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The carbonate radical as one-electron oxidant of carbohydrates in alkaline media

  • Magnus Carlsson , David Stenman , Gábor Merényi and Torbjörn Reitberger
Published/Copyright: June 1, 2005
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Holzforschung
From the journal Volume 59 Issue 2

Abstract

The mechanism by which the carbonate radical anion reacts with D-glucose in alkaline aqueous solutions has been studied by means of γ-radiolysis. From the product analysis it is concluded that the reaction sequence is initiated by a one-electron transfer between the carbonate radical anion and deprotonated D-glucose. In the presence of molecular oxygen, the major, if not only products of this reaction sequence are formic acid, arabinose and gluconic acid and reaction schemes are proposed to account for the observed formation of these products.

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Corresponding author. Teknikringen 56, SE-100 44 Stockholm/Sweden

References

Alfassi, Z.B., Schuler R.H. (1985) Reaction of azide radicals with aromatic compounds. Azide as a selective oxidant. J. Phys. Chem.89:3359–3363.Search in Google Scholar

Avila, D.V., Brown, C.E., Ingold, K.U., Lusztyk, J. (1993) Solvent effects on the competitive beta-scission and hydrogen atom abstraction reactions of the cumyloxyl radical. Resolution of a long-standing problem. J. Am. Chem. Soc.115:466–470.Search in Google Scholar

Buxton, G.V., Greenstock C.L., Helman W.P., Ross A.B. (1988) Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals in aqueous solution. J. Phys. Chem. Ref. Data2(17):513–588.10.1063/1.555805Search in Google Scholar

Choppin, G., Rydberg, J., Liljenzin, J.O. (1995) Radiochemistry and Nuclear Chemistry, 2nd edition. Butterworth and Heinemann, Oxford.Search in Google Scholar

Clifton, C.L., Huie R.E. (1993) Rate constants for some hydrogen abstraction reactions of the carbonate radical. Int. J. Chem. Kinet.25(3):199–203.10.1002/kin.550250308Search in Google Scholar

Gilbert, B.C., Holmes, R.G.G., Laue, H.A.H., Norman, R.O.S. (1976) Electron spin resonance studies. Part L. Reactions of alkoxyl radicals generated from alkyl hydroperoxides and titanium(III) ion in aqueous solution. J. Chem. Soc. Perkin Trans.2:1047.Search in Google Scholar

Hodges, G.R., Ingold, K.U. (1999) Cage-escape of geminate radical pairs can produce peroxynitrate from peroxynitrite under a wide variety of experimental conditions. J. Am. Chem. Soc.121:10695–10701.10.1021/ja991077uSearch in Google Scholar

Izatt, R.M., Rytting, J.H., Hansen, L.D., Christensen, J.J. (1966) Thermodynamics of proton dissociation in dilute aqueous solution. V. An entropy titration study of adenosine, pentoses, hexoses, and related compounds. J. Am. Chem. Soc.88:2641–2645.Search in Google Scholar

Konya, K.G., Paul, T., Lin, S., Lusztyk, J., Ingold, K.U. (2000) Laser flash photolysis studies on the first superoxide thermal source. First direct measurements of the rates of solvent-assisted 1,2-hydrogen atom shifts and a proposed new mechanism for this unusual rearrangement. J. Am. Chem. Soc.11:7518.Search in Google Scholar

Merényi, G., Lind, J., Goldstein, S. (2002) Thermochemical properties of α-hydroxy-alkoxyl radicals in aqueous solution. J. Phys. Chem. A106(46):11127–11129.10.1021/jp021478nSearch in Google Scholar

Nakao, L.S., Ouchi, D., Augusto, O. (1999) Oxidation of acetaldehyde by peroxynitrite and hydrogen peroxide/iron(II). Production of acetate, formate, and methyl radicals. Chem. Res. Toxicol.12:1010–1018.Search in Google Scholar

Serjeant, E.P., Dempsey R. (1979) Ionisation Constants of Organic Acids in Aqueous Solution. IUPAC Chemical Data Series No 23, Pergamon Press.Search in Google Scholar

Stanbury, D.M. (1989) Reduction potentials involving inorganic free radicals in aqueous solution. Adv. Inorg. Chem.33:69–138.10.1016/S0898-8838(08)60194-4Search in Google Scholar

Stenman, D., Carlsson M., Jonsson, M., Reitberger T. (2003) Reactivity of the carbonate radical anion towards lignin and carbohydrate model compounds. J. Wood Chem. Technol.23(1):47–69.Search in Google Scholar

Stenman, D., Carlsson M., Reitberger T. (2004) Peroxynitrite mediated delignification of pulp. A comparative study on bleaching properties of the carbonate and hydroxyl radicals. J. Wood Chem. Technol. 24(2), in press.10.1081/WCT-200026553Search in Google Scholar

von Sonntag, C., Schuchmann, H.-P. (1997) Peroxyl radicals in aqueous solution. In: Peroxyl Radicals, Ed. Alfassi, Z. John Wiley & Sons Ltd, Chichester. pp. 173–234.10.2166/wst.1997.0074Search in Google Scholar

Published Online: 2005-06-01
Published in Print: 2005-02-01

©2005 by Walter de Gruyter Berlin New York

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