Macrocyclic compound as ionophores in lead(Ⅱ) ion-selective electrodes with excellent response characteristics

Macrocyclic compounds,such as crown ethers,azacrown ethers,thiacrown ethers,calixarenes and porphyrins,which act as ionophores in lead(Ⅱ) ion-selective electrodes,are systematically summarized based on the latest literatures.The molecular structure characteristics of the ionophores are general-ized.The modification regulations for the substituted ionophores are elaborated with the purpose of improving the response features of the lead(Ⅱ) ion-selective electrodes assembled by them.It is pointed out that the introduction of pendant moieties which contain soft base coordination centers like N,S and P atoms is in favor of adjusting the cavity size and conformation of the macrocyclic com-pounds.Furthermore,there is synergic effect between the cavity and the donor sites of the ligand and thus the selective complexation of lead ions is easily realized,resulting in significant avoidance of the interference from other metal ions.The macrocyclic ionophore having the best response characteris-tics thus far was found to be N,N'-dimethylcyanodiaza-18-crown-6 with the detection limit of 7.0×10-8(14.5 μg/L),which is one of the uncommon ionophores that can really eliminate the interference from silver and mercury ions.The selectivity coefficients of the ionophore for lead ions over other metal ions,such as alkali,alkaline earth and transition metal ions are in the order of 10-4 or smaller,where the se-lectivity coefficient of lead(Ⅱ) over mercury(Ⅱ) ions is much lower,down to 8.9×10-4.The structure de-sign idea for high-performance ionophore is proposed according to present results.The incorporation of nitrogen atom,especially cyano group or thiocyano group or amino/imino groups,rather than thio atom alone could result in new excellent lead ionophores.The aborative design for metacyclophanes containing aromatic nitrogen atoms with the aim of creating excellent ionophores would also become a potential research trend.The lead(Ⅱ) ion-selective electrodes have shown widely potential applications in the potentiometric titration,and flow injection potentiometry,and in the direct determination of lead in stack emissions of lead smelters,and assay of lead in rocks,particularly in the direct measurements of trace amount of lead(Ⅱ) in human hair,blood,edible oil,food,water,and air.