Effects of the phenacetin metabolite 4-nitrosophenetol on glycolysis and pentose phosphate pathway in human red cells

Biol Chem Hoppe Seyler. 1993 Jan;374(1):37-49. doi: 10.1515/bchm3.1993.374.1-6.37.

Abstract

Human erythrocytes exposed to 4-nitrosophenetol showed marked alterations of their endogenous metabolism. Rapid ferrihemoglobin formation mediated by the NADPH-dependent enzymic cycling of the nitrosoarene ("Kiese cycle") and extensive GSSG production caused an immediate drain of G-6-P into the pentose phosphate pathway at maximal flow. Despite a 2.4-fold increase in glucose phosphorylation rate and a branching ratio of 97:3 between pentose phosphate pathway and Embden-Meyerhof pathway, the G-6-P supply was obviously insufficient to meet the immense NADPH demand. Thus, a significant recycling of pentose phosphate pathway-derived F-6-P was observed in the order of 65%. Comparison of NADPH regeneration and ferrihemoglobin formation indicates the "Kiese cycle" to be a minor mechanism in ferrihemoglobin production in the case of high 4-nitrosophenetol concentrations. Most probably, reactive intermediates of 4-nitrosophenetol other than N-hydroxy-4-phenetidine, i.e. bicyclic arylamines and glutathione S-conjugates are formed which produce ferrihemoglobin without involvement of NADPH. The experiments have shown that red cells are remarkable robust to tackle the massive oxidative stress as elicited by 4-nitrosophenetol. The immediate metabolic response of the pentose phosphate pathway allows rapid regeneration of reduced glutathione. Thereby, SH-containing enzymes are effectively protected and/or regenerated and hemolysis is kept minimal. Hence, red cells are favourably suited for clearing the blood from N-oxygenated arylamines before they can reach more sensitive target organs.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Adenosine Triphosphate / blood
  • Carbon Dioxide / blood
  • Erythrocytes / drug effects*
  • Erythrocytes / metabolism
  • Glycolysis / drug effects*
  • Hexokinase / blood
  • Humans
  • Methemoglobin / biosynthesis
  • NAD / blood
  • NADP / blood
  • Pentose Phosphate Pathway / drug effects*
  • Phenacetin / analogs & derivatives*
  • Phenacetin / blood
  • Phenacetin / pharmacology

Substances

  • NAD
  • Carbon Dioxide
  • 4-nitrosophenetole
  • NADP
  • Adenosine Triphosphate
  • Methemoglobin
  • Hexokinase
  • Phenacetin