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[摘要]：A new 1,3-diderivative of calix[4]arene appended with hydroxymethyl salicylyl imine has been synthesized and its on recognition toward biologically relevant Mn+ ions studied. The receptor H2L showed selectivity toward Zn2+ by switch-on fluorescence among the 12 metal ions studied with a detection limit of 192 ppb. The interaction of Zn2+ with HA, has been further supported by absorption studies, and the stoichiometry of the complex formed (1:1) has been established on the basis of absorption and ESI MS. Competitive ion titrations carried out reveal that the Zn2+ can be detected even in the presence of other metal ions of bioimportance. The mode of interaction of Zn2+ with conjugate has been established by a fleet of computational calculations carried out in a cascade manner, either on the ligand or on the complex, wherein the final optimizations were carried out by the density functional theory (DFT) and found that the Zn2+ and Cd2+ indeed bind differently. In situ prepared [ZnL] complex responds to both inorganic phosphate as well as AM P. ADP, and ATP with a minimum detection limit of 426 ppb wherein the Zn2+ from the complex is detached and recomplexed by the added phosphate moiety. It has been possible to build an INHIBIT logic gate for the conjugate using Zn2+ and HPO42- as inputs by monitoring the fluorescence emission band at 444 nm as output. The amino acid sensing abilities of [ZnL] have been explored by fluorescence and absorbance spectroscopy where it showed selectivity toward Cys, Asp, and His through the formation of the Zn2+ complex of these amino acids by chelating through their side chain moieties. Thus, while H2L is selective for Zn2+ among it number of cations, the [ZnL] is selective toward phosphate among a number of anions and also toward Asp, Cys, and His among the naturally occurring amino acids. |
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