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蛋白质晶体中高密度四铼簇的形成及其在医学成像中的意义。

Formation of a highly dense tetra-rhenium cluster in a protein crystal and its implications in medical imaging.

作者信息

Brink Alice, Helliwell John R

机构信息

Department of Chemistry, University of the Free State, Nelson Mandela Drive, Bloemfontein, 9301, South Africa.

School of Chemistry, University of Manchester, Brunswick Street, Manchester M13 9PL, UK.

出版信息

IUCrJ. 2019 Jun 13;6(Pt 4):695-702. doi: 10.1107/S2052252519006651. eCollection 2019 Jul 1.

Abstract

The fact that a protein crystal can serve as a chemical reaction vessel is intrinsically fascinating. That it can produce an electron-dense tetranuclear rhenium cluster compound from a rhenium tri-carbonyl tri-bromo starting compound adds to the fascination. Such a cluster has been synthesized previously , where it formed under basic conditions. Therefore, its synthesis in a protein crystal grown at pH 4.5 is even more unexpected. The X-ray crystal structures presented here are for the protein hen egg-white lysozyme incubated with a rhenium tri-carbonyl tri-bromo compound for periods of one and two years. These reveal a completed, very well resolved, tetra-rhenium cluster after two years and an intermediate state, where the carbonyl ligands to the rhenium cluster are not yet clearly resolved, after one year. A dense tetranuclear rhenium cluster, and its technetium form, offer enhanced contrast in medical imaging. Stimulated by these crystallography results, the unusual formation of such a species directly in an situation has been considered. It offers a new option for medical imaging compounds, particularly when considering the application of the pre-formed tetranuclear cluster, suggesting that it may be suitable for medical diagnosis because of its stability, preference of formation and biological compatibility.

摘要

蛋白质晶体能够充当化学反应容器这一事实本身就极具吸引力。它能从三羰基三溴化铼起始化合物生成电子密度高的四核铼簇化合物,更是增添了这种魅力。此前已经合成过这样的簇合物,它是在碱性条件下形成的。因此,在pH 4.5条件下生长的蛋白质晶体中合成该簇合物就更加出人意料。这里展示的X射线晶体结构是关于用三羰基三溴化铼化合物孵育一到两年的鸡蛋清溶菌酶的。这些结果显示,两年后形成了一个完整的、分辨率很高的四核铼簇,而一年后则处于一种中间状态,此时铼簇的羰基配体尚未清晰分辨出来。致密的四核铼簇及其锝形式在医学成像中能提供增强的对比度。受这些晶体学结果的启发,人们考虑了在特定情况下直接形成这种物质的不寻常过程。这为医学成像化合物提供了一种新选择,特别是考虑到预先形成的四核簇的应用时,这表明它可能因其稳定性、形成偏好和生物相容性而适用于医学诊断。

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