The Haber-Weiss cycle – 70 years later

Abstract The chain reactions HO• + H2O2 → H2O + O2•- + H+ and O2•- + H+ + H2O2 → O2 + HO• + H2O, commonly known as the Haber-Weiss cycle, were first mentioned by Haber and Willst?tter in 1931. George showed in 1947 that the second reaction is insignificant in comparison to the fast dismutation of superoxide, and this finding appears to have been accepted by Weiss in 1949. In 1970, the Haber-Weiss reaction was revived by Beauchamp and Fridovich to explain the toxicity of superoxide. During the 1970s various groups determined that the rate constant for this reaction is of the order of 1 M-1s-1 or less, which confirmed George's conclusion. The reaction of superoxide with hydrogen peroxide was dropped from the scheme of oxygen toxicity, and superoxide became the source of hydrogen peroxide, which yields hydroxyl radicals via the Fenton reaction, Fe 2+ + H2O2 → Fe3+ + HO- + HO•. In 1994, Kahn and Kasha resurrected the Haber-Weiss reaction again, but this time the oxygen was believed to be in the singlet (1∆g) state. As toxicity arises not from a Fenton-catalysed Haber-Weiss reaction, but from the Fenton reaction, the Haber-Weiss reaction should not be mentioned anymore.

[1]  J. Kehrer.  The Haber-Weiss reaction and mechanisms of toxicity. , 2000, Toxicology.

[2]  W. Koppenol.  Names for inorganic radicals (IUPAC Recommendations 2000) , 2000 .

[3]  S. Liochev,et al.  The mechanism of "Fenton-like" reactions and their importance for biological systems. A biologist's view. , 1999, Metal ions in biological systems.

[4]  J. Booker,et al.  Discussion-•-— »-— — — — — , 1998 .

[5]  M. Kasha,et al.  Singlet molecular oxygen in the Haber-Weiss reaction. , 1994, Proceedings of the National Academy of Sciences of the United States of America.

[6]  W. Koppenol.  The centennial of the Fenton reaction. , 1993, Free radical biology & medicine.

[7]  J. Rush,et al.  Pulse radiolytic studies of the reaction of perhydroxyl/superoxide O2- with iron(II)/iron(III) ions. The reactivity of HO2/O2- with ferric ions and its implication on the occurrence of the Haber-Weiss reaction , 1985 .

[8]  H. S. Mason,et al.  Oxidases and Related Redox Systems , 1982 .

[9]  R. Kyle,et al.  Fritz Haber. , 1981, JAMA.

[10]  W. Bors,et al.  Superoxide anions do not react with hydroperoxides , 1979, FEBS letters.

[11]  L. Pauling.  The discovery of the superoxide radical , 1979 .

[12]  B. Bielski,et al.  Kinetics of the interaction of HO/sub 2/ and O/sub 2//sup -/ radicals with hydrogen peroxide. The Haber--Weiss reaction. [Gamma radiation] , 1979 .

[13]  B. Bielski.  REEVALUATION OF THE SPECTRAL AND KINETIC PROPERTIES OF HO2 AND O2‐ FREE RADICALS , 1978 .

[14]  J. Foos,et al.  THE REACTION BETWEEN SUPEROXIDE ANION AND HYDROGEN PEROXIDE , 1978 .

[15]  W. Koppenol,et al.  THE HABER‐WEISS CYCLE , 1978 .

[16]  W. Melhuish,et al.  Study of the Haber–Weiss reaction using a sensitive method for detection of OH radicals , 1978 .

[17]  A. Finazzi-Agro’,et al.  An attempt to evaluate the rate of the haber‐weiss reaction by using ·OH radical scavengers , 1977, FEBS letters.

[18]  G. Scholes.  Professor J. J. Weiss, 1905-1972. , 1972, International journal of radiation biology and related studies in physics, chemistry, and medicine.

[19]  I. Fridovich,et al.  A mechanism for the production of ethylene from methional. The generation of the hydroxyl radical by xanthine oxidase. , 1970, The Journal of biological chemistry.

[20]  J. Rabani,et al.  Acid dissociation constant and decay kinetics of the perhydroxyl radical , 1970 .

[21]  I. Fridovich,et al.  Superoxide dismutase. An enzymic function for erythrocuprein (hemocuprein). , 1969, The Journal of biological chemistry.

[22]  C. Ferradini,et al.  Radiolyse de solutions acides et aérées de peroxyde d'hydrogène , 1969 .

[23]  D. Irvine,et al.  A possible structure for the higher oxidation state of metmyoglobin. , 1955, The Biochemical journal.

[24]  P. George.  The chemical nature of the second hydrogen peroxide compound formed by cytochrome c peroxidase and horseradish peroxidase. 2. Formation and decomposition. , 1953, The Biochemical journal.

[25]  P. George.  The chemical nature of the second hydrogen peroxide compound formed by cytochrome c peroxidase and horseradish peroxidase. I. Titration with reducing agents. , 1953, The Biochemical journal.

[26]  P. George.  The third intermediate compound of horseradish peroxidase and hydrogen peroxide. , 1953, The Journal of biological chemistry.

[27]  D. Irvine,et al.  The reaction between metmyoglobin and hydrogen peroxide. , 1952, The Biochemical journal.

[28]  G. Stein,et al.  The action of X-rays on ferrous and ferric salts in aqueous solutions , 1952, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[29]  P. George.  Chemical Nature of the Secondary Hydrogen Peroxide Compound Formed by Cytochrome-C Peroxidase and Horseradish Peroxidase , 1952, Nature.

[30]  J. Weiss.  Possible Biological Significance of the Action of Ionizing Radiations on Nucleic Acids , 1952, Nature.

[31]  W. Barb,et al.  Reactions of ferrous and ferric ions with hydrogen peroxide. Part I.—The ferrous ion reaction , 1951 .

[32]  A. K. Rodopulo.  [Oxidation of tartaric acid in wine in the presence of heavy metal salts (activation of oxygen by iron)]. , 1951, Izvestiia Akademii nauk SSSR. Seriia biologicheskaia.

[33]  G. Stein,et al.  Detection of Free Hydroxyl Radicals by Hydroxylation of Aromatic Compounds , 1950, Nature.

[34]  I. Kolthoff,et al.  Redox recipes. I. Reaction between ferrous iron and peroxides. General considerations , 1949 .

[35]  W. Barb,et al.  Reactions of Ferrous and Ferric Ions with Hydrogen Peroxide , 1949, Nature.

[36]  J. Weiss,et al.  Reaction between Hydrogen Peroxide and Iron Salts , 1949, Nature.

[37]  E. Abel.  Über die katalytische Zersetzung von Wasserstoffsuperoxyd durch Eisensalze II , 1948 .

[38]  P. George.  Some experiments on the reactions of potassium superoxide in aqueous solutions , 1947 .

[39]  D. Keilin,et al.  Haemocuprein and Hepatocuprein, Copper-Protein Compounds of Blood and Liver in Mammals , 1938 .

[40]  D. Keilin,et al.  Hæmocuprein, a Copper-Protein Compound of Red Blood Corpuscles , 1938, Nature.

[41]  J. Weiss.  Reaction Mechanism of the Enzymes Catalase and Peroxidase in the Light of the theory of Chain Reactions , 1937 .

[42]  Fritz Haber,et al.  The catalytic decomposition of hydrogen peroxide by iron salts , 1934 .

[43]  E. W. Neuman.  Potassium Superoxide and the Three‐Electron Bond , 1934 .

[44]  W. C. Bray,et al.  FERRYL ION, A COMPOUND OF TETRAVALENT IRON , 1932 .

[45]  R. Willstätter,et al.  Unpaarigkeit und Radikalketten im Reaktionsmechanismus organischer und enzymatischer Vorgänge , 1931 .

[46]  G. Lehmann,et al.  Über die Einwirkung von Hydroperoxyd auf Ferrosalz (Studien über die Oxydationsvorgänge) , 1928 .

[47]  W. Franke,et al.  Über den Mechanismus der Oxydationsvorgänge. XII. Die Aktivierung des Hydroperoxyds durch Eisen , 1927 .

[48]  A. L. Marshall.  The Mechanism of Reactions photosensitized by Mercury Vapor , 1925 .

[49]  H. Wieland.  Über den Mechanismus der Oxydationsvorgänge , 1913 .

[50]  H. Fenton.  XLI.—The constitution of a new dibasic acid, resulting from the oxidation of tartaric acid , 1896 .

[51]  H. Fenton,et al.  LXXIII.—Oxidation of tartaric acid in presence of iron , 1894 .