII species is a chemical reaction whose mechanistic pathway has not been yet fully understood. However, it is known that there is production of radical species centered at both the oxygen and carbon. The mechanism should therefore involve a ²-scission after the formation of the initial oxyradicals through a still unknown way. This research project suggests the synthesis of cyclic peroxides of the classes 1,2-dioxetane and 1,2,4-trioxolane, and the mechanistic study of the reductive cleavage of those peroxides by FeII, from thermodynamic and kinetic studies backed by reaction products determination by direct and indirect methods. The evaluation of the generating capacity of radicalar species from the reductive cleavage reaction will be done according to the structure of those formed species and their yields, and the peroxides will be tested against Plasmodium microorganisms. The mechanism of action of those peroxidic drugs involve the reductive cleavage of the peroxide by a free heme group inside the Plasmodium parasite, which results in the formation of carbon-centered radicals, that can attack and alkylate biomolecules that are vital to the survival of the parasite, which is destroyed or inactivated. The determination of the operating mechanism and the energetics of cyclic peroxides made in this project will be correlated to the antimalarial activity of those peroxides. (AU)

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Scientific publications (13)
(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)
LOPES, NICOLAS S.; CISCATO, LUIZ FRANCISCO M. L. Kinetic parameters for the reaction of 1,2,4-trioxolanes and artemisinin with iron(II): New evidence for the source of antimalarial activity. CHEMICAL BIOLOGY & DRUG DESIGN, v. 91, n. 1, p. 328-331, JAN 2018. Web of Science Citations: 1.
SALATINO, CARLA T.; MELO, DIEGO U.; YOSHITAKE, ARIANE M.; SGARBI, LUCAS S.; HOMEM-DE-MELLO, PAULA; BARTOLONI, FERNANDO H.; CISCATO, LUIZ F. M. L. Mechanistic model for the firefly luciferin regeneration in biomimetic conditions: a model for the in vivo process?. ORGANIC & BIOMOLECULAR CHEMISTRY, v. 15, n. 16, p. 3479-3484, APR 28 2017. Web of Science Citations: 2.
SILVA, ADRIANA F.; OLIVEIRA, JR., VANI X.; SILVA, LEANDRO S.; PINHEIRO, ANA A. S.; CISCATO, LUIZ F. M. L. Antiplasmodial activity of alkyl-substituted 1,2-dioxetanes against Plasmodium falciparum. Bioorganic & Medicinal Chemistry Letters, v. 26, n. 20, p. 5007-5008, OCT 15 2016. Web of Science Citations: 1.
LOPES, NICOLAS S.; YOSHITAKE, ARIANE M.; SILVA, ADRIANA F.; OLIVEIRA, JR., VANI X.; SILVA, LEANDRO S.; PINHEIRO, ANA A. S.; CISCATO, LUIZ FRANCISCO M. L. Antimalarial Effect of 3-Methoxy-1,2-Dioxetanes on the Erythrocytic Cycle of Plasmodium falciparum. CHEMICAL BIOLOGY & DRUG DESIGN, v. 86, n. 6, p. 1373-1377, DEC 2015. Web of Science Citations: 6.
KHALID, MUHAMMAD; OLIVEIRA, MARCELO A.; SOUZA, JR., SERGIO P.; CISCATO, LUIZ F. M. L.; BARTOLONI, FERNANDO H.; BAADER, WILHELM J. Efficiency of intermolecular chemiluminescence systems lacks significant solvent cavity effect in binary toluene/diphenylmethane mixtures. JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, v. 312, p. 81-87, NOV 1 2015. Web of Science Citations: 8.
BARTOLONI, FERNANDO HEERING; DE OLIVEIRA, MARCELO ALMEIDA; MONTEIRO LEITE CISCATO, LUIZ FRANCISCO; AUGUSTO, FELIPE ALBERTO; BASTOS, ERICK LEITE; BAADER, WILHELM JOSEF. Chemiluminescence Efficiency of Catalyzed 1,2-Dioxetanone Decomposition Determined by Steric Effects. Journal of Organic Chemistry, v. 80, n. 8, p. 3745-3751, APR 17 2015. Web of Science Citations: 19.
ALVES, J.; BOARO, A.; DA SILVA, J. S.; FERREIRA, T. L.; KESLAREK, V. B.; CABRAL, C. A.; ORFAO, JR., R. B.; CISCATO, L. F. M. L.; BARTOLONI, F. H. Lophine derivatives as activators in peroxyoxalate chemiluminescence. PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES, v. 14, n. 2, p. 320-328, 2015. Web of Science Citations: 8.
KHALID, MUHAMMAD; SOUZA, JR., SERGIO P.; CISCATO, LUIZ F. M. L.; BARTOLONI, FERNANDO H.; BAADER, WILHELM J. Solvent viscosity influence on the chemiexcitation efficiency of inter and intramolecular chemiluminescence systems. PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES, v. 14, n. 7, p. 1296-1305, 2015. Web of Science Citations: 10.
SCHRAMM, STEFAN; MONTEIRO LEITE CISCATO, LUIZ FRANCISCO; OESAU, PASCAL; KRIEG, REIMAR; RICHTER, JAN FRANK; NAVIZET, ISABELLE; ROCA-SANJUAN, DANIEL; WEISS, DIETER; BECKERT, RAINER. Investigations on the synthesis and chemiluminescence of novel 2-coumaranones - II. ARKIVOC, n. 5, p. 44-59, 2015. Web of Science Citations: 11.
WUERFEL, HENDRYK; CISCATO, LUIZ FRANCISCO MONTEIRO LEITE; WEISS, DIETER; GOERLS, HELMAR; BECKERT, RAINER. Synthesis of Extended Chromophores Derived From 5,5-Dimethyloxyluciferin by Barton-Kellogg Methodology. SYNTHESIS-STUTTGART, v. 46, n. 8, p. 1114-1120, APR 2014. Web of Science Citations: 0.
CISCATO, LUIZ FRANCISCO M. L.; BARTOLONI, FERNANDO H.; COLAVITE, ALINE S.; WEISS, DIETER; BECKERT, RAINER; SCHRAMM, STEFAN. Evidence supporting a 1,2-dioxetanone as an intermediate in the benzofuran-2(3H)-one chemiluminescence. PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES, v. 13, n. 1, p. 32-37, 2014. Web of Science Citations: 18.
DE OLIVEIRA, MARCELO ALMEIDA; BARTOLONI, FERNANDO HEERING; AUGUSTO, FELIPE ALBERTO; MONTEIRO LEITE CISCATO, LUIZ FRANCISCO; BASTOS, ERICK LEITE; BAADER, WILHELM JOSEF. Revision of Singlet Quantum Yields in the Catalyzed Decomposition of Cyclic Peroxides. Journal of Organic Chemistry, v. 77, n. 23, p. 10537-10544, DEC 7 2012. Web of Science Citations: 38.
BARTOLONI, FERNANDO H.; DE OLIVEIRA, MARCELO A.; AUGUSTO, FELIPE A.; CISCATO, LUIZ FRANCISCO M. L.; BASTOS, ERICK L.; BAADER, WILHELM J. Synthesis of Unstable Cyclic Peroxides for Chemiluminescence Studies. Journal of the Brazilian Chemical Society, v. 23, n. 11, p. 2093-2103, NOV 2012. Web of Science Citations: 13.

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