jo2022372_si_002.cif (42.8 kB)
Lower Rim 1,3-Di{4-antipyrine}amide Conjugate of Calix[4]arene: Synthesis, Characterization, and Selective Recognition of Hg2+ and Its Sensitivity toward Pyrimidine Bases
dataset
posted on 2012-02-03, 00:00 authored by Jayaraman Dessingou, Khatija Tabbasum, Atanu Mitra, Vijaya
Kumar Hinge, Chebrolu P. RaoThe structurally characterized lower rim 1,3-di{4-antipyrine}amide
conjugate of calix[4]arene (L) exhibits high selectivity
toward Hg2+ among other biologically important metal ions, viz., Na+, K+, Ca2+, Mg2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, Pb2+, and Ag+ as studied by fluorescence,
absorption, and ESI MS. L acts as a sensor for Hg2+ by switch-off fluorescence and exhibits a lowest detectable
concentration of 1.87 ± 0.1 ppm. The complex formed between L and Hg2+ is found to be 1:1 on the basis of absorption
and fluorescence titrations and was confirmed by ESI MS. The coordination
features of the mercury complex of L were derived on the basis of DFT computations and found that the Hg2+ is bound through
an N2O2 extending from both the arms to result
in a distorted octahedral geometry with two vacant sites. The nanostructural
features such as shape and size obtained using AFM and TEM distinguishes L from its Hg2+ complex and were different from
those of the simple mercuric perchlorate. L is also suited
to sense pyrimidine bases by fluorescence quenching with a minimum
detection limit of 1.15 ± 0.1 ppm in the case of cytosine. The
nature of interaction of pyrimidine bases with L has
been further studied by DFT computational calculations and found to
have interactions through a hydrogen bonding and NH-π interaction
between the host and the guest.