NMR studies of the paramagnetic complex Fe(II)-bleomycin.

NMR studies of the paramagnetic complex Fe(II)-bleomycin.
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顺磁性复合物 Fe(II)-博莱霉素的 NMR 研究。

DOI:
10.1021/bi962748t
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发表时间:
1997
期刊:
Biochemistry.
影响因子:
--
通讯作者:
QueJr,L
QueJr,L
中科院分区:
--
文献类型:
--
作者:
Lehmann,TE;Ming,LJ;Rosen,ME;QueJr,L

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The coordination chemistry of the iron(II) complex of the antitumor drug bleomycin has been extensively investigated with a number of spectroscopic and chemical techniques. However, the actual structure of this complex is not established. In this report, we present NMR studies of the paramagnetic Fe(II)BLM and use one- and two-dimensional methods to assign the paramagnetically shifted features to particular protons. The data analysis points toward the primary and secondary amines of the β-aminoalanine fragment, the pyrimidine and imidazole rings, and the amide nitrogen of the β-hydroxyhistidine fragment as ligands to the metal center. Correlation of theT1values with the metal−proton distances derived from the NMR-generated solution structure of HOO-Co(III)BLM [Wu, W., Vanderwall, D. E., Lui, S. M., Tang, X.-J., Turner, C. J., Kozarich, J. W., & Stubbe, J. (1996)J. Am. Chem. Soc. 118, 1268−1280] indicates that the two metallobleomycins share similar structures. The chemical shifts as well as theT1values of the sugar protons indicate that these fragments are close but not bound to the metal in Fe(II)BLM.