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

Abstract

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 Cu(2+) and Zn(2+) 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-Cu(2+)) and dizinc(II) [Zn2(R)2](NO3)2 (R-Zn(2+)) 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 Cu(2+)and Zn(2+) ions even in the presence of other commonly coexisting ions such as Na(+), K(+), Mg(2+), Ca(2+), Mn(2+), Fe(2+), Fe(3+), Co(2+), Ni(2+), Cd(2+), and Hg(2+). Quantification of the fluorescence titration analysis shows that the chemosensor R can indicate the presence of Cu(2+)and Zn(2+) even at very low concentrations of 17.3 and 16.5 ppb, respectively. R-Zn(2+) 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(-), CO3(2-), HCO3(-), N3(-), SO4(2-), PPi, AMP, ADP, and ATP in an aqueous medium. The propensity of R as a bioimaging fluorescent probe to detect Cu(2+) and Zn(2+) 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-Cu(2+) shows better cytotoxicity and sensitivity toward cancer cells over noncancer cells than R and R-Zn(2+) under identical conditions, with the appearance of apoptotic bodies.

A highly selective “ON–OFF” probe for colorimetric and fluorometric sensing of Cu2+in water

“…[64][65][66][67][68] To the best of our knowledge, limited work has been carried out in the development of diformyl phenol based probes for selective colorimetric sensing of Cu 2+ and only two examples are there that represent quenching based detection of Cu 2+ (ESI Chart 1 †). 58,69 Furthermore, involvement of tautomeric equilibrium has not been explored till date.…”

Research Progress in the Sensing Ensembles for Pyrophosphate

“…图 1 PPi 荧光传感器 1 Figure 1 Fluorescent sensor for PPi based on compound 1 金属配合物作为阴离子比色、荧光传感器/体系, 具 有较高灵敏度和选择性、较短的响应时间等优势 [18,19] .…”

A colorimetric chemosensor for the sequential detection of copper(II) and cysteine

“…In particular, Cu 2+ is the third most abundant essential trace element in the human body. Various redox processes, enzyme functions, and pigments are dependent on copper ions as cofactors [5][6][7]. However, excess concentration of Cu 2+ in the neuronal cytoplasm can cause Wilson and Menkes disease [8,9].…”