Molecular Tweezers-like Calix[4]arene Based Alkaline Earth Metal Cation (Ca2+, Sr2+, and Ba2+) Chemosensor and Its Imaging in Living Cells and Zebrafish.
Molecular Tweezers-like Calix[4]arene Based Alkaline Earth Metal Cation (Ca2+, Sr2+, and Ba2+) Chemosensor and Its Imaging in Living Cells and Zebrafish.
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DOI：
10.1021/acs.inorgchem.9b02364
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发表时间：
2019-10
影响因子：
4.6
通讯作者：
Jun-An Fang;Jiang-Lin Zhao;Xian Liao;Xi Zeng;Kai Chen;Xiaoyuan Wei;Shao-Bo Su;Qing-Ying Luo;C. Redshaw;Zongwen Jin
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文献类型：
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作者：
Jun-An Fang;Jiang-Lin Zhao;Xian Liao;Xi Zeng;Kai Chen;Xiaoyuan Wei;Shao-Bo Su;Qing-Ying Luo;C. Redshaw;Zongwen Jin
尽管碱土金属阳离子在我们的日常生活中发挥着重要作用，但由于缺乏令人满意的精确度和快速方便的检测手段，其含量的快速定量分析领域很少受到关注。在本研究中，我们设计了一套基于杯[4]芳烃化学传感器L的分子钳，它被发现表现出高的选择性和灵敏度对Ca 2+，Sr 2+，Ba 2+（通过紫外-可见和荧光方法）与低检测限的数量级为10-7至10-8 M和高缔合常数（的数量级为106）。更重要的是，传感器L不仅可以识别Ca 2+，Sr 2+，Ba 2+，而且还可以通过它们的紫外-可见光谱中的不同红移（560 nm的L·Ca 2+，570 nm的L·Sr 2+，和580 nm的L·Ba 2+复合物）来区分这三种阳离子，这归因于它们不同的原子半径。一种罕见的协同效应的识别机制已被证明由1H NMR光谱滴定。传感器L通过络合后的三羟甲基氨基甲烷与碱土金属离子的协同作用构建了一个高屏蔽场。另外，在传感器L中乙酰氧基甲基的存在导致细胞渗透性的增强，因此，传感器L在活细胞和斑马鱼中表现出优异的感测和成像（体内）。
Although alkaline earth metal cations play an important role in our daily life, little attention has been paid to the field of fast quantitative analysis of their content due to a lack of satisfactory precision and a fast and convenient means of detection. In this study, we have designed a set of molecular tweezers based on the calix[4]arene chemosensor L, which was found to exhibit high selectivity and sensitivity toward Ca2+, Sr2+, and Ba2+ (by UV-vis and fluorescence methods) with low detection limits of the order of 10-7 to 10-8 M and high association constants (of the order of 106). More significantly, sensor L not only can recognize Ca2+, Sr2+, and Ba2+ but also can further discriminate between these three cations via the differing red shifts in their UV-vis spectra (560 nm for L·Ca2+, 570 nm for L·Sr2+, and 580 nm for L·Ba2+ complex) which is attributed to their different atomic radii. A rare synergistic effect for the recognition mechanism has been demonstrated by 1H NMR spectroscopic titration. Sensor L constructed a high shielding field by the cooperation of Tris with alkaline earth metal ion after complex. Additionally, the presence of acetoxymethyl group in sensor L results in enhancement of cell permeability, and as a consequence, sensor L exhibited excellent sensing and imaging (in vivo) in living cells and in zebrafish.