Genistein is a naturally occurring polyphenol belonging to the family of flavonoids with estrogenic properties and proven antioxidant, anti-inflammatory, and hormonal effects. Genistein and its derivatives are involved in radical scavenging activity by way of mechanisms based on sequential proton-loss electron transfer. In view of this role, a detailed structural characterization of its bare deprotonated form, [geni-H]−, generated by electrospray ionization, has been performed by tandem mass spectrometry and infrared multiple photon dissociation (IRMPD) spectroscopy in the 800−1800 cm−1 spectral range. Quantum chemical calculations at the B3LYP/6- 311+G(d,p) level of theory were carried out to determine geometries, thermochemical data, and anharmonic vibrational properties of low-lying isomers, enabling to interpret the experimental spectrum. Evidence is gathered that the conjugate base of genistein exists as a single isomeric form, which is deprotonated at the most acidic site (7-OH) and benefits from a strong intramolecular H-bond interaction between 5-OH and the adjacent carbonyl oxygen in the most stable arrangement.

IRMPD Spectroscopy of Bare Monodeprotonated Genistein, an Antioxidant Flavonoid / Paciotti, Roberto; Chiavarino, Barbara; Coletti, Cecilia; Scuderi, Debora; Re, Nazzareno; Corinti, Davide; Rotari, Lucretia; Fornarini, Simonetta; Crestoni, Maria Elisa. - In: ACS OMEGA. - ISSN 2470-1343. - 7:23(2022), pp. 19535-19544. [10.1021/acsomega.2c01236]

IRMPD Spectroscopy of Bare Monodeprotonated Genistein, an Antioxidant Flavonoid

Barbara Chiavarino;Davide Corinti;Lucretia Rotari;Simonetta Fornarini;Maria Elisa Crestoni
2022

Abstract

Genistein is a naturally occurring polyphenol belonging to the family of flavonoids with estrogenic properties and proven antioxidant, anti-inflammatory, and hormonal effects. Genistein and its derivatives are involved in radical scavenging activity by way of mechanisms based on sequential proton-loss electron transfer. In view of this role, a detailed structural characterization of its bare deprotonated form, [geni-H]−, generated by electrospray ionization, has been performed by tandem mass spectrometry and infrared multiple photon dissociation (IRMPD) spectroscopy in the 800−1800 cm−1 spectral range. Quantum chemical calculations at the B3LYP/6- 311+G(d,p) level of theory were carried out to determine geometries, thermochemical data, and anharmonic vibrational properties of low-lying isomers, enabling to interpret the experimental spectrum. Evidence is gathered that the conjugate base of genistein exists as a single isomeric form, which is deprotonated at the most acidic site (7-OH) and benefits from a strong intramolecular H-bond interaction between 5-OH and the adjacent carbonyl oxygen in the most stable arrangement.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11573/1637712
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