Scott R A, Zumft W G, Coyle C L, Dooley D M
Department of Chemistry, University of Georgia, Athens 30602.
Proc Natl Acad Sci U S A. 1989 Jun;86(11):4082-6. doi: 10.1073/pnas.86.11.4082.
N2O reductase (N2O----N2) is the terminal enzyme in the energy-conserving denitrification pathway of soil and marine denitrifying bacteria. The protein is composed of two identical subunits and contains eight copper ions per enzyme molecule. The magnetic circular dichroism spectrum of resting (oxidized) N2O reductase is strikingly similar to the magnetic circular dichroism spectrum of the CuA site in mammalian cytochrome c oxidase [Greenwood, C., Hull, B. C., Barber, D., Eglinton, D. G. & Thomson, A. J. (1983) Biochem. J. 215, 303-316] and is unlike the magnetic circular dichroism spectra of all other biological copper chromophores obtained to date. Sulfur (or chlorine) scatterers are required to fit the copper extended x-ray absorption fine structure data of both the oxidized and reduced forms of N2O reductase. Satisfactory fits require a Cu-N or Cu-O [denoted Cu-(N, O)] interaction at 2.0 A, a Cu-(S, Cl) interaction at 2.3 A and an additional Cu(S, Cl) interaction at approximately 2.6 A (oxidized) or approximately 2.7 A (reduced). Approximately eight sulfur ions (per eight copper ions) at approximately 2.3 A are required to fit the extended x-ray absorption fine structure data for both the oxidized and reduced N2O reductase. The 2.3-A Cu-(S, Cl) distance is nearly identical to that previously determined for the CuA site in cytochrome c oxidase. A 2.6-2.7 A Cu-(S, Cl) interaction is also present in resting and fully reduced cytochrome c oxidase. Comparison of the N2O reductase sequence, determined by translating the structural NosZ gene, with cytochrome c oxidase subunit II sequences from several sources indicates that a Gly-Xaa-Xaa-Xaa-Xaa-Xaa-Cys-Ser-Xaa-Xaa-Cys-Xaa-Xaa-Xaa-His stretch is highly conserved. This sequence contains three of the probable ligands (two cysteines and one histidine) in a CuA-type site. Collectively these data establish that Pseudomonas stutzeri N2O reductase contains CuA-type sites.
一氧化二氮还原酶(N2O→N2)是土壤和海洋反硝化细菌能量守恒反硝化途径中的末端酶。该蛋白质由两个相同的亚基组成,每个酶分子含有八个铜离子。静止(氧化)的一氧化二氮还原酶的磁圆二色光谱与哺乳动物细胞色素c氧化酶中CuA位点的磁圆二色光谱惊人地相似[格林伍德,C.,赫尔,B.C.,巴伯,D.,埃格林顿,D.G.和汤姆森,A.J.(1983年)《生物化学杂志》215,303 - 316],与迄今获得的所有其他生物铜发色团的磁圆二色光谱不同。需要硫(或氯)散射体来拟合一氧化二氮还原酶氧化态和还原态的铜扩展X射线吸收精细结构数据。令人满意的拟合需要在2.0埃处有一个Cu - N或Cu - O[表示为Cu - (N, O)]相互作用,在2.3埃处有一个Cu - (S, Cl)相互作用,以及在约2.6埃(氧化态)或约2.7埃(还原态)处有一个额外的Cu(S, Cl)相互作用。拟合氧化态和还原态一氧化二氮还原酶的扩展X射线吸收精细结构数据需要在约2.3埃处大约有八个硫离子(每八个铜离子)。2.3埃的Cu - (S, Cl)距离与先前确定的细胞色素c氧化酶中CuA位点的距离几乎相同。在静止和完全还原的细胞色素c氧化酶中也存在2.6 - 2.7埃的Cu - (S, Cl)相互作用。通过翻译结构NosZ基因确定的一氧化二氮还原酶序列与来自多个来源的细胞色素c氧化酶亚基II序列的比较表明,一个甘氨酸 - Xaa - Xaa - Xaa - Xaa - Xaa - 半胱氨酸 - 丝氨酸 - Xaa - Xaa - 半胱氨酸 - Xaa - Xaa - Xaa - 组氨酸片段高度保守。该序列在一个CuA型位点中包含三个可能的配体(两个半胱氨酸和一个组氨酸)。这些数据共同表明,施氏假单胞菌一氧化二氮还原酶含有CuA型位点。