Analysis and Chemistry of Novel Protein Oxidation Markers in Vivo

作者：Henning Christian; Liehr Kristin; Girndt Matthias; Ulrich Christof; Glomb Marcus A^*

来源：Journal of Agricultural and Food Chemistry, 2018, 66(18): 4692-4701.

DOI：10.1021/acs.jafc.8b00558

• carbohydrate chemistry
• oxidative stress
• Maillard reaction
• glyoxal
• glycolaldehyde
• carboxymethyl lysine
• hydroxyethyl lysine
• high performance liquid chromatography
• mass spectrometry
• plasma
• hemodialysis

Proteins continually undergo spontaneous oxidation reactions, which lead to changes in structure and function. The quantitative assessment of protein oxidation adducts provides information on the level of exposure to reactive precursor compounds with a high oxidizing potential and reactive oxygen species (ROS). In the present work, we introduce N-6-(2-hydroxyethyl)lysine as a novel marker based on the ratio of glycolaldehyde and its oxidized form glyoxal. The high analytical potential was proven with a first set of patients undergoing hemodialysis versus healthy controls, in comparison with well established parameters for oxidative stress. In vitro experiments with N-1-t-BOC-lysine and N-1-t-BOC-arginine enlightened the mechanistic relationship of glycolaldehyde and glyoxal. Oxidation was strongly dependent on the catalytic action of the epsilon-amino moiety of lysine. Investigations on the formation of N-6-carboxymethyl lysine revealed glycolaldehyde-imine as the more reactive precursor, even though an additional oxidative step is required. As a result, a novel and very effective alternative mechanism was unraveled.

• 出版日期2018-5-9