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Mechanistic investigation of dehydration and deamination in photochemical formation of quinone methides


Basarić, Nikola; Škalamera, Đani; Mlinarić-Majerski, Kata; Vančik, Hrvoj; Wan, Peter
Mechanistic investigation of dehydration and deamination in photochemical formation of quinone methides // 2015 International Chemical Congres of Pacific Basin Societis
Honolulu, 2015. str. 1095-1095 (poster, međunarodna recenzija, sažetak, znanstveni)


Naslov
Mechanistic investigation of dehydration and deamination in photochemical formation of quinone methides

Autori
Basarić, Nikola ; Škalamera, Đani ; Mlinarić-Majerski, Kata ; Vančik, Hrvoj ; Wan, Peter

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
2015 International Chemical Congres of Pacific Basin Societis / - Honolulu, 2015, 1095-1095

Skup
2015 International Chemical Congres of Pacific Basin Societis

Mjesto i datum
Honolulu, Hawaii, 15-20.12.2015

Vrsta sudjelovanja
Poster

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
Quinone methide ; benzoxete ; photodehydration ; photodeamination ; laser flash photolysis ; cryochemistry ; IR spectroscopy

Sažetak
Quinone methides (QM) are reactive intermediates in photochemistry of phenols that react with proteins, 1 and DNA.2 Moreover, some classes of antitumor antibiotics exert their action on metabolic formation of QMs. Consequently, simple QMs which can be photo-generated in dehydration and deamination of suitably substituted phenols are potentially viable anticancer agents.3 Different classes of QMs have been characterized by laser flash photolysis (LFP).4 However, many mechanistic aspects of QM formation in the photo-dehydration have still not been fully understood. For example, Popik et al. claim that benzoxete (BO) is formed as an intermediate in the photo-dehydration, 5 whereas theoretical work of Meier suggests that QM should be the dominant species.6 Therefore, an investigation of the photo-dehydration mechanism under cryogenic conditions was conducted by IR spectroscopy. The results indicate that both species BO and QM are formed in the photoreaction. Photo-deamination reaction has been applied for the QM generation, but a detailed mechanistic investigation has never been conducted. An investigation of photochemical reactivity in a series of cresol derivatives 2-5 was carried out by preparative irradiations, fluorescence and LFP. The results unravel possible pathways in the excited state leading to the overall deamination. It was demonstrated by LFP that attack of nucleophiles to QM formed from 5 generates new QM species. Such reactivity is of particular importance in biological systems since it enables DNA cross-linking.

Izvorni jezik
Engleski

Znanstvena područja
Kemija



POVEZANOST RADA


Projekt / tema
HRZZ-IP-2014-09-6312 - Supramolekulska kontrola fotokemijskih reakcija eliminacije (Nikola Basarić, )

Ustanove
Institut "Ruđer Bošković", Zagreb