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通过1H NMR光谱对高铁血红蛋白1和4的高自旋形式的铁血红素共振进行归属:与从X射线晶体学获得的结构数据进行比较。

Assignment of the ferriheme resonances of the high-spin forms of nitrophorins 1 and 4 by 1H NMR spectroscopy: comparison to structural data obtained from X-ray crystallography.

作者信息

Shokhireva Tatiana Kh, Smith Kevin M, Berry Robert E, Shokhirev Nikolai V, Balfour Celia A, Zhang Hongjun, Walker F Ann

机构信息

Department of Chemistry, The University of Arizona, Tucson, Arizona 85721-0041, USA.

出版信息

Inorg Chem. 2007 Jan 8;46(1):170-8. doi: 10.1021/ic061407t.

Abstract

In this work, we report the assignment of the majority of the ferriheme resonances of high-spin nitrophorins (NPs) 1 and 4 and compare them to those of NP2, published previously. It is found that the structures of the ferriheme complexes of NP1 and NP4, in terms of the orientation of the histidine imidazole ligand, can be described with good accuracy by NMR techniques and that the angle plot proposed previously for the high-spin form of the NPs (Shokhireva, T. Kh.; Shokhirev, N. V.; Walker, F. A. Biochemistry 2003, 42, 679-693) describes the angle of the effective nodal plane of the axial histidine imidazole in solution. There is an equilibrium between the two heme orientations (A and B), which depends on the heme cavity shape, which can be altered by mutation of amino acids with side chains (phenyl vs tyrosyl) near the potential position where a heme vinyl group would be in one of the isomers. The A:B ratio can be much more accurately measured by NMR spectroscopy than by X-ray crystallography.

摘要

在本研究中,我们报道了高自旋硝普蛋白(NPs)1和4的大多数高铁血红素共振峰的归属,并将它们与之前发表的NP2的共振峰进行比较。研究发现,就组氨酸咪唑配体的取向而言,NP1和NP4的高铁血红素配合物的结构可以通过核磁共振技术精确描述,并且先前为NPs的高自旋形式提出的角度图(Shokhireva, T. Kh.; Shokhirev, N. V.; Walker, F. A. Biochemistry 2003, 42, 679 - 693)描述了溶液中轴向组氨酸咪唑有效节面的角度。两种血红素取向(A和B)之间存在平衡,这取决于血红素腔的形状,而血红素腔的形状可通过在潜在位置附近具有侧链(苯基与酪氨酰基)的氨基酸突变来改变,在其中一种异构体中该潜在位置会有一个血红素乙烯基。通过核磁共振光谱法比通过X射线晶体学能够更准确地测量A:B比率。

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