Development of Novel Sensors Using Macrocyclic Polyamines as Sensory Elements

以大环多胺及其相关化合物为传感元件，构建了一种新型的化学传感器。结果表明：(1)大环多胺液膜电极对腺苷核苷酸和二羧酸盐等有机阴离子具有很强的电位响应和明显的选择性。观察到了基于客体分子内电荷大小或电荷间距的电位选择性。(2)在实验pH下，这些电极对非离子形式的邻苯二酚和相关化合物也表现出电位响应。系统的研究表明，质子喷射是一种可能的对未带电分子进行电位响应的机制。(3)作为阴离子选择性液膜电极的新型传感元件，Sapporrin(扩展的卟啉)和胞嘧啶-侧链三胺被考察。(4)以多胺为主体制备了阴离子响应型Langmuir-Blodgett膜传感器。通过循环伏安法检测分析物诱导的渗透率变化来评价有机阴离子的选择性。

A novel type of chemical sensors were constructed by using macrocyclic polyamines and related compounds as sensory elements. Potentiometric responses and selectivities were investigated and the following results were obtained, demonstrating a remarkable potentiality of this class of hosts as novel sensory elements.(1) The macrocyclic polyamine liquid membrane electrodes showed strong potentiometric responses and marked selectivities for organic anions such as adenosine nucleotides and dicarboxylates. Potentiometric selectivities based on the magnitude of charge or the distance between charges within the guest molecule were observed.(2) These electrodes also showed potentiometric responses to catechol and related compounds that are in the nonionic forms at the experimental pH. A systematic investigation demonstrated proton ejection as a possible mechanism for potentiometric responses to the uncharged molecules.(3) Sapphyrin (expanded porphyrin) and cytosine-pendant triamine were examined as novel sensory elements for anion-selective liquid membrane electrodes.(4) Anion responsive Langmuir-Blodgett (LB) membrane sensors were fabricated with polyamine hosts. Selectivities for organic anions were evaluated on the basis of analyte-induced permeability changes detected by cyclic voltammetry.