Development and application of high-performance electrochemical sensors for detecting biologically active substances

包括离子选择电极在内的电化学传感器的开发和应用一直是研究的热点。在这项研究中，我们用高氧杯[3]芳烃和杯芳烃衍生物开发了新型的有机铵离子选择电极。这些具有C_3或C_6对称性的衍生物对初级有机铵离子具有较好的识别能力。由于伯铵离子是C_3对称的质子供体，所以带有C_3对称排列质子受体的受体可以与伯铵离子相互作用。此外，这些衍生物的苯酚残基的芳香壁产生的疏水空腔可能有助于有机铵离子的非极性部分的包合。在筛选高氧杯[3]芳烃和杯[6]芳烃衍生物对包括生物胺在内的各种有机铵离子的反应过程中，我们发现tris(methoxyphenylpropyloxy)hexahomooxacalix[3]arene-triethyl醚对5-羟色胺反应强烈，而对叔丁基杯[6]芳烃-六乙酸六乙酯对乙铵反应强烈。这表明高氧杯[3]芳烃的空腔足够展开，可以与5-羟色胺等大分子相互作用，而杯[6]芳烃的空腔非常小，导致与乙基铵的有效相互作用。我们还发现，杯[8]芳烃比杯[6]芳烃具有更大的空腔，它对具有复杂结构的生物活性胺起反应，如去甲麻黄碱。杯[8]芳烃类化合物利用较大的空腔，在质子受体位置选择合适的位置与伯胺类化合物相互作用，有效识别体积大、结构复杂的有机铵离子，并应用离子选择电极分析了多胺类化合物与大肠杆菌细胞外膜的相互作用。这一结果以及本研究中取得的其他结果可以通过本报告后面所述的参考文献看到。

The development and application of electrochemical sensors including ion selective electrode continue to be an area of focus. In this study, we developed new organic ammonium ion selective electrodes using homooxacalix[3]arene and calixarene derivatives. These derivatives with C_3 or C_6 symmetry are known to be effective in the recognition of primary organic ammonium ions. Since primary ammonium ions act as C_3-symmetrical proton donors, receptors bearing a C_3 symmetrically arranged proton acceptor site can interact with primary ammonium ions. Moreover, the hydrophobic cavities generated by the aromatic walls of phenol residues of these derivatives are potentially useful for the inclusion of non polar moieties of organic ammonium ions. In the process of screening homooxacalix[3]arene and calix[6]arene derivatives for responses to various organic ammonium ions including biogenic amines, we found that tris(methoxyphenylpropyloxy)hexahomooxacalix[3]arene-triethyl ether, responds strongly to serotonin, while p-tert-butylcalix[6]arene-hexaacetic acid hexaethyl ester responds to ethylammonium. This suggested that the cavity of homooxacalix[3]arene was spread out enough to interact with large molecules such as serotonin, while the cavity of calix[6]arene was so small, leading to effective interaction with ethylammonium. We also found that calix[8]arene, having larger cavity than calix[6]arene, responded to biologically active amines having a complicated structure, such as norephedrine. Calix[8]arene derivatives made effective recognition of bulky and complicated organic ammonium ions, using a large cavity and choosing an appropriate position at the proton acceptor sites to interact with these primary amines.We also applied ion selective electrodes to analyze the interaction between polyamines and the outer membrane of Escherichla coli cells. This and other results obtained in this study can be seen through references described in the back of this report.