Molecular Tweezers-like Calix[4]arene Based Alkaline Earth Metal Cation (Ca2+, Sr2+, and Ba2+) Chemosensor and Its Imaging in Living Cells and Zebrafish

  • Inorg Chem. 2019 Nov 4;58(21):14720-14727. doi: 10.1021/acs.inorgchem.9b02364.
Jun-An Fang  1  2 ,  Jiang-Lin Zhao  1 ,  Xian Liao  2 ,  Xi Zeng  2 ,  Kai Chen  3 ,  Xiao-Yuan Wei  1 ,  Shao-Bo Su  1 ,  Qing-Ying Luo  1 ,  Carl Redshaw  4 ,  Zongwen Jin  1
Affiliations
  • 1. Institute of Biomedical & Health Engineering, Shenzhen Institutes of Advanced Technology , Chinese Academy of Sciences , 1068 Xueyuan Avenue , Shenzhen 518055 , China.
  • 2. Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, School of Chemistry and Chemical Engineering , Guizhou University , Guiyang 550025 , China.
  • 3. Jiangsu Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, School of Environmental Science and Engineering , Nanjing University of Information Science & Technology , Nanjing 210044 , China.
  • 4. Department of Chemistry & Biochemistry , University of Hull , Hull HU6 7RX , U.K.
PMID: 31613605 DOI: 10.1021/acs.inorgchem.9b02364
Abstract

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.

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