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Zn(II) complexation promotes isomerization and oxidative rearrangements of naringenin: evidence from IR ion spectroscopy and DFT calculations.

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Title: Zn(II) complexation promotes isomerization and oxidative rearrangements of naringenin: evidence from IR ion spectroscopy and DFT calculations.
Authors: Rotari, Lucretia1 (AUTHOR), Vergine, Valeria1 (AUTHOR), Berden, Giel2,3 (AUTHOR), Oomens, Jos2,3 (AUTHOR), Chiavarino, Barbara1 (AUTHOR) barbara.chiavarino@uniroma1.it, Corinti, Davide1 (AUTHOR) davide.corinti@uniroma1.it, Crestoni, Maria Elisa1 (AUTHOR)
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. 3/31/2026, Vol. 55 Issue 13, p5290-5300. 11p.
Subjects: Zinc compounds, Isomerization, Chemical reactions, Mass spectrometry, Infrared spectroscopy, Oxidation-reduction reaction, Density functional theory
Abstract: Flavonoids are widespread natural polyphenols whose biological activity is closely connected to their ability to coordinate essential transition metals and modulate redox processes. In particular, complexation with metal ions such as Zn(II) can profoundly influence their structural, chemical, and antioxidant properties, with implications for metal trafficking and biological function. In this work, we combine tandem mass spectrometry, infrared multiple photon dissociation (IRMPD) spectroscopy, and density functional theory calculations to elucidate the gas-phase structures and dissociation pathways of Zn(II) complexes with the conjugate base of naringenin (Nar) and its structural chalcone (ChNar) isomer. IRMPD spectra of [Zn(Nar-H)]+ reveal a well-defined coordination motif involving the O4 and O5 oxygen atoms of the flavanone scaffold. Notably, the Zn complex of naringenin chalcone displays an identical spectroscopic fingerprint, suggesting Zn-assisted isomerization of the chalcone into the naringenin form upon metal coordination. When activated, both complexes dissociate to form a fragment at m/z 271, corresponding to a formally oxidized naringenin species by hydride loss. Spectroscopic characterization of this product suggests a mixture of protonated apigenin and genistein isomers. Mechanistic insight from calculated potential energy surfaces supports this evidence, demonstrating how metal coordination can promote isomerization reactions. Overall, this study highlights the multifaceted role of Zn(II) in directing flavonoid reactivity and redox chemistry and underscores the potential of IRMPD spectroscopy to unravel metal-mediated transformations in bioinorganic systems. [ABSTRACT FROM AUTHOR]
Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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Items – Name: Title
  Label: Title
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  Data: Zn(II) complexation promotes isomerization and oxidative rearrangements of naringenin: evidence from IR ion spectroscopy and DFT calculations.
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  Data: <searchLink fieldCode="AR" term="%22Rotari%2C+Lucretia%22">Rotari, Lucretia</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Vergine%2C+Valeria%22">Vergine, Valeria</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Berden%2C+Giel%22">Berden, Giel</searchLink><relatesTo>2,3</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Oomens%2C+Jos%22">Oomens, Jos</searchLink><relatesTo>2,3</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Chiavarino%2C+Barbara%22">Chiavarino, Barbara</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> barbara.chiavarino@uniroma1.it</i><br /><searchLink fieldCode="AR" term="%22Corinti%2C+Davide%22">Corinti, Davide</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> davide.corinti@uniroma1.it</i><br /><searchLink fieldCode="AR" term="%22Crestoni%2C+Maria+Elisa%22">Crestoni, Maria Elisa</searchLink><relatesTo>1</relatesTo> (AUTHOR)
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  Data: <searchLink fieldCode="JN" term="%22Dalton+Transactions%3A+An+International+Journal+of+Inorganic+Chemistry%22">Dalton Transactions: An International Journal of Inorganic Chemistry</searchLink>. 3/31/2026, Vol. 55 Issue 13, p5290-5300. 11p.
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  Data: <searchLink fieldCode="DE" term="%22Zinc+compounds%22">Zinc compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Isomerization%22">Isomerization</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+reactions%22">Chemical reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Mass+spectrometry%22">Mass spectrometry</searchLink><br /><searchLink fieldCode="DE" term="%22Infrared+spectroscopy%22">Infrared spectroscopy</searchLink><br /><searchLink fieldCode="DE" term="%22Oxidation-reduction+reaction%22">Oxidation-reduction reaction</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functional+theory%22">Density functional theory</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: Flavonoids are widespread natural polyphenols whose biological activity is closely connected to their ability to coordinate essential transition metals and modulate redox processes. In particular, complexation with metal ions such as Zn(II) can profoundly influence their structural, chemical, and antioxidant properties, with implications for metal trafficking and biological function. In this work, we combine tandem mass spectrometry, infrared multiple photon dissociation (IRMPD) spectroscopy, and density functional theory calculations to elucidate the gas-phase structures and dissociation pathways of Zn(II) complexes with the conjugate base of naringenin (Nar) and its structural chalcone (ChNar) isomer. IRMPD spectra of [Zn(Nar-H)]+ reveal a well-defined coordination motif involving the O4 and O5 oxygen atoms of the flavanone scaffold. Notably, the Zn complex of naringenin chalcone displays an identical spectroscopic fingerprint, suggesting Zn-assisted isomerization of the chalcone into the naringenin form upon metal coordination. When activated, both complexes dissociate to form a fragment at m/z 271, corresponding to a formally oxidized naringenin species by hydride loss. Spectroscopic characterization of this product suggests a mixture of protonated apigenin and genistein isomers. Mechanistic insight from calculated potential energy surfaces supports this evidence, demonstrating how metal coordination can promote isomerization reactions. Overall, this study highlights the multifaceted role of Zn(II) in directing flavonoid reactivity and redox chemistry and underscores the potential of IRMPD spectroscopy to unravel metal-mediated transformations in bioinorganic systems. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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RecordInfo BibRecord:
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        Value: 10.1039/d5dt03119b
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      – Code: eng
        Text: English
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        PageCount: 11
        StartPage: 5290
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      – SubjectFull: Zinc compounds
        Type: general
      – SubjectFull: Isomerization
        Type: general
      – SubjectFull: Chemical reactions
        Type: general
      – SubjectFull: Mass spectrometry
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      – SubjectFull: Infrared spectroscopy
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      – SubjectFull: Oxidation-reduction reaction
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      – SubjectFull: Density functional theory
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      – TitleFull: Zn(II) complexation promotes isomerization and oxidative rearrangements of naringenin: evidence from IR ion spectroscopy and DFT calculations.
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            NameFull: Rotari, Lucretia
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            – D: 31
              M: 03
              Text: 3/31/2026
              Type: published
              Y: 2026
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