Differentially selective chemosensor with fluorescence off–on responses on Cu2+ and Zn2+ ions in aqueous media and applications in pyrophosphate sensing, live cell imaging, and cytotoxicity

Sellamuthu Anbu, Rajendran Ravishankaran, M. Fátima C. Guedes da Silva, Anjali A. Karande, Armando J. L. Pombeiro

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159 Citations (Scopus)


A new benzoyl hydrazone based chemosensor R is synthesized by Schiff base condensation of 2,6-diformyl-4-methylphenol and phenyl carbohydrazide and acts as a highly selective fluorescence sensor for Cu2+ and Zn2+ ions in aqueous media. The reaction of R with CuCl2 or ZnCl2 forms the corresponding dimeric dicopper(II) [Cu2(R)(CH3O)(NO3)]2(CH3O)2 (R-Cu2+) and dizinc(II) [Zn2(R)2](NO3)2 (R-Zn2+) complexes, which are characterized, as R, by conventional techniques including single-crystal X-ray analysis. Electronic absorption and fluorescence titration studies of R with different metal cations in a CH3CN/0.02 M HEPES buffer medium (pH = 7.3) show a highly selective binding affinity only toward Cu2+and Zn2+ ions even in the presence of other commonly coexisting ions such as Na+, K+, Mg2+, Ca2+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+, Cd2+, and Hg2+. Quantification of the fluorescence titration analysis shows that the chemosensor R can indicate the presence of Cu2+and Zn2+ even at very low concentrations of 17.3 and 16.5 ppb, respectively. R-Zn2+ acts as a selective metal-based fluorescent sensor for inorganic pyrophosphate ion (PPi) even in the presence of other common anions such as F–, Cl–, Br–, I–, CH3COO–, CO32–, HCO3–, N3–, SO42–, PPi, AMP, ADP, and ATP in an aqueous medium. The propensity of R as a bioimaging fluorescent probe to detect Cu2+ and Zn2+ ions in human cervical HeLa cancer cell lines and their cytotoxicity against human cervical (HeLa), breast cancer (MCF7), and noncancer breast epithelial (MCF10a) cells have also been investigated. R-Cu2+ shows better cytotoxicity and sensitivity toward cancer cells over noncancer cells than R and R-Zn2+ under identical conditions, with the appearance of apoptotic bodies.
Original languageEnglish
Pages (from-to)6655-6664
Number of pages10
JournalInorganic Chemistry
Issue number13
Publication statusPublished - 12 Jun 2014

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