Solution structure of 5-keto-D-fructose: Relevance to the specificity of hexose kinases

John S. Blanchard, Curtis F. Brewer, Sasha Englard, Gad Avigad

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

5-Keto-D-fructose (5KF) is isolated from cultures of Gluconobacter cerinus growing on D-fructose as the sole carbon source. 5KF is a substrate for hexokinase, fructokinase, and several polyol dehydrogenases. 1H and 13C nuclear magnetic resonance studies show that 5KF exists in different forms in anhydrous dimethyl-d6 sulfoxide and D2O. In dimethyl-d6 sulfoxide, 5KF exists as a spirane dimer with linked furanose and pyranose rings, similar to the structure reported for crystalline 5KF [Hassen, L., Hordvik, A., & Hove, R. (1976) J. Chem. Soc., Chem. Commun., 572]. In D2O, 5KF exists predominantly (>95%) in a β-pyranose form with the 5-keto group hydrated to form a gem-diol. 13C-1H coupling patterns, 13C relaxation measurements, and 13C deuterium-induced differential isotope shifts confirm this structure of 5KF. The phosphorylation of 5KF by fructokinase can be accounted for by an approximately 2% proportion of the β-furanose form in solution at 25°C. Both the β-pyranose and β-furanose forms of 5KF are proposed to be substrates for yeast hexokinase.

Original languageEnglish (US)
Pages (from-to)75-81
Number of pages7
JournalBiochemistry
Volume21
Issue number1
StatePublished - 1982

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Hexoses
Phosphotransferases
fructokinase
Hexokinase
Dimethyl sulfoxide
Dimethyl Sulfoxide
Gluconobacter
L-Iditol 2-Dehydrogenase
Gems
5-ketofructose
Phosphorylation
Deuterium
Substrates
Fructose
Isotopes
Dimers
Yeast
Magnetic Resonance Spectroscopy
Carbon
Yeasts

ASJC Scopus subject areas

  • Biochemistry

Cite this

Solution structure of 5-keto-D-fructose : Relevance to the specificity of hexose kinases. / Blanchard, John S.; Brewer, Curtis F.; Englard, Sasha; Avigad, Gad.

In: Biochemistry, Vol. 21, No. 1, 1982, p. 75-81.

Research output: Contribution to journalArticle

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