Multi-Use NBD-Based Tetra-amino Macrocycle: Fluorescent Probe for Metals and Anions and Live Cell Marker
Multi-Use NBD-Based Tetra-amino Macrocycle: Fluorescent Probe for Metals and Anions and Live Cell Marker
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DOI：
10.1002/chem.201103135
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发表时间：
2012-04-01
影响因子：
4.3
通讯作者：
Varrese, Maria Antonietta
中科院分区：
文献类型：
--
作者：
Amatori, Stefano;Ambrosi, Gianluca;Varrese, Maria Antonietta
配体L(4-(7-nitrobenzo[1，2，5]oxadiazole-4-yl)-1，7-dimethyl-1，4，7，10-tetra-azacyclododecane)是一种多功能的荧光传感器，可用于铜、锌和镉的金属检测，是卤化物荧光金属受体的构建块，也是活细胞内细胞器的标志物。在乙腈溶液中，配体L对金属配位具有络合增强荧光(CHEF)效应。在所研究的所有三种配合物中，金属阳离子都是配位不饱和的，因此，它可以以阴离子物种的形式结合二级配体。讨论了[ZnLCl](ClO4)的晶体结构。CuII和ZnII络合物在卤化物作用下被猝灭，而[CdL]2+物种在乙腈溶液中对卤化物阴离子起OFON传感器的作用。在阴离子存在下，荧光响应的机理取决于所用金属离子的性质，并已通过核磁共振光谱、UV/Vis和荧光技术等光谱方法和计算方法进行了研究。在HeLa细胞上进行的亚细胞定位实验表明，L主要定位在胞浆极化部分的斑点状结构中，该部分被高尔基体占据，发出绿色荧光信号。
Ligand L (4-(7-nitrobenzo[1,2,5]oxadiazole-4-yl)-1,7-dimethyl-1,4,7,10-tetra-azacyclododecane) is a versatile fluorescent sensor useful for CuII, ZnII and CdII metal detection, as a building block of fluorescent metallo-receptor for halide detection, and as an organelle marker inside live cells. Ligand L undergoes a chelation-enhanced fluorescence (CHEF) effect upon metal coordination in acetonitrile solution. In all three complexes investigated the metal cation is coordinatively unsaturated; thus, it can bind secondary ligands as anionic species. The crystal structure of [ZnLCl](ClO4) is discussed. CuII and ZnII complexes are quenched upon halide interaction, whereas the [CdL]2+ species behaves as an OFFON sensor for halide anions in acetonitrile solution. The mechanism of the fluorescence response in the presence of the anion depends on the nature of the metal ion employed and has been studied by spectroscopic methods, such as NMR spectroscopy, UV/Vis and fluorescence techniques and by computational methods. Subcellular localization experiments performed on HeLa cells show that L mainly localizes in spot-like structures in a polarized portion of the cytosol that is occupied by the Golgi apparatus to give a green fluorescence signal.