Singlet oxygen reactions with 9,10-diphenylanthracene peroxide

Wasserman, Harry H.; Scheffer, John R.; Cooper, John O.

doi:10.1021/ja00769a034

Cited by 157 publications

(69 citation statements)

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“…By using well established analytical procedures, an aqueous alkaline solution (pH Ϸ13) of peroxynitrite was allowed to react in separate but parallel experiments with two chemical traps, one specific for singlet oxygen and one specific for the nitroxyl anion, NO Ϫ . Singlet oxygen was trapped as the transannular peroxide (DPAO 2 ) of 9,10-diphenylanthracene (DPA) (25)(26)(27), and the nitroxyl anion was trapped as nitrosylhemoglobin (HbNO) in aqueous solutions of methemoglobin (MetHb) (28), both with very high yields. The effects of bicarbonate ions on the yields of NO …”

mentioning

confidence: 99%

The decomposition of peroxynitrite to nitroxyl anion (NO ⁻ ) and singlet oxygen in aqueous solution

Khan

Kovacic

Kolbanovskiy

et al. 2000

Proc. Natl. Acad. Sci. U.S.A.

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The mechanism of decomposition of peroxynitrite (OONO ؊ ) in aqueous sodium phosphate buffer solution at neutral pH was investigated. The OONO ؊ was synthesized by directly reacting nitric oxide with superoxide anion at pH 13. The hypothesis was explored that OONO ؊ , after protonation at pH 7.0 to HOONO, decomposes into 1 O2 and HNO according to a spin-conserved unimolecular mechanism. Small aliquots of the concentrated alkaline OONO ؊ solution were added to a buffer solution (final pH 7.0 -7.2), and the formation of 1 O2 and NO ؊ in high yields was observed. The 1 O2 generated was trapped as the transannular peroxide (DPAO2) of 9,10-diphenylanthracene (DPA) dissolved in carbon tetrachloride. The nitroxyl anion (NO ؊ ) formed from HNO (pKa 4.5) was trapped as nitrosylhemoglobin (HbNO) in an aqueous methemoglobin (MetHb) solution. In the presence of 25 mM sodium bicarbonate, which is known to accelerate the rate of decomposition of OONO ؊ , the amount of singlet oxygen trapped was reduced by a factor of Ϸ2 whereas the yield of trapping of NO ؊ by methemoglobin remained unaffected. Because NO3 ؊ is known to be the ultimate decomposition product of OONO ؊ , these results suggest that the nitrate anion is not formed by a direct isomerization of OONO ؊ , but by an indirect route originating from NO ؊ .nitrosylhemoglobin ͉ diphenylanthracene endoperoxide P eroxynitrite is a potent oxidant formed by the near diffusioncontrolled reaction of nitric oxide (NO ⅐ ) and superoxide ion (O 2 Ϫ ) (1). Both nitric oxide and superoxide are produced by activated macrophages (2, 3), neutrophils (4), and endothelial cells (5, 6). There is evidence that peroxynitrite is formed in significant concentrations in vivo (7-9) and may contribute to an increased risk for cancer (10), artherosclerosis (11), stroke (12), and other diseases (13). Peroxynitrite is a stable anion in alkaline solution (pKa of 6.8); however, once protonated, it decomposes rapidly with a half-life of less than 1 s at physiological pH at 37°C (14), generating reactive species that readily react with biomolecules such as lipids (15), amino acids (16), and DNA (17). Central to the question of the biochemistry of peroxynitrite is the mechanism of decomposition and the identity of the reactive species, a subject of intense research and controversy (18-21). Speculations about the decomposition mechanisms are largely based on kinetic and thermodynamic considerations (22). It has been shown that bicarbonate ion enhances the rate of disappearance of peroxynitrite, leading to the proposal of a nitrosoperoxycarbonate anion adduct, with a distinctly different chemistry from that of OONO Ϫ (19). We reported previously that the mere acidification of an aqueous peroxynitrite solution resulted in chemiluminescence at 1,270 nm characteristic of the deactivation of singlet oxygen (23). By comparing the intensity of this emission to that of 1 O 2 generated by the reaction of hydrogen peroxide (H 2 O 2 ) with hypochlorite anion (OCl Ϫ ), which is known to be stoichiometric (24), it wa...

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mentioning

confidence: 99%

The decomposition of peroxynitrite to nitroxyl anion (NO ⁻ ) and singlet oxygen in aqueous solution

Khan

Kovacic

Kolbanovskiy

et al. 2000

Proc. Natl. Acad. Sci. U.S.A.

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“…The amount of 1 O 2 generated from the decomposition of OONO Ϫ was estimated by comparing the yield of formation of the endoperoxide DPAO 2 (25) to the yield of DPAO 2 resulting from 1 O 2 generated by the extensively studied reaction of H 2 O 2 with NaOCl under comparable conditions. Both H 2 O 2 (30%, 12.5 M) and NaOCl (Ϸ0.7 mM) were diluted with 1 M KOH solution to Ϸ75 mM (which is equivalent to the peroxynitrite concentration of 75 mM used in parallel experiments).…”

Section: Estimation Of Singlet Oxygen Yields From Peroxynitrite Decommentioning

confidence: 99%

mentioning

confidence: 99%

The decomposition of peroxynitrite to nitroxyl anion (NO-) and singlet oxygen in aqueous solution

Khan

Kovacic

Kolbanovskiy

et al. 2000

Proceedings of the National Academy of Sciences

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The mechanism of decomposition of peroxynitrite (OONO ؊ ) in aqueous sodium phosphate buffer solution at neutral pH was investigated. The OONO ؊ was synthesized by directly reacting nitric oxide with superoxide anion at pH 13. The hypothesis was explored that OONO ؊ , after protonation at pH 7.0 to HOONO, decomposes into 1 O2 and HNO according to a spin-conserved unimolecular mechanism. Small aliquots of the concentrated alkaline OONO ؊ solution were added to a buffer solution (final pH 7.0 -7.2), and the formation of 1 O2 and NO ؊ in high yields was observed. The 1 O2 generated was trapped as the transannular peroxide (DPAO2) of 9,10-diphenylanthracene (DPA) dissolved in carbon tetrachloride. The nitroxyl anion (NO ؊ ) formed from HNO (pKa 4.5) was trapped as nitrosylhemoglobin (HbNO) in an aqueous methemoglobin (MetHb) solution. In the presence of 25 mM sodium bicarbonate, which is known to accelerate the rate of decomposition of OONO ؊ , the amount of singlet oxygen trapped was reduced by a factor of Ϸ2 whereas the yield of trapping of NO ؊ by methemoglobin remained unaffected. Because NO3 ؊ is known to be the ultimate decomposition product of OONO ؊ , these results suggest that the nitrate anion is not formed by a direct isomerization of OONO ؊ , but by an indirect route originating from NO ؊ .nitrosylhemoglobin ͉ diphenylanthracene endoperoxide P eroxynitrite is a potent oxidant formed by the near diffusioncontrolled reaction of nitric oxide (NO ⅐ ) and superoxide ion (O 2 Ϫ ) (1). Both nitric oxide and superoxide are produced by activated macrophages (2, 3), neutrophils (4), and endothelial cells (5, 6). There is evidence that peroxynitrite is formed in significant concentrations in vivo (7-9) and may contribute to an increased risk for cancer (10), artherosclerosis (11), stroke (12), and other diseases (13). Peroxynitrite is a stable anion in alkaline solution (pKa of 6.8); however, once protonated, it decomposes rapidly with a half-life of less than 1 s at physiological pH at 37°C (14), generating reactive species that readily react with biomolecules such as lipids (15), amino acids (16), and DNA (17). Central to the question of the biochemistry of peroxynitrite is the mechanism of decomposition and the identity of the reactive species, a subject of intense research and controversy (18-21). Speculations about the decomposition mechanisms are largely based on kinetic and thermodynamic considerations (22). It has been shown that bicarbonate ion enhances the rate of disappearance of peroxynitrite, leading to the proposal of a nitrosoperoxycarbonate anion adduct, with a distinctly different chemistry from that of OONO Ϫ (19).We reported previously that the mere acidification of an aqueous peroxynitrite solution resulted in chemiluminescence at 1,270 nm characteristic of the deactivation of singlet oxygen (23). By comparing the intensity of this emission to that of 1 O 2 generated by the reaction of hydrogen peroxide (H 2 O 2 ) with hypochlorite anion (OCl Ϫ ), which is known to be stoichiometric (24), it was...

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“…4 or the use of 9,10-diphenylanthracene peroxide 5 and its water soluble analogue 1,4-endoperoxide of 3-(4-methyl-1-naphthyl)propionic acid. 6 The reactions involving singlet oxygen are usually oxidations or addition reactions that afford clean reactions which are consistent with the concept of atom economy.…”

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confidence: 99%

Singlet Oxygen

Richard¹

2009

Synlett

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This feature focuses on a reagent chosen by a postgraduate, highlighting the uses and preparation of the reagent in current research Singlet OxygenCompiled by Jean-Alexandre Richard Jean-Alexandre Richard was born in Tours, France, in 1982. He received his Master degree in 2005 under the guidance of Prof. Ivan Jabin at the University of Le Havre. He is currently pursuing his Ph.D. studies in Rouen under the supervision of Prof. P.-Y. Renard and Dr. A. Romieu. His research interests involve the development of luminescent probes for the detection of enzyme activities.

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Singlet oxygen reactions with 9,10-diphenylanthracene peroxide

Cited by 157 publications

References 3 publications

The decomposition of peroxynitrite to nitroxyl anion (NO ⁻ ) and singlet oxygen in aqueous solution

The decomposition of peroxynitrite to nitroxyl anion (NO ⁻ ) and singlet oxygen in aqueous solution

The decomposition of peroxynitrite to nitroxyl anion (NO-) and singlet oxygen in aqueous solution

Singlet Oxygen

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Singlet oxygen reactions with 9,10-diphenylanthracene peroxide

Cited by 157 publications

References 3 publications

The decomposition of peroxynitrite to nitroxyl anion (NO − ) and singlet oxygen in aqueous solution

The decomposition of peroxynitrite to nitroxyl anion (NO − ) and singlet oxygen in aqueous solution

The decomposition of peroxynitrite to nitroxyl anion (NO-) and singlet oxygen in aqueous solution

Singlet Oxygen

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The decomposition of peroxynitrite to nitroxyl anion (NO ⁻ ) and singlet oxygen in aqueous solution

The decomposition of peroxynitrite to nitroxyl anion (NO ⁻ ) and singlet oxygen in aqueous solution