School of Environment and Life Science, Guangxi Teachers Education University, Guangxi, Nanning 530001, China; Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources (Guangxi Normal University), Ministry of Education of China, China.
Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources (Guangxi Normal University), Ministry of Education of China, China.
Spectrochim Acta A Mol Biomol Spectrosc. 2019 Feb 15;209:141-149. doi: 10.1016/j.saa.2018.10.030. Epub 2018 Oct 16.
A fluorescent sensor L based on a pyrazolopyrimidine core simultaneously detects Cu and Ni ions by photoluminescence quenching, even in the presence of other metal cations. Sensor L possesses high association constants of 5.24 × 10 M and 2.85 × 10 M and low detection limits of 0.043 μM and 0.038 μM for Cu and Ni, respectively. The binding stoichiometry ratios of L to Cu or Ni is 1:1 as determined by Benesi-Hildebrand and Job's plots, and by crystal structures. DFT calculations on L-Cu indicated reduced electron donation from the coordinated pyrazolopyridine to the fused pyrimidine and pendant phenyl group which, together with a smaller HOMO-LUMO orbital gap could favour non-radiative decay and explain the observed fluorescence quenching. Sensor L possessed low cytotoxicity and good imaging characteristics for Cu and Ni in living cells, suggesting potential applications for detecting Cu and Niin vivo.
一种基于吡唑并嘧啶核心的荧光传感器 L 通过光致荧光猝灭同时检测 Cu 和 Ni 离子，即使存在其他金属阳离子也是如此。传感器 L 对 Cu 和 Ni 的结合常数分别高达 5.24×10 M 和 2.85×10 M，检测限分别低至 0.043 μM 和 0.038 μM。通过 Benesi-Hildebrand 和 Job 图谱以及晶体结构确定，L 与 Cu 或 Ni 的结合计量比为 1:1。对 L-Cu 的 DFT 计算表明，配位的吡唑并吡啶向稠合嘧啶和取代苯基的电子供体减少，这与较小的 HOMO-LUMO 轨道间隙一起，有利于非辐射衰减，并解释了观察到的荧光猝灭。传感器 L 在活细胞中对 Cu 和 Ni 具有低细胞毒性和良好的成像特性，这表明其在体内检测 Cu 和 Ni 方面具有潜在应用。
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