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Evidence for a slow and oxygen-insensitive intra-molecular long range electron transfer from tyrosine residues to the semi-oxidized tryptophan 214 in human serum albumin: its inhibition by bound copper (II)

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Abstract

A slow, long range electron transfer (SLRET) in human serum albumin (HSA) is observed from an intact tyrosine (Tyr) residue to the neutral tryptophan (Trp) radical (Trp·) generated in pulse radiolysis. This radical is formed, at neutral pH, through oxidation with Br ·−2 radical anions of the single Trp 214 present. The SLRET rate constant of ~0.2 s−1 determined is independent of HSA concentration and radiation dose, consistent with an intra-molecular process. This is the slowest rate constant so far reported for an intra-molecular LRET. In sharp contrast with the LRET reported for other proteins, the SLRET observed here is insensitive to oxygen, suggesting that the oxidized Trp is inaccessible to—or do not react with radiolytically generated O ·−2 . In N2O-saturated solutions, the SLRET is inhibited by Cu2+ ions bound to the His 3 residue of the N-terminal group of HSA but it is partially restored in O2-saturated solutions.

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Abbreviations

HSA:

Human serum albumin

LRET:

Long range electron transfer

SLRET:

Slow long range electron transfer

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Acknowledgments

This is Document No. NDLR-4892 from the Notre Dame Radiation Laboratory which is supported by the Office of Basic Energy Sciences at the United States Department of Energy.

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Authors and Affiliations

  1. Radiation Laboratory, University of Notre Dame, Notre Dame, IN, 46556, USA

    Larry K. Patterson, David M. Bartels & Gordon L. Hug

  2. Laboratoire de Biochimie, CHU Amiens, place Victor Pauchet, 80054, Amiens, France

    Larry K. Patterson, Jean-Claude Mazière, René Santus & Patrice Morlière

  3. Faculté de Médecine et de Pharmacie, EA4292, Université de Picardie Jules Verne, 1 rue des Louvels, 80036, Amiens, France

    Jean-Claude Mazière & Patrice Morlière

  4. INSERM, ERI12, 1 rue des Louvels, 80036, Amiens, France

    Jean-Claude Mazière & Patrice Morlière

  5. Laboratoire de Biochimie, INSERM ERI 12, CHU Amiens, Hôpital Nord, place Victor Pauchet, 80054, Amiens Cedex 01, France

    Patrice Morlière

  6. Département RDDM, Muséum National d’Histoire Naturelle, 43 rue Cuvier, 75231, Paris, France

    René Santus

Authors
  1. Larry K. Patterson
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  2. Jean-Claude Mazière
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  3. David M. Bartels
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  4. Gordon L. Hug
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  5. René Santus
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  6. Patrice Morlière
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Correspondence to Patrice Morlière.

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Patterson, L.K., Mazière, JC., Bartels, D.M. et al. Evidence for a slow and oxygen-insensitive intra-molecular long range electron transfer from tyrosine residues to the semi-oxidized tryptophan 214 in human serum albumin: its inhibition by bound copper (II). Amino Acids 42, 1269–1275 (2012). https://doi.org/10.1007/s00726-010-0819-5

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  • DOI: https://doi.org/10.1007/s00726-010-0819-5

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