The non-oxidative degradation of ascorbic acid at physiological conditions.
The degradation of L-ascorbate (AsA) and its primary oxidation products, L-dehydroascorbate (DHA) and 2,3-L-diketogulonate (2, 3-DKG) were studied under physiological conditions. Analysis determined that L-erythrulose (ERU) and oxalate were the primary degradation products of ASA regardless of which compound was used as the starting material. The identification of ERU was determined by proton decoupled (13)C-nuclear magnetic resonance spectroscopy, and was quantified by high performance liquid chromatography, and enzymatic analysis. The molar yield of ERU from 2,3-DKG at pH 7.0 37 degrees C and limiting O(2)97%. This novel ketose product of AsA degradation, was additionally qualitatively identified by gas-liquid chromatography, and by thin layer chromatography. ERU is an extremely reactive ketose, which rapidly glycates and crosslinks proteins, and therefore may mediate the AsA-dependent modification of protein (ascorbylation) seen in vitro, and also proposed to occur in vivo in human lens during diabetic and age-onset cataract formation.
Simpson
G L
GL
Mason Eye Institute, and Department of Biochemistry, University of Missouri, School of Medicine, One Hospital Drive, Columbia, MO 65212, USA.
Ortwerth
B J
BJ
D015083:2,3-Diketogulonic Acid / Q000737:chemistry; D001205:Ascorbic Acid / Q000737:chemistry*; D002021:Buffers; D002087:Butyrates / Q000737:chemistry; D002851:Chromatography, High Pressure Liquid; D003459:Crystallins / Q000737:chemistry; D003683:Dehydroascorbic Acid / Q000737:chemistry; D006801:Humans; D006863:Hydrogen-Ion Concentration; D007908:Lens, Crystalline / Q000737:chemistry / Q000378:metabolism; D009682:Magnetic Resonance Spectroscopy; D010070:Oxalates / Q000737:chemistry; D010084:Oxidation-Reduction; D013696:Temperature; D013780:Tetroses / Q000737:chemistry
D002021:Buffers; D002087:Butyrates; D003459:Crystallins; D010070:Oxalates; D013780:Tetroses; D015083:2,3-Diketogulonic Acid; C100073:erythrulose; C011369:threonic acid; D001205:Ascorbic Acid; D003683:Dehydroascorbic Acid