Mass spectrometric evidence of malonaldehyde and 4-hydroxynonenal adductions to radical-scavenging soy peptides

J Agric Food Chem. 2012 Sep 26;60(38):9727-36. doi: 10.1021/jf3026277. Epub 2012 Sep 11.

Abstract

Antioxidative peptides in food systems are potential targets of lipid oxidation-generated reactive aldehydes, such as malonaldehyde (MDA) and 4-hydroxynonenal (HNE). In this study, covalent modifications on radical-scavenging peptides prepared from soy protein hydrolysate by MDA and HNE were characterized by liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS/MS). MS/MS analyses detected the formation of Schiff base type adducts of MDA on the side-chain groups of lysine, histidine, arginine, glutamine, and asparagine residues as well as the N-termini of peptides. MDA also formed a fluorescent product with lysine residues. HNE adducted on lysine residues through Schiff base formation and on histidine, arginine, glutamine, and asparagine residues mainly through Michael addition. Despite the extensive MDA modification, peptide cross-linking by this potential mechanism was undetectable.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Aldehydes / analysis*
  • Aldehydes / chemistry
  • Amino Acids / analysis
  • Amino Acids / chemistry*
  • Chromatography, Liquid / methods
  • Cross-Linking Reagents / chemistry
  • Free Radical Scavengers / chemistry*
  • Lysine / chemistry
  • Malondialdehyde / analysis*
  • Malondialdehyde / chemistry
  • Schiff Bases
  • Soybean Proteins / chemistry*
  • Spectrometry, Mass, Electrospray Ionization / methods*
  • Tandem Mass Spectrometry

Substances

  • Aldehydes
  • Amino Acids
  • Cross-Linking Reagents
  • Free Radical Scavengers
  • Schiff Bases
  • Soybean Proteins
  • Malondialdehyde
  • 4-hydroxy-2-nonenal
  • Lysine