Intermediate in the O-O Bond Cleavage Reaction of an Extradiol Dioxygenase

被引:51
|
作者
Kovaleva, Elena G.
Lipscomb, John D. [1 ]
机构
[1] Univ Minnesota, Dept Biochem Mol Biol & Biophys, Minneapolis, MN 55455 USA
关键词
D O I
10.1021/bi801459q
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
The reactive oxy intermediate of the catalytic cycle of extradiol aromatic ring-cleaving dioxygenases is formed by binding the catecholic substrate and O-2 in adjacent ligand positions of the active site metal [usually Fe(II)]. This intermediate and the following Fe(II)-alkyl-peroxo intermediate resulting from oxygen attack on the substrate have been previously characterized in a crystal of homoprotocatechuate 2,3-dioxygenase (HPCD). Here a subsequent intermediate in which the O-O bond is broken to yield a gem diol species is structurally characterized. This new intermediate is stabilized in the crystal by using the alternative substrate, 4-sulfonylcatechol, and the Glu323Leu variant of HPCD, which alters the crystal packing.
引用
收藏
页码:11168 / 11170
页数:3
相关论文
共 50 条
  • [41] THE O-O BOND ENERGY IN HYDROGEN PEROXIDE
    GLOCKLER, G
    MATLACK, G
    JOURNAL OF CHEMICAL PHYSICS, 1946, 14 (08): : 504 - 505
  • [42] Concerted heavy-atom bond cleavage and proton and electron transfers illustrated by proton-assisted reductive cleavage of an O-O bond
    Costentin, Cyrille
    Hajj, Viviane
    Robert, Marc
    Saveant, Jean-Michel
    Tard, Cedric
    PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2011, 108 (21) : 8559 - 8564
  • [43] Modeling steps in the sMMO reaction cycle: Forming a diiron(IV) complex via acid-assisted O-O bond cleavage of a peroxodiiron(III) intermediate derived from O2
    Banerjee, Saikat
    Draksharapu, Apparao
    Que, Lawrence
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2019, 257
  • [44] Geometric and Electronic Structure of [{Cu(MeAN)}2(μ-η2:η2(O22-))]2+ with an Unusually Long O-O Bond: O-O Bond Weakening vs Activation for Reductive Cleavage
    Park, Ga Young
    Qayyum, Munzarin F.
    Woertink, Julia
    Hodgson, Keith O.
    Hedman, Britt
    Sarjeant, Amy A. Narducci
    Solomon, Edward I.
    Karlin, Kenneth D.
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (20) : 8513 - 8524
  • [45] STUDY ON NUCLEOPHILIC CHARACTER OF RADICALS IN TRANSFER-REACTION ON O-O BOND OF PERACIDS
    FOSSEY, J
    LEFORT, D
    TETRAHEDRON, 1980, 36 (08) : 1023 - 1036
  • [46] DIRECT OBSERVATION OF PUSH EFFECT ON THE HETEROLYTIC O-O BOND-CLEAVAGE REACTION OF ACYLPEROXO-IRON(III) PORPHYRIN ADDUCTS
    YAMAGUCHI, K
    WATANABE, Y
    MORISHIMA, I
    JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1992, (23) : 1709 - 1710
  • [47] MOLECULAR-ORBITALS AND O-O CLEAVAGE OF PEROXIDES
    KIKUCHI, O
    JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN, 1979, 37 (08) : 678 - 688
  • [48] THE MECHANISM OF HYDROPEROXIDE O-O BOND SCISSION ON REACTION OF HYDROPEROXIDES WITH IRON(III) PORPHYRINS
    BRUICE, TC
    BALASUBRAMANIAN, PN
    LEE, RW
    SMITH, JRL
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (23) : 7890 - 7892
  • [49] Electrochemical Formation of FeV(O) and Mechanism of Its Reaction with Water During O-O Bond Formation
    Pattanayak, Santanu
    Chowdhury, Debarati Roy
    Garai, Bikash
    Singh, Kundan K.
    Paul, Amit
    Dhar, Basab B.
    Sen Gupta, Sayam
    CHEMISTRY-A EUROPEAN JOURNAL, 2017, 23 (14) : 3414 - 3424
  • [50] DIRECT OBSERVATION OF THE PUSH EFFECT ON THE O-O BOND-CLEAVAGE OF ACYLPEROXOIRON(III) PORPHYRIN COMPLEXES
    YAMAGUCHI, K
    WATANABE, Y
    MORISHIMA, I
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (10) : 4058 - 4065