New tools for the study of electron transfer reactions in PS II model systems

• Grant number: 12/13807-7
• Support Opportunities: Regular Research Grants
• Start date: November 01, 2012
• End date: October 31, 2014
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Organic Chemistry
• Principal Investigator: Fernando Heering Bartoloni
• Grantee: Fernando Heering Bartoloni
• Host Institution: Centro de Ciências Naturais e Humanas (CCNH). Universidade Federal do ABC (UFABC). Ministério da Educação (Brasil). Santo André , SP, Brazil

Abstract

Electron transfer (ET) reactions play a key role in many biological transformations. When an ET is coupled with a proton transfer (PT), such a reaction is named proton coupled electron transfer (PCET). The PCET mechanism is adequate to rationalize redox reactions that occur in many protein machines. At the photosystem II (PS II) of photosynthesis, the transfer of one electron from a tyrosine residue (Tyr161) to the P680+ cofactor occurs coupled to a PT from Tyr161 to a hydrogen-bonded histidine residue (His199). Model systems that mimic the Tyr161/His199 pair consist, commonly, of a phenolic ring containing an aminomethyl group (-CH2NR2) at the orto position. Studies regarding the electrochemical oxidation of such systems, supplemented by kinetic isotope effect assays, led to a better understanding of thermodynamic and kinetic aspects involved in PCET reactions. This project proposes the preparation of novel 2-(pyrrolidinylmethyl)phenolic compounds derived from 4-byphenylol, as well as containing anthracenic and aryltriazolic moieties. Their oxidation, in order to study PCET phenomena, will be performed through the chemiluminescent peroxyoxalate reaction, once that it was proven that an ET occurs at the rate limiting step of the mechanism of excited states generation of this reaction. Such method, never applied before for the study of PCET reactions, allows the acquisition of kinetic information directly from light emission measurements and enables the correlation between structural aspects of the 2-(pyrrolidinylmethyl)phenolic derivative and the electron transfer efficiency. Therefore, there is the intention of expanding the current set of tools used on the study of PS II model systems. (AU)

Scientific publications

(18)

(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)

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. (12/13807-7, 16/10585-4)

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. (13/17332-6, 12/02428-5, 11/17587-9, 12/13807-7)

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. (14/14866-2, 14/22136-4, 12/13807-7, 12/02428-5)

ORFAO, JR., RONALDO BARROS; ALVES, JESSICA; BARTOLONI, FERNANDO HEERING. Spectroscopic Studies on the Interaction of Metallic Ions with an Imidazolyl-Phenolic System. Journal of Fluorescence, v. 26, n. 4, p. 1373-1380, JUL 2016. (13/17332-6, 14/05813-2, 12/13807-7)

CARNEIRO, LEONARDO M.; BARTOLONI, FERNANDO H.; ANGOLINI, CELIO F. F.; KEPPLER, ARTUR F.. Solvent-free synthesis of nitrone-containing template as a chemosensor for selective detection of Cu(II) in water. SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, v. 267, n. 2, FEB 15 2022. (12/07717-5, 12/13807-7)

KHALID, MUHAMMAD; SOUZA JR, SERGIO P.; CABELLO, MAIDILEYVIS C.; BARTOLONI, FERNANDO H.; CISCATO, LUIZ FRANCISCO M. L.; BASTOS, ERICK L.; EL SEOUD, OMAR A. A.; BAADER, WILHELM J.. Solvent polarity influence on chemiexcitation efficiency of inter and intramolecular electron-transfer catalyzed chemiluminescence. JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, v. 433, p. 11-pg., 2022-12-01. (14/22136-4, 22/02183-4, 12/13807-7)

DE CARVALHO, FABRICIO; COUTINHO-NETO, MAURICIO D.; BARTOLONI, FERNANDO H.; HOMEM-DE-MELLO, PAULA. Substitution by tert-butyl groups facilitates excited state proton transfer in hydroxylated triphenylimidazole frameworks more than it does for oxazole and thiazole analogs. ARKIVOC, n. 2, p. 61+, 2020. (12/13807-7, 17/23416-9)

AUGUSTO, FELIPE A.; BARTOLONI, FERNANDO H.; PAGANO, ANA PAULA E.; BAADER, WILHELM J.. Mechanistic Study of the Peroxyoxalate System in Completely Aqueous Carbonate Buffer. Photochemistry and Photobiology, v. 97, n. 2, NOV 2020. (14/22136-4, 12/13807-7)

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. (12/13807-7, 14/05813-2, 16/10585-4)

AUGUSTO, FELIPE A.; BARTOLONI, FERNANDO H.; CABELLO, MAIDILEYVIS C.; DOS SANTOS, ANA PAULA F.; BAADER, WILHELM J.. Kinetic studies on 2,6-lutidine catalyzed peroxyoxalate chemiluminescence in organic and aqueous medium: Evidence for general base catalysis. JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, v. 382, SEP 1 2019. (14/22136-4, 12/13807-7)

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. (12/02428-5, 12/13807-7)

BOARO, ANDREIA; BARTOLONI, FERNANDO HEERING. Peroxyoxalate High-Energy Intermediate is Efficiently Decomposed by the Catalyst Imidazole. Photochemistry and Photobiology, v. 92, n. 4, p. 546-551, JUL-AUG 2016. (12/13807-7)

DE CARVALHO, FABRICIO; COUTINHO NETO, MAURICIO D.; BARTOLONI, FERNANDO H.; HOMEM-DE-MELLO, PAULA. Density Functional Theory Applied to Excited State Intramolecular Proton Transfer in Imidazole-, Oxazole-, and Thiazole-Based Systems. Molecules, v. 23, n. 5, MAY 2018. (17/23416-9, 12/13807-7)

ORFAO, JR., RONALDO B.; DE CARVALHO, FABRICIO; HOMEM-DE-MELLO, PAULA; BARTOLONI, FERNANDO H.. On the Fluorescent, Steric and Electronic Factors Affecting the Detection of Metallic Ions Using an Imidazolyl-Phenolic Derived Fluorescent Probe. Journal of the Brazilian Chemical Society, v. 28, n. 10, p. 1896-1904, OCT 2017. (14/05813-2, 12/13807-7)

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. (12/02428-5, 12/13807-7)

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. (12/13807-7, 19/15871-3, 16/10585-4)

CABELLO, MAIDILEYVIS C.; BARTOLONI, FERNANDO H.; BAADER, WILHELM J.. An Update on General Chemiexcitation Mechanisms in Cyclic Organic Peroxide Decomposition and the Chemiluminescent Peroxyoxalate Reaction in Aqueous Media(1). Photochemistry and Photobiology, v. N/A, p. 16-pg., 2022-08-03. (22/02183-4, 12/13807-7, 14/22136-4)

DE CARVALHO, FABRICIO; COUTINHO-NETO, MAURICIO D.; BARTOLONI, FERNANDO H.; HOMEM-DE-MELLO, PAULA. Substitution by tert-butyl groups facilitates excited state proton transfer in hydroxylated triphenylimidazole frameworks more than it does for oxazole and thiazole analogs. ARKIVOC, v. N/A, p. 31-pg., 2020-01-01. (12/13807-7, 17/23416-9)