Radiolysis of carbohydrates as studied by ESR and spin-trapping—II

Kuwabara, Mikinori; Zhang, Z.-Y; Inanami, Osamu; Yoshii, Giichi

doi:10.1016/0146-5724(84)90055-4

Cited by 4 publications

(3 citation statements)

References 17 publications

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“…Its interaction with radicals has been studied in the context of polyhydric alcohols and sugars degradation, to the comprehension of which radiation chemical techniques gave a fundamental contribution. The radiation induced free radical reactions of carbohydrates have been comprehensively reviewed in the past and plausible mechanisms for their degradation have been proposed from the analysis of end products. , Also, transient studies have been done by conductivity, and optical measurements. , Spin trapping has been employed with success by Kuwabara et al to identify the radicals formed in the reaction of five carbohydrates (glycerol- d 8 , xylitol, dulcitol, D -sorbitol, and D -mannitol). The general conclusion reached is that carbohydrates show a very weak reactivity toward the hydrated electron and a fast reactivity with the OH radical.…”

Section: Introductionmentioning

confidence: 99%

“…As it was expected from the “high reactivity−lack of selectivity” principle, most of these studies evidenced that a mixture of primary and secondary radical products are formed after OH attack, with a certain prevalence of the more stable glucosidic radicals centered in position C2. Kuwabara et al, definitely demonstrated the preferential formation of a primary carbon hydroxyalkyl radical (C1 position) in the five carbohydrates above (hence in D -sorbitol too), arguing that the C2 acylalkyl radical CHO− · CH−CHOH follows from water elimination, rather than from direct H abstraction. Oxy- and deoxy-compounds, constituted by smaller fragments are found among the final products, but larger molecules are found as well in deoxygenated solutions.…”

Section: Introductionmentioning

confidence: 99%

“…5,6 Also, transient studies have been done by conductivity, 7 and optical measurements. 8,9 Spin trapping has been employed with success by Kuwabara et al 10 to identify the radicals formed in the reaction of five carbohydrates (glycerol-d 8 , xylitol, dulcitol, D-sorbitol, and D-mannitol). The general conclusion reached is that carbohydrates show a very weak reactivity toward the hydrated electron and a fast reactivity with the OH radical.…”

Section: Introductionmentioning

confidence: 99%

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The Selective OH Radical Oxidation of Sorbitylfurfural: A Combined Experimental and Theoretical Study

Emmi¹,

D’Angelantonio²,

Poggi³

et al. 2002

J. Phys. Chem. A

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Sorbitylfurfural (Furalglucitol), widely used in the cosmetic industry as antioxidant and antiinflammatory agent, reacts with hydroxyl radical in neutral aqueous solution with a rate constant almost at the diffusional limit, k 1 = 7.3 × 109 M-1 s-1. Despite the unselective character of the OH radical, addition to the 5‘ position in the furanic ring seems to provide the dominant path. The consequent allylic radical undergoes the cleavage of the C−O bond (k 2 = 1.7 × 106 s-1) in β position to form a pseudo-seven-atom ring via a hydrogen bond between the attacking OH group and the furanic oxygen. A 1,6 H-shift between the two oxygen atoms (k3 = 1.4 × 105 s-1) then precedes a disproportionation reaction which leads to the final products (k4 = 2.0 × 107 M-1 s-1). The proposed mechanism is based on the UV−vis spectra of intermediates and final products obtained after pulse and gamma radiolysis, on nonlinear kinetic fittings of absorbance versus time curves, on quantum-mechanical calculations of electronic transitions and reaction enthalpies. The two most important final products have been isolated and characterized as sorbityl-but-2-enal derivatives by LC-MS.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

The Selective OH Radical Oxidation of Sorbitylfurfural: A Combined Experimental and Theoretical Study

Emmi¹,

D’Angelantonio²,

Poggi³

et al. 2002

J. Phys. Chem. A

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Electron spin resonance study of spin‐trapped radicals from gamma irradiation of glucose oligomers

Thiéry¹,

Thiery²,

Agnel³

et al. 1990

Magnetic Reson in Chemistry

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Comparison of the stable products formed by fast atom bombardment and γ‐irradiation of glycerol

Keough

Ezra

Russell

et al. 1987

Org. Mass Spectrom.

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The major end-products formed by fast atom bombardment (FAB) and y-irradiation of glycerol have been identified using capillary gas chromatographylmass spectrometry. The product distributions differ dramatically. Products resulting from the recombination of either carbon-centered or oxygen-centered radicals are evident for both sources of irradiation. However, the major FAB-generated products are formed by the recombination of carbon-centered [G -HI' radicals with other carbon-centered radicals while the major y-radiolysis products result from the recombination of oxygen-centered [G -HI' radicals with lower-weight carbon-centered species. y-Radiolysis of an N,O-saturated aqueous solution of glycerol, experimental conditions that strongly favor the formation of carboncentered [G -HI' radicals at the expense of the oxygen-centered species, yielded some products that were identical to those produced by FAB of neat glycerol. Finally, the free radicals produced by y-radiolysis of glycerol were investigated by electron spin resonance spectroscopy and spin trapping with 5,5-dimethyl-l-pyrroline-N-oxide. The presence of only the carbon-centered free radical was established by this technique. The implications of these results are discussed.

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Radiolysis of carbohydrates as studied by ESR and spin-trapping—II

Cited by 4 publications

References 17 publications

The Selective OH Radical Oxidation of Sorbitylfurfural: A Combined Experimental and Theoretical Study

The Selective OH Radical Oxidation of Sorbitylfurfural: A Combined Experimental and Theoretical Study

Electron spin resonance study of spin‐trapped radicals from gamma irradiation of glucose oligomers

Comparison of the stable products formed by fast atom bombardment and γ‐irradiation of glycerol

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