Non-covalent strategy for activating separation and detection functionality by use of the multifunctional host molecule thiacalixarene
Non-covalent strategy for activating separation and detection functionality by use of the multifunctional host molecule thiacalixarene
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DOI：
10.1007/s10847-009-9550-9
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发表时间：
2009-03
影响因子：
2.3
通讯作者：
Nobuhiko Iki
中科院分区：
文献类型：
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作者：
Nobuhiko Iki
这篇综述文章提出了一种用于激活分离和检测功能的非共价策略；该策略不是通过广泛的有机合成共价构建的分子受体来发挥作用，而是通过将简单的分子平台与化学“场”或功能成分相结合。对于这样的平台，我们采用了硫杂杯芳烃（其中桥联亚甲基被硫取代的杯芳烃）来证明非共价策略的有用性和硫杂杯芳烃的多功能性。硫杂杯芳烃表现出通过与桥硫和相邻酚氧配位来识别金属离子的固有能力，以及在空腔中包含有机客体分子的能力。此外，硫杂杯芳烃的非共价偶联为体系提供了比硫杂杯芳烃本身更高的功能。本文描述的功能如下：（1）CuII、CdII、PbII等重金属离子预浓缩200倍； (2) 柱前衍生化试剂，用于通过反相 HPLC 高选择性和灵敏地测定亚 ppb 水平的 NiII、AlIII、FeIII 和 TiIVat 含量； (3) 用 TbIII 离子自组装形成发光受体，用于检测 10−10M 水平的 1-乙基喹啉客体； (4) 通过形成 AgI-TbIII-硫代杯芳烃三元超分子复合物，形成 10−9M 水平的 AgI 离子传感系统。这些例子支持非共价策略是一种非常有前途的获得分子平台之外的功能的方法。此外，这些不同的功能表明硫代杯芳烃的多功能性及其对非共价策略的适用性，因为固有的官能团（例如桥硫、酚氧、对位取代基、芳环和疏水空腔）协同发挥这些功能。
This review article proposes a non-covalent strategy for activating separation and detection functionality; this strategy acts not through extensive organic synthesis to a covalently constructed molecular receptor, but by combining a simple molecular platform with a chemical “field” or functional component. For such a platform, we employed thiacalixarenes—calixarenes in which the bridging methylene groups are replaced with sulfur—to demonstrate usefulness of the non-covalent strategy and the multifunctionality of thiacalixarene. Thiacalixarene exhibits inherent abilities to recognize metal ions by coordinating with the bridging sulfur and adjacent phenol oxygen, as well as to include organic guest molecules in the cavity. Moreover, the non-covalent coupling of thiacalixarene provides systems with functions higher than thiacalixarene by itself. The functions described in this paper are as follows: (1) a 200-fold pre-concentration of heavy metal ions such as CuII, CdII, and PbII; (2) a pre-column derivatization reagent for the highly selective and sensitive determination of NiII, AlIII, FeIII, and TiIVat sub-ppb levels with reversed-phase HPLC; (3) the self-assembled formation of a luminescence receptor with TbIIIions for the detection of 10−10M levels of 1-ethylquinolinium guest; and (4) a sensing system for 10−9M levels of AgIions by the formation of the AgI-TbIII-thiacalixarene ternary supramolecular complex. These examples support the non-covalent strategy as a highly promising way to obtain functions beyond that of a molecular platform. In addition, these diverse functions indicate the multifunctionality of thiacalixarene as well as its suitability to the non-covalent strategy, since the inherent functional groups—such as the bridging sulfur, phenol oxygen,p-substituent, aromatic ring, and hydrophobic cavity—synergistically perform the functions.