Development of self-organized materials using anion-controllable interaction

对本课题的研究进行了简要的总结。1)以茜素为报告分子的自组织阴离子传感器作为我们正在进行的用于检测化学和生物重要阴离子的化学传感器的研究项目，我们合成了几个苯基硼酸衍生物作为受体。它与含儿茶酚的茜素作为报告单元的结合使我们能够提出自组织传感器系统。由茜素和邻氨基甲基苯基硼酸组成的自组织荧光传感器在pH为5.5的水-甲醇(1：4w/w)中显示出高选择性的氟离子响应。另一方面，在中性条件下，添加了苯基硼酸的苯基硼酸与茜素染料形成了组装体。焦磷酸盐(PPI)的加入会导致络合物的重组，产生替代的硼酸酯组装，并导致荧光增加。相关的双(锌离子)-苯基硼酸络合物(茜素红S)对植酸盐有选择性反应。2)离子对驱动的分子胶囊利用可逆硼酸酯的酯化反应我们发展了离子对驱动的异二聚体胶囊的形成。虽然1在质子液中不与2相互作用，但在Et4NAcO的存在下，在含有^1H，^1H ROESY和DOSY的核磁共振中观察到了通过含^1H，^1H ROESY和DOSY的核磁共振定量地形成了一个异二聚体胶囊，这是阴离子诱导的硼酸酯形成和Et_4N^模板的直接结果。可逆的硼酸酯化反应使我们能够通过pH切换来选择性地控制胶囊组装。

We briefly summarized the research on the title. 1) Self-organized anion sensors with alizarins as a reporter As our on-going project for developing chemosensors for the detection of chemically and biologically important anions, we synthesized several phenylboronic acid derivatives which act as a receptor moiety. The combination of it with catecholcontained alizarins as a reporter unit allows us to propose self-organized sensor systems. A self-organized fluorescent sensor consisting of alizarin and o-aminomethylphenylboronic acid shows a highly selective fluoride ion-response in H_2O-MeOH (1: 4 w/w) at pH 5.5. On another front, Zn^<II>-DPA (DPA = dipicolylamine)-appended phenylboronic acid forms an assembly with alizarin-dye under neutral conditions. Addition of pyrophosphate (Ppi) causes reorganization of the complex to produce an alternative boronate ester assembly and caused an increase in fluorescence. The related bis (Zn^<II>-DPA)-appended phenylboronic acid - ARS (alizarin red S) ensemble exhibited a selective response for phytate. 2) Ion-pair driven molecular capsule Taken advantage of reversible boronate esterification we have developed the ion pair-driven heterodimeric capsule formation of a cyclotricatechylene 1 and a boronic acid-appended hexahomotrioxacalix [3] arene 2. Although 1 does not interact with 2 in a protic solution, in the presence of Et4NAcO quantitative formation of a heterodimeric capsule via boronate esterification was observed in the NMR containing ^1H, ^1H ROESY and DOSY, a direct result of anion-induced boronate ester formation and the Et_4N^+ template. Reversible boronate esterification allowed us to selectively control capsule assembly using pH switching.