Abstract：
Three kinds of coordination cages and a molecular knot with inductively activated +P-H, N-H, or C-H hydrogen bond donors anchoring in the functionalized cavities were inspected as ionophores to develop polymeric membrane ISEs for potentiometric sensing of environmentally important oxyanions and halides. The proposed ISEs displayed significant preference for perrhenate, phosphate, or chloride with a selectivity pattern distinctively different from the sequence depending on the Gibbs free energy of hydration owing to the high degree of shape, charge, and size selectivity originating from the rigidity and complementarity of the binding cavities. To gain further insight into the response characters of the proposed ISEs, the binding constants of ionophore-anion complexes in the membrane phase were investigated, and the binding affinity, together with the Hofmeister series, correlates well with the determined selectivity pattern of the proposed ISEs. Optimizing the composition of the membrane such as lipophilic additives and plasticizers produced ISEs displaying Nernstian/near-Nernstian potentiometric responses to primary anions with a wide linear range, improved detection limits, good reversibility, and satisfying lifetime. Potentiometric determination of perrhenate, phosphate, and chloride in river water, mineral water, and artificial serum samples was achieved with good recovery and accuracy using the proposed ISEs, demonstrating their potential for real-life applications. These results will shed new light on how novel ionophores could be designed for potentiometric sensing and broaden the scope of host-guest chemistry of coordination cages and molecular knots.
摘要：
三种配位笼和一个分子结具有诱导激活的+P-H，N-H,将锚定在功能化腔中的C-H氢键供体作为离子载体进行检查，以开发聚合物膜ISE，用于对环境重要的氧阴离子和卤化物进行电位传感。拟议的ISE显示出对高铼酸盐的显著偏好，磷酸盐,或氯化物，其选择性模式明显不同于序列，这取决于高度形状的Gibbs水合自由能，charge,和大小选择性源于结合腔的刚性和互补性。为了进一步了解拟议的ISE的响应特征，研究了膜相中离子载体-阴离子复合物的结合常数，和结合亲和力，和Hofmeister系列一起,与所提出的ISE的确定的选择性模式密切相关。优化膜的组成，例如亲脂性添加剂和增塑剂，产生的ISE显示Nernstian/near-Nernstian电位对初级阴离子的响应，具有很宽的线性范围，提高了检测限，良好的可逆性，满足一生。高铼酸盐的电位测定,磷酸盐,和河水中的氯化物，矿泉水,使用拟议的ISE，人工血清样品具有良好的回收率和准确性，展示它们在现实生活中的应用潜力。这些结果将为如何设计新型离子载体以进行电位传感提供新的思路，并拓宽配位笼和分子结的主客体化学的范围。
