Development of self-organized materials using anion-controllable interaction

本文简要总结了对标题的研究。1)自组织阴离子传感器与茜素作为一个报告作为我们正在进行的项目，开发化学传感器检测化学和生物学上重要的阴离子，我们合成了几个苯基硼酸衍生物作为受体部分。它与儿茶酚的茜素作为一个报告单元的组合，使我们能够提出自组织传感器系统。茜素-邻氨基甲基苯硼酸自组织荧光传感器在pH 5.5的水-甲醇（1：4 w/w）介质中对氟离子具有高选择性响应。在另一方面，Zn 2<II>-DPA（DPA =吡啶二甲基胺）-附加的苯基硼酸在中性条件下与茜素染料形成组装体。添加焦磷酸盐（Ppi）引起复合物的重组以产生替代硼酸酯组装并引起荧光增加。相关的双（Zn^<II>-DPA）-附加的苯基硼酸- ARS（茜素红S）系综表现出对植酸的选择性响应。2)离子对驱动的分子胶囊利用可逆的硼酸酯酯化，我们已经开发了离子对驱动的环三儿茶烯1和硼酸附加的六均三氧杂杯[3]芳烃2的异二聚体胶囊形成。虽然1在质子溶液中不与2相互作用，但在Et 4 NAcO存在下，通过硼酸酯化作用定量形成异二聚体胶囊，这在含有^1H、^1H ROESY和DOSY的NMR中观察到，这是阴离子诱导的硼酸酯形成和Et_4N^+模板的直接结果。可逆硼酸酯酯化允许我们使用pH切换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.