Pentacopper(II) complexes of α-aminohydroxamic acids:: uranyl-induced conversion of a 12-metallacrown-4 to a 15-metallacrown-5

被引:23
作者
Parac-Vogt, TN [1 ]
Pacco, A [1 ]
Görller-Walrand, C [1 ]
Binnemans, K [1 ]
机构
[1] Katholieke Univ Leuven, Dept Chem, B-3001 Louvain, Belgium
关键词
copper; dioxouranium(VI); hydroxamic acids; metallacrown; uranyl;
D O I
10.1016/j.jinorgbio.2004.10.023
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
Effects of uranyl on the pentacopper(II) complexes of alpha-leucinehydroxamic acid and alpha-tyrosinehydroxamic acid were studied in water and methanol by means of electrospray ionisation mass spectrometry (ES-MS), absorption spectrophotometry, circular dichroism spectroscopy and proton NMR spectroscopy. All the measurements were consistent with the complete conversion of a 12-metallacrown-4 to a 15-metallacrown-5 upon addition of one equivalent of the uranyl ion. The uranyl ion is accommodated in the cavity formed by five copper(II) ions and five alpha-aminohydroxamate ligands. The 15-metallacrown-5 inclusion complexes have a high affinity for the uranyl ion. Competition studies showed that even in the presence of a large excess of calcium(II), the 15-metallacrown-5 remained stable, and no exchange reactions between calcium(II) and uranyl were observed. Extraction of uranyl from the 15-metallacrown-5 was also not detected in the presence of a large excess of 18-crown-6. Trivalent lanthanide ions can be partially sequestered by the 15-metallacrown-5, however, even these trivalent ions are displaced by uranyl. (C) 2004 Elsevier Inc. All rights reserved.
引用
收藏
页码:497 / 504
页数:8
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