| 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)
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