Lipoxygenases - Structure and reaction mechanism.

Lipid oxidation is a common metabolic reaction in all biological systems, appearing in developmentally regulated processes and as response to abiotic and biotic stresses. Products derived from lipid oxidation processes are collectively named oxylipins. Initial lipid oxidation may either occur by chemical reactions or is derived from the action of enzymes. In plants this reaction is mainly catalyzed by lipoxygenase (LOXs) enzymes and during recent years analysis of different plant LOXs revealed insights into their enzyme mechanism. This review aims at giving an overview of concepts explaining the catalytic mechanism of LOXs as well as the different regio- and stereo-specificities of these enzymes.

[1]  A. Brash,et al.  Enzymatic synthesis of a bicyclobutane fatty acid by a hemoprotein–lipoxygenase fusion protein from the cyanobacterium Anabaena PCC 7120 , 2007, Proceedings of the National Academy of Sciences.

[2]  M. Maccarrone,et al.  In vitro oxygenation of soybean biomembranes by lipoxygenase-2. , 1994, Biochimica et biophysica acta.

[3]  I. Feussner,et al.  Biosynthesis of oxylipins in non-mammals. , 2009, Progress in lipid research.

[4]  C. Wasternack,et al.  Lipoxygenase-mediated metabolism of storage lipids in germinating sunflower cotyledons and β-oxidation of (9Z,11E,13S)-13-hydroxy-octadeca-9,11-dienoic acid by the cotyledonary glyoxysomes , 2005, Planta.

[5]  G. Howe,et al.  Tomato allene oxide synthase and fatty acid hydroperoxide lyase, two cytochrome P450s involved in oxylipin metabolism, are targeted to different membranes of chloroplast envelope. , 2001, Plant physiology.

[6]  I. Feussner,et al.  On the Substrate Binding of Linoleate 9-Lipoxygenases , 2009, Lipids.

[7]  I. Feussner,et al.  The lipid body lipoxygenase from cucumber seedlings exhibits unusual reaction specificity , 1995, FEBS letters.

[8]  A. Fischer,et al.  Activity of soybean lipoxygenase isoforms against esterified fatty acids indicates functional specificity. , 2001, Archives of biochemistry and biophysics.

[9]  O. Seitz,et al.  Cover Picture: Forced Intercalation Probes (FIT Probes): Thiazole Orange as a Fluorescent Base in Peptide Nucleic Acids for Homogeneous Single-Nucleotide-Polymorphism Detection (ChemBioChem 1/2005) , 2005 .

[10]  D. Lawson,et al.  Probing a novel potato lipoxygenase with dual positional specificity reveals primary determinants of substrate binding and requirements for a surface hydrophobic loop and has implications for the role of lipoxygenases in tubers. , 2001, The Biochemical journal.

[11]  I. Feussner,et al.  Conversion of cucumber linoleate 13-lipoxygenase to a 9-lipoxygenating species by site-directed mutagenesis. , 1999, Proceedings of the National Academy of Sciences of the United States of America.

[12]  S. Dahlén,et al.  Leukotrienes and lipoxins: structures, biosynthesis, and biological effects. , 1987, Science.

[13]  E. Sudharshan,et al.  Change in the positional specificity of lipoxygenase 1 due to insertion of fatty acids into phosphatidylcholine deoxycholate mixed micelles. , 1999, Biochemistry.

[14]  I. Feussner,et al.  Formation of oxylipins by CYP74 enzymes , 2006, Phytochemistry Reviews.

[15]  Ivo Feussner,et al.  The lipoxygenase pathway. , 2003, Annual review of plant biology.

[16]  I. Feussner,et al.  Characterization of a 13‐lipoxygenase from virgin olive oil and oil bodies of olive endosperms , 1998 .

[17]  J. Vliegenthart,et al.  Oxidation of dilinoleoyl phosphatidylcholine by lipoxygenase 1 from soybeans. , 1998, Archives of biochemistry and biophysics.

[18]  R. Wiesner,et al.  The oxygenation of cholesterol esters by the reticulocyte lipoxygenase , 1991, FEBS letters.

[19]  G. Mei,et al.  Structural properties of plant and mammalian lipoxygenases. Temperature-dependent conformational alterations and membrane binding ability. , 2008, Biochemistry.

[20]  M. Hamberg,et al.  On the specificity of the oxygenation of unsaturated fatty acids catalyzed by soybean lipoxidase. , 1967, The Journal of biological chemistry.

[21]  Victor A Kenyon,et al.  Tryptophan 500 and arginine 707 define product and substrate active site binding in soybean lipoxygenase-1. , 2004, Biochemistry.

[22]  I. Feussner,et al.  Identification of an amino acid determinant of pH regiospecificity in a seed lipoxygenase from Momordica charantia. , 2008, Phytochemistry.

[23]  A. Brash,et al.  A 49-kDa Mini-lipoxygenase from Anabaena sp. PCC 7120 Retains Catalytically Complete Functionality* , 2008, Journal of Biological Chemistry.

[24]  M. Hammel,et al.  Structural flexibility of the N-terminal beta-barrel domain of 15-lipoxygenase-1 probed by small angle X-ray scattering. Functional consequences for activity regulation and membrane binding. , 2004, Journal of molecular biology.

[25]  E. Sigal,et al.  Oxidation, Lipoxygenase, and Atherogenesis , 1994, Annals of the New York Academy of Sciences.

[26]  I. Feussner,et al.  Oxylipins: structurally diverse metabolites from fatty acid oxidation. , 2009, Plant physiology and biochemistry : PPB.

[27]  A. Brash,et al.  On singular or dual positional specificity of lipoxygenases. The number of chiral products varies with alignment of methylene groups at the active site of the enzyme. , 1990, The Journal of biological chemistry.

[28]  A. Brash,et al.  A single active site residue directs oxygenation stereospecificity in lipoxygenases: stereocontrol is linked to the position of oxygenation. , 2004, Proceedings of the National Academy of Sciences of the United States of America.

[29]  A. Brash,et al.  A comprehensive model of positional and stereo control in lipoxygenases. , 2005, Biochemical and biophysical research communications.

[30]  S. Tatulian,et al.  Uncovering a calcium-regulated membrane-binding mechanism for soybean lipoxygenase-1. , 1998, Biochemistry.

[31]  H. Kindl,et al.  The N-terminal beta-barrel structure of lipid body lipoxygenase mediates its binding to liposomes and lipid bodies. , 2000, European journal of biochemistry.

[32]  J. Vliegenthart,et al.  Positional specificity of corn germ lipoxygenase as a function of pH. , 1972, Biochemical and biophysical research communications.

[33]  D. Lawson,et al.  Mutagenesis and modelling of linoleate-binding to pea seed lipoxygenase. , 2001, European journal of biochemistry.

[34]  H. Gardner.  Soybean lipoxygenase-1 enzymically forms both (9S)- and (13S)-hydroperoxides from linoleic acid by a pH-dependent mechanism. , 1989, Biochimica et biophysica acta.

[35]  I. Feussner,et al.  A lipoxygenase with linoleate diol synthase activity from Nostoc sp. PCC 7120. , 2008, The Biochemical journal.

[36]  E. Oliw,et al.  Plant and fungal lipoxygenases. , 2002, Prostaglandins & other lipid mediators.

[37]  H. Kühn,et al.  The Rabbit 15-Lipoxygenase Preferentially Oxygenates LDL Cholesterol Esters, and This Reaction Does Not Require Vitamin E* , 1998, The Journal of Biological Chemistry.

[38]  N. Keller,et al.  Oxylipins as developmental and host-fungal communication signals. , 2007, Trends in microbiology.

[39]  I. Feussner,et al.  Lipoxygenase-2 oxygenates storage lipids in embryos of germinating barley. , 1997, European journal of biochemistry.

[40]  O. Boutaud,et al.  Identification of a naturally occurring peroxidase-lipoxygenase fusion protein. , 1997, Science.

[41]  C. Wasternack,et al.  Structural Elucidation of Oxygenated Storage Lipids in Cucumber Cotyledons , 1997, The Journal of Biological Chemistry.

[42]  C. Craik,et al.  A primary determinant for lipoxygenase positional specificity , 1991, Nature.

[43]  M. Egmond,et al.  Stereospecificity of the hydrogen abstraction at carbon atom n-8 in the oxygenation of linoleic acid by lipoxygenases from corn germs and soya beans. , 1972, Biochemical and biophysical research communications.

[44]  H. Kindl,et al.  All three acyl moieties of trilinolein are efficiently oxygenated by recombinant His‐tagged lipid body lipoxygenase in vitro , 1998, FEBS letters.

[45]  R. Fletterick,et al.  Burying a charge , 1998, Nature Structural Biology.

[46]  J. Siedow.  PLANT LIPOXYGENASE: STRUCTURE AND FUNCTION , 1991 .

[47]  J. Felsenstein,et al.  A Hidden Markov Model approach to variation among sites in rate of evolution. , 1996, Molecular biology and evolution.

[48]  J. Murray,et al.  Rabbit reticulocyte lipoxygenase catalyzes specific 12(S) and 15(S) oxygenation of arachidonoyl-phosphatidylcholine. , 1988, Archives of biochemistry and biophysics.

[49]  Georg Pohnert,et al.  Diatom/Copepod Interactions in Plankton: The Indirect Chemical Defense of Unicellular Algae , 2005, Chembiochem : a European journal of chemical biology.

[50]  E. Blée,et al.  Impact of phyto-oxylipins in plant defense. , 2002, Trends in plant science.

[51]  A. Brash.  Lipoxygenases: Occurrence, Functions, Catalysis, and Acquisition of Substrate* , 1999, The Journal of Biological Chemistry.

[52]  G. Howe,et al.  Plant immunity to insect herbivores. , 2008, Annual review of plant biology.

[53]  J. Falke,et al.  Mechanism of specific membrane targeting by C2 domains: localized pools of target lipids enhance Ca2+ affinity. , 2007, Biochemistry.

[54]  P. Vachette,et al.  Structural stability of soybean lipoxygenase-1 in solution as probed by small angle X-ray scattering. , 2005, Journal of molecular biology.

[55]  Claus Schneider,et al.  Control of oxygenation in lipoxygenase and cyclooxygenase catalysis. , 2007, Chemistry & biology.

[56]  W. Gerwick,et al.  Biogenesis and biological function of marine algal oxylipins. , 1999, Advances in experimental medicine and biology.

[57]  C. Wasternack,et al.  Jasmonates: an update on biosynthesis, signal transduction and action in plant stress response, growth and development. , 2007, Annals of botany.

[58]  Ivo Feussner,et al.  Lipoxygenases: occurrence, functions and catalysis. , 2006, Journal of plant physiology.

[59]  I. Feussner,et al.  Properties of a mini 9R-lipoxygenase from Nostoc sp. PCC 7120 and its mutant forms. , 2008, Phytochemistry.