Curcumin (Cur) is a natural polyphenol with a wide spectrum of biological activities and appealing therapeutic potential. Herein, it has been delivered by electrospray ionization as gaseous protonated species, [Cur + H] + , and as a Cu(ii) complex, [Cu(Cur - H)] + , a promising antioxidant and radical scavenger. The gas phase structures were assayed by infrared multiple photon dissociation (IRMPD) spectroscopy in both the fingerprint (800-2000 cm -1 ) and hydrogen stretching (3100-3750 cm -1 ) ranges. Comparison between the experimental features and linear IR spectra of the lowest energy structures computed at the B3LYP/6-311+G(d,p) level reveals that bare [Cu(Cur - H)] + exists in a fully planar and symmetric arrangement, where the metal interacts with the two oxygens of the syn-enolate functionality of deprotonated Cur and both OCH 3 groups are engaged in H-bonding with the ortho OH. The effect of protonation on the energetic and geometric determinants of Cur has been explored as well, revealing that bare [Cur + H] + may exist as a mixture of two close-lying isomers associated with the most stable binding motifs. The additional proton is bound to either the diketo or the keto-enol configuration of Cur, in a bent or nearly planar arrangement, respectively.

Vibrational signatures of curcumin's chelation in copper(II) complexes: An appraisal by IRMPD spectroscopy / Corinti, Davide; Maccelli, Alessandro; Chiavarino, Barbara; Maitre, Philippe; Scuderi, Debora; Bodo, Enrico; Fornarini, Simonetta; Crestoni, Maria Elisa. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - 150:16(2019). [10.1063/1.5086666]

Vibrational signatures of curcumin's chelation in copper(II) complexes: An appraisal by IRMPD spectroscopy

Corinti, Davide;Maccelli, Alessandro;Chiavarino, Barbara;Scuderi, Debora;Bodo, Enrico;Fornarini, Simonetta;Crestoni, Maria Elisa
2019

Abstract

Curcumin (Cur) is a natural polyphenol with a wide spectrum of biological activities and appealing therapeutic potential. Herein, it has been delivered by electrospray ionization as gaseous protonated species, [Cur + H] + , and as a Cu(ii) complex, [Cu(Cur - H)] + , a promising antioxidant and radical scavenger. The gas phase structures were assayed by infrared multiple photon dissociation (IRMPD) spectroscopy in both the fingerprint (800-2000 cm -1 ) and hydrogen stretching (3100-3750 cm -1 ) ranges. Comparison between the experimental features and linear IR spectra of the lowest energy structures computed at the B3LYP/6-311+G(d,p) level reveals that bare [Cu(Cur - H)] + exists in a fully planar and symmetric arrangement, where the metal interacts with the two oxygens of the syn-enolate functionality of deprotonated Cur and both OCH 3 groups are engaged in H-bonding with the ortho OH. The effect of protonation on the energetic and geometric determinants of Cur has been explored as well, revealing that bare [Cur + H] + may exist as a mixture of two close-lying isomers associated with the most stable binding motifs. The additional proton is bound to either the diketo or the keto-enol configuration of Cur, in a bent or nearly planar arrangement, respectively.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11573/1269250
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