Study on function-programmed molecular systems based on shape control

我们总结了我们的研究成果：1.大环双(锌(II)-卟啉)协同诱导手性1我们有兴趣开发具有“动态”功能与手性耦合的新型分子体系，使我们能够合成具有大环基构象柔性的冠醚-双(锌(II)-卟啉)共轭化合物。与手性二胺络合时的非手性到手性的转变是由冠层中的K~(++)促进的。此外，冠醚的电离性使我们能够通过液体(1在CH2Cl2中)-(氨基酸在1N KOH水溶液中)两相萃取，用圆二色谱(CD)读出氨基酸的手性。通过这种方式，观察到了冠醚和卟啉在手性诱导中的有趣的协同效应。2.使用15-冠-5衍生的金属卟啉2的自组织手性探针在加入…时没有显示CD光谱作为一种手性二胺，溶液中K^+的存在使我们能够检测到与手性相关的显著CD光谱。这可以归因于[K^+-手性二胺-(2a)_2]络合物的形成。在镁(II)卟啉衍生物2b和手性氨基醇的情况下也观察到了类似的现象。3.自组织分子传感器已被用于金属离子和阴离子的自组织荧光传感器的一种新的设计策略。首先，在中性条件下，茜素红S(ARS)能与苯基硼酸(PBA)有效结合，是选择性检测金属离子的良好荧光指示剂；通过加入金属离子，茜素红-PBA能有效地选择性猝灭荧光。研究还发现，阴离子诱导的苯基硼酸酯能有效地与茜素结合，大大增强了在甲醇中的荧光。这种观察使设计新的自组织阴离子传感系统成为可能。较少

We summarized our research results on the title.1.Cooperative chirality induction using a bis(Zn(II)-prophyrin) with a large ring-size crown ether 1Our interest in developing novel molecular systems possessing "dynamic" functions coupled with chirality let us to synthesize a crown ether-bis(Zn(II)-porphyrin) conjugate with the large ring-based conformation flexibility. The achiral-to-chiral transformation upon complexation with chiral diamines is assisted by K^+ accommodated in the crown moiety. Further, the ionophoric property of crown ether enables us to read out the chirality of amino acids using circular dichroism (CD) spectra through liquid (1 in CH_2Cl_2) - (amino acids in 1N KOH aqueous solution) two-phase extraction. In this way, an intrigued synergistic effect of crown ether and porphyrins was observed on chirality induction.2.A self-organized chiral probe using 15-crown-5-derived metalloporphyrin 2Although 15-crown-5-derived Zn(II)-porphyrin 2a shows no CD spectra when adding … More a chiral diamine, the presence of K^+ in the solution allowed us to detect a significant CD spectra correlated with the chirality. The insight can be ascribed to a [K^+-chiral diamine - (2a)_2] complex formation. Similar phenomena were also observed for the case of Mg(II) porphyrin derivative 2b and chiral aminoalcohols.3.Self-organized molecular sensorsAlizarin-phenylboronic acid interactions have been used in a new design strategy for self-organized fluorescent sensors of metal ions and anions. First, Alizarin Red S (ARS), which binds effectively to phenylboronic acid (PBA) at neutral conditions in water, proved to be an excellent fluorescent indicator for the selective detections of metal ions ; the fluorescent ARS-PBA ensemble causes an efficient and selective quenching in the fluorescence by adding metal ions. It was also found that anion-induced phenylboronates can bind effectively to alizarin and greatly enhance the fluorescence in MeOH. The observation makes it possible to design new self-organized anion sensory systems. Less