Selective synthesis of substituted amino-quinoline derivatives by C-H activation and fluorescence evaluation of their lipophilicity-responsive properties
Selective synthesis of substituted amino-quinoline derivatives by C-H activation and fluorescence evaluation of their lipophilicity-responsive properties
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DOI：
10.1038/s41598-019-53882-z
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发表时间：
2019-11
影响因子：
4.6
通讯作者：
Yasufumi Fuchi;Masaomi Sakuma;Kohei Ohyama;Ryusuke Hagihara;Minaki Kohno;Koichi Hamada;A. Mizutani;S. Karasawa
中科院分区：
文献类型：
--
作者：
Yasufumi Fuchi;Masaomi Sakuma;Kohei Ohyama;Ryusuke Hagihara;Minaki Kohno;Koichi Hamada;A. Mizutani;S. Karasawa
通过钯催化的C-H活化反应，短步骤合成了8位带有苯基芳香基团的推拉型荧光氨基喹啉衍生物（TFMAQ）（TFMAQ-8Ar系列）。通过钯和膦配体的组合，以高产率选择性地控制N-芳基化或C-H活化反应。 TFMAQ-8Ar 类似物在非极性和极性溶剂中表现出荧光溶剂化显色现象。在非极性溶剂中，绝对荧光量子产率较高，而在极性溶剂中荧光几乎被猝灭。 X射线晶体结构分析表明，由于7-氨基处喹啉环和苯环之间的平面结构，TFMAQ-8Ar衍生物在固态下也表现出高荧光发射。通过共焦激光显微镜使用 TFMAQ-8Ar 衍生物对 3T3-L1 细胞进行荧光成像。由于 TFMAQ-8Ar 衍生物的积累，在脂滴处观察到强烈且特定的发射。因此，我们建议 TFMAQ-8Ar 衍生物应成为用于脂滴实时成像的多功能荧光探针。
Push-pull type fluorescent amino-quinoline derivatives (TFMAQ) bearing phenyl aromatic groups in the 8-position (TFMAQ-8Ar series) were synthesized via palladium-catalyzed C-H activation reaction in short steps. TheN-arylation or C-H activation reactions were selectively controlled with high yield by combinations of palladium and phosphine ligands. The TFMAQ-8Ar analogues exhibited fluorescent solvatochromism in non-polar and polar solvents. In non-polar solvent, the absolute fluorescence quantum yield was high, wheareas the fluorescence was almost quenched in polar solvent. The TFMAQ-8Ar derivatives also showed high fluorescence emission at solid state owing to the planar structure between the quinoline ring and phenyl ring at the 7-amino group, as demonstrated by X-ray crystal structure analysis. The fluorescence imaging of 3T3-L1 cell using TFMAQ-8Ar derivatives was performed by confocal laser microscopy. Strong and specific emissions at lipid droplets were observed owing to the accumulation of TFMAQ-8Ar derivatives. Therefore, we propose that the TFMAQ-8Ar derivatives should become a versatile fluorescence probe for the live imaging of lipid droplets.