11B NMR Probes of Copper(II): Finding and Implications of the Cu2+-Promoted Decomposition of ortho-Carborane Deriviatives.
11B NMR Probes of Copper(II): Finding and Implications of the Cu2+-Promoted Decomposition of ortho-Carborane Deriviatives.
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铜 (II) 的 11B NMR 探针：Cu2 促进邻碳硼烷衍生物分解的发现和意义。
DOI：
10.1002/ejic.201600117
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发表时间：
2016
期刊：
影响因子：
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通讯作者：
Ryo Abe and Shin Aoki,
中科院分区：
文献类型：
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作者：
Tomohiro Tanaka;Yukiko Nishiura;Rikita Araki;Takaomi Saido;Ryo Abe and Shin Aoki,
开发非侵入性方法来检测d-区金属离子，如铜（Cu 2+），锌（Zn 2+）和锰（Mn 2+），对于了解它们的生物学作用及其与疾病的关系非常重要。由于11 B是生命系统中的超痕量元素，我们一直对使用11 B NMR探针检测d-区金属离子感兴趣。邻碳硼烷由10个硼原子和2个碳原子组成，已被应用于许多药物和生物活性剂。在这项工作中，我们发现，在Mn 2+或Cu 2+存在下，在中性pH的水溶液中，theo-碳硼烷-侧基cyclen（L3-L5）（cyclen = 1，4，7，10-四氮杂环十二烷）被分解，伴随着4-9当量的cyclen的释放。的B（OH）3。此外，发现含有羟基而不是环戊二烯基单元的碳硼烷衍生物在Cu 2+和相应的络合物如Cu（bpy）的存在下也发生分解，得到10当量的环戊二烯基碳硼烷。通过11 B NMR光谱分析和偶氮甲碱-H测定证实了B（OH）3的存在。这些反应被应用于11B MRI（磁共振成像）探针的Cu 2+。
The development of noninvasive methodologies for the detection of d‐block metal ions such as copper (Cu2+), zinc (Zn2+), and manganese (Mn2+) is important for understanding their biological roles and relationship with diseases. We have been interested in the use of11B NMR probes for the detection of d‐block metal ions, because11B is an ultratrace element in living systems.o‐Carboranes, which consist of ten boron and two carbon atoms, have been applied to numerous drugs and biological active agents. In this work, we found that theo‐carborane‐pendant cyclens (L3–L5) (cyclen = 1,4,7,10‐tetraazacyclododecane) are decomposed in the presence of Mn2+or Cu2+in aqueous solution at neutral pH, accompanied by the release of 4–9 equiv. of B(OH)3. Furthermore, it was found thato‐carborane derivatives that contain hydroxyl groups instead of a cyclen unit also undergo decomposition in the presence of Cu2+and the corresponding complexes such as Cu(bpy) to afford 10 equiv. of B(OH)3, as confirmed by11B NMR spectroscopic analysis and an azomethine‐H assay. These reactions are applied to11B MRI (magnetic resonance imaging) probes for Cu2+.