Synthesis and properties of a series of β-cyclodextrin/nitrone spin traps for improved superoxide detection

Florent Poulhès, Egon Rizzato, Patrick Bernasconi, Roselyne Rosas, Stéphane Viel, Laszlo Jicsinszky, A. Rockenbauer, David Bardelang, Didier Siri, Anouk Gaudel-Siri, Hakim Karoui, Micaël Hardy, Olivier Ouari

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Three new DEPMPO-based spin traps have been designed and synthesized for improved superoxide detection, each carrying a cyclodextrin (CD) moiety but with a different alkyl chain on the phosphorus atom or with a long spacer arm. EPR spectroscopy allowed us to estimate the half-life of the superoxide spin adducts which is close to the value previously reported for CD-DEPMPO (t1/2 ≈ 50-55 min under the conditions investigated). The spectra are typical of superoxide adducts (almost no features of the HO adduct that usually forms with time for other nitrone spin traps such as DMPO) and we show that at 250 μM, the new spin trap enables the reliable detection of superoxide by 1 scan at the position opposite to the corresponding spin trap without the CD moiety. The resistance of the spin adducts to a reduction process has been evaluated, and the superoxide spin adducts are sensitive to ascorbate and glutathione (GSH), but not to glutathione peroxidase/GSH, reflecting the exposed nature of the nitroxide moiety to the bulk solvent. To understand these results, 2D-ROESY NMR studies and molecular dynamics pointed to a shallow or surface self-inclusion of the nitrone spin traps and of nitroxide spin adducts presumably due to the high flexibility of the permethyl-β-CD rim.

Original languageEnglish
Pages (from-to)6358-6366
Number of pages9
JournalOrganic and Biomolecular Chemistry
Volume15
Issue number30
DOIs
Publication statusPublished - Jan 1 2017

Fingerprint

inorganic peroxides
Cyclodextrins
Superoxides
traps
adducts
synthesis
glutathione
Molecular Dynamics Simulation
Glutathione Peroxidase
Phosphorus
Glutathione
Paramagnetic resonance
Half-Life
Molecular dynamics
Spectrum Analysis
Nuclear magnetic resonance
nitrones
Spectroscopy
Atoms
rims

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

Poulhès, F., Rizzato, E., Bernasconi, P., Rosas, R., Viel, S., Jicsinszky, L., ... Ouari, O. (2017). Synthesis and properties of a series of β-cyclodextrin/nitrone spin traps for improved superoxide detection. Organic and Biomolecular Chemistry, 15(30), 6358-6366. https://doi.org/10.1039/c7ob00961e

Synthesis and properties of a series of β-cyclodextrin/nitrone spin traps for improved superoxide detection. / Poulhès, Florent; Rizzato, Egon; Bernasconi, Patrick; Rosas, Roselyne; Viel, Stéphane; Jicsinszky, Laszlo; Rockenbauer, A.; Bardelang, David; Siri, Didier; Gaudel-Siri, Anouk; Karoui, Hakim; Hardy, Micaël; Ouari, Olivier.

In: Organic and Biomolecular Chemistry, Vol. 15, No. 30, 01.01.2017, p. 6358-6366.

Research output: Contribution to journalArticle

Poulhès, F, Rizzato, E, Bernasconi, P, Rosas, R, Viel, S, Jicsinszky, L, Rockenbauer, A, Bardelang, D, Siri, D, Gaudel-Siri, A, Karoui, H, Hardy, M & Ouari, O 2017, 'Synthesis and properties of a series of β-cyclodextrin/nitrone spin traps for improved superoxide detection', Organic and Biomolecular Chemistry, vol. 15, no. 30, pp. 6358-6366. https://doi.org/10.1039/c7ob00961e
Poulhès, Florent ; Rizzato, Egon ; Bernasconi, Patrick ; Rosas, Roselyne ; Viel, Stéphane ; Jicsinszky, Laszlo ; Rockenbauer, A. ; Bardelang, David ; Siri, Didier ; Gaudel-Siri, Anouk ; Karoui, Hakim ; Hardy, Micaël ; Ouari, Olivier. / Synthesis and properties of a series of β-cyclodextrin/nitrone spin traps for improved superoxide detection. In: Organic and Biomolecular Chemistry. 2017 ; Vol. 15, No. 30. pp. 6358-6366.
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