Biochemistry Online: An Approach Based on Chemical Logic

Biochemistry Online





Learning Goals/Objectives for Chapter 8A:  After class and this reading, students will be able to

  • explain why oxidation reactions with ground state dioxygen have a high enough activation energy to make the reactions, although thermodynamically favored, kinetically slow
  • explain, using molecular orbital diagrams the difference between triplet and singlet dioxygen
  • using molecular orbital diagrams and Lewis structures, describe the chemical properties of the reduction products of dioxygen (superoxide, peroxide, and water)
  • explain the ways that biological systems use to enhance dioxygen activity and reduce the effects of reactive oxygen species (ROS) such as superoxide and peroxide
  •  write chemical reactions and mechanisms when appropriate for some reactions of triplet and singlet dioxygen, superoxide, peroxide and the hydroxy free radical
  • describe typical reaction of ROS with lipids, proteins, and nucleic acids and data to support the involvement of ROS in complex diseases and aging.
  • Briefly contrast the production and biological activities of ROS and reactive nitrogen intermediates (RNIs)

A11.  Links and References

  1. Wood, J. et al. Senile hair graying: H2O2-mediated oxidative stress affects human hair color by blunting methionine sulfoxide repair.  FASEB Journal.  Published online before print February 23, 2009 as doi: 10.1096/fj.08-125435
  2. Kerr, R. A Shot of Oxygen to Unleash the Evolution of Animals.  Science 314, 1529 (2006)
  3. Falkowski, P.  Tracings Oxygen's Footprint on Life's Metabolic Evolution.  Science 311, 1724 (2006)
  4. Kerr, R. The Story of O2,  Science.  308, 1730 (2005)
  5. Schriner, S. et al. Extension of Murine Life Span by Overexpression of Catalase Targeted to Mitochondria. Science 308, pg 1909 (2005)
  6. Kujoth, G.C. et al. Mitochondrial DNA Mutations, Oxidative Stress and Apoptosis in Mammalian Aging. Science. 309, pg 481 (2005)
  7. Mattson, M. Pathways towards and away from Alzheimer's disease.  Nature. 430, pg 631 (2004)
  8. Marx, J. How cells endure low oxygen.  Science. 303, pg 1454 (2004)
  9. Fromme, J.C. et al. Structural basis for removal of adenine mispaired with 8-oxoguanine by MutY adenine DNA glycosylase.  Nature. 427, pg 652 (2004).
  10. Cumming, R. et al.  Protein Disulfide Bond Formation in the Cytoplasm during Oxidative Stress.  J. Biol. Chem., 279, 21749 (2004)
  11. Darwin, K. Nathan, C. et al. The proteasome of mhycobacterium tuberculosis is required for resistance to nitric oxide.  Science. 302, pg 1963 (2003)
  12. Wentworth, P. et al. Evidence for Ozone Formation in human atherosclerotic arteries. Science. 302, pg 1053 (2003)
  13. Neumann et al. Essential role for the peroxiredoxin Prdx1 in erythrocyte antioxidant defence and tumor suppression. Nature. 424, pg 561 (2003)
  14. Murphy, C. et al. Genes that act downstream of DAF-16 to influence the lifespan of Caenorhabditis elegans.  Nature. 424, pg 277 (2003)
  15. Wentworth, P. et al. Evidence for Antibody-Catalyzed Ozone formation in bacterial killing and inflammation. Science. 298, pg 2195, 2143 (2002)
  16. Wentworth et al. Antibodies Kill by Producing Ozone.  Science. 298, pg 1319 (2002);
  17. Lin et al. Calorie restriction extends Saccharomyces cerevisiae lifespan by increasing respiration.  Nature. 418, pgs. 287 , 344 (2002) (counterintuitive finding that increased O2 consumption which leads to increased free radical production doesn't decrease lifespan)
  18. Wentworth et. al. Antibody Catalysis of Oxidation of Water.  Science:  293, pg 1806  (2001)
  19. Catling et al.  The Rise of Atmospheric Oxygen. 293, pg 819, 839 (2001)
  20. Lee et al. Vitamin C-Induced Decomposition of Lipid Hydroperoxides to Endogeneous Genotoxins.  Science. 292, pg 2083 (2001)
  21. Prinn etl al. Evidence for Substantial Variations of Atmospheric Hydroxyl Radicals in the Past Two Decades. Science. 292. pg 1882 (2001)
  22. Finkel & Holbrook. Oxidants, Oxidative Stress and the Biology of Aging. Nature. 408. pg 239 (2000)
  23. Oxygenating the atmosphere.  Nature. 410. pg 317 (2001)
  24. The Story of O  Nature. 410. pg 862 (2001)
  25. Kirkwood and Austad.  Why Do We Age?  Nature. 408, pg 233 (2000)
  26. Xiong et al. When did photosynthesis emerge on Earth?  Science. 289. pg 1702or3, 1724 (2000)
  27. Salvemini et al. A Nonpeptidyl mimic of superoxide dismutatse with therapeutic activity in rats.  Science. 286. pg 304 (1999)
  28. Head et al. Bioluminescence illuminated (strucure of aequorin - calcium activated photoprotein)  Nature 405, pg 291, 372 (2000)
  29. Chipping Away at the Causes  of Aging (use microarrays to study gene expression in fibroblasts from normal people and patients with progeria). Science. 287, pg 2390, 2486 (2000)
  30. Lee et al. Gene Expression profile of aging and its retardation by caloric restriction. Science. 295, pg 1390 (1999)
  31. Early Life thrived despite earthly travails.  Science. 284, pg 2111 (1999)
  32. Marshall et al. Nitrosation and oxidation in the regulation of gene expression.  (post-translational oxidation of transcription factors- possibly at thol residues - might regulate gene expression.  FASEB Journal. 14, pg 1889 (2000)


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