Non-Enzymatic Methylglyoxal Formation From glucose Metabolites and Generation of Superoxide Anion Radical During Methylglyoxal-Dependent Cross-Links Reaction

V.Z. Lankin,O.I. Shadyro,A.A. Sladkova,A.K. Tikhaze,K.B. Shumaev,Jie Yin

doi:10.14302/issn.2471-2140.jaa-19-2997

V.Z. Lankin, O.I. Shadyro + Show 4 more

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https://doi.org/10.14302/issn.2471-2140.jaa-19-2997

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Abstract

The paper explores the formation of a-oxoaldehydes during the interaction of glucose metabolites with hydroxyl or alkoxyl radicals. Hydroxyl radicals were generated under radiolysis of aqueous solutions, and alkoxyl radicals (t-BuO) were obtained in the model system tert-butyl hydroperoxide/Fe2+. High-performance liquid chromatography revealed that methylglyoxal was one of the organic products resulting from t-BuO-induced transformations of fructose-1,6-bisphosphate under hypoxic conditions. The interaction of lysine and methylglyoxal one of the main targets of a-oxoaldehydes in proteins was also studied. As chemiluminescence and EPR spectroscopy demonstrated, this reaction generates a methylglyoxal anion radical, a cation-radical of methylglyoxal dialkylamine and a superoxide anion radical. EPR signal of methylglyoxal-derived free radicals was observed in hypoxia, whereas only the trace amounts of these free radicals were recorded in the aerated reaction medium.

Highlights

Ionizing irradiation or metabolic disturbances in the living body can lead to hyperproduction of reactive oxygen species (ROS), which promotes the activation of free radical processes – the phenomenon which can damage some biologically significant molecules [1,2,3]
In the present study we investigate the possibility that the metabolites of glycolysis can create the non-enzymatic formations of methylglyoxal, as well as the possibility of ROS and other free radical products to form in the process of interaction between this high reactive dicarbonyl compound and amino acids
Unlike superoxide, which can be detoxified by superoxide dismutase, hydroxyl radicals cannot be eliminated by an enzymatic reaction

Summary

Introduction

Ionizing irradiation or metabolic disturbances in the living body can lead to hyperproduction of reactive oxygen species (ROS), which promotes the activation of free radical processes – the phenomenon which can damage some biologically significant molecules [1,2,3]. Substances with phosphoether bonds in their structure play an important role in biosystems Such compounds as fructose-1,6-bisphosphate (Fru-1,6-P2) and glyceraldehyde-3-phosphate (G-3-P) are glucose (Glc) metabolites which are formed during glycolysis. Since the interaction of oxygen-centered radicals with the monosaccharides leads to the formation of physiologically reactive carbonyl and dicarbonyl compounds [11], monosaccharide phosphates and their analogues The latter ones being the main metabolites of glycolysis can be assumed to undergo the similar free radical transformations, which form α-oxoaldehydes. In the present study we investigate the possibility that the metabolites of glycolysis can create the non-enzymatic formations of methylglyoxal, as well as the possibility of ROS and other free radical products to form in the process of interaction between this high reactive dicarbonyl compound and amino acids

Materials and Methods

Results and Discussion

Conclusions