A nonheme iron(II) complex that models the redox cycle of lipoxygenase

被引：42

作者：

Kim, J

Zang, Y

Costas, M

Harrison, RG

Wilkinson, EC

Que, L

机构：

[1] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA

[2] Univ Minnesota, Ctr Met Biocatalysis, Minneapolis, MN 55455 USA

来源：

JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY | 2001年 / 6卷 / 03期

关键词：

lipoxygenase; model compounds; nonheme iron; peroxo complexes;

D O I：

10.1007/s007750000198

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 air-stable complex [Fe(6-Me-3-TPA) (O2CAr)](+) [1; 6-Me-3-TPA= tris(6-me thyl-2-pyridylmethyl)amine] has been synthesized as a model for the iron(II) site of lipoxygenase. This iron(II) complex reacts with 0.5 equiv ROOH to form a yellow species. which has been formulated as [Fe-III(OH)(6-Me-3-TPA)(O2CAr)](+) (2) by electrospray mass spectrometry. Addition of more ROOH converts 2 into a purple species, which is characterized by electrospray ionization mass spectrometry and resonance Raman spectroscopy as [Fe-III(OOR)(6-Me-3-TPA)(O2CAr)](+). The purple species is metastable and decomposes via Fe-O bond homolysis to regenerate the starting iron(II) complex. These metal-centered transformations parallel the changes observed for lipoxygenase in its reaction with its product hydroperoxide.

引用

收藏

页码：275 / 284

页数：10

相关论文

共 41 条

[1] THE 3-DIMENSIONAL STRUCTURE OF AN ARACHIDONIC-ACID 15-LIPOXYGENASE [J].

BOYINGTON, JC ;

GAFFNEY, BJ ;

AMZEL, LM .

SCIENCE, 1993, 260 (5113) :1482-1486

[2] Spectroscopic study of [Fe2(O2)(OBz)2{HB(pz′)3}2]:: Nature of the μ-1,2 peroxide-Fe(III) bond and its possible relevance to O2 activation by non-heme iron enzymes [J].

Brunold, TC ;

Tamura, N ;

Kitajima, N ;

Moro-oka, Y ;

Solomon, EI .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (23) :5674-5690

[3] SPECTRA-STRUCTURE CORRELATION OF ALKYL PEROXIDES [J].

BUDINGER, PA ;

MOONEY, JR ;

GRASSELLI, JG ;

FAY, PS ;

GUTTMAN, AT .

ANALYTICAL CHEMISTRY, 1981, 53 (06) :884-889

[4] Spectroscopic and theoretical studies of mononuclear copper(II) alkyl- and hydroperoxo complexes: Electronic structure contributions to reactivity [J].

Chen, P ;

Fujisawa, K ;

Solomon, EI .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (41) :10177-10193

[5] MODELS FOR ALPHA-KETO ACID-DEPENDENT NONHEME IRON ENZYMES - STRUCTURES AND REACTIVITY OF [FE-II(L)(O(2)CCOPH)](CLO4) COMPLEXES [J].

CHIOU, YM ;

QUE, L .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (14) :3999-4013

[6] CO-ORDINATION NUMBER OF TRANSITION-METAL IONS .7. AN EVALUATION OF STERIC FACTORS IN STABILISATION OF HIGH-SPIN 5-CO-ORDINATE NICKEL(2) COMPLEXES OF MULTIDENDATE ALPHA-PYRIDYL LIGANDS [J].

DAMOTA, MM ;

RODGERS, J ;

NELSON, SM .

JOURNAL OF THE CHEMICAL SOCIETY A -INORGANIC PHYSICAL THEORETICAL, 1969, (13) :2036-&

[7] DIOXYGEN BINDING TO DIFERROUS CENTERS - MODELS FOR DIIRON OXO PROTEINS [J].

DONG, YH ;

MENAGE, S ;

BRENNAN, BA ;

ELGREN, TE ;

JANG, HG ;

PEARCE, LL ;

QUE, L .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (05) :1851-1859

[8] MECHANISM OF ASYMMETRIC EPOXIDATION .2. CATALYST STRUCTURE [J].

FINN, MG ;

SHARPLESS, KB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (01) :113-126

[9] The structure of mammalian 15-lipoxygenase reveals similarity to the lipases and the determinants of substrate specificity [J].

Gillmor, SA ;

Villasenor, A ;

Fletterick, R ;

Sigal, E ;

Browner, MF .

NATURE STRUCTURAL BIOLOGY, 1997, 4 (12) :1003-1009

[10] LIPID-PEROXIDATION BY SYNTHETIC ANALOGS OF IRON BLEOMYCIN - POSSIBLE ROLE OF A LOW-SPIN (HYDROPEROXO)IRON(III) INTERMEDIATE IN LIPID-PEROXIDATION INDUCED BY BLEOMYCIN [J].

GUAJARDO, RJ ;

MASCHARAK, PK .

INORGANIC CHEMISTRY, 1995, 34 (04) :802-808

← 1 2 3 4 5 →