Synthesis and spin-trapping properties of a new spirolactonyl nitrone

Yongbin Han; Beatrice Tuccio; Robert Lauricella; Antal Rockenbauer; Jay L. Zweier; Frederick A. Villamena

doi:10.1021/jo702434u

Synthesis and spin-trapping properties of a new spirolactonyl nitrone

Yongbin Han, Beatrice Tuccio, Robert Lauricella, Antal Rockenbauer, Jay L. Zweier, Frederick A. Villamena

Research output: Contribution to journal › Article › peer-review

27 Scopus citations

Abstract

(Chemical Equation Presented) Spin trapping using electron paramagnetic resonance (EPR) spectroscopy is commonly employed for the identification of transient radicals in chemical and biological systems. A spirolactonyl-nitrone with rigid H-bond acceptor, 7-oxa-1-azaspiro[4.4]non-1-en-6-one 1-oxide, CPCOMPO, has been synthesized and characterized, and its spin-trapping properties were investigated. The rate of formation of CPCOMPO-O₂H was determined using competition kinetics between the superoxide/hydroperoxyl radical (O₂ ^•-/HO₂ ^•) trapping by CPCOMPO and the spontaneous dismutation of this radical in aqueous media. The rate constant of 60 M^-1·s^-1 is the highest rate constant thus far observed at neutral pH for any nitrones using the kinetic method employed. Decay kinetics were also experimentally investigated for CPCOMPO-O₂H. The effect of rigid H-bond acceptor on the stability of the CPCOMPO-O₂H were computationally rationalized and compared to that of EMPO-O₂H, which has flexible H-bond acceptor, and results show the need of a "loose" H-bond acceptor for improved adduct stability.

Original language	English (US)
Pages (from-to)	2533-2541
Number of pages	9
Journal	Journal of Organic Chemistry
Volume	73
Issue number	7
DOIs	https://doi.org/10.1021/jo702434u
State	Published - Apr 4 2008
Externally published	Yes

ASJC Scopus subject areas

Organic Chemistry

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title = "Synthesis and spin-trapping properties of a new spirolactonyl nitrone",

abstract = "(Chemical Equation Presented) Spin trapping using electron paramagnetic resonance (EPR) spectroscopy is commonly employed for the identification of transient radicals in chemical and biological systems. A spirolactonyl-nitrone with rigid H-bond acceptor, 7-oxa-1-azaspiro[4.4]non-1-en-6-one 1-oxide, CPCOMPO, has been synthesized and characterized, and its spin-trapping properties were investigated. The rate of formation of CPCOMPO-O2H was determined using competition kinetics between the superoxide/hydroperoxyl radical (O2 •-/HO2 •) trapping by CPCOMPO and the spontaneous dismutation of this radical in aqueous media. The rate constant of 60 M-1·s-1 is the highest rate constant thus far observed at neutral pH for any nitrones using the kinetic method employed. Decay kinetics were also experimentally investigated for CPCOMPO-O2H. The effect of rigid H-bond acceptor on the stability of the CPCOMPO-O2H were computationally rationalized and compared to that of EMPO-O2H, which has flexible H-bond acceptor, and results show the need of a {"}loose{"} H-bond acceptor for improved adduct stability.",

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T1 - Synthesis and spin-trapping properties of a new spirolactonyl nitrone

AU - Han, Yongbin

AU - Tuccio, Beatrice

AU - Lauricella, Robert

AU - Rockenbauer, Antal

AU - Zweier, Jay L.

AU - Villamena, Frederick A.

PY - 2008/4/4

Y1 - 2008/4/4

N2 - (Chemical Equation Presented) Spin trapping using electron paramagnetic resonance (EPR) spectroscopy is commonly employed for the identification of transient radicals in chemical and biological systems. A spirolactonyl-nitrone with rigid H-bond acceptor, 7-oxa-1-azaspiro[4.4]non-1-en-6-one 1-oxide, CPCOMPO, has been synthesized and characterized, and its spin-trapping properties were investigated. The rate of formation of CPCOMPO-O2H was determined using competition kinetics between the superoxide/hydroperoxyl radical (O2 •-/HO2 •) trapping by CPCOMPO and the spontaneous dismutation of this radical in aqueous media. The rate constant of 60 M-1·s-1 is the highest rate constant thus far observed at neutral pH for any nitrones using the kinetic method employed. Decay kinetics were also experimentally investigated for CPCOMPO-O2H. The effect of rigid H-bond acceptor on the stability of the CPCOMPO-O2H were computationally rationalized and compared to that of EMPO-O2H, which has flexible H-bond acceptor, and results show the need of a "loose" H-bond acceptor for improved adduct stability.

AB - (Chemical Equation Presented) Spin trapping using electron paramagnetic resonance (EPR) spectroscopy is commonly employed for the identification of transient radicals in chemical and biological systems. A spirolactonyl-nitrone with rigid H-bond acceptor, 7-oxa-1-azaspiro[4.4]non-1-en-6-one 1-oxide, CPCOMPO, has been synthesized and characterized, and its spin-trapping properties were investigated. The rate of formation of CPCOMPO-O2H was determined using competition kinetics between the superoxide/hydroperoxyl radical (O2 •-/HO2 •) trapping by CPCOMPO and the spontaneous dismutation of this radical in aqueous media. The rate constant of 60 M-1·s-1 is the highest rate constant thus far observed at neutral pH for any nitrones using the kinetic method employed. Decay kinetics were also experimentally investigated for CPCOMPO-O2H. The effect of rigid H-bond acceptor on the stability of the CPCOMPO-O2H were computationally rationalized and compared to that of EMPO-O2H, which has flexible H-bond acceptor, and results show the need of a "loose" H-bond acceptor for improved adduct stability.

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Synthesis and spin-trapping properties of a new spirolactonyl nitrone

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