Modulation of excited-state photodynamics of ESIPT probe 1′-hydroxy-2′-acetonaphthone (HAN) on interaction with bovine serum albumin

Sayed, Mhejabeen; Balayan, Jyoti; Singh, Prabhat Kumar; Pal, Haridas

doi:10.1016/j.jphotochem.2020.112651

Cited by 8 publications

(1 citation statement)

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“…Whatever the conditions (electrochemical, chemical, or photochemical conditions) described in the literature or in this study, the reduced naphthoquinone derivatives thus unambiguously correspond to the emitting species. ,, The peculiar emission properties of F-PDO with or without thiols could be thus attributed to an excited-state intramolecular photoinduced transfer (ESIPT) mechanism (keto–enol tautomerization, Figure ) induced by the presence of the benzoyl moiety and the formation of strong hydrogen bonding between the dihydronaphthoquinone core and the acyl residue (Figure ). This ESIPT process can be influenced by the nature of the solvent and has been described for closely related chemical structures such as ortho -hydroxy-acetophenone and derivatives, , 2,5-dihydroxyacetophenone, or 1-hydroxy-2-acetonaphthone, − to cite a few (Figure ).…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Photochemical Properties of Fluorescent Metabolites Generated from Fluorinated Benzoylmenadiones in Living Cells

et al. 2023

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This work describes the reactivity and properties of fluorinated derivatives (F-PD and F-PDO) of plasmodione (PD) and its metabolite, the plasmodione oxide (PDO). Introduction of a fluorine atom on the 2-methyl group markedly alters the redox properties of the 1,4-naphthoquinone electrophore, making the compound highly oxidizing and particularly photoreactive. A fruitful set of analytical methods (electrochemistry, absorption and emission spectrophotometry, and HRMS-ESI) have been used to highlight the products resulting from UV photoirradiation in the absence or presence of selected nucleophiles. With F-PDO and in the absence of nucleophile, photoreduction generates a highly reactive ortho-quinone methide (o-QM) capable of leading to the formation of a homodimer. In the presence of thiol nucleophiles such as β-mercaptoethanol, which was used as a model, o-QMs are continuously regenerated in sequential photoredox reactions generating mono- or disulfanylation products as well as various unreported sulfanyl products. Besides, these photoreduced adducts derived from F-PDO are characterized by a bright yellowish emission due to an excited-state intramolecular proton transfer (ESIPT) process between the dihydronapthoquinone and benzoyl units. In order to evidence the possibility of an intramolecular coupling of the o-QM intermediate, a synthetic route to the corresponding anthrones is described. Tautomerization of the targeted anthrones occurs and affords highly fluorescent stable hydroxyl-anthraquinones. Although probable to explain the intense visible fluorescence emission also observed in tobacco BY-2 cells used as a cellular model, these coupling products have never been observed during the photochemical reactions performed in this study. Our data suggest that the observed ESIPT-induced fluorescence most likely corresponds to the generation of alkylated products through reduction species, as demonstrated with the β-mercaptoethanol model. In conclusion, F-PDO thus acts as a novel (pro)-fluorescent probe for monitoring redox processes and protein alkylation in living cells.

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