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基于国内外最新研究文献,系统总结了应用于高性能铅离子选择电极的大环化合物载体,具体涉及到冠醚、氮杂冠醚、硫醚、杯芳烃和卟啉等.归纳了其分子结构特征,重点论述了以提高铅离子选择电极性能为目的所做的取代改性规律.指出在大环化合物中对称性地引入含有软碱配位中心如氮原子、硫原子和磷原子的取代基,不仅能调节大环化合物的空腔大小和构型,而且取代基还能够和空腔一起发挥协同络合作用,实现对铅离子的选择性络合,避免其他离子干扰.迄今为止性能最优异的大环化合物衍生物载体是在氮杂冠醚中引入极性的氰基基团形成的N,N′-二甲基腈乙基二氮杂-18-冠-6载体,它对铅离子的检出限低7.0×10-8(14.5μg/L).碱金属、碱土金属和过渡金属离子的干扰系数均在10-4数量级及其以下,其中汞离子的干扰系数低至为8.9×10-4,成为目前难得的能够真正排除银离子和汞离子干扰的少数载体之一.依据现有研究结果,提出了高性能载体分子的设计思路,即在大环化合物中引入氮原子,尤其是引入氰基或硫氰基或(亚)氨基而不是仅引入硫原子能够获得新型高选择性铅离子载体;精心设计含芳香氮原子的环番也不失为新型铅离子载体的研究方向.铅离子选择电极在电位滴定、流动注射电位测量分析、冶炼厂烟道排泄废气检测、岩石铅含量化验、尤其是在头发、血液、食用油、食品、水和空气等痕量铅的测定中展现出了广阔的应用前景.
Based on the latest research literature at home and abroad, the macrocyclic compound carriers applied to high performance lead ion selective electrodes are systematically summarized, including crown ethers, aza crown ethers, thioethers, calixarenes and porphyrins, etc. The molecular structures Characteristics, the emphasis is laid on the substitution and modification rules for the purpose of improving the performance of the lead ion selective electrode.It is pointed out that the symmetric introduction of the substituent containing a soft base coordination center such as a nitrogen atom, a sulfur atom and a phosphorus atom into the macrocyclic compound , Not only can adjust the size and configuration of the macrocyclic cavity size, but also with the cavity and substituents can also play a synergistic complexing effect, to achieve selective complexation of lead ions, to avoid interference from other ions. So far the best performance Of the macrocyclic compound derivative carrier is a N, N’-dimethylnitrile ethyldiazepin-18-crown-6 carrier formed by introducing a polar cyano group into aza crown ethers, which is sensitive to lead ions The detection limit was 7.0 × 10-8 (14.5 μg / L) .The interference coefficients of alkali metals, alkaline earth metals and transition metal ions were all in the order of 10-4, and the interference coefficient of mercury ion was as low as 8.9 × 10-4, become the rare to really ruled out Ions and mercury ions.According to the existing research results, the design idea of high performance carrier molecule is proposed, which is to introduce nitrogen atom into macrocyclic compound, especially to introduce cyano or thiocyanato or Amino instead of introducing only sulfur atoms to obtain a new type of highly selective lead ion carrier; well-designed ring containing aromatic nitrogen atoms is also the research direction of the new lead ion carrier.Pelectrophoresis of lead ion selective electrode in the potential measurement, flow injection potential measurement and analysis, Smelter flue gas emissions testing, testing of rock lead content, especially in the hair, blood, cooking oil, food, water and air trace trace lead showed a broad application prospects.