The carbonate radical as one-electron oxidant of carbohydrates in alkaline media
-
Magnus Carlsson
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.
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
©2005 by Walter de Gruyter Berlin New York
Articles in the same Issue
- Obituary
- The role of non-phenolic lignin in chlorate-forming reactions during chlorine dioxide bleaching of softwood kraft pulp
- Study of the oxygen effect on mechanical pulp lignin using an improved lignin isolation method
- Quantitative 1H NMR analysis of alkaline polysulfide solutions
- A comparative study on the degradation of cotton linters induced by carbonate and hydroxyl radicals generated from peroxynitrite
- The carbonate radical as one-electron oxidant of carbohydrates in alkaline media
- Leaf-fiber lignins of Phormium varieties compared bysolid-state 13C NMR spectroscopy
- Antifungal activity of iridoid glycosides from the heartwood of Gmelina arborea
- Antioxidant activity of different components of pine species
- Dislocations in Norway spruce fibres and their effect on properties of pulp and paper
- Isolation and identification of antifungal compounds from Amboyna wood
- Biomechanical pulping of spruce wood chips with Streptomyces cyaneus CECT 3335 and handsheet characterization
- Three-dimensional visualisation of bacterial decay in individual tracheids of Pinus sylvestris
- Mass loss and moisture dynamics of Scots pine (Pinus sylvestris L.) exposed outdoors above ground in Sweden
- The influence of cation and anion structure of new quaternary ammonium salts on adsorption and leaching
- Speciation of arsenic and chromium in the leachate from chromated copper arsenate (CCA) type C treated southern pine (Pinus spp.)
- Metal chelation studies relevant to wood preservation.1. Complexation of propyl gallate with Fe2+
- Comparison of UV and confocal Raman microscopy to measure the melamine–formaldehyde resin content within cell walls of impregnated spruce wood
- Comparison of Pinus taeda L. wood property calibrations based on NIR spectra from the radial-longitudinal and radial-transverse faces of wooden strips
- Detection of failures of adhesively bonded joints using the acoustic emission method
- Effect of cross-sectional change of a board specimen on stress wave velocity determination
- Comments on the experimental methodology for determination of the hygro-mechanical properties of wood
- Properties of chemically and mechanically isolated fibres of spruce (Picea abies [L.] Karst.). Part 1: Structural and chemical characterisation
- Properties of chemically and mechanically isolated fibres of spruce (Picea abies[L.] Karst.). Part 2: Twisting phenomena
Articles in the same Issue
- Obituary
- The role of non-phenolic lignin in chlorate-forming reactions during chlorine dioxide bleaching of softwood kraft pulp
- Study of the oxygen effect on mechanical pulp lignin using an improved lignin isolation method
- Quantitative 1H NMR analysis of alkaline polysulfide solutions
- A comparative study on the degradation of cotton linters induced by carbonate and hydroxyl radicals generated from peroxynitrite
- The carbonate radical as one-electron oxidant of carbohydrates in alkaline media
- Leaf-fiber lignins of Phormium varieties compared bysolid-state 13C NMR spectroscopy
- Antifungal activity of iridoid glycosides from the heartwood of Gmelina arborea
- Antioxidant activity of different components of pine species
- Dislocations in Norway spruce fibres and their effect on properties of pulp and paper
- Isolation and identification of antifungal compounds from Amboyna wood
- Biomechanical pulping of spruce wood chips with Streptomyces cyaneus CECT 3335 and handsheet characterization
- Three-dimensional visualisation of bacterial decay in individual tracheids of Pinus sylvestris
- Mass loss and moisture dynamics of Scots pine (Pinus sylvestris L.) exposed outdoors above ground in Sweden
- The influence of cation and anion structure of new quaternary ammonium salts on adsorption and leaching
- Speciation of arsenic and chromium in the leachate from chromated copper arsenate (CCA) type C treated southern pine (Pinus spp.)
- Metal chelation studies relevant to wood preservation.1. Complexation of propyl gallate with Fe2+
- Comparison of UV and confocal Raman microscopy to measure the melamine–formaldehyde resin content within cell walls of impregnated spruce wood
- Comparison of Pinus taeda L. wood property calibrations based on NIR spectra from the radial-longitudinal and radial-transverse faces of wooden strips
- Detection of failures of adhesively bonded joints using the acoustic emission method
- Effect of cross-sectional change of a board specimen on stress wave velocity determination
- Comments on the experimental methodology for determination of the hygro-mechanical properties of wood
- Properties of chemically and mechanically isolated fibres of spruce (Picea abies [L.] Karst.). Part 1: Structural and chemical characterisation
- Properties of chemically and mechanically isolated fibres of spruce (Picea abies[L.] Karst.). Part 2: Twisting phenomena