Nalpha-(1-deoxy-D-fructos-1-yl)-L-histidine ("D-Fructose-L-histidine"): a potent copper chelator from tomato powder

J Agric Food Chem. 2007 Dec 12;55(25):10373-81. doi: 10.1021/jf072092i. Epub 2007 Nov 16.

Abstract

Dried fruits and vegetables are known for their high content of D-fructose-amino acids, or Amadori compounds, which appear at the initial step of the Maillard reaction and may participate in redox reactions mediated by trace metals. In this study, we investigated complexation between Cu(II) and N(alpha)-(1-deoxy-D-fructos-1-yl)-L-histidine (D-fructose-L-histidine, FruHis). The content of FruHis in two types of commercial tomato powders was estimated by GLC-MS, using single ion monitoring of trimethylsilylated FruHis hydroxyoximate, as 40 mg/100 g, whereas the concentration of free histidine in the powder samples was about 53 mg/100 g. The Cu(II)-binding ability of FruHis was studied along with structurally related molecules L-histidine, dipeptide L-carnosine, and N(alpha)-(1-deoxy-D-fructos-1-yl)-L-arginine (FruArg) at 25 degrees C using pH-potentiometric titrations. Analysis of the titration curves showed that formation of Cu(II)-FruHis complex species occurs at pH values as low as 2 and that the complexes were redox stable in the pH range 2-10.5, at least for the time of the experiment. At physiological pH, Cu(II) and FruHis form a dominant coordination species of composition MLH-1 (log beta = 5.67), with a presumably deprotonated anomeric hydroxyl group of the fructose portion. The apparent stability constant of 1:1 complexes formed by FruHis and Cu(II) in neutral aqueous solutions is about 10(4) times higher than similar values calculated for L-histidine, L-carnosine, and FruArg. FruHis nearly completely protected hydroxyl radical-mediated fragmentation of polymeric DNA in the presence of the Cu/H2O2/ascorbate system, whereas neither of the reference compounds could inhibit the DNA fragmentation as efficiently in similar conditions. These results warrant further investigation of FruHis as a potential food-related antioxidant.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Chelating Agents / analysis*
  • Chelating Agents / chemistry
  • Copper / chemistry*
  • Food Preservation*
  • Fruit / chemistry
  • Gas Chromatography-Mass Spectrometry
  • Histidine / analogs & derivatives*
  • Histidine / analysis
  • Histidine / chemistry
  • Hydrogen-Ion Concentration
  • Monosaccharides / analysis*
  • Monosaccharides / chemistry
  • Solanum lycopersicum / chemistry*

Substances

  • Chelating Agents
  • Monosaccharides
  • Nalpha-(1-deoxy-D-fructos-1-yl)-L-histidine
  • Histidine
  • Copper